Composition, membrane, structure, composition set, and method for repairing concrete structures

Abstract

A composition with improved curability and a technique relating thereto are provided. [Solution] A composition containing an unsaturated polyester resin (A) and a compound (B) having a radically polymerizable double bond, and having a 5°C surface curing time T5 of 20 hours or less as measured by the following method 1. (Method 1) The composition is applied in an amount of 0.5 kg / m to a mortar test plate (dimensions: 10 mm × 70 mm × 150 mm) prepared in accordance with JIS R 5201:2015 in a 23°C environment. 2 The composition is applied with a brush so as to obtain a test specimen that is a coating film. The test specimen is then left to stand in a 5°C environment, and the time from immediately after preparation of the composition until the tackiness of the coating film surface disappears is measured, and this is defined as the 5°C surface curing time T5 (hours).

Description

[Technical Field]

[0001] The present invention relates to a composition, a film, a structure, a composition set, and a method for repairing a concrete structure. [Background technology]

[0002] There is a method for repairing a concrete structure in which a composition is applied to the surface of the concrete structure, and then the composition is hardened to form a film on the surface of the concrete structure.

[0003] Patent Document 1 discloses a concrete structure reinforcement in which at least a reinforcing layer and a protective layer are sequentially provided on the surface of the concrete structure, with the aim of providing a reinforcement and a reinforcement method for a concrete structure that allows the base of the concrete structure to be visually confirmed and has excellent reinforcement performance for the concrete structure and the effect of suppressing the generation of harmful gases. The reinforcement layer has a basis weight of 500 to 1000 g / m. 2 The document also discloses a reinforcement for concrete structures, which has a structure in which a glass fiber sheet having an opening size of 1 to 25 mm and a cured product of an adhesive for concrete structures are integrated, the protective layer is a coating film of a protective paint containing an inorganic component, and the difference in refractive index between the glass fiber sheet and the cured product of the adhesive for concrete structures is less than 0.04. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2023-143912 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides compositions with improved curability. [Means for solving the problem]

[0006] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result, have found that a composition containing an unsaturated polyester resin (A) and a compound (B) having a radically polymerizable double bond, and having a 5°C surface curing time T5 of 20 hours or less as measured by a specific method, can improve curability, thereby completing the present invention.

[0007] According to the present invention, there are provided a composition, a film, a structure, a composition set, and a method for repairing a concrete structure, as shown below.

[0008] [1] an unsaturated polyester resin (A); a compound (B) having a radical polymerizable double bond, A composition having a surface cure time T5 at 5°C of 20 hours or less as measured by Method 1 below. (Method 1) In a 23°C environment, the composition was applied at a rate of 0.5 kg / m to a mortar test plate (dimensions: 10 mm x 70 mm x 150 mm) prepared in accordance with JIS R 5201:2015. 2 The composition is applied with a brush so as to obtain a test specimen that is a coating film. The test specimen is then left to stand in a 5°C environment, and the time from immediately after preparation of the composition until the tackiness of the coating film surface disappears is measured, and this is defined as the 5°C surface curing time T5 (hours). [2] The composition according to [1], wherein the content of the unsaturated polyester resin (A) in the composition is 1 part by mass or more and 50 parts by mass or less, when the total amount of resin components in the composition is 100 parts by mass. [3] The composition according to [1] or [2], wherein the compound (B) contains a (meth)acrylic monomer (b1). [4] The composition according to [3], wherein the content of the (meth)acrylic monomer (b1) in the composition is 10 parts by mass or more and 90 parts by mass or less, when the total amount of resin components in the composition is 100 parts by mass. [5] 5. The composition according to claim 1, wherein the compound (B) comprises a urethane (meth)acrylate (b2). [6] The composition according to [5], wherein the content of the urethane (meth)acrylate (b2) in the composition is 1 part by mass or more and 50 parts by mass or less, when the total amount of resin components in the composition is 100 parts by mass. [7] The composition according to any one of [1] to [6], further comprising a radical polymerization initiator. [8] The composition according to [7], wherein the radical polymerization initiator comprises one or more organic peroxides selected from the group consisting of ketone peroxides, peroxyketals, hydroperoxides, hydroxyperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates. [9] The composition according to any one of [1] to [8], further comprising a reducing agent.

[10] The reducing agent is a compound containing a central metal selected from the group consisting of iron, copper, cobalt, nickel, manganese, zinc, and calcium, and a carboxylate ion, a halide ion, a nitrate ion, a sulfate ion, or a PF6 - , SbF6 - , AsF6 - , BF4 - and B(C6F5)4 - and one or more ligands selected from the group consisting of:

[11] The composition according to any one of [1] to

[10] , which is used for repairing a concrete structure.

[12] A film comprising a cured product of the composition according to any one of [1] to

[11] .

[13] A structure comprising a substrate and the film according to

[12] on the surface of the substrate.

[14] A composition set comprising the composition according to any one of [1] to

[11] , a composition (P1) containing the unsaturated polyester resin (A), the compound (B), and a radical polymerization initiator; A two-component mixed composition set in which the unsaturated polyester resin (A), the compound (B), and a composition (P2) containing a reducing agent are contained in separate containers.

