Radical polymerizable resin composition and pipe repair lining material

Abstract

Provided is a radical-polymerizable resin composition which has excellent curability in a temperature range of about 50-80 DEG C and excellent storage stability in a low-temperature range of 20 DEG C or less. This radical-polymerizable resin composition contains a radical-polymerizable resin (A), an ethylenically unsaturated compound (B), a free group-containing compound (C), and a curing agent (D). The free radical-containing compound (C) is 2, 2, 6, 6-tetramethylpiperidine-1-oxygen free radical and an analogue thereof. The curing agent (D) has a 10-hour half-life temperature of 40 DEG C to 120 DEG C.

Description

Technical Field

[0001] The invention relates to a free radical polymerizable resin composition and a pipe repair lining material.

[0002] This application claims priority based on Japanese Patent Application No. 2022-173529 filed in Japan on October 28, 2022, the contents of which are incorporated herein by reference. Background Art

[0003] In recent years, the aging of underground pipes such as water pipes, agricultural water pipes, and industrial water pipes has become increasingly serious, and various methods for repairing them have been proposed.

[0004] For example, Patent Document 1 discloses a method for repairing a pipe. The method for repairing a pipe includes the following curing step: a tubular prepreg is made to fit tightly against the inner wall of a pipe buried underground, compressed air is supplied to the interior of the prepreg, and warm water or steam is flowed into the interior of the prepreg, thereby curing the prepreg. In addition, it is described that a prepreg obtained by impregnating a reinforcing material composed of fibers and the like with a thermosetting resin composition can be used as the prepreg. It is described that as the thermosetting resin composition, a thermosetting resin composition obtained by dissolving a resin such as an unsaturated polyester resin, an epoxy acrylate resin, etc. in an ethylenically unsaturated compound such as styrene and (meth)acrylate can be used.

[0005] According to Patent Document 2, it is necessary to simultaneously achieve extended storage stability and rapid curing for a prepreg comprising a radical polymerizable resin and a curing agent. Patent Document 2 discloses a product having a usable time of more than 60 hours at 20°C and a gelling time of less than 10 minutes at 70°C by combining an epoxy (meth)acrylate resin and a urethane (meth)acrylate resin with a specific curing agent.

[0006] Furthermore, Patent Document 3 discloses that an acid component is added to an unsaturated polyester resin and a specific curing agent is combined to achieve a usable life of 180 days or more at 40° C. and a gelation time of 1 minute or less at 150° C.

[0007] On the other hand, due to the increase in the glass content of prepregs for pipe and channel repair and the influence of water leakage associated with the progress of deterioration of existing pipes, a radical polymerizable resin composition having excellent curability at a lower temperature is desired.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent No. 2501048

[0011] Patent Document 2: Japanese Patent No. 6460999

[0012] Patent Document 3: Japanese Patent No. 6653713 Summary of the invention

[0013] Problems to be solved by the invention

[0014] The present invention is proposed to solve the above-mentioned problems, and its purpose is to provide a free radical polymerizable resin composition and a pipe repair lining material, wherein the free radical polymerizable resin composition has excellent curing properties in a temperature range of about 50°C to 80°C and excellent storage stability in a low temperature range of 20°C or less.

[0015] Means for solving problems

[0016] The present invention includes the following aspects.

[0017] [1] A radical polymerizable resin composition comprising a radical polymerizable resin (A), an ethylenically unsaturated compound (B), a free radical-containing compound (C) and a curing agent (D),

[0018] The free radical-containing compound (C) is 2,2,6,6-tetramethylpiperidin-1-oxyl free radical and its analogs,

[0019] The 10-hour half-life temperature of the curing agent (D) is 40° C. to 120° C.

[0020] [2] The radically polymerizable resin composition according to [1], wherein the curing agent (D) comprises at least one curing agent selected from the group consisting of diacyl peroxides, peroxydicarbonates, peroxyesters, peroxyketals and dialkyl peroxides.

[0021] [3] The free radical polymerizable resin composition according to [1] or [2], characterized in that the curing agent (D) comprises at least one curing agent selected from the group consisting of dilauroyl peroxide, bis(4-tert-butylcyclohexyl) peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-hexyl peroxy-2-ethylhexanoate and tert-butyl peroxybenzoate.

[0022] [4] The radically polymerizable resin composition according to any one of [1] to [3], wherein the content of the ethylenically unsaturated compound (B) is 10 to 95% by mass relative to the total of the radically polymerizable resin (A) and the ethylenically unsaturated compound (B).

[0023] [5] The radical polymerizable resin composition according to any one of [1] to [4], wherein the content of the radical-containing compound (C) is 0.005 to 1.000 parts by mass relative to 100 parts by mass of the total of the radical polymerizable resin (A) and the ethylenically unsaturated compound (B).

[0024] [6] The radical polymerizable resin composition according to any one of [1] to [5], wherein the content of the curing agent (D) is 0.5 to 5.0 parts by mass based on 100 parts by mass of the total of the radical polymerizable resin (A) and the ethylenically unsaturated compound (B).

[0025] [7] The radically polymerizable resin composition according to any one of [1] to [6], further comprising a metal soap (E).

[0026] [8] The radically polymerizable resin composition according to [7], wherein the metal contained in the metal soap (E) is at least one metal selected from the group consisting of chromium, manganese, iron, cobalt, nickel and copper.

[0027] [9] The radically polymerizable resin composition according to any one of [1] to [8], further comprising a fiber substrate (F).

[0028]

[10] A cured product, which is a cured product of the radical polymerizable resin composition according to any one of [1] to [9], characterized in that it is used as a pipe repair lining material.

[0029]

[11] A pipe repair lining material using the radical polymerizable resin composition according to any one of [1] to [9].

[0030]

[12] A pipe channel, which is repaired using the pipe repair lining material described in

[11] .

