JP2019064260A - Tracking laminate sheet for concrete structure or structure having rust part, and construction method therefor - Google Patents

Abstract

To provide a tracking laminate sheet for concrete structure tracking defect parts due to crack, fissure or the like of a concrete structure, and uneven part visibly, and capable of easily protecting or reinforcing them, or a tracking laminate for a structure having a rust part capable of easily preventing progress of rust.SOLUTION: There is provided a tracking laminate sheet 100 used for concrete structure or for a structure having a rust part, having a resin layer 120 and a pressure sensitive adhesive layer 110, stress during 5% tensile of about 10 N/cm or less. residual stress after 5 min. during 30% tensile of about 10 N/cm or less, visible light transmission of about 80.0% or more.SELECTED DRAWING: Figure 1

Description

  The present disclosure relates to a compliant laminated sheet for a concrete structure or a structure having a rust portion, and a method of applying the same.

  Conventionally, in concrete structures such as bridges, tunnels, and elevated roads, when cracks, cracks, exposed rebars, etc., which lead to exfoliation of concrete pieces, etc. are found, a coating agent for preventing exfoliation of concrete with respect to such defective points A method of reinforcing by applying an adhesive, a method of applying a reinforcing fiber layer after application of an adhesive, and reinforcing, or a reinforcing fiber layer and a pressure-sensitive adhesive layer containing an inorganic filler having a large particle diameter, etc. Methods such as applying reinforcing articles have been used.

  For the exposed and rusted rebar, etc., a rustproofing agent was applied to suppress the progress of rusting.

  In Patent Document 1 (Japanese Patent Application Laid-Open No. 2006-342538), a concrete is applied to the surface of a concrete structure, an undercoating resin is applied to the application surface, and a fiber base material is adhered to the application surface. A method of repairing a structure, wherein the viscosity of the undercoat resin is 4,000 mPa · s to 100,000 mPa · s, the thixotropic index is 2.0 to 5.0, and the viscosity of the top coat resin is 100 mPa · s. The repair method of the concrete structure which is 4,000 mPa · s or more and thixotropic index is 1.0 or more and less than 2.0 is described.

  Patent Document 2 (Japanese Unexamined Patent Publication No. 2017-119995) discloses a pressure-sensitive adhesive layer containing a tacky acrylic polymer and inorganic fine particles having a particle diameter of 1 to 500 μm, and a fiber sheet disposed in the pressure-sensitive adhesive layer Directly applying the adhesive article to a concrete structure, wherein the adhesive article comprises an adhesive layer on both main surfaces of the article, wherein the adhesive structure prevents peeling of the concrete structure. The method of construction of the sex articles is described.

  Patent document 3 (Unexamined-Japanese-Patent No. 2005-060803) describes the corrosion prevention method of steel materials which is filled with a zinc paste in the defect | deletion location by corrosion of steel materials, and affixes and shields zinc foil from on it.

  Patent Document 4 (Japanese Patent Application Laid-Open No. 2016-056411) is a rust treating agent used for galvanized steel materials having rust, which is (a) epoxy resin, (b) acetylacetone, (c) rust preventive pigment, (D) A main ingredient containing an extender and (e) a solvent, and a curing agent, and the viscosity after mixing the main ingredient and the curing agent is 50 to 3,800 mPa · s (20 ° C.) , Rust treatment agent is described.

Unexamined-Japanese-Patent No. 2006-342538 JP, 2017-119995, A JP, 2005-060803, A JP, 2016-056411, A

  However, the repair method or anti-corrosion method of applying the coating agent or the adhesive to the defective portion requires complicated work steps and time, and there is a need to partially seal the road during work, etc. Normally, immediately after finding a defective portion, work is not performed, and the defective portion is marked with a marker or the like, and after the work permission is given, reinforcement or corrosion prevention work is performed. As a result, before performing such a construction, a small piece of concrete or the like may fall, which may lead to an accident, or there may be a further progress of rust.

  Reinforcing articles comprising a reinforcing fiber layer and a pressure-sensitive adhesive layer containing an inorganic filler having a large particle size, etc. are excellent in the reinforcing effect, but generally have high rigidity and are opaque. When applied to a part, it can not be confirmed whether the article concerned follows sufficiently and adheres, nor can it be observed that the concrete structure and the exposed reinforcing bars deteriorate with time.

  Since the rustproofing agent containing a rust inhibitor such as zinc powder is also generally opaque, it is not possible to observe the temporal change of the rusted part to which the treating agent is applied.

  Therefore, immediately after finding the defective portion, in the state of the defective portion or in a state where a marker such as a marker can be visually recognized, the defective portion of the concrete structure is tracked at least temporarily following the uneven portion. A simple protection or reinforcement means that can be reinforced or has been desired.

  Immediately after finding a rusted portion such as an exposed reinforcing bar, a simple means is desired to follow at least the rusted portion and suppress the progress of the rust in a state where it can be visually recognized.

  The present disclosure is a concrete structure capable of visibly following a defect in a concrete structure due to a crack, a crack or the like, or an uneven non-land portion, and at least temporarily and easily protecting or reinforcing the concrete structure. A compliant laminate sheet for a body or a compliant laminate sheet for a structure having a rusted portion which can visually follow at least a rusted portion of a structure and can easily suppress the progress of rust.

  According to one embodiment of the present disclosure, a resin layer and a pressure sensitive adhesive layer are provided, and the stress at 5% tension is about 10 N / cm or less, and the residual stress after 5 minutes at 30% tension is A compliant laminate sheet having a visible light transmittance of about 80.0% or more and used for a concrete structure or a structure having a rust portion (hereinafter referred to as It may be simply referred to as "laminated sheet".

  According to another embodiment of the present disclosure, there is provided a roll body in which the laminated sheet of the above embodiment is rolled.

  According to another embodiment of the present disclosure, there is provided a concrete structure comprising the steps of applying the laminated sheet of the above embodiment to a surface such as a defect of a concrete structure, and making the laminated sheet follow the surface. There is provided a method of applying a laminated sheet to at least temporarily protect a surface, such as a defect, in a visible manner.

  According to another embodiment of the present disclosure, a process of applying the laminated sheet of the above embodiment so as to cover the rusted part of a structure having a rusted part, and a laminated sheet on the surface of the rusted part and the structure There is provided a method of applying a laminated sheet that suppresses the progress of rust so that the surface of a structure having a rusted portion can be visually recognized.

  When the compliant laminated sheet of the present disclosure is used for a concrete structure, the concrete structure visibly follows defects, cracks, etc. of the concrete structure, and uneven lands as irregularities. Can be protected or reinforced at least temporarily and easily.

  When the compliant laminated sheet of the present disclosure is used for a structure having a rusted part, it can visually follow the rusted part of the structure and the like, and can suppress the progress of rust in the rusted part. .

  The conformable laminated sheet for a concrete structure or a structure having a rust portion according to the present disclosure has a predetermined tensile stress, and thus adheres to a rust portion, a defective portion and an uneven portion which is uneven. Since it can be combined and has a predetermined residual stress, it prevents defects such as peeling due to sheet shrinkage even if it is applied to a rusted part, a defective part and an inland part when the sheet is stretched. be able to.

  The above description should not be taken as disclosing all embodiments of the invention and all advantages associated with the invention.

1 is a cross-sectional view of a compliant laminate sheet in accordance with an embodiment of the present disclosure. It is sectional drawing of the concrete structure which applied the compliant laminated sheet of one embodiment of this indication with respect to the inland part. It is a top view and a side view of a flattery nature test device. It is a photograph regarding the followability test of the follow-up laminated sheet in the embodiment of Example 1 of this indication and comparative example 4. FIG. It is a side view of a stab test apparatus. It is a photograph regarding a fold when the compliance laminated sheet in the embodiment of Example 1 of this indication and comparative example 4 is rolled up to a 3-inch pipe of 100 mm of outer diameter. It is sectional drawing of the structure which applied the compliant laminated sheet of one embodiment of this indication to a rust part and a concavo-convex part. (A) is a front view of the test piece in an antirust test, (b) is sectional drawing of the test piece in cutting-plane line A-A '.

