JP6495000B2 - Construction method of fiber sheet laminate - Google Patents

Description

The present invention relates to a peeling prevention method for preventing the peeling of concrete pieces from concrete structures such as bridges such as railways and roads, elevated roads, tunnels, and buildings.

In concrete structures, steel materials corrode due to salt damage, neutralization, etc., and the expansion pressure at that time causes cracks in the concrete structure, causing concrete pieces to peel off from the surface layer. In order to solve this problem, various methods for preventing the flaking have been proposed. Most of them are methods for preventing a piece of concrete from being peeled off from a concrete structure by adhering a fiber sheet to the surface of the concrete structure to be repaired using an adhesive. Usually, after washing and roughening the concrete surface, applying a primer, applying a net-like fiber sheet, curing the adhesive, and applying a weather-resistant paint outdoors where UV degradation is a concern Has been done. When there are a lot of unevenness and bubbles on the concrete surface, an adjustment material may be applied before applying the fiber sheet to smooth the surface. The peeling prevention method includes the following steps: (1) Washing / graining step, (2) Primer step, (3) Undercoat step, (4) Fiber sheet bonding step, (5) Top coat step, (6) Weather resistant paint Examples of the application process (1 to 2 times) include 6 to 7 processes (7 to 8 processes if there is unevenness adjustment). This process was a construction that consisted of many operations, and had the following problems.

1) There are many kinds of materials to be used and the number of processes is large, so the construction cost is high.
2) Skill is required for the work of impregnating the fiber sheet with the adhesive. If the impregnation is insufficient, air bubbles remain between the fiber sheet and the adhesive, and the adhesive strength between the surface of the concrete structure and the fiber sheet is low. And the peeling prevention effect is not fully exhibited.
3) During the impregnation operation of the adhesive resin, the adhesive resin may sag or scatter and contaminate the surroundings.
4) In the case of repairing outdoor structures, protective coating is required to prevent deterioration caused by ultraviolet rays from sunlight, etc., which increases the labor for construction.

A method for solving such a problem has been proposed.
For example, a concrete stripping prevention sheet (Patent Document 1) characterized in that a fiber yarn net and a nonwoven fabric are bonded and integrated, and the reinforcing fiber is solidified with a transparent or translucent base resin and integrated. The fiber sheet made of FRP sheet having flexibility at normal temperature is placed on a flat surface with the side to be applied to the concrete structure facing upward, and a putty-like adhesive resin having a predetermined viscosity is applied, and this adhesive resin is applied. Bonding method of fiber sheet (Patent Document 2) for attaching sheet coated with concrete to the surface of concrete structure, bonding the protective layer and adhesive coating layer to the adhesive surface of the adhesive coating layer to the concrete structure A sheet for repairing / reinforcing / deteriorating a concrete structure characterized by forming an adhesive layer (Patent Document 3) has been proposed.
A composition (A) mainly composed of 95 to 50 parts by weight of a vinylidene fluoride resin and 5 to 50 parts by weight of a methacrylate ester resin is used as a surface layer, and 95 to 5 parts by weight of a methacrylate ester resin, vinylidene fluoride A fluororesin weathering film (Patent Document 4), characterized in that the back layer is a composition (B) mainly composed of 5 to 95 parts by weight of a resin and 0.1 to 15 parts by weight of an ultraviolet absorber; A fluororesin system comprising a cement molded product and a laminate comprising a film mainly composed of a fluororesin selected from a reinforcing base layer and a vinylidene fluoride homopolymer and copolymer. A film-coated cement molded article (Patent Document 5) is described.
Patent Document 6 discloses (A) 100 parts by weight of one or more resins selected from unsaturated polyester resins, vinyl ester resins, urethane (meth) acrylate resins, and polyester (meth) acrylate resins; Impregnating a resin composition containing 01 to 20 parts by weight and (C) 0 to 200 parts by weight of an inorganic or organic filler with at least one selected from a biaxial mesh, a triaxial mesh and a fiber layered body. It is a curable material for preventing concrete peeling.

Patent Document 1 is a laminate in which a fiber yarn net is bonded to a non-woven fabric, and is not bonded to a weather-resistant film. When used outdoors, it is necessary to separately apply a weather-resistant paint. There was a problem that the number increased.
Patent Document 2 uses an acrylic resin as a base resin and does not use a resin containing fluorine.
Patent Document 3 describes that a fluorine-based resin is used for an outer layer that provides functions such as weather resistance, antifouling properties, waterproofness, and salt barrier properties. However, the laminating method is a method in which an outer layer and a reinforcing layer (fiber sheet) are bonded using an adhesive for laminating, and a bonding layer made of a non-woven fabric is laminated on the side bonded to the concrete surface. . The present invention uses a specific pressure-sensitive adhesive for bonding a fiber sheet, and exhibits sufficient peeling prevention performance without providing a non-woven fabric layer.
Patent Document 4 does not describe a combination with a net-like fiber sheet, and does not describe that it is attached to a concrete structure for protection.
Patent Document 5 does not describe a primer or an acrylic pressure-sensitive adhesive, and does not describe a use as a countermeasure against peeling of a concrete piece.
Patent Document 6 has a problem that the number of work steps is increased as compared to the present invention because there are steps of performing light irradiation and heat treatment, and the work of applying a weather-resistant paint is increased in a place where weather resistance is required.

