JP2017008626A - Protective structure and protection method for cement hardened body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a protective structure and a protection method for a cement hardened body that suppress cracking of a carbon film of a protective sheet.SOLUTION: A protective structure for a cement hardened body (a protective structure 100 for concrete) includes a protective sheet 300 that covers a cement hardened body structure (a concrete structure 200) and a surface of the cement hardened body structure through an adhesive layer 400. The protective sheet is a laminated body that includes a resin layer 310 and a carbon film 350 laminated on the resin layer 310. The adhesive layer 400 is a hardened resin layer containing a hardened modified silicone resin and a hardened epoxy resin. The configuration allows cracking of the carbon film 350 of the protective sheet 300 to be suppressed.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a protective structure for a hardened cementitious structure and a protective construction method for a hardened cementitious structure.

  Concrete is gradually neutralized by carbon dioxide in the air. When neutralization proceeds to the inside of the concrete, the reinforcing bars corrode and the strength of the concrete structure is greatly reduced. For this reason, Japanese Patent Application Laid-Open No. 2003-342084 (Patent Document 1) proposes a technique for preventing the neutralization of concrete by applying a coating material made of an epoxy resin composition or the like to the surface of a concrete structure. . In order to eliminate the necessity of sequentially forming many layers such as primer, putty, undercoat, intermediate coat, and top coat in the method of applying the coating material to the surface of the concrete structure in this way, construction time and labor As a means for reducing the above, Japanese Unexamined Patent Application Publication No. 2014-9508 (Patent Document 2) includes a concrete structure and a protective sheet that covers the surface of the concrete structure, and the protective sheet is a base material made of resin, A concrete structure protection structure and a concrete structure protection method including a carbon film, preferably a diamond-like carbon film, have been proposed.

JP 2003-342084 A JP 2014-9508 A

  In the technology of Japanese Patent Application Laid-Open No. 2014-9508 (Patent Document 2), vibration of a concrete structure, opening and closing of a crack generated in the concrete structure (for example, caused by vibration generated by passage of a vehicle such as a train), and As a result of repeated stress applied to the protective sheet due to shrinkage of the concrete structure itself (due to temperature changes), the carbon film of the protective sheet may crack and the neutralization prevention effect may be impaired. .

  An object of this invention is to provide the protection construction method of the cement hardening body protective structure and cement hardened body structure which suppress the crack of a carbon film in view of the above point.

  As a result of intensive studies, the present inventors have found that the above object can be achieved by covering the surface of the hardened cementitious structure with a protective sheet via an epoxy-modified silicone adhesive layer. It came to complete.

(1)
The hardened cementitious body protective structure of the present invention includes a hardened cementitious structure and a protective sheet that covers the surface of the hardened cementitious structure via an adhesive layer. The protective sheet is a laminate including a resin layer and a carbon film laminated on the resin layer. The adhesive layer is a cured resin layer containing a modified silicone resin cured product and an epoxy resin cured product.

  With this configuration, cracking of the carbon film of the protective sheet can be suppressed. Therefore, for example, even when a stress is repeatedly applied to the protective sheet, the carbon film of the protective sheet is hardly cracked, so that neutralization of the hardened cement body can be effectively prevented.

  In the present invention, a resin composition containing a modified silicone resin and an epoxy resin is used as an adhesive for the formation of the adhesive layer. For example, unlike the case where an epoxy resin is used as an adhesive, an excellent elastic modulus, Effectively suppresses cracks in the carbon film. Further, unlike the case of using, for example, a urethane resin, silicone resin, rubber resin, or the like as an adhesive, it effectively suppresses low-molecular bleed-out, deterioration due to a solvent, etc., and is therefore excellent in practicality.

(2)
The adhesive layer preferably has a stress (10% modulus) at 10% elongation of 0.7 N / mm ² or less according to JIS K6251 “Vulcanized rubber and thermoplastic rubber—How to obtain tensile properties”.
With this configuration, it is possible to effectively absorb stress from the hardened cement building to the carbon film of the protective sheet, and to preferably suppress cracking of the carbon film.