  The compliant laminate sheet in the first embodiment includes a resin layer and a pressure-sensitive adhesive layer, and the stress at 5% tension is about 10 N / cm or less, and after 5 minutes at 30% tension. The residual stress of is about 10 N / cm or less, and the visible light transmittance is about 80.0% or more, and is used for a concrete structure or a structure having a rusted part. When the laminated sheet having such a configuration is used for a concrete structure, the laminated sheet follows the concrete structure visibly with respect to a defective portion due to a crack of the concrete structure, a crack, or the like, and an uneven land portion. It can be protected or reinforced at least temporarily and easily. In the case of a sheet having poor followability, a void is generated between the sheet and the defective portion or the inland part, and moisture and the like enter through the void, and thus the deterioration of the concrete structure may be promoted.

  When the laminated sheet having such a configuration is used for a structure having a rusted part, the laminated sheet can follow visibly the rusted part of the structure and the like, and can prevent the entry of moisture, salt and the like. Can control the progression of In the case of a sheet having poor followability, a void is generated between the sheet and the rusted part, and moisture, salt and the like enter through the void, and there is a possibility that the progress of rust can not be suppressed. If the structure to be applied is, for example, a concrete structure having a rusted part such as a reinforcing bar, the laminated sheet can also protect or reinforce such a structure at least temporarily and easily.

  The resin layer in the compliant laminate sheet in the first embodiment can include a polyolefin film, and the thickness of the resin layer can be about 0.05 mm or more and less than about 0.25 mm. When the resin layer which concerns is employ | adopted, the followable | trackability to a rust part, a defect location, an inland part etc., and stab resistance can be improved more.

  The pressure-sensitive adhesive layer in the compliant laminate sheet in the first embodiment can include a (meth) acrylic pressure-sensitive adhesive layer, and the thickness of the pressure-sensitive adhesive layer is about 0.3 mm or more And less than about 1.5 mm. When such a pressure-sensitive adhesive layer is employed, sufficient adhesion can be expressed with respect to various structures such as a concrete structure, and creases are generated when the laminated sheet is wound in a roll. Can also be prevented.

  The resin layer in the compliant laminate sheet in the first embodiment can be provided with an inorganic particle-containing treatment layer on at least one side thereof. Since the processing layer which concerns is excellent in affinity with a pressure sensitive adhesive layer, the interlayer adhesiveness with a pressure sensitive adhesive layer can be improved more.

  The compliant laminate sheet in the first embodiment may not include a reinforcing layer having a visible light transmittance of less than about 80.0%. Since the laminated sheet of the present disclosure can be configured not to include an opaque reinforcing layer such as a fabric, even after applying the laminated sheet to various structures such as a concrete structure, rusted portions, defective portions, marks, etc. Can be seen.

  The compliant laminate sheet in the first embodiment has a reinforcing layer having a stress at 5% tension of greater than about 10 N / cm and a residual stress after 5 minutes at 30% tension of greater than about 10 N / cm. It does not have to be included. The laminated sheet of the present disclosure can be configured not to include such a reinforcing layer, so that the laminated sheet can be applied with good followability to rusted portions of a structure and defective portions and inland portions of a concrete structure. In addition, even when the laminated sheet is stretched and applied to a rusted part, a defective part and an inland part, it is possible to prevent a defect such as peeling due to shrinkage of the laminated sheet.

  The compliant laminate sheet in the first embodiment has a piercing strength of about 30 N or more, a T-peel strength of about 5 N / cm or more, and a maximum tension of about 20 to about 60 N / cm, depending on the use environment, application, etc. It can further have at least one property selected from the group consisting of strength, a yield point of about 15% or more, and 90 degree peel strength to concrete blocks of about 5 N / cm or more.

  The compliant laminate sheet in the first embodiment has a release liner on the surface of the pressure-sensitive adhesive layer opposite to the resin layer-applied surface, and on the surface of the resin layer opposite to the pressure-sensitive adhesive layer-applied surface. It can be set as the structure in which the peeling process is not performed. With such a configuration, even if the laminated sheet is stacked or wound in a roll, blocking can be prevented, and the laminated sheet is attached to various structures such as a concrete structure, and the like. Another laminated sheet can also be laminated and stuck on top.

  Since the compliant laminate sheet in the first embodiment has predetermined tensile stress and residual stress, it can be in the form of a roll wound in a roll.

  The construction method of the compliant laminate sheet according to the first embodiment to a concrete structure comprises the steps of applying the laminate sheet to a surface such as a defect of the concrete structure, and causing the laminate sheet to follow the surface And. This construction method does not require any skill level and requires a short time in a short period of time compared to the conventional construction method that requires an application means at the time of construction, and a failure point due to cracks, cracks, etc. of the concrete structure, unevenness or uneven land The part can be at least temporarily protected visibly. Here, "at least temporarily protect" is not limited to permanent protection or reinforcement of the concrete structure, but is a first-aid measure to prevent the falling of a small piece of concrete or the like before reinforcement work of the concrete structure. Protection or reinforcement is intended to be included. Thus, the laminated sheet of the present disclosure can also be used for emergency patches, which can temporarily protect concrete structures.

  The method of applying the structure according to the first embodiment to the structure having the rusted portion of the compliant laminated sheet includes the step of applying the laminated sheet to cover the rusted portion of the structure, and the rusted portion and the structure Allowing the laminated sheet to follow the surface. This construction method suppresses the progress of rusting while making the rusted portion of the structure visible in a short time and easily, without requiring a degree of skill, as compared with the conventional construction method requiring application means at the time of construction. can do. If the structure is, for example, a concrete structure having rusted parts, such as rebar, this method of construction can also at least temporarily protect such a structure.

  Hereinafter, the present invention will be described in more detail for the purpose of illustrating representative embodiments of the present invention, but the present invention is not limited to these embodiments.

  In the present disclosure, "film" also includes an item called "sheet", and conversely, "sheet" includes an item called "film".

  In the present disclosure, the “concrete structure” includes not only reinforced concrete but also a structure of cement-based material such as concrete without rebar, mortar and the like.

  In the present disclosure, “(meth) acrylic” means acrylic or methacrylic, and “(meth) acrylate” means acrylate or methacrylate.

  In the present disclosure, "abbreviation" is meant to include variations caused by manufacturing or measurement errors and the like, and it is intended that variations of about ± 20% are allowed.

  In the present disclosure, “preventing the progress of rust” is not limited to completely preventing the progress of rust but can be intended to delay the progress of rust, and, for example, each measurement of a rust test to be described later It can be intended to give a "good" result in the interval.

  The compliant laminate sheet according to an embodiment of the present disclosure includes a resin layer and a pressure-sensitive adhesive layer, and the laminate sheet has a stress at 5% tension of about 10 N / cm or less and 30% tension. The residual stress after 5 minutes at the time is about 10 N / cm or less, and the visible light transmittance is about 80.0% or more, and it is used for a concrete structure or a structure having a rusted part .

  The compliant laminated sheet 100 according to an embodiment of the present disclosure is shown in cross section in FIG. 1, and a concrete structure 250 in which the compliant laminated sheet 200 is applied to an inland portion is shown in cross section in FIG. FIG. 7 shows a structure 750 in which the laminated sheet 700 is applied to cover the rusted portion 710.

<< Characteristics of laminated sheet >>
<Stress at 5% tension>
Since the compliant laminate sheet of the present disclosure has a stress at 5% tensile strength of about 10 N / cm or less, the uneven lands and rusted areas 710 of the structures 250 and 750 as shown in FIGS. Etc. can be followed and pasted together. The stress at 5% tension of the laminated sheet is more preferably about 9 N / cm or less or about 8 N / cm or less from the viewpoint of followability. The lower limit value of the stress is not particularly limited. For example, in consideration of puncture resistance, it may be about 1 N / cm or more, about 2 N / cm or more, or about 3 N / cm or more. it can.

<Residual stress after 5 minutes at 30% tension>
The compliant laminate sheet of the present disclosure has a residual stress after 5 minutes at 30% tension of about 10 N / cm or less, so the sheet may be applied to inland areas or the like in a stretched state. It is possible to prevent problems such as peeling due to the shrinkage of The residual stress after 5 minutes at 30% tension of the laminated sheet is more preferably about 9 N / cm or less or about 8 N / cm or less from the viewpoint of preventing peeling. The lower limit value of the residual stress is not particularly limited, but may be about 1 N / cm or more, about 2 N / cm or more, or about 3 N / cm or more.

