JP2024046405A - Method for manufacturing laminate and method for protecting or repairing structure - Google Patents

Abstract

To provide a method for manufacturing a laminate, capable of preventing cracks in a structure and repairing cracks that have occurred, even if cracks have occurred in the structure.SOLUTION: A method for manufacturing a laminate for protecting or repairing a structure according to the present invention includes: a first layer forming step for forming a first layer by hardening a material of the first layer; and a second layer forming step for forming a second layer on a first surface of the first layer, wherein the material of the first layer comprises a hardenable component and an ion-releasing compound capable of releasing a cation or an anion.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for manufacturing a laminate used to protect or repair a structure. The present invention also relates to a method for protecting or repairing a structure.

In structures such as bridges and tunnels, cracks may develop long after they are constructed. The strength of a structure with cracks decreases. Furthermore, if moisture such as rainwater seeps into cracked areas, the structure becomes more susceptible to deterioration. Since many of these structures support social infrastructure such as traffic and transportation, they cannot be easily rebuilt or demolished. Furthermore, large-scale repairs or reinforcement is difficult when infrastructure functions are stopped.

For this reason, a method of repairing structures involves applying a repair agent to the cracked areas. The following Patent Document 1 discloses a method of reinforcing a concrete substrate in which a reinforcing material containing a water-soluble calcium salt is applied to the concrete substrate, and then a concrete surface strengthening agent is applied.

JP 2021-054708 A

In Patent Document 1, a reinforcing material containing a water-soluble calcium salt is permeated into a concrete structure. Also, in Patent Document 1, a surface strengthening agent is permeated into the concrete structure and hardens to form a hardened body, thereby reinforcing deteriorated areas and increasing surface strength. In Patent Document 1, while the areas permeated with the surface strengthening agent are effectively reinforced, the areas not permeated are not reinforced, and the reinforcement of the surface layer is limited. It is not easy to penetrate the surface strengthening agent deeply, particularly in areas where the penetration direction is unfavorable due to gravity, such as ceilings.

With the conventional method of applying a repair agent to cracked areas, structures can be successfully repaired and the strength of the repaired structure can be increased. However, conventional repair agents are applied to areas where cracks have already occurred, and are not used to prevent cracks.

An object of the present invention is to provide a method for manufacturing a laminate that can prevent cracks in a structure and, even if cracks occur in the structure, can repair the cracks that have occurred. The present invention also relates to a method for protecting or repairing a structure that can prevent cracks in the structure and, even if cracks occur in the structure, can repair the cracks that have occurred.

In this specification, the following laminate manufacturing method and structure protection or repair method are disclosed.

Item 1. A method for producing a laminate for protecting or repairing a structure, the method comprising: a first layer forming step of curing a material for the first layer to form the first layer; and a step of forming the first layer. a second layer forming step of forming a second layer on the first surface, wherein the material of the first layer contains a curable component and an ion-releasing property capable of releasing cations or anions; A method for producing a laminate, including a compound.

Item 2. The method for manufacturing a laminate described in Item 1, wherein the second layer forming step includes a step of applying a material for the second layer onto the first surface of the first layer, and a step of drying the material for the second layer.

Item 3. Item 3. The method for manufacturing a laminate according to Item 1 or 2, wherein the material of the second layer is liquid at 23°C.

Item 4. The method for manufacturing a laminate according to any one of items 1 to 3, wherein the material of the second layer includes an acrylic resin, a urethane resin, a fluororesin, or a silicone resin.

Item 5. The method for producing a laminate according to any one of items 1 to 4, wherein the ion-releasing compound includes a compound capable of releasing cations, and the compound capable of releasing cations is calcium silicate, tricalcium silicate, dicalcium silicate, calcium aluminate, calcium aluminoferrite, calcium hydroxide, calcium oxide, calcium acetate, calcium lactate, barium lactate, calcium sulfate, calcium chloride, calcium nitrate, or calcium hydrogen carbonate.

Item 6. The ion-releasing compound includes a compound capable of releasing anions, and the compound capable of releasing anions includes sodium hydrogen phosphate, potassium carbonate, potassium hydrogen carbonate, ammonium carbonate, ammonium hydrogen carbonate, sodium carbonate, carbonic acid. Item 6. The method for producing a laminate according to any one of Items 1 to 5, which is sodium hydrogen carbonate or calcium hydrogen carbonate.

Section 7. Item 7. The method for producing a laminate according to any one of Items 1 to 6, wherein the structure is a concrete structure.

Item 8. A method for protecting or repairing a structure, comprising a step of placing a first layer material on the surface of the structure, a first layer forming step of curing the first layer material to form a first layer, and a second layer forming step of forming a second layer on the first surface of the first layer, the first layer material including a curable component and an ion-releasing compound capable of releasing cations or anions.

Item 9. The method for protecting or repairing a structure described in Item 8, wherein the second layer forming step includes a step of applying a material for the second layer onto the first surface of the first layer, and a step of drying the material for the second layer.

Item 10. The method for protecting or repairing a structure according to item 8 or 9, wherein the material of the second layer is liquid at 23°C.

Item 11. The method for protecting or repairing a structure according to any one of items 8 to 10, in which the material of the first layer is placed on the surface of the structure that has been scraped in the placing step.

Item 12. The method for protecting or repairing a structure according to any one of items 8 to 11, wherein the placing step is a step of applying the material of the first layer onto the surface of the structure.

Item 13. The method for protecting or repairing a structure according to any one of items 8 to 12, wherein the material of the second layer includes an acrylic resin, a urethane resin, a fluororesin, or a silicone resin.

Item 14. The method for protecting or repairing a structure according to any one of items 8 to 13, wherein the structure is a concrete structure.

A method for manufacturing a laminate according to the present invention is a method for manufacturing a laminate for protecting or repairing a structure. The method for manufacturing a laminate according to the present invention includes a first layer forming step of curing the material of the first layer to form the first layer, and on the first surface of the first layer, and a second layer forming step of forming a second layer. In the method for manufacturing a laminate according to the present invention, the material of the first layer includes a curable component and an ion-releasing compound capable of releasing cations or anions. Since the method for manufacturing a laminate according to the present invention has the above configuration, it is possible to prevent cracks in the structure, and even if cracks occur in the structure, the cracks that have occurred can be repaired. be able to.

The method for protecting or repairing a structure according to the present invention includes a step of disposing a first layer material on the surface of the structure, and curing the first layer material to form the first layer. and a second layer forming step of forming a second layer on the first surface of the first layer. In the method for protecting or repairing a structure according to the present invention, the material of the first layer includes a curable component and an ion-releasing compound capable of releasing cations or anions. Since the method for protecting or repairing a structure according to the present invention has the above configuration, it is possible to prevent cracks in the structure, and even if a crack occurs in the structure, the generated crack can be prevented. It can be repaired.

FIG. 1 is a cross-sectional view that illustrates a structure using a laminate obtained by a method for producing a laminate according to one embodiment of the present invention.

The present invention is described in detail below.

(Laminate)
The method for producing a laminate according to the present invention is a method for producing a laminate for protecting or repairing a structure. The method for producing a laminate according to the present invention includes a first layer forming step of curing a material of a first layer to form a first layer, and a second layer forming step of forming a second layer on a first surface of the first layer. The obtained laminate includes a first layer and a second layer disposed on the first surface side of the first layer. In the method for producing a laminate according to the present invention, the material of the first layer includes a curable component and an ion-releasing compound capable of releasing cations or anions (hereinafter, may be referred to as "ion-releasing compound").