(3)
The adhesive layer is preferably obtained by a reaction between a first agent containing a modified silicone resin and an epoxy curing agent and a second agent containing an epoxy resin and a silanol condensation catalyst.
With this configuration, it is possible to obtain good adhesiveness and good weather resistance regardless of the degree of unevenness and / or cracks that may be present on the surface of the hardened cementitious structure.

(4)
The adhesive layer is preferably a cured product of a one-component adhesive resin composition containing a modified silicone resin, an epoxy resin, a silanol condensation catalyst, and an epoxy curing agent.
With this configuration, poor curing is less likely to occur because the uniformity of the adhesive resin composition used for curing is good, and thus good adhesiveness can be easily obtained.
(5)
The adhesive layer is preferably a cured product of an adhesive resin composition including a modified silicone resin and an epoxy resin having a content of 1 part by weight or more and 100 parts by weight or less based on 100 parts by weight of the modified silicone resin.
By being more than the said lower limit, the favorable toughness of an adhesive layer can be obtained, and favorable elasticity of an adhesive layer can be obtained by being the said upper limit or less. Therefore, the crack of the carbon film of a protective sheet can be suppressed preferably.

(6)
The method for protecting a cement cured body structure of the present invention includes a modified silicone resin and an epoxy resin on at least one of the surface of the cement cured body structure and the surface of the protective sheet in which the resin layer and the carbon film are laminated. A step of providing a layer of the adhesive resin composition, and a step of bonding the surface of the cement cured body structure and the surface of the protective sheet through the adhesive resin composition.
With this configuration, a cured cemented body protective structure that can suppress cracking of the carbon film of the protective sheet is obtained.

It is typical sectional drawing which shows an example of the cement hardening body protection structure of 1st Embodiment. The other example of 1st Embodiment is shown. The further another example of 1st Embodiment is shown. 1 shows a schematic configuration of an atmospheric pressure plasma CVD apparatus used in Examples. It is typical explanatory drawing of the fatigue-resistance test method performed in the Example.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the following description, the same elements are denoted by the same reference numerals, and their names and functions are also the same. Therefore, detailed description thereof will not be repeated.

[First Embodiment]
FIG. 1 is a schematic cross-sectional view showing an example of the cemented body protection structure of the present invention.
A concrete protective structure 100 shown in FIG. 1 includes a concrete building 200, a protective sheet 300, and an adhesive layer 400 interposed therebetween.

  The concrete building 200 includes concrete 210 and a core material 220 such as a reinforcing bar. The concrete 210 is obtained by mixing cement, water, gravel, sand, and the like and hardening the cement by a hydration reaction. The concrete structure 200 may be a newly installed object or an object to be repaired. Examples of the concrete structure 200 include concrete viaducts (particularly beams and columns), concrete girder bridges, electrical poles, buildings, houses, and the like.

  The protective sheet 300 includes a resin layer 310 and a carbon film 350 laminated so as to be in contact with the resin layer 310. The protective sheet 300 is provided so that the resin layer 310 is in contact with the adhesive layer 400, and covers the concrete building 200 through the adhesive layer 400.

  The resin layer 310 may be made of resin, for example, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyamide, acrylic resin, phenol resin, melamine resin, epoxy resin, urea resin, vinyl chloride resin, polyethylene, polypropylene, and the like. Can be mentioned.

  The film thickness of the resin layer 310 is, for example, 1 μm or more and 1000 μm or less, preferably 10 μm or more and 500 μm or less. Being equal to or higher than the lower limit is preferable in that an effect of suppressing the neutralization of the concrete 210 can be easily obtained. It is preferable that it is below the upper limit value in terms of obtaining good adhesion workability of the protective sheet 300 to the hardened cementitious structure (concrete structure 200).

The linear expansion coefficient of the resin layer 310 based on JIS K7197 is preferably 10 × 10 ⁻⁵ / K or less, and more preferably 5 × 10 ⁻⁵ / K or less. By being below the upper limit, it is easy to prevent cracking of the resin layer 310 itself and to suppress cracking of the carbon film 350 following the crack.