[15] The composition set according to

[14] , wherein the 5°C pot life UT5 measured by the following method 2 is 0.1 hours or more and 5.0 hours or less. (Method 2) The composition (P1) and the composition (P2) are placed in a thermostatic bath set at 5°C for at least 2 hours and allowed to stand until the temperature reaches 5°C. Next, 25 g of the composition (P1) and 25 g of the composition (P2) are weighed into a 100 mL disposable cup and mixed until the color is uniform to obtain a mixed solution. Next, a thermocouple is inserted into the center of the mixed solution to record the temperature and time, and the time PT from the start of measurement until the exothermic temperature reaches its peak is measured. The value obtained by multiplying the PT by a coefficient of 0.6 is the 5°C usable time UT5 (hours).

[16] A method for repairing a concrete structure using the composition set according to

[14] or

[15] , A step (1) of mixing the composition (P1) and the composition (P2) to obtain a mixed liquid; an application step (2) of applying the mixed liquid to the surface of the concrete structure; A method for repairing a concrete structure, comprising:

[17]

[16] The method for repairing a concrete structure according to

[16] , further comprising, before step (2), step (3) of attaching a fiber sheet to the surface of the concrete structure.

[18]

[17] The method for repairing a concrete structure according to

[17] , wherein the fiber sheet contains one or more fibers selected from the group consisting of glass fiber, carbon fiber, (meth)acrylic resin fiber, polyethylene fiber, nylon 6 fiber, nylon 6,6 fiber, polyester fiber, polypropylene fiber, vinylon fiber, aramid fiber, polyparaphenylene benzoxazole fiber, and surface-treated products thereof.

[19] A composition having a surface cure time T5 at 5°C of 20 hours or less as measured by Method 1 below. (Method 1) In a 23°C environment, the composition was applied at a rate of 0.5 kg / m to a mortar test plate (dimensions: 10 mm x 70 mm x 150 mm) prepared in accordance with JIS R 5201:2015. 2 The composition is applied with a brush so as to obtain a test specimen that is a coating film. The test specimen is then left to stand in a 5°C environment, and the time from immediately after preparation of the composition until the tackiness of the coating film surface disappears is measured, and this is defined as the 5°C surface curing time T5 (hours). [Effects of the Invention]

[0009] According to the present invention, a composition with improved curability can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, embodiments of the present invention will be described in detail.

[0011] In this specification, the notation "a to b" in the description of a range of values ​​means a to b, unless otherwise specified. For example, "1 to 5% by mass" means "1% by mass to 5% by mass." Furthermore, the lower and upper limits of a range of values ​​can be arbitrarily combined with the lower and upper limits of other ranges of values.

[0012] Unless otherwise specified, each of the components and materials exemplified in this specification may be used alone or in combination of two or more.

[0013] In this specification, the term "(meth)acrylic" represents a concept that encompasses both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate."

[0014] <Composition> The composition of this embodiment has a surface curing time T5 at 5° C. of 20 hours or less, as measured by the following method. A preferred composition of this embodiment contains an unsaturated polyester resin (A) and a compound (B) having a radically polymerizable double bond, and has a 5°C surface curing time T5 of 20 hours or less as measured by the following method. (method) In a 23°C environment, the composition was applied at a rate of 0.5 kg / m to a mortar test plate (dimensions: 10 mm x 70 mm x 150 mm) prepared in accordance with JIS R 5201:2015. 2 The composition is applied with a brush so that the coating film is obtained as a test specimen (hereinafter, the test specimen may also be referred to as the coating film). The test specimen is then left to stand in a 5°C environment, and the time from immediately after preparation of the composition until the tackiness of the coating film surface disappears is measured, and this is taken as the 5°C surface cure time T5 (hours).

[0015] According to the investigations of the present inventors, it has been found that there is a relationship between the 5° C. surface curing time T5 of a composition and the curability of the composition. As a result of further investigations based on the above findings, the present inventors have found that the curability of the composition can be improved by setting the 5°C surface curing time T5, measured by the above method, to 20 hours or less, and have completed the present invention.

[0016] From the viewpoint of further improving curability, the surface curing time T5 of the composition of this embodiment is 20 hours or less, preferably 18 hours or less, more preferably 16 hours or less, even more preferably 14 hours or less, even more preferably 13 hours or less, even more preferably 12 hours or less, even more preferably 11 hours or less, even more preferably 10 hours or less, even more preferably 9 hours or less, and even more preferably 8 hours or less. The lower limit of the surface curing time T5 of the composition of this embodiment is not particularly limited, and may be, for example, 1 hour or more, 3 hours or more, or 5 hours or more.

[0017] From the viewpoint of further improving curability, the surface curing time T5 of the composition of the present embodiment is preferably from 1 hour to 20 hours, more preferably from 1 hour to 18 hours, even more preferably from 1 hour to 16 hours, even more preferably from 1 hour to 14 hours, even more preferably from 1 hour to 13 hours, even more preferably from 1 hour to 12 hours, even more preferably from 1 hour to 11 hours, even more preferably from 1 hour to 10 hours, even more preferably from 3 hours to 9 hours, and even more preferably from 5 hours to 8 hours.