JP2013-19146A JP 2009-162033 A Japanese Patent Laid-Open No. 2004-27718 JP-A-1-262133 Japanese Unexamined Patent Publication No. 2000-25019 JP 2004-018719 A

In order to solve the above-mentioned problems, the present invention provides a fiber sheet laminate having sufficient flaking prevention performance and durability, and by using the fiber sheet laminate, the construction period can be shortened and the construction cost can be reduced. Provides a flaking prevention method.

The present invention is a method for constructing a fiber sheet laminate performed by the following steps,
1st process The concrete adhesive agent used as the 1st layer is apply | coated to the concrete surface.
2nd process The fiber sheet laminated body used as a 2nd layer is affixed on the 1st layer. The fiber sheet laminate is a fiber sheet in which an A layer is laminated on one side of the B layer, an acrylic pressure-sensitive adhesive is applied to the other side of the B layer, and the fiber sheet is adhered to the surface of the applied acrylic pressure-sensitive adhesive. A laminate, layer A,
It is a laminated body which laminates | stacks in order of B layer, an acrylic adhesive layer, and a fiber sheet. The fiber sheet side of the fiber sheet laminate is affixed to the concrete adhesive side. The A layer is a resin composition containing 100 to 50% by mass of a polyvinylidene fluoride resin and 0 to 50% by mass of a polymethacrylate resin (the total of both is 100% by mass), and the B layer is a polyfluorinated resin. It contains 0 to 50% by mass of vinylidene resin and 100 to 50% by mass of polymethacrylate resin (the total of both is 100% by mass) . It is a resin composition which contains 1-15 mass parts ultraviolet absorber in B layer. The acrylic adhesive has a storage modulus of 5.0 × 10 ³ to 1 at 25 ° C. and 1.0 Hz.
It is an acrylic pressure-sensitive adhesive having 0 × 10 ⁶ Pa and tan δ at 100 ° C. and 1.0 Hz of 0.8 or less.
The thickness of the A layer is 5 to 100 [mu] m, the thickness of the B layer is Ri 5 to 100 [mu] m der, fiber sheet, glass fibers, vinylon fibers, polyolefin fibers, with one or more of the group consisting of nylon fibers Ah is, concrete adhesive is a room temperature curing type acrylic resin composition, coating amount of concrete adhesive is 0.1~1.0kg / ^{m 2,} the resin composition 100 parts by weight, containing pigment 1-100 parts by weight, a method of constructing the thick 10~100μm der Ru said fibrous sheet laminate of the adhesive layer when the acrylic pressure-sensitive adhesive, an acrylic adhesive, acrylic It is a copolymer of at least one kind (monomer A) of C (carbon number) 2 to C12 alkyl ester of an acid and at least one kind (monomer B) of a functional group-containing acrylic monomer, and monomer A and monomer It is a construction method of the fiber sheet laminate in which the copolymerization ratio of B is 99.99 / 0.01 to 70/30 by mass ratio.
The acrylic pressure-sensitive adhesive is a copolymer of butyl acrylate (BA) and acrylic acid (AA), and the copolymerization ratio of butyl acrylate (BA) and acrylic acid (AA) is 99.9 / 0.0. It is a construction method of the fiber sheet laminate that is 1-70 / 30
The acrylic adhesive is a construction method of the fiber sheet laminate using 0.3 to 4 parts by mass of a crosslinking agent in terms of solid content with respect to 100 parts by mass of the acrylic adhesive.
The pigment is calcium carbonate, the ultraviolet absorber is triazine, the cross-linking agent is an isocyanate cross-linking agent, and 50 to 100 parts by mass of the pigment is added to the B layer with respect to 100 parts by mass of the resin composition of the B layer. Used, the coating amount of the adhesive for concrete is 0.2 to 1.0 kg / m ² , the acrylic pressure-sensitive adhesive is a copolymer of butyl acrylate (BA) and acrylic acid (AA), and butyl acrylate (BA) It is a construction method of this fiber sheet laminated body whose copolymerization ratio of acrylic acid (AA) is 90 / 10-70 / 30 by mass ratio.

Since the quality is stabilized by using the fiber sheet laminate of the present invention, it is possible to perform high-quality construction with little variation in various characteristics when performing on-site construction. In addition, the net-like fiber sheet, which is a reinforcing material, and a polyvinylidene fluoride-based resin laminate containing highly durable polyvinylidene fluoride are integrated, so the process can be greatly shortened and the construction cost can be reduced compared to conventional methods. Can be.

It is a figure which shows the example of the load and displacement curve by an autograph in the punching resistance test.

The acrylic system in the present invention may refer to, for example, a (meth) acrylic system. (Meth) acrylic refers to, for example, a compound having an acrylic group or a methacrylic group.
The polyvinylidene fluoride-based resin laminate is a laminate of layer A and layer B, and is a laminate excluding a fiber sheet.
The fiber sheet laminate of the present invention is a laminate in which an A layer, a B layer, an acrylic adhesive layer (hereinafter sometimes referred to as an adhesive layer) composed of an acrylic adhesive, and a fiber sheet are laminated in this order.