  Various carbon films are used as the carbon film 350, and a diamond-like carbon (DLC) film is preferable from the viewpoint of neutralization suppressing effect and further from the viewpoint of suppressing permeation of oxygen and / or water vapor. The DLC film is an amorphous film including both a diamond structure (sp3 bond) and a graphite structure (sp2 bond). Further, hydrogen may or may not be included. The mixing ratio of the diamond structure and the graphite structure and the hydrogen content are not particularly limited. More specifically, ta-C, aC, ta-C: H, and aC: H are mentioned.

  In the present invention, since the adhesive layer 400 that can effectively suppress cracking of the carbon film 350 is used, for example, even a carbon film having a hardness measured by the nanoindentation method of 1 GPa or more is allowed. . Note that the nanoindentation method is a method in which an indenter (for example, a nano-order needle) is pressed into the surface of a material, and the hardness, Young's modulus, and the like of a minute region are measured from the load and the amount of displacement. As an example, it can be measured as follows. Using a Triboscope made by Hystron, a triangular pyramid-shaped diamond indenter called a Belkovic indenter was applied to the sample surface at a right angle, and a load was gradually applied from the carbon film surface to a pushing amount of 10% of the film thickness of the carbon film. Gradually return the load to zero. A value P / A obtained by dividing the maximum load P at this time by the projected area A of the indenter contact portion is calculated as the hardness.

  The film thickness of the carbon film 350 is, for example, not less than 0.01 μm and not more than 1 μm, preferably not less than 0.02 μm and not more than 0.5 μm. Being equal to or higher than the lower limit is preferable in that a neutralization suppressing effect can be easily obtained. It is preferable that it is not more than the above upper limit in that it is easy to suppress cracking of the carbon film of the protective sheet.

  The protective sheet 300 can be manufactured by using the resin layer 310 as a base material and forming the carbon film 350 by various vapor deposition methods. For example, specific examples of the vapor deposition method include a plasma CVD method and a sputtering method. Furthermore, examples of the plasma CVD method include an atmospheric pressure plasma CVD method and a plasma CVD method under high vacuum.

  The adhesive layer 400 is made of a cured resin including a modified silicone resin cured product and an epoxy resin cured product. This cured resin is a polymer alloy of a modified silicone resin cured product and a cured epoxy resin product. Preferably, it has a sea-island structure in which the modified silicone resin cured product is a main component, and the epoxy resin cured product phase is dispersed in the modified silicone resin cured product phase. Thus, the adhesive layer 400 has both toughness derived from the cured epoxy resin and elasticity derived from the modified silicone resin cured product.

  The cured resin constituting the adhesive layer 400 is prepared by curing an adhesive resin composition including a modified silicone resin, an epoxy resin, and a curing agent for curing each resin. The adhesive resin composition may be a so-called one-component resin composition or a two-component mixture of a so-called two-component mixed resin composition. In the case of a one-component resin composition, the work is easy and the work efficiency is good, and further, the curing of the adhesive resin composition to be cured is difficult to cause poor curing, Therefore, good adhesiveness can be easily obtained. In the case of a two-component mixed resin composition, the adhesiveness is good regardless of the degree of unevenness and / or cracks on the surface of the hardened cementitious structure, and it is preferable in that the weather resistance is also good.

When the adhesive resin composition is a one-component type, examples of the adhesive resin composition include a mixture containing a modified silicone resin, an epoxy resin, a silanol condensation catalyst, and an epoxy curing agent.
When the adhesive resin composition is a two-component mixture of a two-component mixed resin composition, examples of the first agent and the second agent include the following. The first agent contains a modified silicone resin, and the second agent contains an epoxy resin. In this case, the first agent further includes an epoxy curing agent, and the second agent further includes a silanol condensation catalyst.