[0018] In this embodiment, a method for measuring the tackiness of the coating film surface may be, for example, a method in which ball tackiness is measured using a ball tack tester in accordance with JIS Z0237:2009 under an environment of a temperature of 23°C and a relative humidity of 50%.

[0019] <Unsaturated polyester resin (A)> The unsaturated polyester resin (A) of this embodiment may be, for example, a polymer of an unsaturated polybasic acid and a polyhydric alcohol. Examples of unsaturated polybasic acids include maleic acid, maleic anhydride, fumaric acid, itaconic acid, and citraconic acid. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol, hydrogenated bisphenol A, and ethylene oxide or propylene oxide derivatives of bisphenol A.

[0020] The unsaturated polyester resin (A) of this embodiment is preferably diluted with a solvent.

[0021] The solvent used to dilute the unsaturated polyester resin (A) of this embodiment preferably contains one or more solvents selected from the group consisting of 2-hydroxyethyl (meth)acrylate, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, methyl (meth)acrylate, ethyl (meth)acrylate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, styrene, toluene, xylene, ethylbenzene, and benzene, and more preferably contains one or more solvents selected from the group consisting of 2-hydroxyethyl (meth)acrylate and styrene.

[0022] The unsaturated polyester resin (A) of this embodiment is preferably diluted with a solvent to a concentration of 1% by mass to 70% by mass, and more preferably 10% by mass to 50% by mass.

[0023] From the viewpoint of further improving curability, the content of the unsaturated polyester resin (A) in the composition of this embodiment is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 45 parts by mass or less, even more preferably 7 parts by mass or more and 40 parts by mass or less, even more preferably 15 parts by mass or more and 35 parts by mass or less, and even more preferably 25 parts by mass or more and 33 parts by mass or less, when the total amount of the resin components in the composition is 100 parts by mass. The content of the unsaturated polyester resin (A) may or may not include the solvent.

[0024] <Compound (B) Having a Radically Polymerizable Double Bond> The compound (B) having a radical polymerizable double bond of the present embodiment has a radical polymerizable double bond, and therefore, by using it in combination with a radical polymerization initiator described below, good curability can be obtained by radical polymerization.

[0025] From the viewpoint of further improving curability, the compound (B) having a radically polymerizable double bond of the present embodiment preferably contains a compound having a (meth)acrylic group, more preferably contains a compound having a (meth)acryloyl group, and even more preferably contains one or more selected from the group consisting of (meth)acrylic monomers; epoxy (meth)acrylates obtained by reacting an unsaturated monobasic acid with an epoxy resin; urethane (meth)acrylates obtained by reacting a polyvalent isocyanate and a polyol with a (meth)acrylate having an active hydrogen; polyester (meth)acrylates obtained by reacting a polyhydric alcohol and a polybasic acid or anhydride thereof with (meth)acrylic acid; polyether (meth)acrylates; alkyd (meth)acrylates; and silicone (meth)acrylates, and even more preferably contains one or more selected from the group consisting of (meth)acrylic monomers and urethane (meth)acrylates. Here, the (meth)acrylic monomer does not include urethane (meth)acrylate.

[0026] From the viewpoint of further improving curability, the content of the compound (B) having a radically polymerizable double bond in the composition of the present embodiment is preferably 50 parts by mass or more and 99 parts by mass or less, more preferably 55 parts by mass or more and 95 parts by mass or less, even more preferably 60 parts by mass or more and 93 parts by mass or less, even more preferably 65 parts by mass or more and 85 parts by mass or less, and even more preferably 67 parts by mass or more and 75 parts by mass or less, when the total amount of the resin components in the composition is 100 parts by mass.

[0027] <(Meth)acrylic monomer (b1)> From the viewpoint of further improving curability, the compound (B) of this embodiment preferably contains a (meth)acrylic monomer (b1).

[0028] From the viewpoint of further improving curability, the (meth)acrylic monomer (b1) of the present embodiment preferably has one to six (meth)acryloyl groups in the molecule, more preferably has one to four (meth)acryloyl groups in the molecule, even more preferably has one to two (meth)acryloyl groups in the molecule, and even more preferably has one (meth)acryloyl group in the molecule.