The polyvinylidene fluoride resin (PVDF) of the present invention refers to a homopolymer of vinylidene fluoride or a copolymer of a monomer copolymerizable with vinylidene fluoride. Examples of the copolymerizable monomer include tetrafluoroethylene, hexafluoropropylene, ethylene trifluoride chloride, and vinyl fluoride.
In these, the homopolymer of vinylidene fluoride is preferable at a durable point.

The polymethacrylate ester resin (PMMA) of the present invention is a homopolymer of methyl methacrylate or a copolymer of monomers copolymerizable with methyl methacrylate, for example, polymethyl methacrylate and acrylic rubber. This means a blended product. Examples of the copolymerizable monomer include methacrylic acid esters having 2 to 4 carbon atoms, acrylate esters having 1 to 8 carbon atoms such as butyl acrylate, styrene, α-methylstyrene, acrylonitrile, acrylic acid, and the like. And ethylenically unsaturated monomers. In these, the homopolymer of methyl methacrylate is preferable at the point of adhesiveness with a fiber sheet.

The mixing ratio of the polyvinylidene fluoride-based resin and the polymethacrylic ester-based resin in the A layer of the present invention is as follows when the total of the polyvinylidene fluoride-based resin and the polymethacrylate-based resin is 100% by mass 100 to 50% by mass and 0 to 50% by mass of a polymethacrylate resin are preferable, and 100 to 75% by mass of a polyvinylidene fluoride resin and 0 to 25% by mass of a polymethacrylate resin are more preferable. If the polyvinylidene fluoride resin is less than 50% by mass, the properties of the polyvinylidene fluoride resin such as weather resistance and stain resistance may be deteriorated.

The mixing ratio of the polyvinylidene fluoride-based resin and the polymethacrylic acid ester-based resin in the B layer of the present invention is as follows. 0 to 50% by mass and 50 to 100% by mass of a polymethacrylate resin are preferable, and 0 to 25% by mass of a polyvinylidene fluoride resin and 75 to 100% by mass of a polymethacrylate resin are more preferable. If the polyvinylidene fluoride resin exceeds 50% by mass, adhesion to the fiber sheet may be hindered.

The thickness of the A layer of the present invention is 5 to 100 μm, the thickness of the B layer is preferably 5 to 100 μm, the thickness of the A layer is 10 to 60 μm, and the thickness of the B layer is 10 to 10 μm. More preferably, it is 60 μm. If the thickness of the A layer and the B layer is less than 5 μm, the weather resistance may be hindered, and even if the thickness of the A layer and the B layer exceeds 100 μm, various performances may reach a limit.

The acrylic adhesive of the present invention has a storage elastic modulus at 25 ° C. and 1.0 Hz of 5.0 × 10 ^{3 to} 1.0 × 10 ⁶ Pa, and a tan δ at 100 ° C. and 1.0 Hz of 0.00. It is preferable that it is 8 or less. More preferably, the storage elastic modulus at 25 ° C. and 1.0 Hz is 1.0 × 10 ^{4 to} 1.0 × 10 ⁶ Pa, and the tan δ at 100 ° C. and 1.0 Hz is 0.6 or less. When the storage elastic modulus is less than 5.0 × 10 ³ Pa, the cohesive force of the adhesive is reduced, and after the adhesive film is attached to the adherend, there are places where the adhesive film is displaced from the adherend or peeled off. There is a possibility that the adhesiveness of the fiber sheet is lowered and the punching resistance is lowered when it is produced or attached to concrete. When the storage elastic modulus exceeds 1.0 × 10 ⁶ Pa, the pressure-sensitive adhesive is too hard and cannot follow the unevenness of the adherend, and may crack and decrease the punching resistance. When tan δ exceeds 0.8, the heat resistance deteriorates, and after the adhesive film is attached to the adherend, the adhesive film may be displaced from the adherend or peeled off by heat such as sunlight.
The storage elastic modulus and loss factor tan δ can be measured using a viscoelasticity measuring device manufactured by Rheometric Scientific. The storage elastic modulus of the present invention was the storage elastic modulus G ′ at 25 ° C. in a shear mode and a frequency of 1.0 Hz. The tan δ of the present invention was a value obtained from the ratio (G ″ / G ′) of the storage elastic modulus G ′ and the loss elastic modulus G ″ at 100 ° C. in a shear mode and a frequency of 1.0 Hz.