  Although it does not specifically limit as a modified silicone resin, Preferably it is a moisture hardening type modified silicone resin, and has a hydrolysable silicon group in this case. The modified silicone resin having a hydrolyzable silicon group has a polymer selected from the group consisting of a polyether polymer, a polyolefin polymer and an acrylic polymer as a main chain (a portion excluding the hydrolyzable silicon group). Therefore, the main chain may be a polymer of a monomer selected from the group consisting of an alkylene oxide component, an olefin component, and an acrylic component, and this polymer may be a homopolymer or a copolymer. In the case of a copolymer, the copolymer component may be selected from the group consisting of an alkylene oxide component, an olefin component, an acrylic component, and other vinyl components.

Examples of the alkylene oxide component include ethylene oxide, propylene oxide, butylene oxide and the like. The main chain is preferably polypropylene oxide mainly composed of propylene oxide units from the viewpoints of elongation after curing and viscous handling.
An isobutylene is mentioned as an olefin component.

  Examples of the acrylic component 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, 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, trimethylolpropane tri (meth) ) Acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy acrylate, polyester acrylate, urethane acrylate, 2-hydroxyethyl ( (Meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) Acrylate, 4-hydroxybutyl (meth) acrylate, 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-hydroxyethylphthalic acid, 2-[(meth) acryloyloxy] ethyl 2- And hydroxypropylphthalic acid. In the case where the acrylic polymer is a copolymer of other vinyl monomer components, hydrolyzable silicon groups can be introduced by copolymerizing vinyl monomer components having hydrolyzable silicon groups.

  It is preferable that the main chain contains an acrylic unit from the viewpoint of good weather resistance. Furthermore, from the viewpoint of weather resistance, the content of the acrylic unit in the main chain is preferably 5% by weight or more and 20% by weight or less.

The hydrolyzable silicon group is not particularly limited, and examples thereof 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. Here, the number of hydrolyzable groups bonded to silicon atoms in the hydrolyzable silicon group is preferably 1 or more and 3 or less. Further, the hydrolyzable group bonded to one silicon atom may be one kind or plural kinds. Furthermore, the hydrolyzable group and the non-hydrolyzable group may be bonded to one silicon atom. The hydrolyzable silicon group is preferably an alkoxysilyl group such as a monoalkoxysilyl group, a dialkoxysilyl group, or a trialkoxysilyl group in terms of excellent stability and easy handling.
The modified silicone resins may be used alone or in combination of two or more.

  The number average molecular weight of the modified silicone resin having a hydrolyzable silicon group is, for example, 1,000 or more and 500,000 or less, 1,000 or more and 100,000 or less, 10,000 or more and 30,000 or less, and 4,000 or more and 500. 4,000 or less, or 4,000 or more and 30,000 or less. It is preferable that it is more than the said lower limit from the point that the hardening time of adhesive resin composition is short, or the adhesive strength after hardening is favorable. It is preferable that the viscosity is not more than the upper limit because the viscosity of the adhesive resin composition is appropriate and the handleability is good.

  The silanol condensation catalyst is used for curing the modified silicone resin composition in a short time. Examples of the silanol condensation catalyst include poly (dialkylstannoxane) disilicate compounds, tin catalysts such as monoalkyl tin esters and dialkyl tin esters, 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, and dibutyltin. Examples include dimethoxide, dibutyltin diphenoxide, dibutyltin diacetylacetonate, dibutyltin acetoacetate, stannous octoate and the like.
Examples of the organic titanates include titanium alkoxides such as tetrabutyl titanate, tetraisopropyl titanate, tetramethyl titanate, tetra (2-ethylhexyl titanate) triethanolamine titanate, titanium tetraacetylacetonate, titanium ethylacetoacetate, octyleneglycol. And titanium chelates such as rate.
A silanol condensation catalyst may be used independently and may be used together 2 or more types.

  The content of the silanol condensation catalyst in the adhesive composition is 0.1 parts by weight or more and 10 parts by weight or less, preferably 1 part by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the modified silicone resin. It is preferable from the point of shortening of hardening time that it is more than the said lower limit. It is preferable that it is below the upper limit in terms of ensuring physical properties such as adhesive strength.