The laminate manufacturing method according to the present invention has the above-mentioned configuration, so that cracks in the structure can be prevented, and even if cracks occur in the structure, the cracks can be repaired. More specifically, when the laminate is placed on the structure, the ion-releasing compound in the laminate (particularly the first layer) releases ions, generating poorly water-soluble salts and forming concretions. As a result, the area where the laminate is placed and its surroundings are densified, and cracks in the structure can be prevented, and even if cracks occur in the structure, the cracks can be repaired, and the structure can be maintained in a stable state for a long period of time (increasing durability). The present invention contributes to preventive maintenance of structures. The present invention contributes to preventive maintenance of both newly constructed structures and existing structures. In addition, in the present invention, the first layer is formed first using the ion-releasing compound, and then the second layer is formed. As a result, cracks in the structure can be effectively prevented, and even if cracks occur in the structure, the cracks can be effectively repaired.

In the method for manufacturing a laminate according to the present invention, when the laminate comes into contact with moisture etc. adhering to the ground or a structure at a location where the laminate is arranged, the laminate (especially the first When the ion-releasing compound in the layer) releases ions, a poorly water-soluble salt can be generated at the contact surface between moisture and the laminate. That is, in the method for manufacturing a laminate according to the present invention, it is possible to generate a layer of a poorly water-soluble salt on the surface of the obtained laminate. The produced slightly water-soluble salt further increases the strength of the area where the laminate is placed and its surroundings. Note that the above-mentioned poorly water-soluble salt is generally thought to be formed over several months to several years. In addition, the produced slightly water-soluble salt effectively suppresses further contact between the laminate and moisture, thereby effectively suppressing deterioration of the laminate and the structure.

The above structure is not particularly limited. Examples of the above-mentioned structures include concrete structures and the like. Examples of the above-mentioned concrete structures include insulators (grout parts) placed on the outer surfaces of buildings, tunnels, and piping. Examples of the above-mentioned tunnels include underground tunnels, submarine tunnels, and mountain tunnels. From the viewpoint of exhibiting the effects of the present invention even more effectively, the structure is preferably a concrete structure. The above structure may be an underground structure.

The laminate obtained by the method for manufacturing a laminate according to the present invention is suitably used for voids (gap) in structures. The above-mentioned laminate is suitably used for cracks or fissures in structures. The above-mentioned laminate is suitably used for gaps (joints) at joints between members in a structure. Further, the above-mentioned laminate is suitably used at the boundary between a structure and the ground on the back side of the structure. Furthermore, the above-mentioned laminate is suitably used as a sheath material. Specifically, the above-mentioned laminate is suitably used as a sheath material for an insulator (grout portion) disposed on the outer surface of an anchor, cable, piping, or the like. The above-mentioned laminate is suitably used for protecting the outer surface of an insulator disposed on the outer surface of an anchor, cable, piping, etc.

Furthermore, at final waste disposal sites, waterproof sheets are sometimes installed at the boundary between concrete structures and the ground. Furthermore, in the NATM construction method, which is one of the construction methods for excavating a tunnel, a waterproof sheet may be installed at the boundary between the tunnel (concrete lining) and the ground behind the tunnel. The laminate obtained by the method for manufacturing a laminate according to the present invention is suitably used as a material for the above-mentioned waterproof sheet.

From the viewpoint of exhibiting the effects of the present invention even more effectively, the laminate is preferably a laminate for protecting or repairing a structure containing concrete. From the viewpoint of exhibiting the effects of the present invention even more effectively, the laminate is preferably used by being placed on the surface of a structure containing concrete. The above-mentioned laminate may be a laminate for protecting or repairing a structure including the ground and concrete. The laminate may be used by being placed on the surface of a structure including the ground and concrete.

The thickness of the laminate is preferably 0.06 mm or more, more preferably 0.12 mm or more, and even more preferably 0.25 mm or more, and is preferably 27 mm or less, more preferably 21 mm or less, and even more preferably 15.5 mm or less. When the thickness of the laminate is equal to or greater than the lower limit and equal to or less than the upper limit, the effects of the present invention can be more effectively achieved.

The thickness of the first layer is preferably 0.05 mm or more, more preferably 0.1 mm or more, even more preferably 0.2 mm or more, and is preferably 25 mm or less, more preferably 20 mm or less, even more preferably 15 mm or less. If the thickness of the first layer is equal to or greater than the lower limit and equal to or less than the upper limit, the protective and repairing effects can be further enhanced.

The thickness of the second layer is preferably 0.01 mm or more, more preferably 0.02 mm or more, and even more preferably 0.05 mm or more, and is preferably 2 mm or less, more preferably 1 mm or less, and even more preferably 0.5 mm or less. When the thickness of the second layer is equal to or greater than the lower limit and equal to or less than the upper limit, the ion release property toward the structure can be more efficiently exhibited.

In the laminate, the first layer is usually a layer disposed on the surface of the structure. In the laminate, the first layer is preferably disposed on the surface of the structure. The laminate is preferably arranged on the surface of the structure from the first layer side. The laminate is preferably arranged on the structure on a surface (second surface) side of the first layer opposite to the first surface. In this case, the effects of the present invention can be exhibited even more effectively. In this case, since the second layer prevents the first layer from coming into contact with moisture more than necessary, the laminate (specifically, the ion-releasing properties of the first layer) It is possible to suppress the elution of ions from compounds (compounds) more than necessary. As a result, since the ion-releasing compound can efficiently release ions to the structure, the structure can be maintained in a stable state for a long period of time.

The following describes in detail each component used in the method for manufacturing the laminate according to the present invention.

[First Layer]
The laminate includes a first layer. A material of the first layer includes a curable component and an ion-releasing compound. The first layer preferably includes a cured product of the curable component and the ion-releasing compound. The cured product of the curable component may be a semi-cured product of the curable component.

<Curable component>
The above-mentioned curable component is a curable component. The above-mentioned curable component may be liquid at 23°C, paste-like at 23°C, or semi-solid at 23°C. Examples of the curable component include a curable resin, a curing agent, a photopolymerization initiator, and the like. The curable component preferably includes the curable resin and the curing agent. The curable component is preferably a mixture of the curable resin and the curing agent. Each of the curable resin, curing agent, and photopolymerization initiator may be used alone or in combination of two or more.

The above-mentioned curable resins include silicone resins, epoxy resins, acrylic resins, unsaturated polyester resins, polyurea resins, urethane resins, phenolic resins, vinyl ester resins, and naphthoxazine resins. The above-mentioned silicone resins may be modified silicone resins. The above-mentioned curable resins may be used alone or in combination of two or more kinds.

The curable resin may be a one-component curable resin or a two-component curable resin. Examples of the one-component curable resin include thermosetting resins, photocurable resins, moisture curable resins, and the like. From the viewpoint of improving workability on site, the curable resin preferably contains a moisture-curable resin, and is preferably a moisture-curable resin. The above-mentioned curable resin may or may not be used in combination with a curing agent. It is preferable that the two-component curable resin is used in combination with a curing agent.

From the viewpoint of improving the strength of the cured product and the adhesion to the structure, the curable resin preferably contains an epoxy resin, and is preferably an epoxy resin.

From the viewpoint of improving workability on site, the curable resin preferably contains a silicone resin, and more preferably contains a modified silicone resin. From the viewpoint of improving workability on site, the silicone resin is preferably a moisture-curable modified silicone resin. The moisture-curable modified silicone resin has a hydrolyzable silicon group. The modified silicone resin having the hydrolyzable silicon group has a polyether polymer, a polyolefin polymer, or an acrylic polymer as the main chain (a portion excluding the hydrolyzable silicon group). Therefore, examples of monomers that are materials for the main chain include alkylene oxide monomers, olefin monomers, and acrylic monomers. The curable resin may be a polymer. The polymer may be a homopolymer or a copolymer. When the polymer is a copolymer, examples of monomers used include alkylene oxide monomers, olefin monomers, acrylic monomers, and vinyl monomers. The modified silicone resin may be used alone or in combination of two or more types.