Examples of the acrylic pressure-sensitive adhesive include ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, 2-methylbutyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, and n-octyl. At least one C (carbon number) 2 to C12 alkyl ester (monomer A) of acrylic acid such as acrylate, isooctyl acrylate, n-nonyl acrylate, isononyl acrylate, and the like, acrylic acid, methacrylic acid, acrylamide, N-methylol It is possible to use a copolymer with at least one of functional group-containing acrylic monomers such as acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (monomer B). That. The copolymerization ratio of the monomer A and the monomer B is preferably 99.99 / 0.01 to 70/30, more preferably 99.90 / 0.10 to 75/25 in terms of mass ratio.
A particularly suitable acrylic copolymer is a copolymer of butyl acrylate (BA) and acrylic acid (AA). In this acrylic copolymer, the copolymerization ratio of butyl acrylate (BA) and acrylic acid (AA) is preferably 99.9 / 0.1 to 70/30, and 99.5 / 0.5 to 80 in terms of mass ratio. / 20 is more preferable. When AA is less than 0.1% by mass, there is a possibility that it becomes impossible to control the physical properties of the adhesive in combination with the crosslinking agent. When AA exceeds 30% by mass, the glass transition point (Tg) is increased, sticking to an adherend at a low temperature is deteriorated, and workability may be lowered.
The weight average molecular weight (Mw) of the acrylic copolymer is preferably 200,000 to 1,000,000, more preferably 400,000 to 800,000. Such molecular weight can be adjusted by the amount of the polymerization initiator or by adding a chain transfer agent. If the weight average molecular weight (Mw) is less than 200,000, the cohesive strength of the acrylic copolymer is lowered, and there is a possibility that adhesive residue on the adherend and peeling of the adhesive film may occur. If it exceeds 1,000,000, the acrylic copolymer is too hard and may not be able to follow the unevenness of the adherend.

The acrylic pressure-sensitive adhesive can be added with additives such as a cross-linking agent, a tackifier, an ultraviolet absorber, and a light stabilizer, if necessary. As for the thickness of the adhesion layer in the case of apply | coating an acrylic adhesive, 10-100 micrometers is preferable.
Examples of the crosslinking agent include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, and amine-based crosslinking agents. These may be used singly or in combination of two or more. Particularly suitable crosslinking agents include isocyanate-based crosslinking agents. The amount of the crosslinking agent used is preferably 0.3 to 4 parts by mass and more preferably 0.5 to 3 parts by mass in terms of solid content with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive. If the cross-linking agent is less than 0.3 parts by mass, the cohesive force of the acrylic adhesive is low, and when the adhesive film is peeled off from the adherend, adhesive residue may be generated on the adherend and re-peelability may not be obtained. There is sex. When the isocyanate cross-linking agent exceeds 4 parts by mass, the acrylic pressure-sensitive adhesive becomes too hard to follow the irregularities on the surface of the adherend, and there is a possibility that air bubbles will be involved when the pressure-sensitive adhesive film is applied.
Examples of the isocyanate crosslinking agent include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylene diisocyanate, diphenylmethane-4,4′-diisocyanate, diphenylmethane. -2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, polyvalent isocyanate compounds such as lysine isocyanate, etc. Is mentioned. These may be used singly or in combination of two or more.

The tackifier can be selected in consideration of the softening point, compatibility with each component, and the like. For example, terpene resin, rosin resin, hydrogenated rosin resin, coumarone / indene resin, styrene resin, aliphatic petroleum resin, alicyclic petroleum resin, terpene-phenol resin, xylene resin, other aliphatic hydrocarbon resin Or an aromatic hydrocarbon resin etc. are mentioned. These may be used singly or in combination of two or more.

The ultraviolet absorber can be selected in consideration of the ultraviolet absorptivity and compatibility with the acrylic pressure-sensitive adhesive to be used. Examples thereof include hydroquinone, benzotriazole, benzophenone, triazine, and cyanoacrylate. These may be used singly or in combination of two or more.
The ultraviolet absorber kneaded into the resin composition constituting the B layer of the present invention may be any compatible one, and a high molecular weight ultraviolet absorber is preferable in order to prevent volatilization. For example, benzotriazole series, oxalic acid series, benzophenone series, hindered amine series, and many other known types can be used. For example, 2- (3,5-di-alpha-dimethylbenzyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3- t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3 5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2-ethoxy-2'-ethyl oxac acid bisanilide, 2-ethoxy-5-t-butyl-2'-ethyl oxac acid bisanilide, 2-hydroxy-4-n-octoxybenzophenone, bis (1,2,2,6,6-pentimethyl-4-piperdyl) seba Bis (1,2,2,6,6-tetramethyl-4-piperdyl) sebacate, dimethyl-2- (4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl) ethanol, 1- [2-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-t-tetramethylpiperidine and the like can be mentioned.
The usage-amount of the ultraviolet absorber of this invention is 100 mass parts with respect to 100 mass parts of resin compositions (total of polyvinylidene fluoride resin 0-50 mass% and polymethacrylic acid ester resin 100-50 mass%) of B layer. 0.1-15 mass parts is preferable and 0.5-5 mass parts is more preferable. If the amount is less than 0.1 parts by mass, the amount of UV absorption is small, and the performance as UV protection may be insufficient. Even if it exceeds 15 parts by mass, the effect does not change and the cost may increase.

The light stabilizer can be selected in consideration of compatibility with the acrylic pressure-sensitive adhesive to be used, thickness, and the like. Examples thereof include hindered amine compounds, hindered phenol compounds, benzoate compounds, nickel complex compounds, and the like. These may be used singly or in combination of two or more.

  As the fiber sheet to be bonded in the present invention, a net-like fiber sheet that is generally commercially available can be used. Examples thereof include glass fibers, vinylon fibers, polyolefin fibers such as polyethylene fibers and polypropylene fibers, nylon fibers, polyester fibers, polyamide fibers, aramid fibers, carbon fibers, and basalt fibers. Among these, one or more members selected from the group consisting of glass fiber, vinylon fiber, polyolefin fiber, and nylon fiber are preferable in terms of cost and adhesive performance.