  It does not specifically limit as an epoxy resin, What is necessary is just a resin which has an epoxy group. Specific examples include those in which a glycidyl group is bonded to a compound selected from the group consisting of unsaturated aliphatic compounds, alicyclic compounds, aromatic compounds, and heterocyclic compounds. From the viewpoint of the neutralization suppressing effect, it is preferable to include an aromatic compound.

Examples of the epoxy resin include bisphenol type epoxy resins such as bisphenol A type, bisphenol F type, bisphenol S type and hydrogenated products thereof; glycidyl ether type epoxy resins such as polypropylene glycol diglycidyl ether type epoxy resins; Ester type epoxy resins such as glycidyl ester type epoxy resins; Novolak type epoxy resins such as phenol novolak type and cresol novolak type, bisphenol A novolak type epoxy resins and hydrogenated products thereof; Trisphenol type such as triphenolmethane type epoxy resin Multifunctional epoxy resin; triglycidyl isocyanurate type, tetraglycidyl diaminodiphenylmethane type, tetraglycidyl metaxylenediamine type, hydan Nitrogen-containing polyfunctional epoxy resins such as in-type; condensed ring-type epoxy resins such as naphthalene type; biphenyl-type epoxy resins; dicyclopentadiene-type epoxy resins; ether ester-type epoxy resins; 3,4-epoxycyclohexylmethyl-3 An epoxy resin having an alicyclic structure such as', 4'-epoxycyclohexanecarboxylate; a urethane type epoxy resin; a rubber-modified epoxy resin having a rubber skeleton such as polybutadiene and acrylonitrile butadiene rubber (NBR) can be used.
An epoxy resin may be used individually by 1 type, and may use 2 or more types together.

  The content of the epoxy resin in the adhesive composition is, for example, 1 to 100 parts by weight, preferably 2 to 80 parts by weight, with respect to 100 parts by weight of the modified silicone resin. By being more than the said lower limit, favorable toughness can be obtained in the adhesive layer after hardening, and favorable elasticity can be obtained in the adhesive layer after hardening by being below the said upper limit. Therefore, the crack of the carbon film of a protective sheet can be suppressed preferably.

Examples of the epoxy curing agent include amine compounds. Examples of amine compounds include aliphatic tertiary amines such as N, N-dimethylpropylamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N-methylpiperidine, and N, N′-dimethylpiperazine. Alicyclic tertiary amines, benzyldimethylamine, dimethylaminomethylphenol, aromatic tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol, ethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylene Aliphatic diamines such as hexamine, trimethylene diamine, hexamethylene diamine, tetramethylene diamine, alicyclic diamines such as 1,3-bis (aminomethyl) cyclohexane, isophorone diamine, norboldene diamine, diaminodiphenylmethane, Metaphenylene Aromatic diamines such as diamines may be mentioned.
In addition to the above, examples of the epoxy curing agent include polyamide resins; imidazoles such as 2-ethyl-4-methylimidazole; and compounds such as carboxylic acid anhydrides such as phthalic anhydride.

Further, the epoxy curing agent may be a latent curing agent such as ketimine that is blocked with an active amine and activated under predetermined conditions such as moisture. For example, ketimine exists stably in the absence of moisture, but generally becomes a primary amine due to the presence of moisture and reacts with an epoxy resin. Specifically, 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-tri Examples include eicosadiene and 2,4,15,17-tetramethyl-5,8,11,14-tetraaza-4,14-octadecadien.
Epoxy curing agents may be used alone or in combination of two or more.

  The content of the epoxy curing agent in the adhesive resin composition is, for example, 20 parts by weight or more and 60 parts by weight or less, and preferably 30 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the epoxy resin. Alternatively, when a latent curing agent is used as the epoxy curing agent, the total number of epoxy groups in the epoxy resin relative to the total number of active amino groups generated by activation (total number of moles of epoxy groups / total number of active amino groups). The number of moles) is, for example, 0.8 or more and 1.2 or less, preferably 0.9 or more and 1.1 or less. It is preferable from the viewpoint of the elastic modulus of the cured film that it is at least the above lower limit value, and it is preferable from the viewpoint of storage stability that it is at most the above upper limit value.