Examples of the alkylene oxide monomer include ethylene oxide, propylene oxide, and butylene oxide. From the viewpoint of improving elongation and viscous handling properties after curing, the alkylene oxide monomer is preferably polypropylene oxide. The above polypropylene oxide is obtained by polymerizing propylene oxide.

Examples of the olefin monomer include isobutylene.

The acrylic monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, and benzyl (meth)acrylate. benzyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylol propionate, pentaerythritol tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, epoxy(meth)acrylate, polyester(meth)acrylate, urethane(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, Examples of the acrylic polymer include 2-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 3-hydroxy-3-methylbutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, 2-[(meth)acryloyloxy]ethyl 2-hydroxyethyl phthalate, and 2-[(meth)acryloyloxy]ethyl 2-hydroxypropyl phthalate. When the acrylic polymer is a polymer in which other vinyl monomer components are copolymerized, a hydrolyzable silicon group can be introduced by copolymerizing a vinyl monomer component having a hydrolyzable silicon group.

From the viewpoint of improving weather resistance, the main chain of the modified silicone resin preferably has a structural unit derived from an acrylic monomer. The modified silicone resin may be an acrylic modified silicone resin.

From the viewpoint of improving weather resistance, the content of structural units derived from acrylic monomers in 100% by weight of the main chain in the modified silicone resin is preferably 5% by weight or more, and preferably 20% by weight or less.

Examples of the hydrolyzable silicon group include a halogenated silyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximesilyl group, an amidosilyl group, and an alkoxysilyl group.

The number of hydrolyzable groups bonded to silicon atoms in the hydrolyzable silicon group is preferably 1 or more, and preferably 3 or less. The number of hydrolyzable groups bonded to one silicon atom may be one, or two or more. The above-mentioned hydrolyzable group and non-hydrolyzable group may be bonded to one silicon atom. The hydrolyzable silicon group is preferably a monoalkoxysilyl group, a dialkoxysilyl group, or a trialkoxysilyl group because they have excellent stability and are easy to handle.

When the curable resin contains the modified silicone resin, the curable resin preferably contains a silanol condensation catalyst. The curable resin preferably contains the modified silicone resin and a silanol condensation catalyst. By using the silanol condensation catalyst, the modified silicone resin can be cured in a short time. The silanol condensation catalyst may be used alone or in combination of two or more.

The above-mentioned silanol condensation catalysts include tin catalysts such as monoalkyltin esters and dialkyltin esters; poly(dialkylstannoxane) disilicate resins; and organic titanates.

Examples of the monoalkyltin ester include butyltin tris(2-ethylhexanoate). Examples of the dialkyltin ester include dibutyltin acetate, dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin dioleate, dibutyltin dimethoxide, dibutyltin diphenoxide, dibutyltin diacetylacetonate, dibutyltin acetoacetate, and stannous octoate.

Examples of the organic titanates include titanium alkoxides such as tetrabutyl titanate, tetraisopropyl titanate, tetramethyl titanate, and tetra(2-ethylhexyltitanate) triethanolamine titanate; titanium tetraacetylacetonate, titanium ethyl acetoacetate, and octylene. Examples include titanium chelates such as glycolate.

The content of the silanol condensation catalyst is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, preferably 10 parts by weight or less, more preferably 5 parts by weight or less, relative to 100 parts by weight of the modified silicone resin. When the content of the silanol condensation catalyst is equal to or more than the lower limit, the material of the resin layer containing the modified silicone resin can be cured in a short time, and the resin layer can be obtained well in a short time. When the content of the silanol condensation catalyst is equal to or less than the upper limit, the adhesive strength of the resin layer can be increased.

Examples of the silicone resin include organopolysiloxanes having two or more alkenyl groups bonded to silicon atoms. The main chain of the organopolysiloxane is generally a diorganosiloxane polymer, but may have a partially branched structure or a cyclic structure. Examples of the alkenyl group that the organopolysiloxane has include a vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, butenyl group, 1-methyl-2-propenyl group, petenyl group, hexenyl group, octenyl group, and a cyclohexenyl group.

Examples of the curing agent (crosslinking agent) for the silicone resin include organohydrogenpolysiloxane having two or more SiH groups. The organohydrogenpolysiloxane mentioned above includes phenylmethylhydrogenpolysiloxane, 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, methyl endblocked with trimethylsiloxy groups at both ends. Hydrogenpolysiloxane, dimethylsiloxane-methylhydrogensiloxane copolymer with both ends blocked by trimethylsiloxy groups, dimethylpolysiloxane with both ends blocked with dimethylhydrogensiloxy groups, dimethylsiloxane-methylhydrogensiloxane blocked with both ends with dimethylhydrogensiloxy groups Polymers, methylhydrogensiloxane/diphenylsiloxane copolymers with trimethylsiloxy groups blocked at both ends, and methylhydrogensiloxane/diphenylsiloxane-dimethylsiloxane copolymers blocked with trimethylsiloxy groups at both ends.

The above-mentioned epoxy resins include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and hydrogenated products thereof; glycidyl ether type epoxy resins such as polypropylene glycol diglycidyl ether type epoxy resin; Epoxy resin; ester type epoxy resin such as phthalate diglycidyl ester type epoxy resin; novolac type epoxy resin such as phenol novolac type epoxy resin, bisphenol A novolac type epoxy resin, cresol novolac type epoxy resin, and hydrogenated products thereof; Trisphenol-type polyfunctional epoxy resins such as triphenolmethane-type epoxy resins; triglycidyl isocyanurate-type epoxy resins, tetraglycidyldiaminodiphenylmethane-type epoxy resins, tetraglycidyl metaxylene diamine-type epoxy resins, and hydantoin-type epoxy resins. Nitrogen ring type polyfunctional epoxy resin; condensed ring type epoxy resin such as naphthalene type epoxy resin; biphenyl type epoxy resin; dicyclopentadiene type epoxy resin; ether ester type epoxy resin; 3,4-epoxycyclohexylmethyl-3',4 Examples include epoxy resins having an alicyclic structure such as '-epoxycyclohexanecarboxylate; urethane-type epoxy resins; and rubber-modified epoxy resins having a rubber skeleton such as polybutadiene and acrylonitrile butadiene rubber (NBR).

When the curable resin contains the epoxy resin, it is preferable that the curable resin contains a curing agent for the epoxy resin (epoxy curing agent). In other words, it is preferable that the curable component contains the epoxy resin and the epoxy curing agent.

Examples of the epoxy resin curing agent (epoxy curing agent) include amine compounds, imidazole compounds, amide compounds, and cyano compounds. Examples of the amine compounds include ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, their amine adducts, metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone. Examples of the imidazole compounds include methylimidazole, 2-ethyl-4-methylimidazole, 1-isobutyl-2-methylimidazole, 1-benzyl-2-methylimidazole, 2-ethyl-4-methylimidazole, ethylimidazole, isopropylimidazole, 2,4-dimethylimidazole, phenylimidazole, undecylimidazole, heptadecylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole. Examples of the amide compounds include polyamides. Examples of the cyano compounds include dicyandiamide.

The epoxy resin may be a latent curing agent such as ketimine, in which the active amine is blocked and which becomes active under certain conditions such as moisture. For example, ketimine is stable in the absence of moisture, but generally becomes a primary amine in the presence of moisture and reacts with the epoxy resin. Examples of the latent curing agent include 2,5,8-triaza-1,8-nonadiene, 2,10-dimethyl-3,6,9-triaza-2,9-undecadiene, 2,10-diphenyl-3,6,9-triaza-2,9-undecadiene, 3,11-dimethyl-4,7,10-triaza-3,10-tridecadiene, 3,11-diethyl-4,7,10-triaza-3,10-tridecadiene, 2,4,12,14-tetramethyl-5,8,11-triaza-4,11-pentadecadiene, 2,4,20,22-tetramethyl-5,12,19-triaza-4,19-trieicosadiene, and 2,4,15,17-tetramethyl-5,8,11,14-tetraaza-4,14-octadecadiene.