In the present invention, a pigment may be used in order to improve the weather resistance (decrease the yellowing index) by matching the hue with the casing to be constructed. The pigment is preferably contained in the polyvinylidene fluoride resin laminate. The pigment of the present invention can be used for both the A layer and the B layer, but it is preferably used for the B layer because of its great effect.
The pigment of the present invention may be either an inorganic pigment or an organic pigment. As the inorganic pigment, for example, a composite oxide inorganic pigment that is said to form a new crystal structure by firing two or more metal oxides and develop color by crystal field splitting can be used as a main colored pigment. The main complex oxide inorganic pigments include rutile and bridelite type titanium yellow, mainly composed of TiO ₂ · Sb ₂ O ₃ · BaO · NiO · Cr ₂ O ₃ , ZnO · Fe ₂ O ₃ · zinc spinel crystals mainly composed of Cr ₂ O ₃ - iron brown, cobalt blue-based spinel crystals mainly composed of _{CoO · Al 2 O 3 · Cr} 2 O 3, TiO 2 · CoO · NiO · Green system consisting primarily of ZnO, spinel type of black system mainly composed of CuO · _Cr 2 _{O 3} and _{CuO · Fe 2 O 3 · Mn} 2 O 3, violet system or the like is composed of CoO and _Mn 2 _{O 3} is there. In addition to these colored pigments, rutile titanium oxide, zinc white, calcium carbonate, barium sulfate, and other inorganic pigments can be used.
Examples of the organic pigment include the following. Examples of monoazo pigments include azo lakes (lake red C, watch red, prilliant carmine 6B, etc.) and benzimidazolones (PV orange HL, etc.). Examples of the disazo pigment include diarylide yellow (permanent yellow HR and the like) and pyrazolone (benzidine red and the like). Examples of the condensed azo pigment include condensed azo type (condensed azo yellow, condensed azo red, etc.). Examples of polycyclic pigments include quinacridone (such as quinacridone red dioxazine (such as dioxazine violet)), isoindolinone (such as yellow 3RLT), and vat (such as perylene red, perinone orange, and indanthrone blue). Phthalocyanine series (phthalocyanine blue, phthalocyanine green, etc.).
When the pigment is used in the A layer, the amount of the pigment of the present invention is preferably 0 to 100 parts by mass and more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resin composition of the A layer. When the pigment is used in the B layer, the amount of the pigment of the present invention is preferably 0 to 100 parts by mass and more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resin composition of the B layer. If it exceeds 100 parts by mass, the yellowing index may increase.

The manufacturing method of the polyvinylidene fluoride resin laminate of the present invention is composed of two layers, and the manufacturing method is not particularly limited, but generally a method carried out by melt extrusion molding is used. In addition to commonly used single-screw extruders, twin-screw extruders are also used for melt extrusion molding, but in the case of a two-layer configuration, a co-extrusion molding method in which a plurality of layers are bonded together is used. It is preferred to use. A co-extrusion method using a T-die that uses a plurality of extruders to bond the resin in a molten state to form a multi-layer is called a multi-manifold die, and after a plurality of resin layers are made into a film state There are a method of adhering by adhesion, and a method of spreading a plurality of resins and then spreading them into a film. Also, a multilayer film can be formed by a method using a round die, which is called an inflation molding method.
In addition, there is no particular limitation on the method of mixing an additive such as a pigment or an ultraviolet absorber into the polyvinylidene fluoride resin laminate, but for example, a resin and an additive are mixed in advance in a resin composition, A melt kneading method using the extruder used may be used.

The method for applying the acrylic pressure-sensitive adhesive and the method for adhering the fiber sheet are not particularly limited, and general methods are used.
For example, a method in which an acrylic pressure-sensitive adhesive is directly applied to layer B of the polyvinylidene fluoride-based resin laminate, and then a fiber sheet is bonded to the surface of the applied acrylic pressure-sensitive adhesive, and a separator described later is further bonded thereto. (Direct coating method) In addition, an acrylic pressure-sensitive adhesive is coated on the separator, and the fiber sheet is placed on the separator. Then, the acrylic pressure-sensitive adhesive is again coated on the fiber sheet, and after drying, the above-mentioned polyvinylidene fluoride There is a method (transfer coating method) of transferring three layers of an acrylic pressure-sensitive adhesive, a fiber sheet, and an acrylic pressure-sensitive adhesive on the separator to the surface of the B layer of the resin-based resin laminate.
A separator can be provided on the surface of the fiber sheet laminate on which the pressure-sensitive adhesive layer of the present invention is provided and the fiber sheet is attached to the side where the acrylic adhesive is applied and the fiber sheet is attached.
As the separator, a known general separator can be used. For example, a silicone release agent is applied to the PET film surface, and a silicone release agent is applied to the polyethylene side of a laminate film of paper and polyethylene. And the like.

In the construction method using the fiber sheet laminate of the present invention, as a first step, a concrete adhesive to be a first layer is applied to the concrete surface. Here, examples of the adhesive for concrete include a low viscosity type and a high viscosity type. These can also be used in combination. The low viscosity type is easy to impregnate the concrete frame. The high viscosity type cannot be expected to be impregnated, but can secure the coating thickness after one application.