  The adhesive resin composition may further contain other additives as necessary. Examples of other additives include dehydrating agents, epoxy silane coupling agents, antioxidants, fillers, plasticizers, sagging inhibitors, ultraviolet absorbers, pigments, solvents, and fragrances.

  The layer thickness of the adhesive layer 400 is, for example, 100 μm or more and 1000 μm or less, preferably 200 μm or more and 800 μm or less. Being equal to or higher than the lower limit is preferable from the viewpoint of obtaining good elasticity, and being equal to or lower than the upper limit is preferable from the viewpoint of film formation.

The stress at the time of 10% elongation according to JIS K6251 of the adhesive layer 400 is, for example, 0.7 N / mm ² or less, preferably 0.5 N / mm ² or less, more preferably 0.3 N / mm ² or less. Thereby, the stress from the concrete building 200 to the carbon film 350 of the protective sheet 300 is effectively absorbed, and the crack of the carbon film 350 can be preferably suppressed.

  At the time of construction of the concrete protective structure 100, as the above-mentioned adhesive resin composition, a non-heated or heated product to which water is further added is used. When heated, the temperature can be, for example, 40 ° C. or more and 80 ° C. or less. It is preferable that it is more than the said lower limit from the point which acquires sufficient adhesive force in a short time. It is preferable that it is not more than the above upper limit value in order to prevent the protective sheet 300 from being damaged.

  The viscosity of the adhesive resin composition at the time of construction conforms to JIS K6833, and the initial viscosity at 23 ° C. and 50% RH is 10 Pa · S or more and 1000 Pa · S or less (the initial viscosity refers to the rotor of the BS type viscometer) Preferably used and measured at a rotation speed of 10 rpm). It is preferable from the point of workability that it becomes moderate viscosity that it is more than the said lower limit. That it is below the said upper limit becomes favorable for the adhesiveness to the unevenness | corrugation of the concrete building 200 surface, and is preferable at the point of adhesiveness.

  In the construction of the concrete protection structure 100, the above-described adhesive is applied to the surface of the concrete building 200, the surface of the concrete building 200 and the surface of the resin layer 310 of the protection sheet 300, or the surface of the resin layer 310 of the protection sheet 300. A layer of resin composition is provided. The method of providing the adhesive resin composition layer is not particularly limited, such as a coating method, a dipping method, or a spray method. Examples of the coating method include coating using a roll, a spatula, a trowel, etc., ironing, brushing, and flow coating. When apply | coating using a roll, a rubber-made or metallic roll can be used, Furthermore, it can apply | coat in the aspect of 2 rolls or 3 rolls.

  Then, the surface of the concrete building 200 and the surface of the resin layer 310 of the protective sheet 300 are bonded together through a layer of the adhesive resin composition, and bonded by curing and curing.

  In addition, the base adjustment coating film may be provided in advance on the surface of the concrete building 200 as necessary, and the layer of the adhesive resin composition may be provided on the base adjustment coating film. Examples of the base adjustment coating include ethylene vinyl acetate resin, acrylic resin, and acrylic cation emulsion.

  The evaluation method for the neutralization of concrete can be generally performed by cutting out a concrete specimen to expose a cross section and utilizing the color reaction of phenolphthalein.

[Other examples]
In the said embodiment, although the resin layer 310 side of the protective sheet 300 comprised from the resin layer 310 and the carbon film 350 illustrated the aspect provided so that the concrete building 200 might be covered via the contact bonding layer 400, this invention Is not limited to this form.

For example, as shown in FIG. 2, the protective sheet 300 a configured by the resin layer 310 and the carbon film 350 may be provided so that the carbon film 350 side covers the concrete building 200 via the adhesive layer 400. . In this case, since the carbon film 350 is not directly affected by the external environment (for example, wind and rain, flying objects, etc.), it is easy to suppress cracking of the carbon film.
Further, as shown in FIG. 3, in the protective sheet 300 b, another resin layer 320 may be interposed between the resin layer 310 and the carbon film 350. Examples of the material of the other resin layer 320 include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyamide, acrylic resin, phenol resin, melamine resin, epoxy resin, urea resin, vinyl chloride resin, polyethylene, and polypropylene. The linear expansion coefficient (measured value based on JIS K7197) of another resin layer 320 is, for example, 10 × 10 ⁻⁵ / K or less, preferably 5 × 10 ⁻⁵ / K or less.