[0029] From the viewpoint of further improving curability, the (meth)acrylic monomer (b1) of the present embodiment is preferably an acrylic acid alkyl ester such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, or dodecyl acrylate; an acrylic acid aryl ester such as phenyl acrylate or benzyl acrylate; a methacrylic acid ester such as methoxyethyl acrylate, ethoxyethyl acrylate, or propoxy acrylate; Alkoxyalkyl acrylates such as butoxyethyl acrylate, butoxyethyl acrylate, and ethoxypropyl acrylate; acrylic acid and its salts such as alkali metal acrylates; acrylic acid and its salts such as alkali metal methacrylates; methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, and dodecyl methacrylate; methacrylic acid phenyl, aryl methacrylates such as benzyl methacrylate; alkoxyalkyl methacrylates such as methoxyethyl methacrylate, ethoxyethyl methacrylate, propoxyethyl methacrylate, butoxyethyl methacrylate, ethoxypropyl methacrylate; halogenated vinyl compounds such as 2-chloroethyl acrylate, 2-chloroethyl methacrylate; acrylic acid esters of alicyclic alcohols such as cyclohexyl acrylate; methacrylic acid esters of alicyclic alcohols such as cyclohexyl methacrylate; acrylo Aziridine group-containing polymerizable compounds such as acryloyl aziridine, methacryloyl aziridine, 2-aziridinylethyl acrylate, and 2-aziridinylethyl methacrylate; epoxy group-containing vinyl monomers such as glycidyl ether of acrylic acid, glycidyl ether of methacrylic acid, diglycidyl ether of acrylic acid, 2-ethylglycidyl ether of acrylate, and 2-ethylglycidyl ether of methacrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate;The copolymer may include one or more compounds selected from the group consisting of hydroxyl group-containing vinyl compounds such as monoesters of acrylic acid or methacrylic acid with polypropylene glycol or polyethylene glycol, and adducts of lactones with 2-hydroxyethyl (meth)acrylate; fluorine-containing vinyl monomers such as fluorine-substituted alkyl methacrylates and fluorine-substituted alkyl acrylates; amide group-containing vinyl monomers such as methacrylamide, N-methylolmethacrylamide, N-methoxyethylmethacrylamide, and N-butoxymethylmethacrylamide; organosilicon group-containing vinyl compound monomers such as γ-(meth)acryloxypropyltrimethoxysilane; and dicyclopentenyloxyethyl (meth)acrylate, more preferably one or two or more compounds selected from the group consisting of hydroxyalkyl (meth)acrylates and dicyclopentenyloxyethyl (meth)acrylate, and even more preferably one or two or more compounds selected from the group consisting of hydroxyethyl (meth)acrylate and dicyclopentenyloxyethyl (meth)acrylate;

[0030] From the viewpoint of further improving curability, the content of the (meth)acrylic monomer (b1) in the composition of the present embodiment is preferably 10 parts by mass or more and 90 parts by mass or less, more preferably 30 parts by mass or more and 80 parts by mass or less, even more preferably 50 parts by mass or more and 70 parts by mass or less, and even more preferably 55 parts by mass or more and 65 parts by mass or less, when the total amount of the resin components in the composition is 100 parts by mass.

[0031] <Urethane (meth)acrylate (b2)> From the viewpoint of further improving curability, the compound (B) of this embodiment preferably contains a urethane (meth)acrylate (b2). The urethane (meth)acrylate (b2) of this embodiment is a (meth)acrylate having a urethane bond. The urethane (meth)acrylate (b2) is, for example, a radical-polymerizable unsaturated group-containing oligomer that can be obtained by reacting a compound having at least one active hydrogen group, an isocyanate compound, and a hydroxyl group-containing (meth)acrylate compound.

[0032] The method for producing the urethane (meth)acrylate (b2) is not particularly limited, but examples thereof include a method of reacting an active hydrogen group-containing compound with an isocyanate compound to prepare an isocyanate-terminated prepolymer, followed by reaction with a hydroxy group-containing (meth)acrylate compound, and a method of reacting a hydroxy group-containing (meth)acrylate compound with an isocyanate compound, followed by reaction with an active hydrogen group-containing compound. These production methods are prepared by appropriately selecting and preparing a (meth)acryloyl group-containing radically polymerizable unsaturated monomer other than a hydroxy group-containing (meth)acrylate compound, or a solvent, from the viewpoint of production stability, etc.

[0033] Specific examples of the active hydrogen group-containing compound used in the urethane (meth)acrylate (b2) are not particularly limited as long as they have at least one active hydrogen group and react with an isocyanate compound, and include, for example, one or more compounds selected from the group consisting of polymers and low-molecular-weight polyols having active hydrogen groups, such as polyester polyols including dimer polyols, polyether polyols, polycarbonate polyols, (meth)acrylic polyols, silicone polyols, castor oil-based polyols, fluorine-based polyols, olefin polyols, and polythiol compounds.

[0034] From the viewpoint of further improving curability, the content of the urethane (meth)acrylate (b2) in the composition of the present embodiment is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 3 parts by mass or more and 40 parts by mass or less, even more preferably 5 parts by mass or more and 35 parts by mass or less, even more preferably 7 parts by mass or more and 25 parts by mass or less, and even more preferably 9 parts by mass or more and 15 parts by mass or less, when the total amount of the resin components in the composition is 100 parts by mass.

[0035] <Radical polymerization initiator> The composition of the present embodiment preferably contains a radical polymerization initiator from the viewpoint of further improving curability.

[0036] From the viewpoint of further improving curability, the radical polymerization initiator of the present embodiment preferably contains one or more organic peroxides selected from the group consisting of ketone peroxides, peroxyketals, hydroperoxides, hydroxyperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates, and more preferably contains one or more organic peroxides selected from the group consisting of cumyl hydroperoxide, benzoyl peroxide, dibenzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl- Examples of peroxides include 2,5-bis(t-butylperoxy)hexyne-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, bis(4-t-butylcyclohexyl)peroxydicarbonate, diisopropyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, azobisisobutyronitrile, azobiscarbonamide, benzoyl m-methylbenzoyl peroxide, m-toluoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, and t-butyl peroxybenzoate. Among these, the compound preferably includes one or more selected from the group consisting of dibenzoyl peroxide, benzoyl m-methylbenzoyl peroxide, m-toluoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, and t-butyl peroxybenzoate, and more preferably includes cumyl hydroperoxide.