[0031] Effects of the Invention

[0032] According to the present invention, a radical polymerizable resin composition can be provided which has excellent curability in a temperature range of about 50° C. to 80° C. and excellent storage stability at 20° C. or lower. DETAILED DESCRIPTION

[0033] Hereinafter, the present invention will be described in more detail. It should be noted that the present invention is not limited to the embodiments described below.

[0034] “~” means a value greater than or equal to the value before the description “~” and less than or equal to the value after the description “~”. “(Meth)acrylic-” is a general term for acrylic- and methacrylic-, and “(meth)acrylate” is a general term for acrylate and methacrylate.

[0035] The term “ethylenically unsaturated bond” refers to a double bond formed between carbon atoms other than carbon atoms forming an aromatic ring, and the term “ethylenically unsaturated compound” refers to a compound having an ethylenically unsaturated bond.

[0036] The “weight average molecular weight Mw” (hereinafter, also simply referred to as “Mw”) and the “number average molecular weight Mn” (hereinafter, also simply referred to as “Mn”) are molecular weights calculated in terms of standard polystyrene and obtained by gel permeation chromatography (GPC) measurement.

[0037] [Radical polymerizable resin composition]

[0038] The radical polymerizable composition according to one embodiment of the present invention comprises a radical polymerizable resin (A), an ethylenically unsaturated compound (B), a free radical-containing compound (C) and a curing agent (D). The radical polymerizable composition according to one embodiment of the present invention may further comprise a metal soap (E), a fiber substrate (F) or other additives (G) as required.

[0039] (Radical polymerizable resin (A))

[0040] The radical polymerizable resin according to the present embodiment is not particularly limited as long as it has one or more radical reactive functional groups in the molecule.

[0041] Examples of the radical polymerizable resin (A) include unsaturated polyester resins (A1), epoxy (meth)acrylate resins (A2), and urethane (meth)acrylate resins (A3).

[0042] Among the examples of the radical polymerizable resin (A), unsaturated polyester resin (A1) and epoxy (meth)acrylate resin (A2) are preferred from the viewpoint of strength and chemical resistance of the cured product.

[0043] [Unsaturated polyester resin (A1)]

[0044] The unsaturated polyester resin (A1) is not particularly limited as long as it is obtained by polycondensing a polyol and an unsaturated polyacid with at least one selected from a saturated polyacid and a monoacid used as required. The so-called unsaturated polyacid is a polyacid having an ethylenically unsaturated bond, and the so-called saturated polyacid is a polyacid not having an ethylenically unsaturated bond. The unsaturated polyester resin may be used alone or in combination of two or more.

[0045] <Polyol>

[0046] Polyols are not particularly limited as long as they are compounds having more than two hydroxyl groups. Among them, preferably ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, pentanediol, hexylene glycol, neopentyl glycol, 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, glycerol, bisphenol A oxidized ethylene adducts and bisphenol A oxidized propylene adducts, more preferably ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, hydrogenated bisphenol A, bisphenol A oxidized ethylene adducts and bisphenol A oxidized propylene adducts, further preferably propylene glycol, diethylene glycol, neopentyl glycol. Polyols can be used alone or in combination of two or more.

[0047] <Unsaturated polyacid>

[0048] The unsaturated polyacid is not particularly limited as long as it is a compound or anhydride thereof having an ethylenically unsaturated bond and having more than two carboxyl groups. For example, maleic acid, maleic anhydride, fumaric acid, citraconic acid, itaconic acid, chloromaleic acid, etc. can be cited. Among them, from the viewpoint of heat resistance and mechanical strength of the cured product, maleic anhydride, fumaric acid, citraconic acid, itaconic acid and chloromaleic acid are preferred, and maleic anhydride and fumaric acid are more preferred. The unsaturated polyacid can be used alone or in combination of two or more.

[0049] <Saturated polyacid>

[0050] Saturated polyacid is not particularly limited as long as it is a compound or its anhydride without olefinic unsaturated bonds and with more than 2 carboxyl groups. For example, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, methylene tetrahydrophthalic anhydride, nitrophthalic acid, tetrahydrophthalic anhydride, halogenated phthalic anhydride, oxalic acid, malonic acid, azelaic acid, glutaric acid and hexahydrophthalic anhydride etc. can be enumerated. Wherein, from the viewpoint of the heat resistance and mechanical strength of cured product etc., preferably phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, methylene tetrahydrophthalic anhydride and tetrahydrophthalic anhydride, more preferably phthalic anhydride, isophthalic acid and terephthalic acid. The saturated polybasic acid may be used alone or in combination of two or more.

[0051] <Monoacid>

[0052] As the monoacid, dicyclopentadiene maleate, benzoic acid and its derivatives, cinnamic acid and its derivatives can be cited, preferably dicyclopentadiene maleate. Dicyclopentadiene maleate can be synthesized from maleic anhydride and dicyclopentadiene by a known method. By using a monoacid, the viscosity of the unsaturated polyester resin can be reduced, and the amount of styrene used can be reduced. The monoacid can be used alone or in combination of two or more.

[0053] 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 further 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 becomes better. It should be noted that in this specification, the "weight average molecular weight" is a value converted to standard polystyrene measured by gel permeation chromatography (GPC: gel permeation chromatography).

[0054] The unsaturation degree of the unsaturated polyester resin (A1) is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and further preferably 70 to 100 mol%. If the unsaturation degree is within the above range, the moldability of the thermosetting resin composition containing the unsaturated polyester resin (A1) becomes better. The unsaturation degree of the unsaturated polyester resin (A1) can be calculated by the following formula using the molar number of the unsaturated polyacid and the saturated polyacid used as the raw material. Among them, the number of unsaturated groups in the unsaturated polyacid is set to 1.