The epoxy resin can be reacted with the epoxy curing agent to obtain a cured epoxy resin.

From the viewpoint of exhibiting the effects of the present invention even more effectively, the epoxy resin preferably contains an epoxy resin having an aromatic skeleton, and is preferably a bisphenol A type epoxy resin or a bisphenol F type epoxy resin. More preferred.

From the viewpoint of exhibiting the effects of the present invention even more effectively, the epoxy curing agent is preferably an amine curing agent (amine compound).

A urethane resin can be obtained by subjecting a polyol compound to a curing reaction with an isocyanate compound. The above polyol compounds include bisphenol A, bisphenol F, phenol novolac, cresol novolac, cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, dimethyldicyclohexylmethanediol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexane. Diols, polyester polyols, polyether polyols, acrylic polyols, polymers obtained by dehydration condensation of polybasic acids and polyhydric alcohols, and ring-opening polymerization of lactones such as ε-caprolactone or α-methyl-ε-caprolactone. Examples include polymers obtained by

Examples of the isocyanate compounds include polyisocyanate compounds. Examples of the polyisocyanate compounds include aromatic polyisocyanates, alicyclic polyisocyanates, aliphatic polyisocyanates, and the like. Examples of the aromatic polyisocyanate include phenylene diisocyanate, toluene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylthane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate. . Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate. Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

From the viewpoint of exerting the effects of the present invention more effectively, the polyol compound is preferably a polyester polyol, a polyether polyol, or an acrylic polyol. From the viewpoint of exerting the effects of the present invention more effectively, the curing agent (isocyanate compound) of the polyol compound is preferably diphenylmethane diisocyanate or toluene diisocyanate.

The mixing ratio of the polyol compound and the isocyanate compound can be changed as appropriate depending on the combination of the types of polyol compound and isocyanate compound. The amount of the isocyanate compound is preferably an amount such that the amount of hydroxyl groups in the polyol compound is equal to the amount of isocyanate groups (NCO amount) in the isocyanate compound.

Examples of the above-mentioned phenol resins include novolak-type phenol, biphenol-type phenol, naphthalene-type phenol, dicyclopentadiene-type phenol, aralkyl-type phenol, and dicyclopentadiene-type phenol.

Hexamethylenetetramine and paraformaldehyde are examples of hardeners for the above phenolic resins.

Examples of the vinyl ester resin include a reaction product of an epoxy resin and an unsaturated monobasic acid. Examples of the epoxy resin include bisphenol A type diglycidyl ether and its high molecular weight homologues, novolak type polyglycidyl ether and its high molecular weight homologs, and aliphatic glycidyl ethers such as 1,6-hexanediol diglycidyl ether. can be mentioned. Examples of the unsaturated monobasic acids include acrylic acid and methacrylic acid. Examples of the reaction products of the epoxy resin and the acrylic acid and methacrylic acid include epoxy (meth)acrylate and the like.

Examples of the curing agent for the vinyl ester resin include organic peroxides. Examples of the organic peroxides include ketone peroxides, perbenzoates, hydroperoxides, diacyl peroxides, peroxyketals, hydroperoxides, diallyl peroxides, peroxyesters, and peroxydicarbonates.

When the curable resin contains the vinyl ester resin, the curable component may contain a radically polymerizable unsaturated monomer. Examples of the radically polymerizable unsaturated monomer include styrene monomer, α-, o-, m-, p-alkyl, nitro, cyano, amide, and ester derivatives of styrene, styrene-based monomers such as chlorostyrene, vinyltoluene, and divinylbenzene, dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, and chloroprene; ethyl (meth)acrylate, methyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, and (meth)acrylate. Examples of such (meth)acrylic acid esters include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofuryl (meth)acrylate, acetoacetoxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and phenoxyethyl (meth)acrylate; (meth)acrylic acid amides such as (meth)acrylic acid amide and (meth)acrylic acid N,N-dimethylamide; vinyl resins such as (meth)acrylic acid anilide; unsaturated dicarboxylic acid diesters such as diethyl citraconic acid; monomaleimide resins such as N-phenylmaleimide; and N-(meth)acryloylphthalimide.

The content of the curable component in 100% by weight of the material of the first layer is preferably 20% by weight or more, more preferably 30% by weight or more, even more preferably 50% by weight or more, and preferably 95% by weight. % or less, more preferably 70% by weight or less, still more preferably 60% by weight or less. When the content of the curable component is not less than the lower limit and not more than the upper limit, the effects of the present invention can be exhibited even more effectively.

In 100% by weight of the material of the first layer, the content of the curable resin is preferably 20% by weight or more, more preferably 30% by weight or more, even more preferably 50% by weight or more, and preferably 95% by weight or less, more preferably 70% by weight or less, even more preferably 60% by weight or less. When the content of the curable resin is equal to or more than the lower limit and equal to or less than the upper limit, the effect of the present invention can be more effectively exhibited.

In 100% by weight of the first layer, the content of the cured product of the curable component is preferably 20% by weight or more, more preferably 30% by weight or more, even more preferably 50% by weight or more, and preferably 95% by weight or less, more preferably 70% by weight or less, even more preferably 60% by weight or less. When the content of the cured product of the curable component is equal to or more than the above lower limit and equal to or less than the above upper limit, the effects of the present invention can be more effectively exhibited.

<Ion-releasing compound>
The material of the first layer includes an ion-releasing compound capable of releasing cations or anions.

The ion-releasing compound may be a compound capable of releasing a cation, a compound capable of releasing an anion, or a compound capable of releasing both a cation and an anion. Often, it may be a mixture of a compound capable of releasing a cation and a compound capable of releasing an anion. The ion-releasing compound may include a compound capable of releasing a cation, or a compound capable of releasing an anion, and a compound capable of releasing a cation and a compound capable of releasing an anion. It may also include. As for the said ion-releasing compound, only 1 type may be used, and 2 or more types may be used together.

It is preferable that the ion-releasing compound is capable of generating a poorly water-soluble salt. It is preferable that the ion-releasing compound generates a poorly water-soluble salt by contact with moisture or the like attached to the ground or a structure. It is preferable that the ion-releasing compound releases cations or anions due to water or moisture that reaches the location where the laminate (particularly the first layer) is arranged. Specifically, when the ion-releasing compound is a compound capable of releasing cations, it is preferable that the cations released from the ion-releasing compound and the anions dissolved in moisture or the like react chemically to form a poorly water-soluble salt. When the ion-releasing compound is a compound capable of releasing anions, it is preferable that the anions released from the ion-releasing compound and the cations dissolved in moisture or the like react chemically to form a poorly water-soluble salt. In addition, when the ion-releasing compound is a compound capable of releasing both cations and anions, or a mixture of a compound capable of releasing cations and a compound capable of releasing anions, it is preferable that the cations and anions released from the ion-releasing compound move to a medium such as moisture and form a poorly water-soluble salt at the point where they meet.

The ion-releasing compound may be an inorganic salt, an ion exchange resin, or an ion complex.

The above-mentioned ion-releasing compounds include calcium silicate, tricalcium silicate, dicalcium silicate, calcium aluminate, calcium aluminoferrite, calcium hydroxide, calcium oxide, calcium acetate, calcium lactate, barium lactate, calcium sulfate, calcium chloride, calcium nitrate, calcium hydrogen carbonate, sodium hydrogen phosphate, potassium carbonate, potassium hydrogen carbonate, ammonium carbonate, ammonium hydrogen carbonate, sodium carbonate, and sodium hydrogen carbonate. The above-mentioned ion-releasing compounds are preferably these ion-releasing compounds. These ion-releasing compounds can generate poorly water-soluble salts more effectively.