[0037] From the viewpoint of further improving curability, the content of the radical polymerization initiator in the composition of the present embodiment is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 7 parts by mass or less, and even more preferably 2 parts by mass or more and 5 parts by mass or less, when the total amount of the resin components in the composition is taken as 100 parts by mass.

[0038] <Reducing agent> The composition of the present embodiment preferably contains a reducing agent from the viewpoint of further improving curability.

[0039] From the viewpoint of further improving the curability, the reducing agent of the present embodiment preferably contains a central metal selected from the group consisting of iron, copper, cobalt, nickel, manganese, zinc, and calcium, and an ion selected from the group consisting of carboxylate ions, halide ions, nitrate ions, sulfate ions, PF6 - , SbF6 - , AsF6 - , BF4 - and B(C6F5)4 - and one or more ligands selected from the group consisting of:

[0040] From the viewpoint of further improving curability, the central metal contained in the metal complex of this embodiment preferably includes one or more cations selected from the group consisting of iron cations and cobalt cations, and more preferably includes a cobalt cation.

[0041] From the viewpoint of further improving curability, the ligand contained in the metal complex of this embodiment preferably contains one or more carboxylate ions selected from the group consisting of acetate ion, ethylhexanoate ion, octanoate ion, neodecanoate ion, naphthenate ion, and acetoacetonatocarboxylate ion, and more preferably contains an ethylhexanoate ion.

[0042] For these reasons, the reducing agent of the present embodiment preferably contains cobalt 2-ethylhexanoate from the viewpoint of further improving the curability.

[0043] From the viewpoint of further improving curability, the content of the reducing agent in the composition of the present embodiment is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 7 parts by mass or less, and even more preferably 2 parts by mass or more and 5 parts by mass or less, when the total amount of the resin components in the composition is 100 parts by mass.

[0044] <Other ingredients> The composition of the present embodiment may contain, in addition to the above components, polymerization inhibitors, waxes, inorganic fillers, photopolymerization initiators, photosensitizers, tackifiers, silane coupling agents, antioxidants, organic solvents, thickeners, etc., within the scope of not impairing the effects of the present invention. Furthermore, depending on the application, the composition may contain thixotropic agents, elastomer components, etc.

[0045] <Inorganic filler> The composition of the present embodiment preferably contains an inorganic filler from the viewpoint of further improving the mechanical strength. From the viewpoint of further improving mechanical strength, the inorganic filler of the present embodiment preferably contains one or more selected from the group consisting of silica; oxides such as alumina, titanium oxide, and magnesium oxide; carbonates such as calcium carbonate and magnesium carbonate; and hydroxides such as aluminum hydroxide and magnesium hydroxide, and more preferably contains silica.

[0046] From the viewpoint of further improving the balance of mechanical strength and curability, the content of the inorganic filler in the composition of the present embodiment is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 3 parts by mass or more and 15 parts by mass or less, and even more preferably 5 parts by mass or more and 10 parts by mass or less, when the total amount of the resin components in the composition is 100 parts by mass.

[0047] <Thickener> The composition of the present embodiment preferably contains a thickener from the viewpoint of further improving moldability. From the viewpoint of further improving moldability, the thickener of the present embodiment preferably comprises one or more selected from the group consisting of acrylic thickeners such as polyacrylic acid and acrylic copolymers; urethane associative thickeners; alkali-swelling thickeners; copolymer thickeners such as modified polyoxyethylene-urethane block copolymers; cellulose thickeners such as methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and hydrophobically modified hydroxycellulose; surfactants such as polyethylene glycol ethers and nonionic surfactants; polysaccharides such as alginates, guar gum, and mannan; water-soluble resins such as polyvinyl alcohol and polyvinylpyrrolidone; and a solution of polycarboxylic acid amide, and more preferably comprises a solution of polycarboxylic acid amide.

[0048] From the viewpoint of further improving the performance balance between moldability and curability, the content of the thickener in the composition of this embodiment is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.5 parts by mass or more and 5 parts by mass or less, and even more preferably 1 part by mass or more and 3 parts by mass or less, when the total amount of the resin components in the composition is 100 parts by mass.

[0049] <Curability> The surface curing time T 20 From the viewpoint of further improving the curability, the surface curing time T at 20°C of the composition of this embodiment is preferably 12 hours or less, more preferably 10 hours or less, even more preferably 9 hours or less, even more preferably 8 hours or less, even more preferably 6 hours or less, and even more preferably 5 hours or less. 20 The lower limit of the time is not particularly limited, but may be, for example, 1 hour or more, or 2 hours or more.

[0050] The surface curing time T 20From the viewpoint of further improving the curability, the curing time is preferably 1 hour or more and 12 hours or less, more preferably 1 hour or more and 10 hours or less, even more preferably 1 hour or more and 9 hours or less, even more preferably 1 hour or more and 8 hours or less, even more preferably 1 hour or more and 6 hours or less, and even more preferably 2 hours or more and 5 hours or less.