[0055] Unsaturation (mol%) = {(number of moles of unsaturated polyacid) / (number of moles of unsaturated polyacid + number of moles of saturated polyacid)} × 100

[0056] The acid value of the unsaturated polyester resin (A1) is not particularly limited. From the viewpoint of water resistance and chemical resistance, the acid value of the unsaturated polyester resin (A1) is preferably 0 to 50 mgKOH / g, more preferably 3 to 40 mgKOH / g, and even more preferably 5 to 30 mgKOH / g.

[0057] The unsaturated polyester resin (A1) can be synthesized, for example, using the above-mentioned raw materials by the method described in the Polyester Resin Handbook (Nikkan Kogyo Shimbun, published in 1988). The various conditions in the synthesis of the unsaturated polyester resin (A1) can be appropriately set according to the raw materials used and their amounts. Usually, an esterification reaction under pressure or reduced pressure can be adopted at a temperature of 140 to 230° C. in a gas flow of an inert gas such as nitrogen. In the esterification reaction, an esterification catalyst can be used as needed. As examples of esterification catalysts, known catalysts such as manganese acetate, dibutyltin oxide, stannous oxalate, zinc acetate and cobalt acetate can be cited. The esterification catalyst can be used alone or in combination of two or more.

[0058] As an example of the synthesis of the unsaturated polyester resin (A1), for example, the following method can be mentioned: the esterification reaction is carried out under the above reaction conditions, and the reaction is terminated when the acid value reaches 5 to 30 mgKOH / g. In this example, unreacted monomers may be contained at the time of the completion of the reaction.

[0059] As a commercial item of the said unsaturated polyester resin (A1), "RIGOLRACK (registered trademark)" etc. are mentioned, for example by Showa Denko K.K..

[0060] 〔Epoxy (meth)acrylate resin (A2)〕

[0061] As epoxy (meth) acrylate resin (A2), it is a compound having an ethylenically unsaturated bond obtained by a ring-opening reaction of an epoxy group and a carboxyl group. The above-mentioned epoxy group is an epoxy group in an epoxy compound (a) having two or more epoxy groups, and the above-mentioned carboxyl group is a carboxyl group of an unsaturated monobasic acid (b) having an ethylenically unsaturated bond and a carboxyl group. The so-called unsaturated monobasic acid is a monobasic acid having an ethylenically unsaturated bond. Such epoxy (meth) acrylate resin (A2) can include, for example, "リポキシ (registered trademark)" manufactured by Showa Denko K.K. The epoxy (meth) acrylate resin can be used alone or in combination of two or more.

[0062] The acid value of the epoxy (meth)acrylate resin (A2) is not particularly limited. From the viewpoint of chemical resistance and water resistance, the acid value of the epoxy (meth)acrylate resin (A2) is preferably 0 to 50 mgKOH / g, more preferably 0 to 40 mgKOH / g, and even more preferably 0 to 30 mg / g.

[0063] The weight average molecular weight of the epoxy (meth)acrylate resin (A2) is not particularly limited. The weight average molecular weight of the epoxy (meth)acrylate resin (A2) is preferably 700 to 30,000, more preferably 700 to 20,000, and even more preferably 700 to 15,000.

[0064] <Epoxy Compounds>

[0065] 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 bisphenol epoxy resin, hydrogenated bisphenol epoxy resin and novolac phenol epoxy resin can be used. Such epoxy resin can further improve the mechanical strength and corrosion resistance of the cured product.

[0066] Examples of the bisphenol-type epoxy resin include bisphenol-A, bisphenol-F, bisphenol-S, tetrabromobisphenol-A and other bisphenols obtained by reacting epichlorohydrin or methyl epichlorohydrin; or bisphenol-A glycidyl ether, condensates of the above bisphenol compounds and epichlorohydrin or methyl epichlorohydrin.

[0067] Examples of the hydrogenated bisphenol epoxy resin include hydrogenated bisphenol epoxy resins obtained by reacting glycidyl ether of hydrogenated bisphenol A with a bisphenol compound such as bisphenol A, bisphenol F, bisphenol S, and tetrabromobisphenol A.

[0068] Examples of the novolac phenol type epoxy resin include a novolac phenol type epoxy resin obtained by reacting phenol novolac or cresol novolac with epichlorohydrin or methyl epichlorohydrin.

[0069] Among epoxy resins, from the viewpoint of chemical resistance, bisphenol-type epoxy resins are preferred, and bisphenol A epoxy resins are more preferred.

[0070] <Unsaturated monobasic acid>

[0071] As the unsaturated monocarboxylic acid, there is no particular limitation 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 further preferably acrylic acid. The epoxy (meth) acrylate resin (A2) obtained by reacting at least one selected from (meth) acrylic acid with an epoxy resin has high hydrolysis resistance relative to acids and alkalis, and therefore, can further improve the corrosion resistance of the cured product.

[0072] When the epoxy compound and the unsaturated monobasic acid are subjected to a ring-opening reaction, the amount of the unsaturated monobasic acid used is preferably 0.3 to 1.5 equivalents, more preferably 0.4 to 1.2 equivalents, and particularly preferably 0.5 to 1.0 equivalents relative to 1 equivalent of the epoxy group of the epoxy compound. If the amount of the unsaturated monobasic acid used is within the range of 0.3 to 1.5 equivalents relative to 1 equivalent of the epoxy group of the epoxy compound, a cured product having sufficient hardness can be obtained by a free radical polymerization reaction of the thermosetting resin composition containing the epoxy (meth)acrylate resin (A2).

[0073] The epoxy (meth)acrylate resin (A2) can be synthesized by a known synthesis method, for example, a method in which an epoxy compound and an unsaturated monobasic acid are dissolved in a solvent as required in the presence of an esterification catalyst and reacted at a temperature of 70 to 150° C., preferably 80 to 140° C., and more preferably 90 to 130° C.