Visible light transmittance
The compliant laminate sheet of the present disclosure has a visible light transmittance of about 80.0% or more, which is obtained by using the measurement method described in detail in the following examples. And a mark applied to the defective portion can be easily viewed. The visible light transmittance of the laminated sheet is more preferably about 85.0% or more, or about 87.0% or more, from the viewpoint of visibility. The upper limit value of the visible light transmittance is not particularly limited, but may be specified as about 100% or less, less than about 100%, or about 99.9% or less.

<Any property>
The compliant laminate sheet of the present disclosure may have at least one of the following characteristics in addition to the above-described characteristics in consideration of the usage environment, the usage conditions, and the like.

(Steel strength)
The compliant laminate sheet of the present disclosure can have a puncture strength of about 30 N or more, about 40 N or more, or about 50 N or more. The upper limit value of the puncture strength is not particularly limited, but may be defined as about 70 N or less, about 65 N or less, or about 60 N or less. The laminated sheet having such puncture strength can exhibit sufficient durability even if, for example, a structure having a sharp rusted portion or a concrete surface having a sharp concrete piece.

(T-type peeling strength)
The compliant laminate sheet of the present disclosure can have a T-peel strength of about 5 N / cm or more, about 5.5 N / cm or more, or about 6 N / cm or more. The upper limit value of the T-type peel strength is not particularly limited, but may be specified as about 30 N / cm or less, about 25 / cm or less, or about 20 N / cm or less. Since the laminated sheet having such T-type peel strength is excellent in interlayer adhesion between the resin layer and the pressure-sensitive adhesive layer, sufficient protective or reinforcing effects and various rustproofing effects on various structures such as a concrete structure are obtained. Can be

(Maximum tensile strength)
The compliant laminate sheet of the present disclosure can have a maximum tensile strength of about 20 N / cm or more, about 23 N / cm or more, or about 25 N / cm or more, and about 60 N / cm or less, about 55 N / cm or less, or It can have a maximum tensile strength of about 50 N / cm or less. The lamination sheet which has the largest tensile strength which concerns is excellent by the balance of uneven | corrugated flattery property and stab-resistance.

(Yield point)
The compliant laminate sheet of the present disclosure can have a yield point of about 15% or more, about 18% or more, or about 20% or more. The upper limit value of the yield point is not particularly limited, but may be defined as about 35% or less, about 30% or less, or about 25% or less. The laminated sheet having such a yield point can further improve the unevenness followability.

(90 degree peel strength to concrete block)
The compliant laminate sheet of the present disclosure can have a 90 degree peel strength to concrete blocks of about 5 N / cm or more, about 5.5 N / cm or more, or about 6 N / cm or more. The upper limit value of the peel strength is not particularly limited, but may be specified as about 20 N / cm or less, about 15 / cm or less, or about 10 N / cm or less. Since the laminated sheet having such peel strength has sufficient adhesion even if it is a concrete structure having a rusted portion, a defective portion or a landless portion, such a structure can be further protected or reinforced. You can also control the progression.

  The various characteristics described above can be obtained by appropriately adjusting the materials, thicknesses, and the like of the resin layer and the pressure-sensitive adhesive layer constituting the laminate sheet described below.

<< Resin layer >>
The resin layer is capable of imparting at least one performance such as puncture resistance, followability to inland parts, weatherability, antifouling property, waterproofness, moisture resistance, salt resistance etc., such as various types of concrete structures etc. Any material that can be a material that functions as a protective layer or a reinforcing layer of a structure and that can impart predetermined tensile stress, residual stress, and visible light transmittance to the laminated sheet of the present disclosure It may be The material of the resin layer is not limited to the following, but one or two or more resins such as polyolefin, polyvinyl chloride and polyurethane can be used, for example. The resin layer may be laminated on the pressure-sensitive adhesive layer by melt extrusion of the resin, coating, solvent casting, etc., or may be applied to the pressure-sensitive adhesive layer in the form of a film or sheet in advance. . The resin layer may have a single layer or laminated structure. A gas barrier layer such as an inorganic vapor deposition layer can be applied to one side or both sides of the resin layer. Since the resin layer which has the gas barrier layer which concerns is excellent in moisture resistance and waterproofness, advancing of rust can be suppressed more.

Polyolefin
Among the above resin materials, polyolefin is preferable, and specifically, polyethylene such as low density polyethylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer, etc., one or two or more kinds, lamination or It can be used as a blend. Among polyolefins, an ionomer and a linear low density polyethylene which is a metallocene catalyst system or a Ziegler catalyst system polyethylene is preferable from the viewpoint of followability, puncture resistance, and the like. Such polyethylene can be obtained by copolymerizing ethylene and an α-olefin having 4 to 12 carbon atoms at a relatively low pressure in the presence of a catalyst. The density of such polyethylene can be in the range of about 0.91 to about 0.95 g / cm ³ , and the melt flow rate (MFR) can be in the range of about 0.3 to about 3 g / 10 min.

In particular, a resin layer having a configuration including linear low density polyethylene / ethylene-vinyl acetate copolymer / linear low density polyethylene / ethylene-vinyl acetate copolymer / linear low density polyethylene has transparency, followability, and resistance to Performance such as piercing property can be further improved. In the case of such a configuration, the density of the linear low density polyethylene used in the outermost layer and the central part is also in the range of about 0.91 to about 0.95 g / cm ³ in consideration of transparency, followability, stickiness and the like. Can be The ethylene-vinyl acetate copolymer can impart flexibility to the resin layer, and the vinyl acetate content in this copolymer is at least about 3% by mass or about from the viewpoint of flexibility, moldability, etc. It can be in the range of 5% by weight or more, about 25% by weight or less, or about 20% by weight or less.

<Other additive ingredients>
The resin layer is a filler, a plasticizer, a pigment, a dye, a reinforcing agent, a reinforcing agent, a flame retardant, an ultraviolet absorber, an antioxidant, a stabilizer, a rust inhibitor, and the like as long as the resin layer does not cause a problem such as transparency. And the like may be included.

  For example, when using metal powder, such as zinc, as a rust inhibitor, there is a possibility that the transparency of a lamination sheet may fall by rust of the metal powder itself concerned. Therefore, the addition amount of such a metal powder is preferably about 0.1% by mass or less of the entire resin layer, and more preferably not contained in the resin layer, from the viewpoint of transparency.

<thickness>
The thickness of the resin layer is about 0.05 mm or more, about 0.07 mm or more, or about 0.10 mm or more, less than about 0.25 mm, about 0.23 mm or less, from the viewpoint of puncture resistance, followability, etc. Or it can be about 0.20 mm or less.

<Inorganic particle-containing treatment layer>
The resin layer can be provided with an inorganic (eg, silica) particle-containing treatment layer on at least one side thereof. When the layering of the laminated sheet is considered, the inorganic particle-containing treatment layer is preferably applied to both sides of the resin layer. Such a treated layer can improve the interlayer adhesion to the pressure-sensitive adhesive layer shown below, in particular, a (meth) acrylic pressure-sensitive adhesive, as compared to general surface treatment such as corona treatment. It is considered that this is because the inorganic particle-containing treatment layer is excellent in affinity to the (meth) acrylic pressure-sensitive adhesive. The affinity can be evaluated, for example, by a commonly used water drop contact angle test, and in terms of interlayer adhesion, such a contact angle is about 70 degrees or less, about 65 degrees or less, or about 60 degrees. It is preferable that it is below the degree. In addition, silica particles as an antiblocking agent mixed in the film or applied to the film surface to prevent blocking are used in a minimum amount to reduce the contact area between the films. Therefore, in such a film, the interlayer adhesion to the pressure-sensitive adhesive layer can not be sufficiently developed. Other than silica, other inorganic particles such as alumina, titanium oxide and calcium carbonate can also be used. Silica is preferable from the viewpoint of hydrophilicity and cost.

  The inorganic particle-containing treatment layer may be formed, for example, by applying and drying a mixed solution containing silica sol, a resin binder, and, optionally, a surfactant and water to a resin film to which corona treatment is optionally applied. it can. As the resin binder, for example, an aqueous resin binder such as a urethane resin, a (meth) acrylic resin, or a (meth) acrylic-modified urethane resin can be used. Here, as the silica sol, "Snowtex (registered trademark) 20" (solid content concentration: 20%) manufactured by Nissan Chemical Industries, Ltd. can be used. The particle diameter of the silica particles contained in the silica sol and the compounding ratio of the silica sol can be appropriately adjusted in consideration of the transparency of the laminated sheet, the interlayer adhesion between the resin layer and the pressure-sensitive adhesive layer, etc. For example, the average particle diameter of the silica particles in the silica sol is preferably in the range of about 5 to about 100 nm from the viewpoint of transparency etc. The ratio is preferably in the range of about 0.5 to about 40 times that of the resin binder.