  Moreover, since it should just be a cement hardening body structure as a protection object for neutralization suppression, in addition to the concrete structure 200, the concrete structure which has a resin-made core material may be sufficient, and a core It may be a concrete structure having no material or a mortar structure.

<Example 1>
1. Production of Protective Sheet A Lumirror series manufactured by Toray Industries, Inc. was prepared as a polyethylene terephthalate (PET) film (hereinafter referred to as PET film). The film thickness of this PET film was 50 μm.

Using a PET film as a base material, a DLC film was formed on one side using an atmospheric pressure plasma CVD apparatus. FIG. 4 shows a schematic configuration of an atmospheric pressure plasma CVD apparatus 900. The atmospheric pressure plasma CVD apparatus 900 includes copper counter electrodes 903 and 905 arranged in parallel to each other, and dielectrics 907 and 909 arranged on the surfaces thereof. An atmospheric gas 911 is supplied between the counter electrodes 903 and 905 from a supply pipe (not shown) at a predetermined flow rate. The atmosphere gas 911 is a mixed gas of C ₂ H _{2 as} a source gas and N ₂ as a dilution gas. A high-frequency voltage is applied between the counter electrodes 903 and 905 by the pulse power source 913, and the atmosphere gas 911 is turned into plasma to become a plasma atmosphere gas.
The PET film (resin layer 310) is inserted between the counter electrodes 903 and 905, and moves in parallel with the counter electrodes 903 and 905 in a state where one surface is in contact with the dielectric 907. At this time, a DLC film is formed on the opposite surface of the PET film (resin layer 310), that is, the surface on the counter electrode 905 side.

  As described above, a protective sheet composed of a PET film and a DLC film formed on one surface thereof was produced. In addition, the film thickness of the DLC film in a protection sheet was 0.5 micrometer as a result of measuring by the method of observing a cross section with a scanning electron microscope (SEM).

2. Fabrication of protective structures for concrete structures
The protective sheet was cut into a size of 150 mm × 50 mm. As shown in FIG. 5, a pair of concrete substrates 211 and 212 were arranged with a gap I of 0.2 mm. On the surfaces of the substrates 211 and 212, a modified silicone resin in which the stress at 10% elongation after curing is 0.25 N / mm ² and the amount of the epoxy resin mixed with 100 parts by weight of the modified silicone resin is 70 parts by weight A two-component modified silicone-epoxy adhesive (adhesive resin composition) in which an agent I containing an epoxy resin and an epoxy curing agent and an agent II containing an epoxy resin and a silanol condensation catalyst are mixed. Applied. The coating amount was 0.5 kg / m ² . The viscosity of the adhesive is in accordance with JIS K 6833, and the initial viscosity at 23 ° C. and 50% RH is 500 Pa · S (the initial viscosity is the viscosity measured at the rotational speed of 10 rpm using the rotor 5 of the BS type viscometer. )Met. Moreover, the adhesive agent was apply | coated to the whole area | region which sticks a protective sheet later.
The protective sheet 300 was bonded so as to straddle both the surfaces of the substrates 211 and 212 so that the PET layer surface on which the DLC film was not formed becomes an adhesive surface.
<Example 2>
As an adhesive, instead of a two-component modified silicone-epoxy adhesive, the stress at 10% elongation after curing is 0.1 N / mm ² , and the amount of the epoxy resin mixed with 100 parts by weight of the modified silicone resin is 3 parts by weight, like in Example 1, except that a one-component adhesive comprising a mixture containing a modified silicone resin, an epoxy resin, a silanol condensation catalyst, and an epoxy curing agent was used. A protective structure for the structure was created.