The compounds capable of releasing the above cations include calcium silicate, tricalcium silicate, dicalcium silicate, calcium aluminate, calcium aluminoferrite, calcium hydroxide, calcium oxide, calcium acetate, calcium lactate, barium lactate, and sulfuric acid. Examples include calcium, calcium chloride, calcium nitrate, and calcium hydrogen carbonate. Only one kind of the above-mentioned compound capable of releasing cations may be used, or two or more kinds thereof may be used in combination.

The compounds capable of releasing the above cations include calcium silicate, tricalcium silicate, dicalcium silicate, calcium aluminate, calcium aluminoferrite, calcium hydroxide, calcium oxide, calcium acetate, calcium lactate, barium lactate, and calcium sulfate. , calcium chloride, calcium nitrate, or calcium hydrogen carbonate. When the above-mentioned compound capable of releasing cations is the above-mentioned preferred compound, the effects of the present invention can be exhibited even more effectively. From the viewpoint of exhibiting the effects of the present invention even more effectively, the compound capable of releasing cations is preferably calcium oxide, calcium chloride, calcium nitrate, calcium acetate, calcium lactate, or barium lactate. , more preferably calcium lactate. From the viewpoint of exhibiting the effects of the present invention even more effectively, the compound capable of releasing cations is preferably a compound capable of releasing calcium ions, and more preferably an organic acid calcium salt. Examples of the organic acid calcium salt include calcium acetate and calcium lactate.

Examples of the compound capable of releasing anions include sodium hydrogen phosphate, potassium carbonate, potassium hydrogen carbonate, ammonium carbonate, ammonium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, and calcium hydrogen carbonate. Only one kind of the above-mentioned anion-releasing compound may be used, or two or more kinds thereof may be used in combination.

From the viewpoint of exhibiting the effects of the present invention even more effectively, the compounds capable of releasing anions include sodium hydrogen phosphate, potassium carbonate, potassium hydrogen carbonate, ammonium carbonate, ammonium hydrogen carbonate, sodium carbonate, and hydrogen carbonate. Preferably it is sodium or calcium bicarbonate. From the viewpoint of exhibiting the effects of the present invention even more effectively, the compound capable of releasing anions is more preferably sodium hydrogen phosphate, sodium carbonate, or sodium hydrogen carbonate, and preferably sodium hydrogen carbonate. is even more preferable. From the viewpoint of exhibiting the effects of the present invention even more effectively, the compound capable of releasing anions is preferably a compound capable of releasing hydrogen carbonate ions (bicarbonate ions) or carbonate ions.

An example of a compound capable of releasing both the above cations and anions is calcium bicarbonate.

From the viewpoint of producing poorly water-soluble salts more effectively, the material of the first layer preferably contains a mixture of a compound capable of releasing cations and a compound capable of releasing anions, and more preferably contains a mixture of a compound capable of releasing calcium ions and a compound capable of releasing bicarbonate ions or carbonate ions. From the viewpoint of producing poorly water-soluble salts more effectively, the material of the first layer preferably contains a compound capable of releasing cations and a compound capable of releasing anions, and more preferably contains a compound capable of releasing calcium ions and a compound capable of releasing bicarbonate ions or carbonate ions.

Examples of the poorly water-soluble salts include calcium carbonate, barium carbonate, calcium phosphate, iron hydroxide, and the like.

From the viewpoint of exerting the effects of the present invention more effectively, the above-mentioned poorly water-soluble salt is preferably calcium carbonate, barium carbonate, calcium phosphate, or iron hydroxide. From the viewpoint of exerting the effects of the present invention more effectively, the above-mentioned ion-releasing compound is preferably capable of generating calcium carbonate, barium carbonate, calcium phosphate, or iron hydroxide as the poorly water-soluble salt. From the viewpoint of exerting the effects of the present invention more effectively, the above-mentioned poorly water-soluble salt is preferably calcium carbonate. From the viewpoint of exerting the effects of the present invention more effectively, the above-mentioned ion-releasing compound is preferably capable of generating calcium carbonate as the poorly water-soluble salt.

The ion-releasing compound may be particulate. The ion-releasing compound may be spherical, may have a shape other than spherical, or may be flat. The ion-releasing compound is preferably spherical.

The particle diameter of the ion-releasing compound is preferably 1.0 μm or more, more preferably 5.0 μm or more, even more preferably 10 μm or more, and is preferably 1000 μm or less, more preferably 500 μm or less, even more preferably 150 μm or less, and particularly preferably 100 μm or less. When the particle diameter of the ion-releasing compound is equal to or greater than the lower limit, the ion-releasing compound is well coated with the coating agent described below, and the dispersibility of the ion-releasing compound in the first layer can be improved. When the particle diameter of the ion-releasing compound is equal to or greater than the lower limit, the viscosity of the material of the first layer can be improved, and the arrangement of the material of the first layer can be improved. When the particle diameter of the ion-releasing compound is equal to or less than the upper limit, the dispersibility of the ion-releasing compound in the first layer can be improved.

The particle size of the ion-releasing compound is preferably an average particle size. The above average particle diameter indicates the number average particle diameter. The average particle diameter of the above-mentioned ion-releasing compound is determined by observing 50 arbitrary ion-releasing compounds with an electron microscope or an optical microscope and calculating the average value.

In the laminate, the surface of the ion-releasing compound may be coated with a coating agent. The ion-releasing compound may be encapsulated in microcapsules. When the ion-releasing compound is an inorganic salt, in the laminate, the surface of the ion-releasing compound is preferably coated with a coating agent. When the ion-releasing compound is an inorganic salt, the laminate preferably includes microcapsules containing the ion-releasing compound as an inclusion. When the surface of the ion-releasing compound is coated with a coating agent or the ion-releasing compound is included in microcapsules, the timing and timing of release of cations or anions from the ion-releasing compound and The amount can be controlled.

The ion-releasing compound coated with the above-mentioned coating agent is activated when moisture such as water or moisture comes into contact with the laminate (especially the first layer) and the moisture diffuses into the inside of the coating agent. Preferably, it is capable of releasing ions or anions. The ion-releasing compound coated with the coating agent may be capable of releasing cations or anions from voids in the coating agent. The ion-releasing compound coated with the coating agent may be able to diffuse into the coating agent and release cations or anions. In these cases, the timing and amount of cations or anions released from the ion-releasing compound can be better controlled.

Preferably, the microcapsules are capable of releasing the ion-releasing compound. It is preferable that the membrane constituting the microcapsule collapses when the microcapsule comes into contact with moisture such as water or moisture. In this case, it is possible to better control the timing and amount of cations or anions released from the ion-releasing compound.

The material of the membrane constituting the microcapsules and the material of the coating agent for covering the surface of the ion-releasing compound can be appropriately selected depending on the type of the ion-releasing compound. Examples of the material of the membrane constituting the microcapsules and the material of the coating agent for covering the surface of the ion-releasing compound include ethyl cellulose, protein, alginic acid, starch, polylactic acid, polybutylene succinate, polybutylene adipate terephthalate, polyurethane, polyvinyl alcohol, polymethyl methacrylate resin, polycarbonate, polyethylene terephthalate, and polybutylene terephthalate.

The thickness of the membrane constituting the microcapsules and the thickness of the coating layer formed by the coating agent are not particularly limited. From the viewpoint of better controlling the timing and amount of cations or anions released from the ion-releasing compound, the thickness of the membrane constituting the microcapsules and the thickness of the coating layer formed by the coating agent are preferably It is 1 μm or more, more preferably 5 μm or more, and preferably 1000 μm or less, more preferably 200 μm or less.