Before this step, it is preferable to take measures against washing and roughening, such as washing the concrete surface if necessary, or correcting unevenness, smoothing, etc., in order to block cracks. . What is marketed can be used as adhesive for concrete used as the 1st layer. For example, any one selected from the group consisting of acrylic resins, epoxy resins, urethane resins, vinyl ester resins, polyester resins, and polymer cement materials can be used. A thixotropic agent, a pigment, an antifoaming agent, a diluent, a curing rate adjusting agent, and the like can be added to the concrete adhesive as long as the performance is not affected. Among these, acrylic adhesives are preferable in consideration of physical properties such as workability and adhesive strength with the fiber sheet laminate. Preferred coating weights in the range of concrete adhesive of the first layer is preferably ^{0.1~1.0kg / m 2, 0.2~0.5kg / m} 2 is more preferable. The method for applying the first layer of the adhesive for concrete is not particularly limited, and for example, a roller, a brush, a trowel, a spatula, or the like can be used.

As a 2nd process, the fiber sheet laminated body used as a 2nd layer is affixed on the 1st layer. When affixing, using a roller, a trowel, a spatula, etc., it is affixed with care so that the concrete adhesive spreads evenly over the adhesive surface so as not to cause wrinkles on the fiber sheet laminate surface. The fiber sheet side of the fiber sheet laminate is affixed with an adhesive for concrete.

As a third step, the laminate bonded to the concrete structure may be fixed with a commercially available anchor pin in consideration of safety at the time of peeling.

As the concrete adhesive of the present invention, a room temperature curable acrylic resin composition is particularly preferred. As the room temperature curable acrylic resin composition, a resin composition containing (meth) acrylate, a polymerization initiator and a decomposition accelerator is preferable. For example, the decomposition which accelerates | stimulates decomposition | disassembly of (meth) acrylate which has an ethylenically unsaturated double bond in 1 molecule disclosed by Unexamined-Japanese-Patent No. 9-302053, a thermal radical polymerization initiator, and a thermal radical polymerization initiator Concrete adhesives containing accelerators can be used.

Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples.
Table 1 shows the types of evaluated acrylic pressure-sensitive adhesives and the coating thickness (thickness) at the time of evaluation.
Acrylic copolymer α: copolymer of butyl acrylate (BA) and acrylic acid (AA) (BA / AA = 90/10, solid content 35% by mass)
Acrylic copolymer β: copolymer of butyl acrylate (BA) and acrylic acid (AA) (BA / AA = 99.95 / 0.05, solid content 35% by mass)
Isocyanate-based crosslinking agent: trifunctional isocyanate which is a trimethylolpropane adduct of tolylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate L-45E, solid content: 45% by mass)

Example 1
The ratio of the polyvinylidene fluoride resin and the polymethacrylic acid ester resin in the A layer and the B layer was changed as shown in Table 1, and the A layer and the B layer were laminated so as to form a film having a thickness of 15 μm. To the film of the B layer, 5 parts by mass of an ultraviolet absorber was added with respect to 100 parts by mass of the resin composition of the B layer. A polyvinylidene fluoride resin and a polymethacrylate resin, and these resins and an ultraviolet absorber were blended in advance and melted and pelletized with a 30 mmφ counter-rotating twin screw extruder to prepare a film. The weather resistance of the obtained laminated film was evaluated. Further, an acrylic pressure-sensitive adhesive a was applied to the surface on the B layer side of the obtained laminated film so as to have a thickness of 50 μm, and the fiber sheet A was adhered to obtain a fiber sheet laminate for a concrete piece flaking prevention method. The fiber sheet laminate was applied and applied to a concrete specimen prepared according to the test method 424-2011 of the NEXCO test method “Part 4 Structure-Related Test Method” at 0.2 kg / m ^2. And punching resistance was evaluated. The fiber sheet laminated body affixed the fiber sheet side to the concrete adhesive side. The results are shown in Table 2.

(Materials used)
Polyvinylidene fluoride resin (PVDF): Arkema, trade name Kaina-720 (a homopolymer of vinylidene fluoride, hereinafter abbreviated as K-720).
Polymethacrylate resin (PMMA): Mitsubishi Rayon Co., Ltd., trade name HIPET HBS (polymethyl methacrylate resin including acrylic rubber, hereinafter abbreviated as HBS)
Ultraviolet absorber: commercial product, triazine acrylic adhesive: a shown in Table 1
Fiber sheet A: VK sheet, manufactured by Denki Kagaku Kogyo Co., Ltd., biaxial vinylon fiber sheet, basis weight 91 g / m ²
Adhesive for concrete: manufactured by Denki Kagaku Kogyo Co., Ltd., acrylic, room temperature curable acrylic resin composition

(Test method)
Weather resistance: Yellowing index (Δb) was measured. Weather resistance acceleration test JIS A 1415, yellowness measurement In accordance with JIS K 7103, the yellowing index (Δb) was calculated as follows. When the yellowing index was 2.0 or more, it was determined that the material was clearly yellowed visually.
Yellowing index (Δb) = yellowness after exposure / initial yellowness punching resistance: Measured according to test method 424-2011 of NEXCO test method “Part 4 Structural Relationship Test Method”. For the measurement, the relationship between load and displacement was recorded using an autograph capable of displacement control, and the maximum load and the displacement at that time were obtained. In the NEXCO standard, if the displacement is 10 mm or more and the maximum load is 1.5 KN or more, it is used as an index indicating that there is a peeling prevention performance. FIG. 1 shows an example of load and displacement curves by an autograph.