Pressure-sensitive adhesive layer
Since the compliant laminate sheet of the present disclosure includes the pressure-sensitive adhesive layer, the concrete structure can be suitably protected or reinforced by simply laminating the laminate sheet to, for example, a concrete structure, In the case where a rusted portion such as rebar is exposed, it is possible to suppress the progress of the rusting of the rusted portion. Therefore, it is possible to construct laminated sheets on various structures easily in a short time regardless of the skill of the worker.

<thickness>
The thickness of the pressure-sensitive adhesive is preferably about 0.3 mm or more, about 0.4 mm or more, or about 0.5 mm or more from the viewpoint of adhesion to various structures. The laminated sheet can be shipped as a single-sheet product, but can also be shipped in the form of a roll. The thickness of the pressure-sensitive adhesive layer is preferably less than about 1.5 mm, less than or equal to about 1.4 mm, or less than or equal to about 1.3 mm from the viewpoint of preventing the occurrence of creases when rolled.

((Meth) acrylic pressure sensitive adhesive〉
The pressure-sensitive adhesive layer may be of any type and is not limited to the following, but from the viewpoint of weatherability, adhesion and the like, a (meth) acrylic pressure-sensitive adhesive layer is preferable. The (meth) acrylic pressure-sensitive adhesive layer is tacky and can contain a partial polymer formed by partially polymerizing a monomer component containing a monofunctional monomer and optionally a polyfunctional (meth) acrylate. . Here, "tackiness" means that the storage modulus (G ') measured at 10 radians / sec at the application temperature (which can be measured at 20 ° C to 22 ° C) is less than about 3 x 10 ⁵ Pascals It means that.

(Monofunctional monomer)
The monofunctional monomer is an alkyl acrylate having 1 to 18 carbon atoms in the alkyl group (hereinafter, sometimes referred to as “C1-18 alkyl acrylate”), and an unsaturated monomer having a vinyl carbonyl group and a polar group (below , Optionally referred to as "polar unsaturated monomers".

  The ratio of the C1-18 alkyl acrylate to the polar unsaturated monomer in the monofunctional monomer is about 70% by mass or more, about 85% by mass or more, based on 100% by mass of the total amount of monofunctional monomers. It is preferable that it is about 87 mass% or more, about 99 mass% or less, or about 98 mass% or less, and the polar unsaturated monomer is about 1 mass% or more or about 2 mass% or more, about 30 mass% or less, about 15 mass % Or less or about 13% by weight or less. When the ratio of the C1-18 alkyl acrylate to the polar unsaturated monomer in the monofunctional monomer is within the above range, the following property to the non-land portion, etc., the adhesion and the retention strength are excellent.

a. C1-18 alkyl acrylate The alkyl acrylate having 1 to 18 carbon atoms in the alkyl group means that the alkyl alcohol has 1 to 18 carbon atoms when viewed as an ester of acrylic acid and alkyl alcohol. It means that. That is, when an alkyl acrylate ^{_{CH 2 = CH-COO-R}} 1 and, ^{R 1} is meant an alkyl group having 1 to 18 carbon atoms.

  It is preferable that the carbon atom number of the alkyl group of alkyl acrylate is four or more, and it is preferable that it is 12 or less. When such an alkyl acrylate is included as a monofunctional monomer, the adhesion or adhesion of the laminated sheet is improved.

  Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, 2 -Ethylhexyl acrylate, n-heptyl acrylate, n-octyl acrylate, isooctyl acrylate, n-nonyl acrylate, isononyl acrylate, n-decyl acrylate, n-undecyl acrylate, n-dodecyl acrylate, n-tridecyl acrylate, n -Tetradecyl acrylate, n-pentadecyl acrylate, n-hexadecyl acrylate, n-heptadecyl acrylate DOO, n- octadecyl acrylate, and the like.

  Among these, n-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, in consideration of transparency, ability to conform to inland areas, adhesion, retention and the like. n-nonyl acrylate, isononyl acrylate and n-decyl acrylate are preferred, and n-butyl acrylate, 2-ethylhexyl acrylate and isooctyl acrylate are more preferred.

b. Polar unsaturated monomer (comonomer)
The polar unsaturated monomer has a vinyl carbonyl group and a polar group.

  As a polar group, a hydroxyl group, a carboxyl group, a carbamoyl group, an amino group, an epoxy group, a nitrile group etc. are mentioned, for example, Among these, a hydroxyl group, a carboxyl group, and an amino group are preferable.

The vinyl carbonyl group refers to a group represented by CH ₂ CHCH—C (= O) —. The vinyl carbonyl group and the polar group may be directly bonded, or may be bonded via a linking group such as an alkylene group.

As a polar unsaturated monomer, for example,
A hydroxyl group-containing unsaturated monomer such as 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, polyethylene glycol acrylate, polypropylene glycol acrylate;
Carboxyl group-containing unsaturated monomers such as acrylic acid;
A carbamoyl group-containing unsaturated monomer such as acrylamide;
Amino group-containing monomers such as N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate;
Epoxy group-containing unsaturated monomers such as glycidyl acrylate;

  Among them, preferred are hydroxyl group-containing unsaturated monomers, carboxyl group-containing unsaturated monomers, and carbamoyl group-containing unsaturated monomers, in consideration of transparency, followability to non-land parts, etc. The contained unsaturated monomer and the carbamoyl group containing unsaturated monomer are more preferable, and the carboxyl group containing unsaturated monomer is further preferable. Specifically, 2-hydroxyethyl acrylate, acrylic acid and acrylamide are preferable, acrylic acid and acrylamide are more preferable, and acrylic acid is more preferable.

(Multifunctional (meth) acrylate)
As polyfunctional (meth) acrylates, for example, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol 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, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate And trimethylolpropane tri (meth) acrylate and tetramethylolmethane tri (meth) acrylate.

  Among these, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, among these, in consideration of transparency, ability to follow non-land areas, adhesion strength, retention strength, etc. Ethylene glycol di (meth) acrylate and polyethylene glycol di (meth) acrylate are preferred.

  The content of the polyfunctional (meth) acrylate in the monomer component is preferably about 0.05 mmol or more or about 0.1 mmol or more and about 0.8 mmol or less with respect to 100 g of the monofunctional monomer. When the content ratio of the polyfunctional (meth) acrylate is in the above-mentioned range, it is excellent in the followability to an inland part or the like, the adhesive strength and the holding power.

(Partial polymer)
A partial polymer is obtained by partially polymerizing a monomer component, and can also be referred to as "a partial polymer of a monomer component".

  Here, the partial polymer refers to a composition in which at least a part of the monomer component is polymerized, and in the composition, a non-reacted ethylenic nonfunctional component derived from a monofunctional monomer or a polyfunctional (meth) acrylate. It refers to one in which a saturated bond (C = C) is present.

  The viscosity at 25 ° C. of the partial polymer can be about 10000 mPa · s or less, about 8000 mPa · s or less, or about 5000 mPa · s or less. The viscosity can also be about 500 mPa · s or more. The partial polymer having a viscosity in the above-mentioned range can be applied with a thickness, so that a laminated sheet excellent in transparency can be obtained, and a laminated sheet excellent in strength, followability, adhesion and retention strength can be obtained. Can. The viscosity specified here is a value measured using a B-type viscometer (BH type) manufactured by Tokyo Keiki Co., Ltd. (Minato-ku, Tokyo, Japan), and the measurement is # 5 or # 6. It carries out at 25 degreeC using a rotor (rotation speed: 20 rpm), and makes the value 1 minute after a measurement start into a measured value.

  The viscosity of the partial polymer changes depending on the degree of progress of the partial polymerization, and as the partial polymerization proceeds, the viscosity of the partial polymer tends to increase. Therefore, the viscosity of the partial polymer can be easily adjusted to a desired range by appropriately adjusting the amount of the polymerization initiator used for the partial polymerization, the reaction time of the partial polymerization, and the like.