[0074] Although it does not specifically limit as a commercial item of the said epoxy (meth)acrylate resin (A2), For example, "LIPOKISI (registered trademark)" etc. manufactured by Showa Denko K.K. are mentioned.

[0075] In addition, the unreacted unsaturated monobasic acid after the synthesis of the epoxy (meth)acrylate resin (A2) is regarded as the ethylenically unsaturated compound (B) mentioned later.

[0076] [Urethane (meth)acrylate resin (A3)]

[0077] As the urethane (meth)acrylate resin, for example, a resin obtained by reacting (meth)acrylic acid with hydroxyl groups or isocyanate groups at both terminals of polyurethane obtained by reacting polyisocyanate with polyol can be used.

[0078] The urethane (meth)acrylate resin may be used alone or in combination of two or more.

[0079] (Ethylenically unsaturated compound (B))

[0080] The ethylenically unsaturated compound according to the present embodiment is not particularly limited as long as it is a compound having one or more ethylenically unsaturated bonds in the molecule.

[0081] Examples of the ethylenically unsaturated compound (B) include styrene, α-, o-, m-, and p-alkyl derivatives of styrene, nitro, cyano, amide, or ester derivatives of styrene, methoxystyrene, divinylbenzene, vinylnaphthalene, and acenaphthylene; diene compounds such as butadiene, 2,3-dimethylbutadiene, isoprene, and chloroprene; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, tert-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, benzene (meth)acrylate, (meth)acrylates such as (meth)acrylic acid esters, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, allyl (meth)acrylate, isobornyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecanol di(meth)acrylate, and trimethylolpropane tri(meth)acrylate; (meth)acrylic acids such as (meth)acrylamide, N,N'-dimethyl (meth)acrylamide, and N,N'-diisopropyl (meth)acrylamide; unsaturated dicarboxylic acid diesters such as diethyl citraconic acid; monomaleimide compounds such as N-phenylmaleimide; N-(meth)acryloylphthalimide, etc. Examples of the α-, o-, m-, and p-alkyl derivatives of styrene include vinyltoluene and tert-butylstyrene.

[0082] The above-mentioned ethylenically unsaturated compound (B) may be used alone or in combination of two or more.

[0083] The ethylenically unsaturated compound (B) is preferably styrene, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; more preferably styrene, methyl (meth)acrylate, ethyl (meth)acrylate, phenoxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; and still more preferably styrene and phenoxyethyl (meth)acrylate.

[0084] The content of the ethylenically unsaturated compound (B) is preferably 10 to 95% by mass, more preferably 30 to 75% by mass, and still more preferably 40 to 60% by mass relative to the total of the radical polymerizable resin (A) and the ethylenically unsaturated compound (B). If the content of the ethylenically unsaturated compound (B) is 10 to 95% by mass relative to the total of the radical polymerizable resin (A) and the ethylenically unsaturated compound (B), the mechanical strength of the cured product can be further improved.

[0085] (Compound containing free radical (C))

[0086] The radical-containing compound (C) according to the present embodiment is not particularly limited as long as it is a compound having one or more free radicals stable in the air in its molecule.

[0087] Examples of free radical-containing compounds (C) include 2,2,6,6-tetramethylpiperidin-1-oxyl radical (TEMPO) and its analogs (structural analogs), 2,2,5,5-tetramethylpyrrolidine-1-oxyl radical and its analogs, butylated hydroxytoluene (BHT), tert-butylhydroquinone (TBHQ), 1,1-diphenyl-2-picrylhydrazyl, galvinoxyl radical, 2-hydroxy-2-azaadamantane, and the like.

[0088] Examples of analogs of 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) include 4-glycidyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-isothiocyanate-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-(2-iodoacetamide)-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-[2-[2-(4-iodophenoxy)ethoxy]carbonyl ]benzoyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl free radical, 4-methoxy-2,2,6,6-tetramethylpiperidin-1-oxyl free radical, 4-carboxy-2,2,6,6-tetramethylpiperidin-1-oxyl free radical, 4-cyano-2,2,6,6-tetramethylpiperidin-1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl free radical benzoate, 4-acetamide-2,2,6,6-tetramethylpiperidin-1-oxyl free radical, 2,2,6,6-tetramethyl-4-(2-propynyloxy)piperidin-1-oxyl free radical, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl free radical, etc. Examples of the analogue of 2,2,5,5-tetramethylpyrrolidine-1-oxyl radical include 16-DOXYL stearic acid radical and 3-carboxy-2,2,5,5-tetramethylpyrrolidine-1-oxyl radical.

[0089] Among the examples of the free radical-containing compound (C), 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO), 4-glycidyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 2-hydroxy-2-azaadamantane, 1,1-diphenyl -2-picrylic hydrazine, butylhydroxytoluene (BHT), tert-butylhydroquinone (TBHQ), more preferably 2,2,6,6-tetramethylpiperidin-1-oxyl free radical (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl free radical, butylhydroxytoluene (BHT), tert-butylhydroquinone (TBHQ), further preferably 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl free radical, butylhydroxytoluene (BHT), tert-butylhydroquinone (TBHQ).

[0090] The radical-containing compound (C) may be used alone or in combination of two or more.

[0091] The content of the radical-containing compound (C) is preferably 0.005 to 1.000 parts by mass, more preferably 0.005 to 0.500 parts by mass, and even more preferably 0.005 to 0.100 parts by mass, based on 100 parts by mass of the total of the radical polymerizable resin (A) and the ethylenically unsaturated compound (B).

[0092] When the content of the radical-containing compound (C) is 0.005 to 1.000 parts by mass, curability in a medium temperature range can be ensured, and a long usable time at 20° C. or less can be ensured.

[0093] (Curing agent (D))

[0094] The curing agent according to the present embodiment is not particularly limited as long as it is a compound having one or more peroxide bonds in the molecule and a 10-hour half-life temperature of 40° C. to 120° C.