<Comparative Example 1>
As the adhesive, instead of the two-component modified silicone-epoxy adhesive, Esdyne # 3450, Esdyne # 3120, and Esdyne Joiner W (all manufactured by Sekisui Chemical Co., Ltd.) ) Was used in the same manner as in Example 1 except that each was used.

<Evaluation of protective structure of concrete building>
Examples 1 and 2 and Comparative Example 1 were evaluated as follows.
1. Evaluation method JIS A1436-2006 "Fatigue resistance test method in the foundation discontinuity part of the coating material for construction" was applied mutatis mutandis, and the fatigue resistance of the protective sheet was evaluated. Specifically, one substrate 211 was fixed, and the other substrate 212 was reciprocated 6 million times along the arrow direction shown in FIG. 5 with an amplitude of 0.04 mm and a period of 0.1 sec. The evaluation test was performed in respective atmospheres of 20 ° C., 60 ° C., and −10 ° C.
Then, the carbon film surface of the protective sheet was observed with an electron microscope (JEOL JSM-5800LV, magnification 5000 times) to determine whether or not the carbon film was cracked.

2. Evaluation results No cracks were observed in the carbon films of the protective sheets according to Examples 1 and 2 under any temperature condition. On the other hand, the carbon film of the protective sheet according to Comparative Example 1 was confirmed to be cracked for all temperature conditions.
Therefore, according to the present invention, it was confirmed that even when stress due to vibration of a concrete building and / or crack opening / closing is repeatedly applied to the protective sheet, the carbon film is hardly cracked or broken.

  Preferred embodiments of the present invention are as described above, but the present invention is not limited to them, and various other embodiments are possible without departing from the spirit and scope of the present invention. Furthermore, the operations and effects described in this embodiment are merely examples, and do not limit the present invention.

  In the present specification, the concrete protective structures 100, 100a, and 100b correspond to the “protective structure of the hardened cement structure” in the claims, the concrete structure 200 corresponds to the “hardened cement structure”, and the protective sheet 300. , 300a, 300b correspond to a “protective sheet”, the resin layer 310 corresponds to a “resin layer”, the carbon film 350 corresponds to a “carbon film”, and the adhesive layer 400 corresponds to an “adhesive layer”.

100, 100a, 100b Concrete protective structure 200 Concrete building 300, 300a, 300b Protective sheet 310 Resin layer 350 Carbon film 400 Adhesive layer

Claims (6)

Hardened cement structure,
A protective sheet that covers the surface of the hardened cementitious structure via an adhesive layer,
The protective sheet is a laminate including a resin layer and a carbon film laminated on the resin layer,
The protective structure for a cement cured body structure, wherein the adhesive layer is a cured resin layer containing a modified silicone resin cured product and an epoxy resin cured product. The protective structure for a hardened cementitious structure according to claim 1, wherein the adhesive layer has a stress at 10% elongation in accordance with JIS K6251 of 0.7 N / mm ² or less.   The adhesive layer is a cured product of an adhesive resin composition in which a first agent containing a modified silicone resin and an epoxy curing agent and a second agent containing an epoxy resin and a silanol condensation catalyst are mixed. A protective structure for a hardened cementitious structure according to 1 or 2.   The hardened cement body according to claim 1 or 2, wherein the adhesive layer is a cured product of a one-component adhesive resin composition containing a modified silicone resin, an epoxy resin, a silanol condensation catalyst, and an epoxy curing agent. Protective structure of the structure.   The adhesive layer is a cured product of an adhesive resin composition including a modified silicone resin and an epoxy resin having a content of 1 part by weight or more and 100 parts by weight or less based on 100 parts by weight of the modified silicone resin. 5. A protective structure for a hardened cementitious structure according to any one of items 1 to 4. Providing a layer of an adhesive resin composition containing a modified silicone resin and an epoxy resin on at least one of the surface of the hardened cement structure, the surface of the protective sheet on which the resin layer and the carbon film are laminated,
Bonding the surface of the hardened cementitious structure and the surface of the protective sheet via the adhesive resin composition;
Protection method for hardened cement structure.

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