  The partial polymer can also be said to contain an unreacted monomer component and a solid content which is a polymer of the monomer component. Here, the solid content in the partial polymer may be about 1% by mass or more, about 2% by mass or more, about 10% by mass or less, or about 7% by mass or less based on the total amount of the partial polymer.

  The solid content in the partial polymer can be determined by measuring the amount of solid content remaining after removal of the unreacted monomer component from the partial polymer. For example, the partial polymer is subjected to an oven at 120 ° C. for 2 hours. The mass after drying can be used as the solid content.

(Photopolymerization initiator in partial polymer)
The partial polymer can be obtained, for example, by mixing a photopolymerization initiator with a monomer component and irradiating light to photopolymerize the monomer component.

As the photopolymerization initiator, for example, an azo compound such as azobisinbutyronitrile;
Benzoins such as benzoin, benzoin methyl ether, benzoisoethyl ether, benzoin propyl ether, benzoin isobutyl ether, α-methylbenzoin, α-phenylbenzoin and the like;
Anthraquinones such as anthraquinone, methylanthraquinone and chloranthraquinone;
Onium salts such as p-methoxybenzenediazonium, hexafluorophosphate, diphenyliodonium, triphenylsulfonium, and the like.

Photopolymerization initiators include, for example, benzyl dialkyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one;
1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl Α such as -1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, etc. -Hydroxyalkylphenones;
2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- (dimethyl) Α) -aminoalkylphenones such as amino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone;
Acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide;
Titanocenes such as bis (5−5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium;
1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 And oxime esters such as -yl]-and 1- (0-acetyl oxime); and the like.

(Light irradiation conditions of partial polymer)
For light irradiation, ultraviolet irradiation or the like can be employed. For example, the monomer component formulated with photoinitiators, irradiation intensity of about 0.05 mW / cm ² or more, or about 0.1 mW / cm ² or more, about 10 mW / cm ² or less, or about 5 mW / cm ² or less, about the irradiation time The partial polymer can be obtained by UV irradiation under conditions of 5 seconds or more, or about 10 seconds or more, about 300 seconds or less, or about 240 seconds or less.

(Components other than partial polymers)
In the present embodiment, the (meth) acrylic pressure-sensitive adhesive may contain components other than the partial polymer.

a. Other Multifunctional (Meth) Acrylate In this embodiment, the (meth) acrylic pressure-sensitive adhesive is one to which a multifunctional (meth) acrylate as described above is further added separately from the above-mentioned partial polymer, It is also good. In the present embodiment, the total amount of the multifunctional (meth) acrylate compounded in the (meth) acrylic pressure-sensitive adhesive is about 0.05 mmol or more, about 0.1 mmol or more, about 0 with respect to 100 g of the monofunctional monomer. .8 mmol or less.

  Here, "the total amount of the multifunctional (meth) acrylate compounded in the (meth) acrylic pressure-sensitive adhesive" means, when present, the polyfunctional (meth) acrylate used as a monomer component for obtaining a partial polymer. And the total amount of polyfunctional (meth) acrylates added to the acrylic pressure-sensitive adhesive composition separately from the partial polymer.

  In the present embodiment, by setting the total amount of the multifunctional (meth) acrylate compounded to the (meth) acrylic pressure-sensitive adhesive to the above range, it is possible to achieve both excellent followability and holding power.

b. The photopolymerization initiator (meth) acrylic pressure-sensitive adhesive layer can be formed by photocuring (such as ultraviolet light), since the pressure-sensitive adhesive layer can be directly formed from the monomer or the partial polymer containing the monomer. It is preferable that the pressure-sensitive adhesive of the pressure-sensitive adhesive layer be referred to as “photo-curable (meth) acrylic pressure-sensitive adhesive” hereinafter. As a photoinitiator, the thing similar to the above is mentioned. A light (ultraviolet ray etc.) curing type pressure sensitive adhesive has the following superiority as compared with other pressure sensitive adhesives such as hot melt coating type and solvent type.
(1) The photo-curable pressure-sensitive adhesive of the present disclosure does not need to contain a solvent, so it can be easily made thicker, for example, 0.3 mm or more, as compared to a solvent-based adhesive or the like. In addition, there is an advantage that air bubbles are not generated at the time of solvent drying.
(2) When forming a pressure-sensitive adhesive layer, the hot melt coating type pressure-sensitive adhesive needs to be melt-extruded without cross-linking the pressure-sensitive adhesive, and therefore has poor adhesion and retention. In addition, if the pressure-sensitive adhesive is melt-extruded on a low heat-resistant substrate such as polyolefin, there is a risk of damaging the resin layer, etc., but the photo-curable pressure-sensitive adhesive of the present disclosure reduces such risk. can do.

  The photopolymerization initiator contained in the (meth) acrylic pressure-sensitive adhesive may be a non-reacted substance of the photopolymerization initiator used for the production of the partial polymer described above, and it is newly added after the production of the partial polymer Although it may be added, the latter is more preferable in consideration of easiness of adjustment of molecular weight of the pressure-sensitive adhesive, productivity and the like.

  The content of the photopolymerization initiator in the (meth) acrylic pressure-sensitive adhesive is about 0.01 parts by mass or more, about 0.05 parts by mass or more, about 1.0 parts by mass with respect to 100 parts by mass of the partial polymer Or less or about 0.5 parts by weight or less.

  The (meth) acrylic pressure-sensitive adhesive is preferably subjected to a defoaming treatment, for example, by a vacuum degassing machine before curing. Thereby, the curing inhibition of the (meth) acrylic pressure-sensitive adhesive due to the contact with air bubbles (air), the appearance defect and the like can be suppressed.

c. The polar unsaturated monomer (meth) acrylic pressure-sensitive adhesive may further contain a polar unsaturated monomer separately from the partial polymer. By containing such a monomer, the adhesive strength of the (meth) acrylic pressure-sensitive adhesive can be adjusted. Here, as the polar unsaturated monomer, the same one as described above is exemplified.

d. Filler The (meth) acrylic pressure-sensitive adhesive preferably contains no filler in consideration of the transparency, but may contain a filler as long as no problem occurs in the transparency. The content of the filler can be about 10% by volume or less based on the total solid content of the (meth) acrylic pressure-sensitive adhesive. The lower limit of the content of the filler is not particularly limited, and can be, for example, about 0.1% by volume or more.

  The shape of the filler is not particularly limited, and fillers having a spherical, plate-like, flake-like, needle-like or the like shape can be used. Among these, spherical fillers are preferable in consideration of the formability to a laminated sheet and the like. From the viewpoint of transparency, the average particle size of the filler is preferably less than about 1 μm. Solid is preferable to hollow from the viewpoint of transparency.

  As the filler, for example, an inorganic filler consisting of an inorganic substance selected from the group consisting of silica, titania, alumina, zirconia, vanadia, ceria, iron oxide, antimony oxide, tin oxide, aluminum / silica, and a combination thereof It can be mentioned.

e. Other Additives The (meth) acrylic pressure-sensitive adhesive may contain additives other than the above as long as no problems occur in transparency, curability and the like. Examples of the additive include plasticizers, tackifiers, pigments, dyes, reinforcing agents, reinforcing agents, flame retardants, antioxidants, ultraviolet absorbers, rust inhibitors, stabilizers and the like.

  For example, when using metal powder, such as zinc, as a rust inhibitor, there is a possibility that the transparency of a lamination sheet may fall by rust of the metal powder itself concerned. Therefore, the addition amount of such metal powder is preferably about 0.1% by mass or less of the entire pressure-sensitive adhesive layer from the viewpoint of transparency, and is not contained in the pressure-sensitive adhesive layer. Is more preferred.

<< Peeling liner >>
In the compliant laminate sheet of the present disclosure, release treatment may be applied to the surface of the resin layer opposite to the pressure-sensitive adhesive layer-applied surface, and in this case, the opposite to the resin layer-applied surface of the pressure-sensitive adhesive layer. It is not necessary to provide a release liner on the side surface. However, when the surface opposite to the pressure-sensitive adhesive layer application surface of the resin layer is not subjected to release treatment, the release liner is provided on the surface opposite to the resin layer-applied surface of the pressure-sensitive adhesive layer. Is preferred. In the case of such a configuration provided with a release liner, since the surface of the resin layer is not subjected to release treatment, the laminated sheet can be stacked and attached.