[0095] When the 10-hour half-life temperature is 40° C. or higher, the storage stability is good, and when the 10-hour half-life temperature is 120° C. or lower, the curability of the resin composition is good.

[0096] The 10-hour half-life temperature can be measured by using benzene as a solvent to prepare a 0.1 mol / L curing agent solution, thermally decomposing the solution at an arbitrary temperature, and measuring the temperature at which the organic peroxide decays to half in 10 hours.

[0097] Examples of the curing agent (D) include diacyl peroxides, peroxydicarbonates, peroxyesters, peroxyketals, and dialkyl peroxides.

[0098] Among the examples of the curing agent (D), from the viewpoint of curability, dilauroyl peroxide, bis(4-tert-butylcyclohexyl) peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylhexanoate, and t-butyl peroxybenzoate are preferred, and bis(4-tert-butylcyclohexyl) peroxycarbonate (e.g., Parloy TCP (manufactured by NOF Corporation)), t-hexyl peroxy-2-ethylhexanoate (e.g., Parcur HO(N) (manufactured by NOF Corporation)), and t-butyl peroxybenzoate (e.g., Parbchl Z (manufactured by NOF Corporation)) are more preferred.

[0099] The curing agent (D) may be used alone or in combination of two or more.

[0100] The content of the curing agent (D) is preferably 0.5 to 5.0 parts by mass, more preferably 1.0 to 5.0 parts by mass, and even more preferably 1.0 to 3.0 parts by mass, based on 100 parts by mass of the total of the radical polymerizable resin (A) and the ethylenically unsaturated compound (B).

[0101] When the content of the curing agent (D) is 0.5 to 5.0 parts by mass based on 100 parts by mass of the total of the radical polymerizable resin (A) and the ethylenically unsaturated compound (B), curability in a medium temperature range can be ensured and a long usable time at 20° C. or less can be ensured.

[0102] (Metallic Soap (E))

[0103] The metal soap according to the present embodiment is not particularly limited as long as it is a salt of a metal and a long-chain fatty acid or an organic acid other than a long-chain fatty acid.

[0104] As examples of long-chain fatty acids, preferably, for example, fatty acids having 7 to 30 carbon atoms are used. Specifically, chain or cyclic saturated fatty acids such as heptanoic acid and 2-ethylhexanoic acid, octanoic 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, triacontanoic acid, and cycloalkane acid, and unsaturated fatty acids such as oleic acid, linoleic acid, and linolenic acid can be mentioned.

[0105] The organic acid other than the long-chain fatty acid is not particularly limited, but is preferably a weak acid compound that is soluble in an organic solvent and has a carboxyl group, a hydroxyl group, or an enol group.

[0106] The metal contained in the metal soap (E) is preferably chromium, manganese, iron, cobalt, nickel, and copper, more preferably manganese, iron, and cobalt, and even more preferably cobalt.

[0107] Specific examples of the metal soap (E) include manganese octylate, cobalt octylate, zinc octylate, vanadium octylate, cobalt naphthenate, copper naphthenate, barium naphthenate, vanadium acetylacetonate, cobalt acetylacetonate, and iron acetylacetonate.

[0108] As the metal soap (E), manganese octylate, cobalt octylate, cobalt naphthenate and the like are preferred, manganese octylate and cobalt octylate are more preferred, and cobalt octylate is further preferred.

[0109] The metal soap (E) may be used alone or in combination of two or more.

[0110] The content of the metal soap (E) is preferably 0 to 5.0 parts by mass, more preferably 0 to 3.0 parts by mass, and even more preferably 0 to 2.0 parts by mass, relative to 100 parts by mass of the total of the curing agent (D).

[0111] When the content of the metal soap (E) is within the above range relative to 100 parts by mass of the total of the curing agent (D), the resin composition can be cured more easily in a medium temperature range of 50°C.

[0112] (Fiber base material (F))

[0113] The radical polymerizable resin composition of the present embodiment may contain a fiber substrate (F) as required, depending on the purpose of use, application, etc. The fiber substrate involved in the present embodiment may include synthetic fibers such as amide, nylon, aromatic polyamide, vinylon, polyester, and phenolic resin, reinforcing fibers such as carbon fiber, glass fiber, metal fiber, and ceramic fiber, and composite fibers thereof. These may be used alone or in combination of two or more.

[0114] Among them, aramid fibers, carbon fibers, and glass fibers are preferred, and glass fibers are more preferred from the viewpoints of strength, hardness, availability, price, and the like.

[0115] As the form of the fiber substrate (F), for example, a sheet, chopped strands, chopped strands, intermediate fibers, etc. can be cited. As the sheet, for example, a sheet formed by aligning a plurality of reinforcing fibers in one direction, a bidirectional fabric such as a plain weave or a twill weave, a multiaxial fabric, a non-hemmed fabric, a nonwoven fabric, a felt, a knitted fabric, a braided rope, a paper made by papermaking of reinforcing fibers, etc. can be cited. Regarding the thickness of the sheet, from the viewpoint of the impregnation property of the resin composition, for example, in the case of a single layer, it is preferably 0.01 to 5 mm, and in the case of stacking multiple layers, the total thickness is preferably 1 to 20 mm, and more preferably 1 to 15 mm.

[0116] Examples of the shape of the fiber base material (F) include a cylindrical shape, a sheet shape, and a tape shape.

[0117] When the fiber substrate (F) is cylindrical, examples include a form in which it is woven into a cylindrical shape in a seamless manner; a form in which a portion of a sheet-like or strip-like substrate is overlapped to form a cylindrical shape, and the overlapped portion is bonded with an adhesive, sewn with thread, or joined by needle punching.