In 100% by weight of the material of the first layer, the content of the ion-releasing compound is preferably 3% by weight or more, more preferably 5% by weight or more, even more preferably 10% by weight or more, particularly preferably 20% by weight or more, and preferably 70% by weight or less, more preferably 50% by weight or less, even more preferably 45% by weight or less, particularly preferably 40% by weight or less. When the content of the ion-releasing compound is equal to or more than the lower limit and equal to or less than the upper limit, cations or anions are released more effectively, and poorly water-soluble salts are produced well. As a result, the sealed area and its surroundings are further densified, and the structure can be maintained in a stable state for a longer period of time.

In the material of the first layer, the content of the ion-releasing compound is preferably 3 parts by weight or more, more preferably 5 parts by weight or more, even more preferably 10 parts by weight or more, particularly preferably 20 parts by weight or more, and preferably 200 parts by weight or less, more preferably 100 parts by weight or less, and even more preferably 70 parts by weight or less, per 100 parts by weight of the curable component. When the content of the ion-releasing compound is equal to or more than the lower limit and equal to or less than the upper limit, cations or anions are released more effectively, and poorly water-soluble salts are produced well. As a result, the area where the laminate is placed and its surroundings are made more dense, and the structure can be maintained in a stable state for a longer period of time.

The total content of the ion-releasing compound and the coating agent in 100% by weight of the material of the first layer is preferably 3% by weight or more, more preferably 5% by weight or more, and preferably 70% by weight. The content is preferably 50% by weight or less. When the total content of the above-mentioned ion-releasing compound and the above-mentioned coating agent is at least the above-mentioned lower limit and below the above-mentioned upper limit, cations or anions can be released even more effectively, and poorly water-soluble salts can be produced satisfactorily. Ru. As a result, the area where the laminate is placed and its surroundings become even more dense, and the structure can be maintained in a stable state for an even longer period of time. When the total content of the ion-releasing compound and the coating agent is below the upper limit, the viscosity when disposing the first layer on the structure is improved, and the ease of disposing the first layer is improved. be able to.

In the first layer (100% by weight), the content of the ion-releasing compound is preferably 3% by weight or more, more preferably 5% by weight or more, even more preferably 10% by weight or more, particularly preferably 20% by weight or more, and is preferably 70% by weight or less, more preferably 50% by weight or less, even more preferably 45% by weight or less, particularly preferably 40% by weight or less. When the content of the ion-releasing compound is equal to or more than the lower limit and equal to or less than the upper limit, cations or anions are released more effectively, and poorly water-soluble salts are produced well. As a result, the sealed area and its surroundings are further densified, and the structure can be maintained in a stable state for a longer period of time.

In the first layer, the content of the ion-releasing compound is preferably 3 parts by weight or more, more preferably 5 parts by weight or more, even more preferably 10 parts by weight or more, particularly preferably 20 parts by weight or more, and preferably 200 parts by weight or less, more preferably 100 parts by weight or less, and even more preferably 70 parts by weight or less, per 100 parts by weight of the cured product of the curable component. When the content of the ion-releasing compound is equal to or more than the lower limit and equal to or less than the upper limit, cations or anions are released more effectively, and poorly water-soluble salts are produced well. As a result, the area where the laminate is placed and its surroundings are further densified, and the structure can be maintained in a stable state for a longer period of time. When the content of the ion-releasing compound is equal to or less than the upper limit, the viscosity when the first layer is placed on the structure can be improved, and the placement of the first layer can be improved.

[Second Layer]
The laminate includes a second layer. In the laminate, the second layer is disposed on a first surface side of the first layer.

From the viewpoint of further increasing the applicability and the viewpoint of further increasing the protection or repair effect of the structure, the material of the second layer is preferably in a liquid state at 23°C.

The material of the second layer preferably contains a resin. The material of the second layer preferably is a resin material.

The resin may be a thermoplastic resin, a curable resin, or the like. From the viewpoint of forming the second layer well, it is preferable that the resin contains a curable resin. Only one type of the resin may be used, or two or more types may be used in combination. When the resin contains a curable resin, it is preferable that the second layer contains a cured product of the curable resin.

Examples of the thermoplastic resin include fluororesin, polyolefin resin, polyvinyl chloride resin, polyamide resin, polycarbonate resin, polystyrene resin, polyester resin, acrylonitrile-butadiene-styrene resin (ABS resin), polyethylene terephthalate (PET), and polymethacrylic resin. Examples include methyl acid (PMMA).

Examples of the polyolefin resins include polyethylene, polypropylene, ethylene-propylene copolymer (EPDM), isobutylene-isoprene copolymer, polystyrene, polybutene, polyisobutylene, polybutadiene, acrylonitrile-butadiene copolymer, ethylene-vinyl acetate copolymer, and ethylene-α-olefin copolymer.

The curable resin may be any of the curable resins described above. Only one type of the curable resin may be used, or two or more types may be used in combination.

From the viewpoint of further improving weather resistance, the material of the second layer preferably contains an acrylic resin, a urethane resin, a fluororesin, or a silicone resin, and more preferably an acrylic resin or a urethane resin. From the viewpoint of further improving the applicability, the material of the second layer is preferably a resin material containing an acrylic resin or a resin material containing a urethane resin.

The curable component in the material of the first layer and the resin in the material of the second layer may be the same or different.

The material of the second layer may be water-based or oil-based. Preferably, the material of the second layer is liquid.

From the viewpoint of exhibiting the effects of the present invention even more effectively, the second layer is preferably insoluble in water.

The content of the resin in 100% by weight of the material of the second layer is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 70% by weight or more, particularly preferably 80% by weight or more. The content is preferably 99.5% by weight or less, more preferably 99% by weight or less, further preferably 95% by weight or less, particularly preferably 90% by weight or less. When the content of the resin is not less than the lower limit and not more than the upper limit, the effects of the present invention can be exhibited even more effectively.

In 100% by weight of the material of the second layer, the content of the curable resin is preferably 50% by weight or more, more preferably 60% by weight or more, even more preferably 70% by weight or more, particularly preferably 80% by weight or more, and preferably 99.5% by weight or less, more preferably 99% by weight or less, even more preferably 95% by weight or less, particularly preferably 90% by weight or less. When the content of the curable resin is equal to or more than the lower limit and equal to or less than the upper limit, the effect of the present invention can be exerted more effectively.

<Other Ingredients>
The first layer may contain other components than the cured product of the curable component, the ion-releasing compound, and the coating agent, as necessary. The second layer may contain other components than the resin, as necessary. Examples of the other components include a diluent, a reaction catalyst, a reaction accelerator, a crosslinking agent, a water absorbing agent, a foam stabilizer, an antioxidant, and a colorant.

(Laminate manufacturing kit)
In the method for producing a laminate according to the present invention, a laminate production kit may be used. The laminate production kit is a laminate production kit for producing the laminate. The laminate production kit includes a material for a first layer and a material for a second layer. In the laminate production kit, the material for the first layer includes a curable component and an ion-releasing compound capable of releasing cations or anions.

In the laminate production kit, the material for the first layer may be housed in a container (first container). In the laminate production kit, the material for the second layer may be housed in a container (second container). The first container and the second container may be separate containers or may be one integrated container. One integrated container may have a partition portion to prevent the material of the first layer and the material of the second layer from coming into contact with each other.

The viscosity of the first layer material and the second layer material is not particularly limited. The viscosity of the first layer material and the second layer material is preferably 0.1 Pa·s or more, more preferably 0.2 Pa·s or more, even more preferably 0.5 Pa·s or more, and is preferably 2000 Pa·s or less, more preferably 1000 Pa·s or less, even more preferably 500 Pa·s or less. When the viscosity of the first layer material and the second layer material is equal to or more than the lower limit and equal to or less than the upper limit, the first layer material and the second layer material can be well positioned by coating or spraying.