Experiment No. 1-1 had a large yellowing index because the ratio in the A layer was outside the range of the present invention. Experiment No. In 1-2, since the ratio in the A layer and the ratio in the B layer were outside the range of the present invention, the yellowing index was large and the maximum load was small. Experiment No. In 1-3, since the ratio in the B layer was out of the range, the yellowing index was large and the maximum load was small.

(Example 2)
Experiment No. Evaluation was performed in the same manner as in Example 1 except that the thickness of the acrylic pressure-sensitive adhesive a was changed as shown in Table 3 using 1-8. The results are shown in Table 3.

(Example 3)
Experiment No. Evaluation was performed in the same manner as in Example 1 except that the type of the acrylic pressure-sensitive adhesive was changed as shown in Table 4 using 1-8. The results are shown in Table 4.

  Experiment No. 3-4 had a small displacement because the storage elastic modulus was outside the range of the present invention. Experiment No. 3-5 had a small displacement because tan δ was out of the range of the present invention.

Example 4
Experiment No. The same procedure as in Example 1 was performed except that a laminated film in which 50 μm of the acrylic pressure-sensitive adhesive a was applied and the thicknesses of the A layer and the B layer were changed as shown in Table 5 was used. The results are shown in Table 5.

(Example 5)
Acrylic adhesive a was applied to a thickness of 50 μm. The same procedure as in Example 1 was conducted except that the amount of the ultraviolet absorber in the resin composition 1-8 was changed to the amount shown in Table 6. The results are shown in Table 6.

(Example 6)
Experiment No. The same procedure as in Example 1 was performed except that 50 μm of the acrylic pressure-sensitive adhesive a was applied in the composition of 1-8 and the type of the fiber sheet was changed as shown in Table 7. The results are shown in Table 7.

(Materials used)
Fiber sheet B: Polypropylene fiber sheet Triaxial sheet Commercial product Weight per unit area 62 g / m ²
Fiber sheet C: Nylon fiber sheet, biaxial sheet commercial product, basis weight 160 g / m ²

(Example 7)
Experiment No. Same as Example 1 except that 50 μm of acrylic pressure-sensitive adhesive a was applied in the composition of 1-8, the pigment was used for the B layer, and the amount shown in Table 8 was used with respect to 100 parts by mass of the resin composition of the B layer. Went to. The results are shown in Table 8.

(Materials used)
Pigment: Calcium carbonate Commercial product

(Example 8)
Experiment No. Using the fiber sheet laminate of 1-5, 1-8 and 1-11, 50 μm of acrylic pressure-sensitive adhesive a was applied, and workability and finish were confirmed. In the test, the time required for constructing an area of 1 m ² , ease of handling, and finished state were confirmed by a worker having pasting work experience. The test was conducted at 20 ° C. In addition, it carried out as a comparison with the conventional method. The results are shown in Table 9.

(Procedure of Conventional Method 1)
(1) The box culvert inner ceiling surface capable of securing an area of 1 m ² is roughened with a water jet.
(2) After drying, a concrete adhesive (trade name: DK-550-003, viscosity 330 mPa · s, room temperature curable acrylic resin composition, manufactured by Denki Kagaku Kogyo Co., Ltd.) was applied with 0.2 kg / m ² with a roller. .
(3) Immediately after application, an undercoat material (trade name: Acrial, manufactured by Denki Kagaku Kogyo Co., Ltd.) is applied with a roller at 0.6 kg / m ² .
(4) Immediately after application, a vinylon fiber sheet (trade name: VK sheet, manufactured by Denki Kagaku Kogyo Co., Ltd.) having a length of 1 m and a width of 1 m is pasted.
(5) After pasting, a top coat material (trade name: Acrial, manufactured by Denki Kagaku Kogyo Co., Ltd.) is applied with 0.3 kg / m ² with a roller.
(6) One day later, a weather-resistant paint (trade name: CF Coat U, manufactured by Denki Kagaku Kogyo Co., Ltd.) is applied with a roller at 0.15 kg / m ² (7) After 6 hours, the same weather-resistant paint is further applied with a roller. Apply 15 kg / m ² .

(Procedure of Conventional Method 2)
(1) The box culvert inner ceiling surface capable of securing an area of 1 m ² is roughened with a water jet.
(2) After drying, 0.15 kg / m ^{2 of} an epoxy resin primer (trade name: for tough guard E-VM, manufactured by Nippon Paint Co., Ltd.) was applied with a roller.
(3) One day later, an intermediate coating material (trade name: Toughguard BD intermediate coating # 100, manufactured by Nippon Paint Co., Ltd.) is applied with 0.5 kg / m ² with a roller.
(4) Immediately after the application, a vinylon fiber sheet (trade name: Trineo TSS-1810-Y software, manufactured by Unitika Ltd.) having a length of 1 m and a width of 1 m is pasted.
(5) After pasting, 0.5 kg / m ² of the intermediate coating material (3) is applied with a roller.
(6) One day later, a top coat material (trade name: Toughguard UD, manufactured by Nippon Paint Co., Ltd.) is applied with a roller at 0.12 kg / m ² .