  Examples of release liners include paper; plastic materials such as polyethylene, polypropylene, polyester, cellulose acetate and the like; and papers coated with such plastic materials. These release liners may have surfaces that have been release treated with silicone or the like. The thickness of the release liner is generally about 5 μm or more, about 15 μm or more, or about 25 μm or more, about 300 μm or less, about 200 μm or less, or about 150 μm or less. Usually, the release liner is released from the laminated sheet prior to application to the concrete structure.

«Reinforcing base material»
The follow-up laminate sheet of the present disclosure preferably does not include a reinforcing layer having a visible light transmittance of less than 80.0% from the viewpoint of visibility and the like. From the viewpoint of generation and the like, it is preferable that the reinforcing layer not have a stress at 5% tension of more than 10 N / cm and a residual stress after 5 minutes at 30% tension of more than 10 N / cm. In particular, a fiber-based reinforcing layer such as a woven fabric, a knitted fabric, and a non-woven fabric is inferior in transparency and hardly stretchable, and therefore, it is more preferable not to include the fiber-based reinforcing layer.

<< Manufacturing method of compliant laminate sheet >>

  The laminated sheet of the present disclosure can be produced, for example, by the following methods (1) to (3). Here, the laminated sheet finally obtained may be in the form of a single-sheet product, or in the form of a roll body wound in a roll shape.

  (1) A pressure-sensitive adhesive is applied on a release liner using a known application method such as knife coating to form a pressure-sensitive adhesive layer, and then a resin layer is melt-extruded on the pressure-sensitive adhesive layer. The method is applied or in the form of a film or sheet, and if necessary, the pressure-sensitive adhesive layer is cured by irradiation with light (such as ultraviolet light). Here, when the inorganic particle-containing treatment layer is provided on the surface of the resin layer, the treatment layer is placed on the pressure-sensitive adhesive layer side and the resin layer is applied. The pressure sensitive adhesive layer may be formed directly on the resin layer.

  (2) A light (ultraviolet ray, etc.) curing type pressure sensitive adhesive is applied on a release liner using a known application means to form an uncured pressure sensitive adhesive layer, and further on the pressure sensitive adhesive layer concerned After applying the release liner, the pressure-sensitive adhesive layer is cured by irradiation with light (such as ultraviolet light). The one release liner can then be removed and the resin layer can be applied to the removal surface using melt extrusion or in the form of a film or sheet. Here, when the inorganic particle-containing treatment layer is provided on the surface of the resin layer, the treatment layer is placed on the pressure-sensitive adhesive layer side and the resin layer is applied.

  (3) A pressure sensitive adhesive is applied on a resin layer in the form of a film or sheet using a known application means to form a pressure sensitive adhesive layer, and a release liner is applied to the pressure sensitive adhesive layer. If necessary, the pressure-sensitive adhesive layer is cured by irradiation with light (such as ultraviolet light). Here, when the inorganic particle-containing treatment layer is provided on the surface of the resin layer, the resin layer is disposed such that the treatment layer is on the pressure-sensitive adhesive layer side. When the surface of the resin layer is provided with a release treatment layer, the release liner may not be applied.

<< Construction method for concrete structure of compliant laminated sheet >>
The laminated sheet of the present disclosure can be applied to the surface of a defective portion and / or an inland portion of a concrete structure by, for example, the following method.

  The pressure-sensitive adhesive layer of the laminated sheet is attached to the surface of the concrete structure such as a defect. Next, the laminated sheet bonded together is pressed by a human hand or a jig or the like to cause the laminated sheet to follow a defective portion, particularly a non-land portion. Here, in the case where the resin layer surface of the laminated sheet is not subjected to peeling treatment, another laminated sheet is further overlapped and stuck on at least a part of the laminated sheet applied to the surface such as a defective portion of the concrete structure. can do.

<Surface treatment of concrete structure>
An acrylic adhesive, epoxy adhesive or synthetic rubber on the surface of the concrete structure before applying the laminated sheet to the fragile surface such as a defect of the concrete structure from the viewpoint of reinforcing the fragile surface of the surface of the concrete structure, etc. Surface treatment agents such as adhesive can be applied. The surface treatment agent may be an accelerated curing resin which accelerates curing when heat, light, moisture or the like is given. The applied surface treatment layer may have a function as a primer layer for the laminated sheet. However, when the laminated sheet of the present disclosure is used as a temporary temporary patch for a concrete structure, such laminated sheet may be removed later, and in such a case, the laminated sheet is used for the concrete structure. It is not necessary to perform surface treatment.

<< Construction method to structure with rust part of compliant laminated sheet >>
The laminated sheet of the present disclosure can be applied to a structure having a rusted part, for example, by the following method.

  The pressure sensitive adhesive layer of the compliant laminate sheet is attached to the surface of the structure so as to cover the rusted portion of the structure. Next, the laminated sheet bonded together is pressed by human hands or a jig or the like to cause the laminated sheet to follow the surface of the rusted portion and the structure. Here, when the peeling process is not performed to the resin layer surface of a lamination sheet, another lamination sheet can be further overlapped and affixed on at least one part of the applied lamination sheet.

  In the present disclosure, the “structure having a rust portion” is not particularly limited as long as it is a structure having a rusted portion. For example, in a concrete structure provided with reinforcing bars or metal bolts, etc., which is used for a building such as a highway, a track, a building, etc., a concrete structure in which exposed reinforcing bars or metal bolts are rusted; A structure made of a corrosive metal, such as a bridge, a pillar, a fence, a handrail, a stair, a roof, a pipe, or a structure including them, a structure having a rusted portion, and the like can be mentioned.

  In the present disclosure, "rust portion" means a portion where rust is generated from various corrosive metals, and is not limited to red rust or brown rust due to iron etc., and various rust portions such as blue rust, black rust, white rust, etc. Can be included.

Examples 1 to 11 and Comparative Examples 1 to 6
Although specific embodiments of the present disclosure are illustrated in the following examples, the present invention is not limited thereto. All parts and percentages are by weight unless otherwise stated.

<material>
The reagents, raw materials, etc. used in this example are shown in Table 1 below.

<Preparation of compliant laminate sheet>
Example 1
94 parts by weight 2EHA, 6 parts by weight AA, and 0.04 parts by weight Irg. 651 was mixed in a nitrogen purged glass vessel. The resulting mixture was irradiated with ultraviolet light with a UV-A lamp, and the mixture was partially polymerized until the viscosity was 1000 mPa · s. The mixture after irradiation with ultraviolet light was treated with 0.08 parts by mass of HDDA, 0.1 parts by mass of Irg. 651 was added to make a mixture for pressure sensitive adhesive.

Then, the resulting pressure-sensitive adhesive mixture is knife-coated to a thickness of 0.5 mm on a silicone-treated releasable PET liner, and then another releasable PET liner is placed on the pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer was ultraviolet-cured by irradiating ultraviolet light of 0.5 mW / cm ² (total energy: 1000 mJ / cm ² ) using a UV-A lamp.

  After curing, the peelable PET liner on one side is removed, and the resin surface is laminated with Tekinas 5-UV (trademark) as the resin layer so that the inorganic particle-containing treatment layer is on the pressure-sensitive adhesive layer side, A laminated sheet was obtained.

(Example 2)
A laminated sheet was produced in the same manner as in Example 1 except that the resin layer was changed from Tekinasi 5-UV (trademark) to Diastar (registered trademark).

(Example 3)
A laminated sheet was produced in the same manner as in Example 1 except that the resin layer was changed from Tekinasi 5-UV (trademark) to Supervernal (trademark).

(Example 4)
A laminated sheet was produced in the same manner as in Example 1 except that the thickness of the pressure-sensitive adhesive layer was changed from 0.5 mm to 0.2 mm.

(Example 5)
A laminated sheet was produced in the same manner as in Example 1 except that the thickness of the pressure-sensitive adhesive layer was changed from 0.5 mm to 0.8 mm.

(Example 6)
A laminated sheet was produced in the same manner as in Example 1 except that the thickness of the pressure-sensitive adhesive layer was changed from 0.5 mm to 1.0 mm.

(Example 7)
A laminated sheet was produced in the same manner as in Example 1 except that the thickness of the pressure-sensitive adhesive layer was changed from 0.5 mm to 1.5 mm.

(Example 8)
A laminated sheet was produced in the same manner as in Example 1 except that the resin layer was changed from Tekinasi 5-UV (trademark) to Technosenlight (trademark).