[0118] In the case of using a cylindrical fiber base material (F), the diameter of the fiber base material (F) is preferably the same as the inner diameter of the pipe to be repaired.

[0119] When a sheet-like substrate is used, the length of the short side of the sheet is preferably slightly greater than the circumference of the inner side of the pipe to be repaired in consideration of the overlap of the sheet when manufacturing the lining material (the portion reserved for applying glue).

[0120] When a strip-shaped substrate is used, the width is not particularly limited, but is preferably 1 / 8 to 1 / 3 of the inner circumference of the pipe to be repaired.

[0121] (Additive (G))

[0122] The radical polymerizable resin composition of the present embodiment may contain various additives (G) such as a colorant, a coupling agent, a surfactant, a wax, and a thixotropic agent as necessary depending on the purpose of use and application.

[0123] The content of the additives can be appropriately adjusted according to the desired physical properties of the cured product of the resin composition manufactured within the range that does not affect the curing performance and storage stability of the radical polymerizable resin composition. The total content of the additives is preferably 0.1 to 700 parts by mass, more preferably 0.1 to 500 parts by mass, and further preferably 0.1 to 300 parts by mass relative to 100 parts by mass of the total radical polymerizable components.

[0124] (Solvent (H))

[0125] The solvent (H) is a component used as needed from the viewpoint of uniformly mixing the components contained in the radical polymerizable resin composition. Its content is not particularly limited and can be appropriately adjusted according to the operability during use. The type of solvent (H) is appropriately selected within the range that does not affect the curing performance and storage stability of the radical polymerizable resin composition according to the type of resin, the use purpose, etc. For example, aliphatic hydrocarbons, aromatic hydrocarbons, ethers, ketones, esters, linear carbonates, etc. can be mentioned. They can be used alone or in combination of two or more.

[0126] Specifically, as aliphatic hydrocarbons, cyclohexane, n-hexane, white spirit, odorless mineral spirits and other mineral spirits can be mentioned. As aromatic hydrocarbons, cycloalkanes, mixtures of cycloalkanes and paraffin, benzene, toluene, quinoline and the like can be mentioned. As ethers, diethyl ether, diisopropyl ether and the like can be mentioned. As ketones, acetone, methyl ethyl ketone, cyclohexanone and the like can be mentioned. As esters, ethyl acetate, butyl acetate, diethyl malonate, diethyl succinate, dibutyl succinate, dibutyl maleate, 2,2,4-trimethylpentanediol diisobutyrate, monoesters and diesters of ketoglutaric acid, pyruvic acid esters, palmitic acid esters, monoesters and diesters of ascorbic acid and the like can be mentioned. As chain carbonates, dimethyl carbonate, diethyl carbonate and the like can be mentioned. In addition, 1,2-dioximes, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, N,N-dimethylformamide, and the like can also be used.

[0127] The solvent (H) may be contained in commercially available products of the radical polymerizable resin (A) and the ethylenically unsaturated compound (B).

[0128] [Method for producing radical polymerizable resin composition]

[0129] The radical polymerizable resin composition of the present embodiment can be manufactured by, for example, a method of kneading one or more of the components of (A) to (D) above, (E), (F), (G) or (H) used as needed. There is no particular limitation on the kneading method, and for example, a double-arm kneader, a pressure kneader, a planetary mixer, a disperser, etc. can be used. The kneading temperature is preferably -10°C to 40°C, more preferably 0°C to 40°C, and most preferably 20°C to 40°C. If the kneading temperature is above -10°C, the kneadability is further improved. If the kneading temperature is below 40°C, the curing reaction during the kneading of the radical polymerizable resin composition can be further suppressed. The kneading time can be appropriately selected according to the components and their ratios.

[0130] There is no particular restriction on the order in which the components are mixed when manufacturing the radical polymerizable resin composition of the present embodiment. For example, if the radical polymerizable resin (A) is mixed with a part or all of the ethylenically unsaturated compound (B) and then the other components are mixed, it is easy to obtain a uniformly mixed radical polymerizable resin composition, which is therefore preferred.

[0131] During kneading, as described above, a solvent may be appropriately used from the viewpoint of uniformly mixing the components.

[0132] In addition, as the radical polymerizable resin (A), a synthesis liquid containing unreacted monomers may be used without separation after synthesis. That is, in one example of the radical polymerizable resin composition, unreacted monomers as a raw material for synthesizing the radical polymerizable resin (A) may be contained.

[0133] [Cured product of resin composition and method for producing the same]

[0134] The cured product of the radical polymerizable resin composition of the present embodiment is obtained by curing the resin composition of the present embodiment described above by a known method. As a method for curing the radical polymerizable resin composition, a method of curing it by heating can be cited. Here, as a specific temperature range for heating, for example, it can be set to a temperature range of 50°C to 200°C.

[0135] [Pipe repair lining material and pipe repair method using the same]

[0136] A pipe repair lining material according to one embodiment of the present invention (sometimes referred to as a pipe repair lining material according to the present embodiment) uses the radical polymerizable resin composition according to the present embodiment described above.

[0137] For example, the pipe repair lining material of this embodiment can be produced by using the polymerizable resin composition of this embodiment including the fiber substrate (F) and impregnating the fiber substrate with components other than the fiber substrate (F).

[0138] In order to repair the laid pipes and canals using the pipe repair lining material of this embodiment, a conventionally known method can be adopted. For example, the pipe repair lining material can be introduced into the pipes and canals in an uncured state or inserted into the pipes and canals while turning the inner and outer sides over, and then the pipe repair lining material can be brought into contact with a heat medium such as warm water or steam to be thermally cured.