(Procedure of the present invention)
(1) The box culvert inner ceiling surface capable of securing an area of 1 m ² is roughened with a water jet.
(2) After drying, a concrete adhesive (trade name: DK-550-003, viscosity 330 mPa · s, room temperature curable acrylic resin composition, manufactured by Denki Kagaku Kogyo Co., Ltd.) was applied with 0.2 kg / m ² with a roller. To do.
(3) Experiment No. The fiber sheet laminates 1-5, 1-8, and 1-11 are attached.
(Test method)
Working time: After roughening the concrete with a water jet, the time from applying the adhesive for concrete (epoxy resin primer in the conventional method 2) to the completion of the weather-resistant paint (the final finish) is completed. Measured. In the case of the present invention, the time until the application of the fiber sheet laminate was completed was measured. The ease of handling (ease of work by workers) and the finished state (appearance of the final finished state) were evaluated.

Since the fiber sheet laminate of the present invention has durability, no top coating material, intermediate coating material, or weather-resistant coating material is required. The conventional method (Experiment No. 8-1 and Experiment No. 8-2) required time for the work time.

Claims (7)

The construction method of the fiber sheet laminated body performed by the following process.
1st process The concrete adhesive agent used as the 1st layer is apply | coated to the concrete surface.
2nd process The fiber sheet laminated body used as a 2nd layer is affixed on the 1st layer. The fiber sheet laminate is a fiber sheet in which an A layer is laminated on one side of the B layer, an acrylic pressure-sensitive adhesive is applied to the other side of the B layer, and the fiber sheet is adhered to the surface of the applied acrylic pressure-sensitive adhesive. It is a laminate, which is a laminate in which an A layer, a B layer, an acrylic pressure-sensitive adhesive layer, and a fiber sheet are laminated in this order. The fiber sheet side of the fiber sheet laminate is affixed to the concrete adhesive side. The A layer is a resin composition containing 100 to 50% by mass of a polyvinylidene fluoride resin and 0 to 50% by mass of a polymethacrylate resin (the total of both is 100% by mass), and the B layer is a polyfluorinated resin. It contains 0 to 50% by mass of vinylidene resin and 100 to 50% by mass of polymethacrylate resin (the total of both is 100% by mass) . It is a resin composition which contains 1-15 mass parts ultraviolet absorber in B layer. The acrylic pressure-sensitive adhesive has a storage elastic modulus at 25 ° C. and 1.0 Hz of 5.0 × 10 ^{3 to} 1.0 × 10 ⁶ Pa, and a tan δ at 100 ° C. and 1.0 Hz of 0.8 or less. It is an acrylic adhesive. The thickness of the A layer is 5 to 100 [mu] m, the thickness of the B layer is Ri 5 to 100 [mu] m der, fiber sheet, glass fibers, vinylon fibers, polyolefin fibers, with one or more of the group consisting of nylon fibers Yes, the concrete adhesive is a room temperature curable acrylic resin composition, the coating amount of the concrete adhesive is 0.1 to 1.0 kg / m ² , and is 1 to 100 parts by mass of the resin composition. containing pigment 100 parts by weight, the construction method of the fibrous sheet laminate according to claim 1, wherein a thickness of the adhesive layer is Ru 10~100μm der when coated with acrylic adhesive. The acrylic adhesive is a copolymer of at least one (monomer A) of C (carbon number) 2 to C12 alkyl ester of acrylic acid and at least one (monomer B) of a functional group-containing acrylic monomer. The construction method of the fiber sheet laminate according to claim 1, wherein the copolymerization ratio of the monomer A and the monomer B is 99.99 / 0.01 to 70/30 by mass ratio. The acrylic pressure-sensitive adhesive is a copolymer of butyl acrylate (BA) and acrylic acid (AA), and the copolymerization ratio of butyl acrylate (BA) and acrylic acid (AA) is 99.9 / 0.1 by mass ratio. It is -70/30. The construction method of the fiber sheet laminated body of one of Claims 1-3. The fiber sheet according to claim 1, wherein the acrylic pressure-sensitive adhesive uses 0.3 to 4 parts by mass of a crosslinking agent in terms of solid content with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive. Laminate construction method. The pigment is calcium carbonate, the ultraviolet absorber is triazine, the crosslinking agent is an isocyanate crosslinking agent, and 50 to 100 parts by mass of pigment is used for the B layer with respect to 100 parts by mass of the resin composition of the B layer. The application amount of the adhesive for concrete is 0.2 to 1.0 kg / m ² , the acrylic pressure-sensitive adhesive is a copolymer of butyl acrylate (BA) and acrylic acid (AA), and butyl acrylate ( The construction method of a fiber sheet laminate according to claim 5, wherein the copolymerization ratio of BA) and acrylic acid (AA) is 90/10 to 70/30 in mass ratio. Spalling prevention method of concrete pieces using the construction method according to claim 1-6 fibrous sheet laminate according one of of the description.

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