[0051] In this embodiment, the surface curing time T 20 can be measured, for example, by the following method. In a 23°C environment, the composition was applied at a rate of 0.5 kg / m to a mortar test plate (dimensions: 10 mm x 70 mm x 150 mm) prepared in accordance with JIS R 5201:2015. 2 The test specimen is then left to stand in an environment at 20°C, and the time from immediately after preparation of the composition until the tackiness of the coating surface disappears is measured, which is the 20°C surface curing time T 20 (hours).

[0052] In this embodiment, a method for measuring the tackiness of the coating film surface may be, for example, a method in which ball tackiness is measured using a ball tack tester in accordance with JIS Z0237:2009 under an environment of a temperature of 23°C and a relative humidity of 50%.

[0053] <Application> The composition of the present embodiment can be used as an adhesive, a sealant, a coating agent, a potting agent, etc. In particular, it is suitable for use in the construction, repair, and reinforcement of bridge piers, road bridge decks, tunnels, chimneys, pipelines, and steel pipes in the fields of civil engineering and construction, which are carried out outdoors. The composition of this embodiment is particularly suitable for use in repairing concrete structures.

[0054] <Manufacturing method> The composition of the present embodiment can be obtained by mixing the above-mentioned components by a known method. However, in order to obtain the composition set described below, it is preferable to separate the compositions into a composition containing the unsaturated polyester resin (A), the compound (B), and a radical polymerization initiator, and a composition containing the unsaturated polyester resin (A), the compound (B), and a reducing agent.

[0055] <Composition set and usage instructions> A preferred embodiment of the composition of the present embodiment is a composition set containing the composition of the present embodiment, which is a two-component mixed type composition set in which a composition (P1) containing the unsaturated polyester resin (A), the compound (B), and a radical polymerization initiator, and a composition (P2) containing the unsaturated polyester resin (A), the compound (B), and a reducing agent are contained in separate containers. Since the composition of this embodiment has improved curability, the composition set of this embodiment also has improved curability.

[0056] In the composition set of this embodiment, composition (P1) and composition (P2) are contained in separate containers and sealed, and when in use, the containers are opened and the contained compositions are mixed together. By packaging each composition separately, the radical polymerization initiator and the reducing agent are prevented from coming into contact with each other and causing a reaction to proceed during storage of the composition, improving the storage stability of the composition, and at the time of use, the two components can be mixed at the site of use to rapidly cure the composition.

[0057] In this embodiment, the composition (P1) and the composition (P2) can be mixed using a conventionally known method, and for example, a static mixer, a rotary mixer (dynamic mixer), or the like can be appropriately selected depending on the application.

[0058] After application of the composition of the present embodiment to a desired target, a curing reaction proceeds and the composition is then completely cured. The time required for complete curing can be adjusted appropriately depending on the component composition of the composition of the present embodiment, the application method, the temperature, and other conditions.

[0059] <Pot life> The 5°C pot life UT5 of the composition set of the present embodiment is preferably 0.1 hours or more, more preferably 0.5 hours or more, and even more preferably 1.0 hour or more from the viewpoint of further improving handleability, and is preferably 5.0 hours or less, more preferably 4.0 hours or less, and even more preferably 3.0 hours or less from the viewpoint of further improving curability.

[0060] The 5°C pot life UT5 of the composition set of the present embodiment is, from the viewpoint of further improving the balance between handleability and curability, preferably from 0.1 hours to 5.0 hours, more preferably from 0.5 hours to 4.0 hours, and even more preferably from 1.0 hour to 3.0 hours.

[0061] In this embodiment, the 5° C. pot life UT5 of the composition set can be measured, for example, by the following method. First, composition (P1) and composition (P2) are placed in a thermostatic bath set at 5°C for at least 2 hours and allowed to stand until the temperature reaches 5°C. Next, 25 g of composition (P1) and 25 g of composition (P2) are weighed into a 100 mL disposable cup and mixed until the color is uniform, obtaining a mixed solution. Next, a thermocouple is inserted into the center of the mixed solution to record the temperature and time, and the time PT from the start of measurement until the exothermic temperature reaches its peak is measured. PT is multiplied by a coefficient of 0.6 to obtain the 5°C usable time UT5 (hours).

[0062] <Membrane> The film of this embodiment includes a cured product of the composition of this embodiment.

[0063] <Structure> The structure of this embodiment includes a substrate and the film of this embodiment on the surface of the substrate.

[0064] <Methods for repairing concrete structures> The method for repairing a concrete structure of this embodiment is a method for repairing a concrete structure using the composition set of this embodiment, and includes a step (1) of mixing composition (P1) and composition (P2) to obtain a mixed liquid, and an application step (2) of applying the mixed liquid to the surface of the concrete structure. Since the composition set of this embodiment has improved hardening properties, the method for repairing a concrete structure of this embodiment requires less time for the composition set to harden, improving workability.

[0065] The concrete structure repair method of this embodiment is suitable for use in repairing bridge piers, road bridge decks, tunnels, chimneys, pipelines, and steel pipes in the fields of civil engineering and construction, which are carried out outdoors.

[0066] The concrete structure repair method of this embodiment may further include step (3) of attaching a fiber sheet to the surface of the concrete structure before step (2), in order to further improve the mechanical strength of the surface of the concrete structure. Step (3) may be carried out before step (1) or between steps (1) and (2).