(Example 9)
A laminated sheet was produced in the same manner as in Example 1 except that the resin layer was changed from Takinas 5-UV (trademark) to Skycoat 5 (trademark).

(Example 10)
A laminated sheet was produced in the same manner as in Example 1 except that the blending amount of 2EHA was changed from 94 parts by mass to 90 parts by mass, and the blending amount of AA was changed from 6 parts by mass to 10 parts by mass.

(Example 11)
A laminated sheet was produced in the same manner as in Example 1 except that the resin layer was changed from Tekinasi 5-UV (trademark) to a functional PE film (ionomer EMAA).

(Comparative example 1)
A laminated sheet was produced in the same manner as in Example 1 except that the resin layer was changed from Tekinasi 5-UV (trademark) to Denka DX film (trademark) # 30. Here, the corona-treated acrylic polymer rich surface was used as the laminated surface for the pressure-sensitive adhesive layer.

(Comparative example 2)
The same procedure as in Example 1 was carried out except that the thickness of the pressure-sensitive adhesive layer was changed from 0.5 mm to 0.2 mm and the resin layer was changed from Takinas 5-UVTM to Denka DX FilmTM # 30. The laminated sheet was prepared. Here, the corona-treated acrylic polymer rich surface was used as the laminated surface for the pressure-sensitive adhesive layer.

(Comparative example 3)
The pressure-sensitive adhesive mixture obtained in Example 1 was knife-coated to a thickness of 0.25 mm on a silicone-treated releasable PET liner, and then the fiber-based reinforcing layer CRENETTE (registered trademark) DN1000 was felt. Placed on the pressure-sensitive adhesive layer. Then, the mixture for pressure-sensitive adhesive obtained in Example 1 is coated with a thickness of 0.25 mm on the reinforcing layer by a tandem-type coating apparatus, and another peelable PET liner is disposed on the pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer was ultraviolet-cured by irradiating ultraviolet light of 0.5 mW / cm ² (total energy: 1000 mJ / cm ² ) using a UV-A lamp.

  After curing, the peelable PET liner on one side was removed, and on the removed surface, TEKANASI 5-UV (trademark) was laminated so that the inorganic particle-containing treatment layer was on the pressure-sensitive adhesive layer side, to obtain a laminated sheet.

(Comparative example 4)
A laminated sheet was produced in the same manner as in Example 1 except that the resin layer was changed from Tekinasi 5-UV (trademark) to a PET film. Here, the corona-treated PET film surface was used as a laminated surface for the pressure-sensitive adhesive layer.

(Comparative example 5)
Vinyl chloride tape no. 51 was used.

(Comparative example 6)
Polyethylene tape for protective materials for underground burial No. I used 55.

<Composition of laminated sheet>
The structures of the laminated sheets in Examples 1 to 11 and Comparative Examples 1 to 6 are shown in Table 2 below.

<Evaluation test>
The following tests 1 to 11 were conducted for each of the above-mentioned laminated sheets, and the results are shown in Table 4.

(Test 1: tensile test)
Each laminated sheet was cut into a size of 25 mm wide × 200 mm long to prepare a test piece. After the peelable PET liner was removed from the test piece, the test piece was attached to a tensile tester (Autograph AGS-X manufactured by Shimadzu Corporation) and tested at a tensile speed of 300 mm / min. From such tensile test, stress at 5% tensile, residual stress after 5 minutes at 30% tensile, maximum stress at 30% tensile, yield point, and maximum tensile strength can be determined.

(Test 2: Tracking test)
As shown in FIG. 3, after fixing a steel template 302 of 3.0 mm thickness imitating an inland part etc. on a transparent glass plate 304 in parallel at intervals of 30 mm width, laminated sheet test piece 300 of 25 mm width. I stuck it so as not to slacken. Thereafter, the central portion of the test piece 300 is pressed for 30 seconds with a 1.5 kg steel material 306 whose contact portion with the test piece 300 is a smooth surface of 20 mm × 30 mm so that load is uniformly applied to the test piece 300. did. Thereafter, the steel material 306 is removed, and the area of the test piece 300 in contact with the glass plate 304 is measured from the back surface of the glass plate 304. The area of the steel product 306 is in contact with the test material 300 (25 mm × It divided by 20 mm, and the followability to an inland part etc. was evaluated from the value (Hereafter, it may be called a contact area rate.). Here, those having a contact area ratio of about 75% or more as shown in the photograph of Example 1 of FIG. 4 are “excellent,” those having a contact area ratio of less than about 75% and about 50% or more The case where the contact area ratio was less than about 50% as shown in the photograph of Comparative Example 1 of FIG. 4 was evaluated as “not good”. The numerical values in parentheses in Table 4 mean the contact area ratio (%).

(Test 3: visible light transmittance)
Color luminometer (Konica Minolta Japan KK: CL-200A) so as to cover the light-receiving portion of the illumination LX ₁ of each sample was measured under sunlight by placing a laminated sheet. It based the measurement sample to the illuminance LX ₀ when not covering the light receiving unit, the visible light transmittance of each laminated sheet was calculated by the equation 1 below.

(Test 4: T-type peel strength)
Each laminated sheet was cut into a size of 25 mm wide × 200 mm long. Here, in order to grasp and pull the laminated sheet of the test piece and the aluminum foil respectively with a tensile tester, the pressure-sensitive adhesive layer at the tip of the laminated sheet was partially removed to form a knob portion. After removing the peelable PET liner from the laminated sheet, the pressure-sensitive adhesive layer of the laminated sheet is crimped to an anodized aluminum foil of about 130 mm in length cut into a width of 30 mm using a 2 kg roller Test pieces were produced. After pressure bonding, the test piece is left for 20 minutes at room temperature, and the test piece is subjected to a tensile test machine (manufactured by Shimadzu Corporation) so that the aluminum foil of the test piece is on the upper side and the horizontal direction is substantially horizontal to the ground. : Attached to autograph AGS-X). While fixing the laminated sheet downward at approximately 90 degrees with respect to the test piece, the aluminum foil is pulled upward at a tensile speed of 300 mm / min so as to be approximately 90 degrees with respect to the test piece. The peel strength was measured.

(Test 5: 90 ° peel strength to concrete block)
Each laminated sheet was cut into a size of 25 mm wide × 200 mm long to prepare a test piece. After removing the peelable PET liner from the test piece, the pressure-sensitive adhesive layer of the test piece was crimped to a construction concrete block (a standard concrete block conforming to JIS A 5406-2010) using a 2 kg roller. After pressure bonding, the concrete block to which the test piece was attached was left at room temperature for 20 minutes. Next, the test piece attached to the concrete block is attached to a tensile tester (Autograph AGS-X manufactured by Shimadzu Corporation), and the tensile speed of the test piece is 300 mm / min upward approximately 90 degrees with respect to the concrete block And the 90 ° peel strength to the concrete block was measured.

(Test 6: piercing strength)
After cutting each laminated sheet into a size of 50 mm wide × 50 mm long and removing the peelable PET liner, as shown in FIG. 5, the pressure-sensitive adhesive layer 510 of the test piece 500 is 20 mm in diameter It stuck on the steel block 502 in which the hole was opened. A steel cone type attachment 504 (Aiko Engineering Co., Ltd .: 031 B) connected to a push pull gauge 506 (Aiko Engineering Co., Ltd.) is disposed above the center of the hole, and the attachment 504 is 300 mm with respect to the test piece The force was pushed at a rate of 1 / min and the maximum force as puncture strength (N) was measured.

(Test 7: Roll appearance test)
A roll is formed by winding each laminated sheet around a 3-inch pipe (inner diameter 76 mm, outer diameter 100 mm) or 6-inch pipe (inner diameter 153 mm, outer diameter 180 mm), and visually observe the occurrence of breakage of the laminated sheet in the roll body It evaluated by. Here, as shown in the photograph of Example 1 in FIG. 6, those in which the crease was not generated are “excellent”, and as shown in the photograph of Comparative Example 4 in FIG. Those that had been evaluated as "impossible".