[0139] [Pipeline repaired using pipe repair lining material]

[0140] A pipe channel (repaired pipe channel of this embodiment) obtained by repairing a pipe channel using a pipe repair lining material of one embodiment of the present invention is a pipe channel formed by repairing an already laid pipe channel using the pipe repair lining material of this embodiment. The repaired pipe channel of this embodiment may include an already laid pipe channel and a cured product of the pipe repair lining material of this embodiment inserted into the already laid pipe channel. The repaired pipe channel of this embodiment may also be a pipe channel obtained by introducing the pipe repair lining material into the pipe channel in an uncured state or inserting the pipe channel into the pipe channel while turning the inner and outer sides over, and then bringing the pipe repair lining material into contact with a heat medium such as warm water or steam to thermally cure it.

[0141] Example

[0142] Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited thereto.

[0143] "Raw materials used in Examples and Comparative Examples (commercially available products)"

[0144] (Ethylenically unsaturated compound (B))

[0145] Styrene: Made by NSスチレンモノマー Co., Ltd.

[0146] Phenoxyethyl methacrylate: Latest PO, manufactured by Kyoeisha Co., Ltd.

[0147] (Compound containing free radical (C))

[0148] 4-Hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl radical: manufactured by Tokyo Chemical Industry Co., Ltd.

[0149] 2,2,6,6-Tetramethylpiperidin-1-oxyl radical: Tokyo Chemical Industry Co., Ltd.

[0150] BHT: 2,6-di-tert-butyl-p-cresol

[0151] TBHQ: tert-butylhydroquinone

[0152] (Curing agent (D))

[0153] Paroil TCP: Made by NOF Corporation, bis(4-tert-butylcyclohexyl) peroxycarbonate, 10-hour half-life temperature is 40.8°C

[0154] Perqua HO(N): Made by NOF Corporation, tert-hexyl peroxy-2-ethylhexanoate, 10-hour half-life temperature is 69.9°C

[0155] Perbular Z: Made by NOF Corporation, tert-butyl peroxybenzoate, 10-hour half-life temperature is 104.3°C

[0156] (Metallic Soap (E))

[0157] Toei Toei 8%: Toei Chemical Co., Ltd., 2-ethylhexanoate cobalt 50%

[0158] Tocoton 8%: Toei Chemical Co., Ltd., manganese 2-ethylhexanoate 53%

[0159] Copper naphthenate 5%: Toei Chemical Co., Ltd., copper naphthenate 50%

[0160] [Manufacturing of Radical Polymerizable Resin]

[0161] (Synthesis example 1)

[0162] "Unsaturated polyester resin"

[0163] In a flask equipped with a stirrer, a reflux condenser, a thermometer, and a gas introduction tube, 25.8 g of maleic anhydride, 21.7 g of isophthalic acid, 16.4 g of terephthalic acid, 12.1 g of propylene glycol, and 41.2 g of neopentyl glycol (containing 10% water) were added, and reacted at 215° C. while heating and stirring. The mixture was cooled when the acid value reached 15 mgKOH / g, thereby obtaining 100 g of the unsaturated polyester resin of this synthesis example. The unsaturated polyester resin obtained was evaluated by the above method, and the results are as follows.

[0164] Unsaturation: 53.5

[0165] Acid value: 15mgKOH / g

[0166] Weight average molecular weight: 9,900

[0167] (Synthesis example 2)

[0168] "Epoxy acrylate resin"

[0169] In a flask equipped with a stirrer, a reflux condenser, a thermometer, and a gas inlet tube, 74 g of bisphenol A epoxy resin and 26 g of acrylic acid were reacted at 120°C while blowing air, and the mixture was cooled when the acid value was 5 mgKOH / g or less to obtain 100 g of epoxy acrylate of this synthesis example. The epoxy acrylate obtained was evaluated by the above method, and the results are as follows.

[0170] Acid value: 5mgKOH / g

[0171] Weight average molecular weight: 780

[0172] <Acid value>

[0173] The acid value of the radical polymerizable resin was determined according to JIS K6901:2008 "Partial acid value (indicator titration method)", by measuring the mass of potassium hydroxide required to neutralize the acid components contained in the unsaturated polyester resin (Synthesis Example 1) and the epoxy acrylate resin (Synthesis Example 2).

[0174] Specifically, the unsaturated polyester resin or epoxy acrylate resin obtained in the above synthesis example was diluted with (B) an ethylenically unsaturated compound to prepare a mixture as a sample for measuring the acid value (sample 1: 65% by mass of unsaturated polyester resin, 35% by mass of styrene, sample 2: 70% by mass of epoxy acrylate resin, 30% by mass of phenoxyethyl methacrylate resin). The mass of potassium hydroxide required to neutralize the acid component contained in the above mixture was measured. Then, the acid value of the unsaturated polyester resin and the epoxy acrylate resin was calculated based on the measured value. "Autoburet UCB-2000" (manufactured by Hiranuma Sangyo Co., Ltd.) was used as a titration device, and a mixed indicator of bromothymol blue and phenol red was used as an indicator.

[0175] <Weight average molecular weight Mw, number average molecular weight Mn and molecular weight distribution Mw / Mn>

[0176] Mw and Mn were measured by GPC under the following measurement conditions, and Mw / Mn was calculated from these measured values.

[0177] (Measurement conditions)

[0178] · Device: "Showadex (registered trademark) GPC-101" (manufactured by Showa Denko K.K.)

[0179] ·Pillar: "Sewage (registered trademark) LF-804" (manufactured by Showa Denko Co., Ltd.)

[0180] Detector: Differential refractometer "Showadex (registered trademark) RI-71S" (manufactured by Showa Denko K.K.)