[0067] When the concrete structure repair method of this embodiment includes step (3), the fiber sheet preferably contains one or more fibers selected from the group consisting of glass fiber, carbon fiber, (meth)acrylic resin fiber, polyethylene fiber, nylon 6 fiber, nylon 6,6 fiber, polyester fiber, polypropylene fiber, vinylon fiber, aramid fiber, polyparaphenylene benzoxazole fiber, and surface-treated products thereof.

[0068] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations can also be adopted. [Example]

[0069] Next, the present invention will be described in detail with reference to examples, but the content of the present invention is not limited to the examples.

[0070] <Raw materials> The compositions shown in Table 1 were obtained using the following raw materials. [Unsaturated polyester resin (A)] Unsaturated polyester resin 1: Unsaturated polyester (diluted to 35% with 2-hydroxyethyl methacrylate, manufactured by DIC Materials, Aqualight CN-450-R) Unsaturated polyester resin 2: Unsaturated polyester (diluted to 25% with styrene, manufactured by DIC Materials, Sandoma CN-351) [Compound (B) having a radically polymerizable double bond] Methacrylic monomer 1: Dicyclopentenyloxyethyl methacrylate (Resonac, DH500) Methacrylic monomer 2: 2-hydroxyethyl methacrylate (Nippon Shokubai Co., Ltd.) Urethane acrylate 1: Urethane acrylate (MIWON, MIRAMER MU3603) [Radical polymerization initiator] Radical polymerization initiator 1: Cumyl hydroperoxide (Trigonox K-80, manufactured by Nouryon Chemical Industries, Ltd.) [Reducing agent] Reducing agent 1: Cobalt 2-ethylhexanoate (Tokyo Fine Chemical Co., Ltd., CO-12E) [Other ingredients] Silica filler 1: Amorphous silica (surface-treated product, manufactured by Nippon Aerosil Co., Ltd., AEROSIL R805) Thickener 1: Polycarboxylic acid amide solution (BYK Japan, RHIEOBYK-405)

[0071] Example 1 <Preparation of Composition (P1)> A stirring device equipped with a stirrer, thermometer, and heater was charged with 30 parts by mass of unsaturated polyester resin 1, 40 parts by mass of methacrylic monomer 1, 20 parts by mass of methacrylic monomer 2, 10 parts by mass of urethane acrylate 1, 8 parts by mass of silica filler 1, and 2 parts by mass of thickener 1, and the mixture was stirred and mixed at 60°C for 30 minutes.The mixture was then cooled to room temperature, and 3 parts by mass of radical polymerization initiator 1 was added, followed by stirring at room temperature for 30 minutes to obtain composition (P1) of Example 1.

[0072] <Preparation of Composition (P2)> A stirring device equipped with a stirrer, thermometer, and heater was charged with 30 parts by mass of unsaturated polyester resin 1, 40 parts by mass of methacrylic monomer 1, 20 parts by mass of methacrylic monomer 2, 10 parts by mass of urethane acrylate 1, 8 parts by mass of silica filler 1, and 2 parts by mass of thickener 1, and the mixture was stirred and mixed at 60°C for 30 minutes.The mixture was then cooled to room temperature, and 3 parts by mass of reducing agent 1 was added.The mixture was stirred at room temperature for 30 minutes, yielding composition (P2) of Example 1.

[0073] (Examples 2 to 6, Comparative Example 1) Compositions (P1) and (P2) were prepared in the same manner as in Example 1, except that the components were used in the proportions (unit: parts by mass) shown in Table 1.

[0074] <5℃ surface curing time T5> For each example and comparative example, composition (P1) and composition (P2) were mixed until homogeneous to prepare a composition. Then, in a 23°C environment, the composition was applied at a rate of 0.5 kg / m to a mortar test plate (dimensions: 10 mm × 70 mm × 150 mm) prepared in accordance with JIS R 5201:2015. 2 The composition was applied with a brush so that the coating was applied to a test specimen. The test specimen was then left to stand in a 5°C environment, and the time from immediately after preparation of the composition until the tackiness of the coating surface disappeared was measured, and this was taken as the 5°C surface curing time T5 (hours). The results are shown in Table 1.

[0075] <Curability> For each example and comparative example, composition (P1) and composition (P2) were mixed until homogeneous to prepare a composition. Then, in a 23°C environment, the composition was applied at a rate of 0.5 kg / m to a mortar test plate (dimensions: 10 mm × 70 mm × 150 mm) prepared in accordance with JIS R 5201:2015. 2 The test specimen was then left to stand in an environment at 20°C, and the time from immediately after preparation of the composition until the tackiness of the coating surface disappeared was measured, which was designated as the 20°C surface curing time T 20 The results are shown in Table 1.

[0076] <5℃ pot life UT5> For each example and comparative example, composition (P1) and composition (P2) were placed in a thermostatic chamber set at 5°C for at least 2 hours and allowed to stand until the temperature reached 5°C. Next, 25 g of composition (P1) and 25 g of composition (P2) were weighed into a 100 mL disposable cup and mixed until the color was uniform, obtaining a mixed solution. A thermocouple was then inserted into the center of the mixed solution to record the temperature and time. PT, the time from the start of measurement until the exothermic temperature reached its peak, was measured, and the value obtained by multiplying PT by a coefficient of 0.6 was used as the 5°C usable time UT5 (hours). The results are shown in Table 1.