(Structure with laminate)
A laminate-attached structure can be obtained by using the laminate obtained by the laminate manufacturing method according to the present invention. The laminate-attached structure includes a structure and the laminate. In the laminate-attached structure, the laminate is disposed on a surface of the structure, and the first layer of the laminate is in contact with the structure.

Since the above structure with a laminate has the above configuration, cracks in the structure can be prevented, and even if cracks occur in the structure, the cracks that have occurred can be repaired. .

In addition, in the structure with the laminate, the second layer prevents the first layer from coming into contact with moisture more than necessary, so that it is possible to prevent ions from eluting more than necessary from the laminate (specifically, the ion-releasing compound in the first layer). As a result, the ion-releasing compound can efficiently release ions toward the structure, so that the structure can be maintained in a stable state for a long period of time.

FIG. 1 is a cross-sectional view schematically showing a structure using a laminate obtained by a method for manufacturing a laminate according to an embodiment of the present invention. Note that, in addition to the laminate, FIG. 1 also shows a structure.

A structure with a laminate 11 shown in FIG. 1 includes a structure 10 and a laminate 5. In the structure 11 with a laminate, the laminate 5 is arranged on the surface of the structure 10. The laminate 5 includes a first layer 1 and a second layer 2. The material of the first layer 1 includes a curable component and an ion-releasing compound. The first layer 1 includes a cured product of a curable component and an ion-releasing compound. The first layer 1 has a first surface 1a and a second surface 1b. The first surface 1a and the second surface 1b are surfaces facing each other in the first layer 1.

In the laminate 5, the second layer 2 is arranged (stacked) on the first surface 1a of the first layer 1. In the laminate 5, the first layer 1 and the second layer 2 are in contact with each other, and are in surface contact with each other. In the laminate 5, the first surface 1a of the first layer 1 and the second layer 2 are in contact.

In the structure 11 with a laminate, the first layer 1 is arranged (laminated) on the surface of the structure 10 . The first layer 1 is arranged on the outside of the structure 10. In the structure 11 with a laminate, the first layer 1 of the laminate 5 and the structure 10 are in contact with each other. In the structure 11 with a laminate, the second surface 1b of the first layer 1 and the structure 10 are in contact with each other. The second layer 2 is arranged on the outside of the structure 10. In the structure 11 with a laminate, the structure 10, the first layer 1, and the second layer 2 are arranged in this order.

When moisture seeps from the back side of the structure 10 to the surface of the structure 10 due to cracks or fissures that exist on the surface of the structure 10 during construction or that have occurred after construction, and the surface of the first layer 1 comes into contact with moisture, the ions contained in the moisture react chemically with the ions released from the ion-releasing compound contained in the first layer 1. Alternatively, when moisture seeps from the back side of the structure 10 to the surface of the structure 10 due to cracks or fissures that exist on the surface of the structure 10 during construction or that have occurred after construction, and the surface of the first layer 1 comes into contact with moisture, the cations and anions released from the ion-releasing compound contained in the first layer 1 react chemically, and poorly water-soluble salts are generated in the cracks or fissures of the structure 10. In other words, the generated poorly water-soluble salts fill the spaces of the cracks or fissures that exist in the structure 10 and are in contact with the first layer 1. The resulting poorly water-soluble salt seals the cracks and fissures on the surface of the structure 10, preventing water from seeping in from the back side, thereby suppressing deterioration of the concrete caused by water.

A portion of the first layer may be located inside the structure. The entire first layer may be located outside the structure. Of the 100 volume% of the first layer, the first layer disposed on the outside of the structure may have a content of 50 volume% or more, a content of 70 volume% or more, or a content of 80 volume% or more. The content may be 95% by volume or more, and may be 100% by volume or less.

(Method of protecting or repairing structures)
The method for protecting or repairing a structure according to the present invention includes a step of disposing a first layer material on the surface of the structure, and curing the first layer material to form the first layer. and a second layer forming step of forming a second layer on the first surface of the first layer. In the method for protecting or repairing a structure, the material of the first layer includes a curable component and an ion-releasing compound capable of releasing cations or anions.

The method for protecting or repairing a structure according to the present invention has the above-mentioned configuration, so that cracks in the structure can be prevented, and even if cracks do occur in the structure, the cracks can be repaired.

In addition, in the method for protecting or repairing a structure, the second layer prevents the first layer from coming into contact with moisture more than necessary, thereby preventing ions from eluting more than necessary from the laminate (specifically, the ion-releasing compound in the first layer). As a result, the ion-releasing compound can efficiently release ions toward the structure, so that the structure can be maintained in a stable state for a long period of time.

The material of the first layer may be the material of the first layer in the manufacturing method of the laminate. From the viewpoint of exerting the effects of the present invention more effectively, it is preferable that the material of the first layer is the material of the first layer in the manufacturing method of the laminate.

The material of the second layer may be the material of the second layer in the manufacturing method of the laminate. From the viewpoint of exerting the effect of the present invention more effectively, the material of the second layer is preferably the material of the second layer in the manufacturing method of the laminate. From the viewpoint of further improving the applicability and further improving the protection or repair effect of the structure, the material of the second layer is preferably liquid at 23°C. From the viewpoint of exerting the effect of the present invention more effectively, the material of the second layer preferably contains an acrylic resin, a urethane resin, a fluororesin, or a silicone resin.

The structure is not particularly limited. Examples of the structure include concrete structures. Examples of the concrete structures include buildings, underground tunnels, undersea tunnels, mountain tunnels, and insulators (grout parts) arranged on the outer surfaces of pipes, etc. From the viewpoint of more effectively exerting the effects of the present invention, it is preferable that the structure is a concrete structure. The structure may be an underground structure.

The surface of the structure on which the first layer material is placed may or may not be etched. From the viewpoint of improving adhesion to the structure, it is preferable that the surface of the structure on which the first layer material is disposed is subjected to a keren treatment. From the viewpoint of improving adhesion to the structure, it is preferable to arrange the material of the first layer on the surface of the structure that has been subjected to the keren treatment in the arrangement step.

From the viewpoint of further enhancing the protective or repair effect of the structure, it is preferable that the above-mentioned disposing step is a step of applying the material of the above-mentioned first layer onto the surface of the structure. From the viewpoint of further enhancing the protective or repair effect of the structure, it is preferable that in the above-mentioned disposing step, the material of the above-mentioned first layer is applied onto the surface of the structure by application. The application may be by spraying.

From the viewpoint of releasing ions even more efficiently to the structure side, the second layer forming step includes forming the material of the second layer on the first surface of the first layer. It is preferable to include a step of applying a material for the second layer, and a step of drying the material of the second layer. From the viewpoint of releasing ions more efficiently from the structure side, in the second layer forming step, the material of the second layer is applied onto the first surface of the first layer by coating. It is preferable that the The application may be by spraying.

The method for drying the material of the second layer is not particularly limited. Examples of methods for drying the material of the second layer include blowing air and heating.

Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples. The invention is not limited only to the following examples.

The following materials were prepared:

<Material of first layer>
(curable component)
Curable component A ("Infraguard CRJ" manufactured by Sekisui Chemical Co., Ltd., 50% by weight of main agent (epoxy resin): 50% by weight of curing agent)
Curing component B (base agent (“jER828” manufactured by Mitsubishi Chemical Corporation) 57% by weight: curing agent (mercaptan compound, “QX40” manufactured by Mitsubishi Chemical Corporation) 43% by weight)

(Ion-releasing compound)
Compounds capable of releasing cations:
Calcium acetate (Nacalai Tesque "Calcium acetate monohydrate JIS special grade reagent")
Compounds capable of releasing anions:
Sodium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., average particle size 100 μm)

(Reaction accelerator)
Tertiary amine compound ("Lubeac DMP-30" manufactured by Nacalai Tesque)

<Material of second layer>
Urethane-based materials ("Urethane-based" in the table, resin materials containing urethane resin, "Water-based FRP/plastic paint" manufactured by Sunday Paint Co., Ltd.)
Acrylic materials ("acrylic" in the table, resin materials containing acrylic resin, "waterproof paint" manufactured by Asahipen Co., Ltd.)