(Test 8: Rust prevention test)
The pressure sensitive adhesive layer of the laminated sheet was attached to a SPCC steel plate of width 53 mm × length 100 mm × thickness 2.0 mm, and the unnecessary portion was cut to prepare a laminated plate having the steel plate and the laminated sheet. A test piece was prepared by forming a cross-shaped flaw 810 as shown in FIG. 8 with a cutter on the laminate sheet of the laminate. Here, the flaws were formed at a position at least about 10 mm away from the end of the test piece in such a manner that the sheet penetrated but the steel plate was not deeply scratched. The width of the wound portion was about 0.5 to about 1 mm.

According to JIS K 5600-7-9 (General test method for paints-Part 7: Long-term durability of coating film-Section 9: Cyclic corrosion test method-salt spray / drying / wetting) cycle D according to JIS K 5600-7-9 It implemented on the conditions shown in the following Table 3.
Here, the location of the test piece in the test tank was changed for each measurement. The test pieces were arranged so as not to contact each other and not to contact the wall of the test chamber.

  The test pieces were taken out of the test tank at measurement intervals shown in Table 3, and after washing with distilled water, the appearance of the test pieces was observed. Here, the width of rust generated at the end portion and the cut portion was measured, and the rustproof performance was evaluated by the size of the maximum width. The maximum width evaluated that the thing of less than 4.00 mm was "excellent", and the thing more than 4.00 mm was evaluated as "impossible." The results of the antirust test in Table 4 show the results after 120 cycles.

(Test 9: Acid resistance test)
The laminated sheet from which the peelable liner has been removed is immersed in 12% hydrochloric acid for 1 week, and then the laminated sheet is taken out to measure the pH of hydrochloric acid and the rubber hardness, maximum tensile strength and weight change after 5 minutes of the laminated sheet. Those with a change of less than 10% were rated as "excellent" and those with a change of 10% or more were rated as "impossible". Here, the measurement of the rubber hardness was performed according to JIS K6253 by a method using a durometer as a measuring instrument, and the measurement of the maximum tensile strength was performed by the same method as the test 1.

(Test 10: alkali resistance test)
The laminated sheet from which the peelable liner has been removed is immersed in a 5% aqueous sodium hydroxide solution for 1 week, and then the laminated sheet is taken out, and the pH of the aqueous sodium hydroxide solution and the rubber hardness of the laminated sheet, maximum tensile strength, and after 5 minutes The change in weight was measured, and those with a change of less than 10% were evaluated as "excellent" and those with a change of 10% or more as "impossible". Here, the measurement of the rubber hardness was performed according to JIS K6253 by a method using a durometer as a measuring instrument, and the measurement of the maximum tensile strength was performed by the same method as the test 1.

(Test 11: Impact resistance test)
The impact resistance of the laminated sheet was evaluated by a Dupont impact resistance test in accordance with JIS K 5600-5-3. Here, a laminate prepared by laminating a pressure-sensitive adhesive layer of a laminated sheet on a steel plate having a thickness of 1.0 mm was used as a test piece. The test piece is placed horizontally on a test bench having a recess large enough to accommodate the weight to be dropped, and a weight of 300 g is dropped onto the test piece from a height of 500 mm. With respect to the test pieces, those in which no cracking and peeling were observed were evaluated as “good”, and those in which either cracking and peeling were observed were evaluated as “impossible”. The test was performed on two test pieces.

<Result>
As can be seen from Table 4 and FIG. 4, any of the compliant laminate sheets of the present disclosure in Examples 1 to 11 is excellent in transparency, antirust performance, acid resistance, alkali resistance, and impact resistance, and is predetermined. Since it has a tensile stress and a residual stress, it has excellent followability to uneven lands and the like as compared to the laminated sheets of Comparative Examples 1 to 6, and it is confirmed that the puncture strength and the like are also excellent. did it.

  When Examples 1 and 4 to 7 are compared, it can be confirmed that the adhesion to a concrete structure is improved as the thickness of the pressure-sensitive adhesive layer increases. However, when preventing generation | occurrence | production of the crease in a roll body, it also turned out that it is preferable that the thickness of a pressure sensitive adhesive layer is less than 1.50 mm.

  Examples 1 to 7 and 10 using a resin layer provided with an inorganic particle-containing treatment layer, and Examples 8 and 9 using a resin layer not provided with such a treatment layer, or a resin layer provided with a corona treatment layer When comparative examples 1 and 2 are compared, it can be confirmed that the configurations of the examples 1 to 7 and 10 are superior in the T-type peel strength as compared with the configurations of the other examples. Therefore, in the constructions of Examples 1 to 7 and 10, since it is more difficult to delaminate the laminated sheet, for example, the laminated sheet is made to follow the inland portion having a large unevenness difference, and the sheet is large. Even when a load is applied, the laminated sheet can sufficiently protect or reinforce the structure without delamination and can suppress the progress of rust.

  Since commercially available tapes having anticorrosion performance as in Comparative Examples 5 and 6 are generally opaque, it is not possible to visually recognize a change with time of defects such as rust and cracks after applying the tape. In addition, these tapes are also inferior in followability to inland parts, rusted parts and the like where the difference in unevenness is large, and voids and the like occur at the bonded portions, and moisture, salt and the like easily penetrate. As a result, it is considered that such a tape is difficult to suppress the progress of cracks, rust, and the like in the long term, as compared with the compliant laminate sheet of the present disclosure. In particular, since these tapes have poor adhesion to concrete and are prone to delamination, such a tendency can be expected to be more pronounced for concrete structures.

  It will be apparent to those skilled in the art that various changes can be made to the embodiments and examples described above without departing from the basic principles of the invention. It will also be apparent to those skilled in the art that various modifications and alterations of the present invention can be implemented without departing from the spirit and scope of the present invention.

100, 200, 700, 800 Compliant laminate sheet 110, 510 Pressure-sensitive adhesive layer 120, 520 Resin layer 250 Concrete structure having non-land portion 300, 500 Laminated sheet test piece 302 Steel template 304 Glass plate 306 Steel material 502 Steel block 504 Steel cone type attachment 506 Push pull gauge 710 Rust part 750 Structure 810 Scratched part 850 steel plate

Claims (11)

A compliant laminate sheet comprising a resin layer and a pressure sensitive adhesive layer, wherein
The laminated sheet is
The stress at 5% tension is less than 10 N / cm,
The residual stress after 5 minutes at 30% tension is 10 N / cm or less, and
Visible light transmittance is 80.0% or more,
A compliant laminated sheet used for a concrete structure or a structure having a rust portion.   The laminated sheet according to claim 1, wherein the resin layer contains a polyolefin film, and the thickness of the resin layer is 0.05 mm or more and less than 0.25 mm.   The pressure-sensitive adhesive layer comprises a (meth) acrylic pressure-sensitive adhesive layer, and the thickness of the pressure-sensitive adhesive layer is 0.3 mm or more and less than 1.5 mm. The laminated sheet described in.   The lamination sheet according to any one of claims 1 to 3, wherein an inorganic particle-containing treatment layer is provided on at least one surface of the resin layer.   The lamination sheet as described in any one of Claims 1-4 which does not contain the reinforcement layer whose visible light transmittance is less than 80.0%.   6. A reinforcing layer according to any one of claims 1 to 5, wherein the stress at 5% tension is greater than 10 N / cm and the residual stress after 5 minutes at 30% tension is not greater than 10 N / cm. Description laminated sheet.   From the group consisting of puncture strength of 30 N or more, T-type peel strength of 5 N / cm or more, maximum tensile strength of 20 to 60 N / cm, yield point of 15% or more, and 90 degree peel strength to concrete blocks of 5 N / cm or more The laminated sheet according to any one of claims 1 to 6, having at least one selected property.   A release liner is provided on the surface of the pressure-sensitive adhesive layer opposite to the resin layer-applied surface, and the surface of the resin layer opposite to the pressure-sensitive adhesive layer-applied surface is not subjected to release treatment. The laminated sheet according to any one of Items 1 to 7.   The roll body by which the lamination sheet as described in any one of Claims 1-8 was wound by roll shape. It is a construction method of the lamination sheet which protects the surface of a concrete structure visibly at least temporarily,
Applying the laminated sheet according to any one of claims 1 to 8 to the surface of a concrete structure;
Allowing the laminated sheet to follow the surface. It is a construction method of the lamination sheet which controls progress of rust so that visual recognition of the surface of a structure which has a rust part,
Applying the laminated sheet according to any one of claims 1 to 8 so as to cover a rusted portion of the structure;
And a step of causing the laminated sheet to follow the surface of the rusted portion and the structure.