[0077] [Table 1]

Claims

1. an unsaturated polyester resin (A); a compound (B) having a radical polymerizable double bond, Surface hardening time T at 5°C measured by the following method 1 ５ The composition of claim 1, wherein the time is 20 hours or less. (Method 1) The composition was applied at a rate of 0.5 kg / m to a mortar test plate (dimensions: 10 mm x 70 mm x 150 mm) prepared in accordance with JIS R 5201:2015 in a 23°C environment. ２ The test specimen is then left to stand in a 5°C environment, and the time from immediately after the preparation of the composition until the tackiness of the coating surface disappears is measured, and the 5°C surface curing time T ５ (hours).

2. 2. The composition according to claim 1, wherein the content of the unsaturated polyester resin (A) in the composition is 1 part by mass or more and 50 parts by mass or less, when the total amount of resin components in the composition is 100 parts by mass.

3. The composition according to claim 1 or 2, wherein the compound (B) comprises a (meth)acrylic monomer (b1).

4. 4. The composition according to claim 3, wherein the content of the (meth)acrylic monomer (b1) in the composition is 10 parts by mass or more and 90 parts by mass or less, when the total amount of resin components in the composition is 100 parts by mass.

5. The composition according to claim 1 or 2, wherein the compound (B) comprises a urethane (meth)acrylate (b2).

6. 6. The composition according to claim 5, wherein a content of the urethane (meth)acrylate (b2) in the composition is 1 part by mass or more and 50 parts by mass or less, when a total amount of resin components in the composition is 100 parts by mass.

7. The composition of claim 1 or 2, further comprising a radical polymerization initiator.

8. 8. The composition according to claim 7, wherein the radical polymerization initiator comprises one or more organic peroxides selected from the group consisting of ketone peroxides, peroxyketals, hydroperoxides, hydroxyperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.

9. The composition of claim 1 or 2, further comprising a reducing agent.

10. The reducing agent is a compound containing a central metal selected from the group consisting of iron, copper, cobalt, nickel, manganese, zinc, and calcium, and an ion selected from the group consisting of carboxylate ions, halide ions, nitrate ions, sulfate ions, and PF ６ － , SbF ６ － , AsF ６ － , B.F. ４ － and B(C ６ F ５ ) ４ － and one or more ligands selected from the group consisting of:

11. The composition according to claim 1 or 2, which is used for repairing concrete structures.

12. A film comprising a cured product of the composition according to claim 1 or 2.

13. A structure comprising a substrate and the film according to claim 12 on a surface of the substrate.

14. A composition set comprising the composition of claim 1 or 2, a composition (P1) containing the unsaturated polyester resin (A), the compound (B), and a radical polymerization initiator; A two-component mixed composition set in which the unsaturated polyester resin (A), the compound (B), and a composition (P2) containing a reducing agent are contained in separate containers.

15. 5°C pot life UT measured by method 2 below ５ The composition set according to claim 14, wherein the time is 0.1 hours or more and 5.0 hours or less. (Method 2) The composition (P1) and the composition (P2) are placed in a thermostatic chamber set at 5°C for 2 hours or more, and allowed to stand until the temperature reaches 5°C. Next, 25 g of the composition (P1) and 25 g of the composition (P2) are weighed into a 100 mL disposable cup and mixed until the color becomes uniform to obtain a mixed solution. Next, a thermocouple is inserted into the center of the mixed solution to record the temperature and time, and the time PT from the start of measurement until the exothermic temperature reaches its peak is measured, and the value obtained by multiplying the PT by a coefficient of 0.6 is the 5°C usable time UT. ５ (hours).

16. A method for repairing a concrete structure using the composition set according to claim 14, comprising: A step (1) of mixing the composition (P1) and the composition (P2) to obtain a mixed liquid; an application step (2) of applying the mixed liquid to the surface of the concrete structure; A method for repairing a concrete structure, comprising:

17. 17. The method for repairing a concrete structure according to claim 16, further comprising, before the step (2), a step (3) of attaching a fiber sheet to the surface of the concrete structure.

18. 18. The method for repairing a concrete structure according to claim 17, wherein the fiber sheet comprises one or more fibers selected from the group consisting of glass fiber, carbon fiber, (meth)acrylic resin fiber, polyethylene fiber, nylon 6 fiber, nylon 6,6 fiber, polyester fiber, polypropylene fiber, vinylon fiber, aramid fiber, polyparaphenylene benzoxazole fiber, and surface-treated products thereof.

19. Surface hardening time T at 5°C measured by the following method 1 ５ The composition of claim 1, wherein the time is 20 hours or less. (Method 1) The composition was applied at a rate of 0.5 kg / m to a mortar test plate (dimensions: 10 mm x 70 mm x 150 mm) prepared in accordance with JIS R 5201:2015 in a 23°C environment. ２ The test specimen is then left to stand in a 5°C environment, and the time from immediately after the preparation of the composition until the tackiness of the coating surface disappears is measured, and the 5°C surface curing time T ５ (hours).

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