[0181] Column temperature: 40℃

[0182] Sample: 0.2 mass % tetrahydrofuran solution of vinyl ester resin

[0183] ·Developing solvent: tetrahydrofuran

[0184] Flow rate: 1.0mL / min

[0185] Sample injection volume: 20μL

[0186] Standard sample: polystyrene

[0187] [Production of Radically Polymerizable Resin Composition]

[0188] (Example 1)

[0189] 55.00 g of the unsaturated polyester resin obtained in Synthesis Example 1, 45.00 g of styrene, 0.06 g of TEMPOL, 0.01 g of BHT, 0.01 g of TBHQ, 1.25 g of Parallel TCP, and 1.00 g of Paraquat HO (N) were added and stirred and mixed at 23° C. to obtain a radical polymerizable resin composition.

[0190] (Examples 2 to 6, Comparative Examples 1 to 6)

[0191] According to the compounding compositions shown in Tables 1 and 2 below, a radical polymerizable resin composition was obtained in the same manner as in Example 1.

[0192] [Evaluation of curability at 55°C]

[0193] In a test tube having an inner diameter of 7.5 mm and a height of 180 mm, the radically polymerizable resin composition blended as shown in Table 1 was placed so as to reach a height of 10 mm.

[0194] A K thermocouple was introduced to monitor the temperature of the radical polymerizable resin composition. The test tube containing the radical polymerizable resin composition was placed in an oil bath at 55°C, and the time required from the time when the temperature of the radical polymerizable resin composition reached 40°C to the time when the temperature reached 60°C was measured as the 55°C gelation time.

[0195] The time from when the temperature of the radical polymerizable resin composition reached 40°C until the curing heat generated by radical polymerization reached a maximum was measured as the 55°C minimum curing time, and the temperature at which the curing heat generated a maximum was measured as the maximum exothermic temperature.

[0196] [Usable time at 20℃]

[0197] In a glass screw bottle having an inner diameter of 20 mm and a height of 80 mm, the blended radical polymerizable resin composition shown in Table 1 was added so that the height was 70 mm. The screw bottle was capped and left to stand at 20°C. The fluidity of the radical polymerizable resin composition was confirmed by appropriately turning the screw bottle upside down. The number of days required until a non-flowing gel was confirmed at the top and bottom of the screw bottle was measured as the usable time at 20°C.

[0198]

[0199]

[0200] The gelation time at 55°C of Example 1-3 using unsaturated polyester resin as the radical polymerizable resin (A) is within 60 minutes and the usable time at 20°C is more than 21 days, whereas the gelation time of Comparative Example 1-3 exceeds 60 minutes or the usable time at 20°C is less than 21 days.

[0201] In addition, Examples 4 to 6 using epoxy (meth)acrylate resin as the radical polymerizable resin (A) have a gelation time of less than 100 minutes at 50°C and a usable time of more than 50 hours at 20°C, whereas Comparative Examples 4-6 have a gelation time and a usable time at 20°C of less than 50 hours.

[0202] Industrial Applicability

[0203] The radical polymerizable resin composition of the present invention has excellent curability in a temperature range of 50 to 80° C. and excellent storage stability at 20° C. or lower, and can therefore be suitably used as a prepreg for pipe and channel repair.

[0204] When the radical polymerizable resin composition of the present invention uses an unsaturated polyester resin as the radical polymerizable resin (A), it has excellent curability at 55° C. and excellent storage stability at 20° C. or lower, and can therefore be suitably used as a prepreg for pipe and channel repair.

[0205] When the radical polymerizable resin composition of the present invention uses an epoxy (meth)acrylate resin as the radical polymerizable resin (A), it has excellent curability at 55° C. and excellent storage stability at 20° C. or lower, and can therefore be suitably used as a prepreg for pipe and canal repair.

Claims

1. A free radical polymerizable resin composition, characterized in that The invention comprises a radical polymerizable resin (A), an ethylenically unsaturated compound (B), a free radical-containing compound (C) and a curing agent (D), The free radical-containing compound (C) is 2,2,6,6-tetramethylpiperidin-1-oxyl free radical and its analogs, The 10-hour half-life temperature of the curing agent (D) is 40° C. to 120° C.

2. The radical polymerizable resin composition according to claim 1, characterized in that The curing agent (D) includes at least one curing agent selected from the group consisting of diacyl peroxides, peroxydicarbonates, peroxyesters, peroxyketals, and dialkyl peroxides.

3. The radical polymerizable resin composition according to claim 1 or 2, characterized in that: The curing agent (D) comprises at least one curing agent selected from dilauroyl peroxide, bis(4-tert-butylcyclohexyl) peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-hexyl peroxy-2-ethylhexanoate and tert-butyl peroxybenzoate. 4 . The radical polymerizable resin composition according to claim 1 , wherein a content of the ethylenically unsaturated compound (B) is 10 to 95% by mass based on the total of the radical polymerizable resin (A) and the ethylenically unsaturated compound (B). 5 . The radical polymerizable resin composition according to claim 1 , wherein the content of the radical-containing compound (C) is 0.005 to 1.000 parts by mass based on 100 parts by mass of the total of the radical polymerizable resin (A) and the ethylenically unsaturated compound (B). 6 . The radical polymerizable resin composition according to claim 1 , wherein the content of the curing agent (D) is 0.5 to 5.0 parts by mass based on 100 parts by mass of the total of the radical polymerizable resin (A) and the ethylenically unsaturated compound (B).

7. The radical polymerizable resin composition according to claim 1 or 2, characterized in that: A metal soap (E) is also contained.

8. The radical polymerizable resin composition according to claim 7, characterized in that The metal contained in the metal soap (E) is at least one metal selected from the group consisting of chromium, manganese, iron, cobalt, nickel and copper.

9. The radical polymerizable resin composition according to claim 1 or 2, characterized in that: A fibrous substrate (F) is also included.

10. A cured product, which is a cured product of the radical polymerizable resin composition according to claim 1 or 2, characterized in that: Lining material for pipe repair.

11. A pipe repair lining material using the radical polymerizable resin composition according to claim 1 or 2.

12. A pipe channel repaired by using the pipe repair lining material according to claim 11.

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