Example 1
Formation of the first layer:
A material for the first layer was obtained by mixing 100 parts by weight of hardenable component A, 50 parts by weight of sodium carbonate, and 50 parts by weight of calcium acetate. The obtained material for the first layer was poured into a formwork (width 12.7 mm × depth 12.7 mm × thickness 25.4 mm) and cured for 7 days under conditions of 23°C and 50% RH to harden the hardenable component A. The material was then removed from the formwork to form the first layer.

Preparation of the laminate:
A resin material containing a urethane resin was applied as a material for the second layer onto the surface (six faces) of the obtained first layer with a brush, and then the applied material was left to stand for 2 hours under conditions of 23° C. and 50% RH to dry and harden, thereby obtaining a laminate. The obtained laminate includes the first layer and the second layer disposed on the surface of the first layer.

(Examples 2 to 4)
A laminate was obtained in the same manner as in Example 1, except that the materials for the first layer and the second layer were set as shown in Table 1.

(Comparative Examples 1 to 4)
A monolayer body was obtained in the same manner as in Example 1, except that the material of the first layer was set as shown in Table 2, and the second layer was not formed.

(evaluation)
(1) Protection and repair effect The second layer side surface (25.4 mm x 12.7 mm) of the laminates obtained in Examples 1 to 4 was polished with No. 80 sandpaper to form the second layer. was removed to expose the first layer to obtain a test specimen. Two SUS plates each having a thickness of 3 mm were placed in parallel at a distance of 15 mm on the bottom of a PP container having a depth of 20 mm or more. The laminate with the first layer exposed above was placed so as to span two SUS plates, with the exposed surface facing downward. Two SUS plates each having a thickness of 3 mm were placed in parallel at a distance of 15 mm on the bottom of a PP container having a depth of 20 mm or more.

Furthermore, for Comparative Examples 1 to 4, similarly to Examples 1 to 4, the single layer bodies (test specimens) of Comparative Examples 1 to 4 were installed so as to straddle two SUS plates.

In Examples 1 and 3 and Comparative Examples 1 and 3, ion-exchanged water was placed in a container to a depth of 4 mm to 10 mm, and the bottom surface of the test specimen was immersed in the water for one month.

In Examples 2 and 4 and Comparative Examples 2 and 4, a 1000 ppm calcium chloride solution was placed in a container to a depth of 4 mm or more and 10 mm or less, and the lower surface of the test specimen was immersed for one month.

After the immersion, the surface of the lower side that had been immersed was closely inspected with the naked eye to see whether particles had precipitated or not.
When the specimens with particles precipitated on the surface were observed using a scanning electron microscope, aggregates of particles with a dense crystal structure (calcium carbonate calcite structure) were observed. The generation of poorly water-soluble salts (calcium carbonate) was judged according to the following criteria.

[Judgment criteria for protection and repair effects]
○: Poorly water-soluble salts are generated. ×: Poorly water-soluble salts are not generated.

(2) Amount of ion elution After immersing the obtained laminate or monolayer in 300 mL of ion-exchanged water and allowing it to stand at 23°C for 5 days, the concentration of sodium ions and calcium ions in the ion-exchanged water after standing was was measured under the following conditions.

[Conditions for measuring sodium ion concentration]
Measuring equipment: HORIBA "LAQUAtwin Na-11"
Temperature: 23°C
After standing, 1 mL of the ion-exchanged water was diluted with 9 mL of ion-exchanged water to obtain solution A. The obtained solution A was dropped onto the electrode section, and the indicated concentration was multiplied by the dilution rate to obtain the sodium ion concentration.

[Calcium ion concentration measurement conditions]
Measuring equipment: Horiba "F-2000PC" (electrode: 6583S-10C)
Temperature: 23°C
After standing, 1 mL of the ion-exchanged water was diluted with 4 mL of ion-exchanged water to obtain solution B. 0.1 mL of an ionic strength adjuster for calcium ion-selective electrodes (Horiba, Ltd., "500-CA-ISA") was added to the obtained solution B, stirred, and then allowed to stand for one minute. The solution was then dropped onto the electrode, and the indicated concentration was multiplied by the dilution rate to obtain the calcium ion concentration.

The structure and results of the laminate or single layer are shown in Tables 1 and 2 below.

In Examples 1 to 4, in which a second layer was provided on the surface of the first layer, the amount of sodium ion or calcium ion elution was suppressed compared to Comparative Examples 1 and 3, in which a second layer was not provided. In other words, the laminates of Examples 1 to 4 were able to suppress the elution of ions more than necessary compared to the single layer bodies of Comparative Examples 1 and 3, and as a result, the structure could be maintained in a stable state for a long period of time.

Reference Signs List 1: First layer 1a: First surface 1b: Second surface 2: Second layer 5: Laminate 10: Structure 11: Structure with laminate

Claims (14)

A method for manufacturing a laminate for protecting or repairing a structure, the method comprising:
a first layer forming step of curing the material of the first layer to form the first layer;
a second layer forming step of forming a second layer on the first surface of the first layer,
A method for manufacturing a laminate, wherein the first layer material includes a curable component and an ion-releasing compound capable of releasing cations or anions. The second layer forming step includes:
applying a second layer of material onto the first surface of the first layer;
and drying the second layer material. The method for manufacturing a laminate according to claim 1 or 2, wherein the material of the second layer is liquid at 23°C. The method for manufacturing a laminate according to claim 1 or 2, wherein the material of the second layer includes an acrylic resin, a urethane resin, a fluororesin, or a silicone resin. the ion-releasing compound comprises a compound capable of releasing a cation,
3. The method for producing a laminate according to claim 1 or 2, wherein the compound capable of releasing cations is calcium silicate, tricalcium silicate, dicalcium silicate, calcium aluminate, calcium aluminoferrite, calcium hydroxide, calcium oxide, calcium acetate, calcium lactate, barium lactate, calcium sulfate, calcium chloride, calcium nitrate, or calcium hydrogen carbonate. the ion-releasing compound includes a compound capable of releasing anions,
3. The anion-releasing compound is sodium hydrogen phosphate, potassium carbonate, potassium hydrogen carbonate, ammonium carbonate, ammonium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, or calcium hydrogen carbonate. A method for manufacturing a laminate. The method for manufacturing a laminate according to claim 1 or 2, wherein the structure is a concrete structure. disposing a first layer of material on a surface of the structure;
a first layer forming step of hardening the material of the first layer to form a first layer;
and a second layer forming step of forming a second layer on the first surface of the first layer,
A method for protecting or repairing a structure, wherein the first layer of material comprises a hardenable component and an ion-releasing compound capable of releasing cations or anions. The second layer forming step
applying a material for the second layer onto the first surface of the first layer;
The method for protecting or repairing a structure according to claim 8, comprising the step of drying the material of the second layer. The method for protecting or repairing a structure according to claim 8 or 9, wherein the material of the second layer is liquid at 23°C. The method for protecting or repairing a structure according to claim 8 or 9, wherein in the placing step, the material of the first layer is placed on the surface of the structure that has been subjected to a cleaning treatment. The method for protecting or repairing a structure according to claim 8 or 9, wherein the arranging step is a step of applying the first layer material on the surface of the structure. The method for protecting or repairing a structure according to claim 8 or 9, wherein the material of the second layer includes an acrylic resin, a urethane resin, a fluororesin, or a silicone resin. The method for protecting or repairing a structure according to claim 8 or 9, wherein the structure is a concrete structure.

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