Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C63/00—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
  • B29C63/02—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor using sheet or web-like material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • E—FIXED CONSTRUCTIONS
  • E04—BUILDING
  • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
  • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
  • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
• • E—FIXED CONSTRUCTIONS
  • E04—BUILDING
  • E04G—SCAFFOLDING; FORMS; SHUTTERING; BUILDING IMPLEMENTS OR AIDS, OR THEIR USE; HANDLING BUILDING MATERIALS ON THE SITE; REPAIRING, BREAKING-UP OR OTHER WORK ON EXISTING BUILDINGS
  • E04G23/00—Working measures on existing buildings
  • E04G23/02—Repairing, e.g. filling cracks; Restoring; Altering; Enlarging

Definitions

• the present invention relates to a peel-preventing composite sheet, a laminate containing the same, and a method for preventing surface peeling of a structure using the same.
• Patent Literature 1 describes a concrete spalling prevention method characterized by forming a high-strength coating film on a concrete surface.
• Patent Document 2 describes a reinforcing coating method for reinforcing the surface of a concrete structure by forming a coating layer containing a continuous glass fiber sheet.
• the peeling prevention layer formed on the structure is required to have sufficient strength and elongation from the viewpoint of retaining the peeling pieces and facilitating the detection of the peeling when it occurs.
• the peeling prevention layer is also required to have a certain degree of transparency in order to observe deformations, cracks, etc. on the surface of the structure.
• the amount of reinforcing fiber such as glass fiber is increased in order to improve the strength and elongation, the transparency of the anti-peeling layer decreases, making it difficult to see the surface of the structure under the anti-peeling layer. .
• One aspect of the present invention is a peel-preventing composite sheet to be placed on the surface of a structure, comprising a cured adhesive and a glass fiber sheet, wherein the cured body has a tensile modulus of 150 to 2700 MPa. and the glass fiber sheet has a basis weight of 150 to 350 g/m 2 .
• the adhesive may be an epoxy adhesive.
• a composite sheet according to one aspect may include the glass fiber sheet and the cured adhesive with which the glass fiber sheet is impregnated.
• the adhesive may be a two-component adhesive containing a first agent containing an epoxy compound and a second agent containing a curing agent, and the cured product comprises the first agent and the It may be a hardened mixture of the second agent.
• a composite sheet according to one aspect may have a spectral transmittance of 30% or more at 380 to 780 nm.
• Another aspect of the present invention relates to a peel-preventing laminate placed on the surface of a structure, the laminate including an undercoat layer formed of a primer and the composite sheet described above.
• the primer may be a primer having a bending strength of 2 N/mm 2 or more as measured according to the NEXCO test method for crack impregnated materials.
• Yet another aspect of the present invention relates to a method for preventing surface spalling of a structure, which comprises an arrangement step of arranging the composite sheet described above on the surface of the structure.
• the arranging step comprises a coating film forming step of forming a coating film containing the adhesive and the glass fiber sheet on the surface of the structure, and curing the coating film to form a coating film on the surface of the structure. and a sheet forming step on which said composite sheet is formed.
• the method according to one aspect may further comprise a pretreatment step of applying a primer onto the surface of the structure to form an undercoat layer, wherein the disposing step comprises applying the composite sheet described above onto the undercoat layer.
• a pretreatment step of applying a primer onto the surface of the structure to form an undercoat layer wherein the disposing step comprises applying the composite sheet described above onto the undercoat layer.
• the disposing step comprises applying the composite sheet described above onto the undercoat layer.
• the present invention relates to, for example, the following ⁇ 1> to ⁇ 10>.
• ⁇ 1> A peel-preventing composite sheet placed on the surface of a structure, including a cured adhesive and a glass fiber sheet, The cured body has a tensile modulus of 150 to 2700 MPa, The composite sheet, wherein the glass fiber sheet has a basis weight of 150 to 350 g/m 2 .
• ⁇ 2> The composite sheet according to ⁇ 1>, wherein the adhesive is an epoxy adhesive.
• ⁇ 3> The composite sheet according to ⁇ 1> or ⁇ 2>, comprising the glass fiber sheet and the cured adhesive with which the glass fiber sheet is impregnated.
• the adhesive is a two-component adhesive containing a first component containing an epoxy compound and a second component containing a curing agent,
• a peeling prevention laminate disposed on a structure surface A laminate comprising an undercoat layer formed of a primer and the composite sheet according to any one of ⁇ 1> to ⁇ 5>.
• ⁇ 7> The laminate according to ⁇ 6>, wherein the primer has a flexural strength of 2 N/mm 2 or more as measured according to NEXCO test method for impregnated cracking material.
• ⁇ 8> A method for preventing surface spalling of a structure, comprising a placement step of placing the composite sheet according to any one of ⁇ 1> to ⁇ 5> on the surface of the structure.
• the arranging step includes a coating film forming step of forming a coating film containing the adhesive and the glass fiber sheet on the surface of the structure; a sheet forming step of curing the coating film to form the composite sheet on the surface of the structure;
• the method according to ⁇ 8> or ⁇ 9>, wherein the disposing step is a step of disposing the composite sheet according to any one of ⁇ 1> to ⁇ 5> on the undercoat layer.
• a composite sheet capable of forming a peel-preventing layer with excellent strength, stretchability, and base visibility. Further, according to the present invention, there are provided a laminate including the composite sheet, and a method for preventing surface spalling of a structure using the composite sheet.
• the composite sheet of the present embodiment is a peel-preventing composite sheet to be placed on the surface of a structure, and includes a cured adhesive and a glass fiber sheet.
• the cured body has a tensile modulus of 150 to 2700 MPa
• the glass fiber sheet has a basis weight of 150 to 350 g/m 2 .
• the composite sheet of the present embodiment it is possible to form an anti-peeling layer that is excellent in strength, stretchability, and base visibility.
• the composite sheet of the present embodiment has excellent strength because the basis weight of the glass fiber sheet is 150 g/m 2 or more.
• the composite sheet of the present embodiment purposely uses an adhesive with a low tensile modulus of cured body as the adhesive, thereby reducing the propagation of stress and allowing the load to be borne over a large area (that is, the unit circumference Therefore, even if the basis weight of the glass fiber sheet is suppressed to 350 g/m 2 or less, excellent elongation is ensured. Further, in the composite sheet of the present embodiment, since the basis weight of the glass fiber sheet is 350 g/m 2 or less, sufficient base visibility is ensured.
• examples of adhesives include epoxy adhesives, urethane adhesives, silicone adhesives, acrylic adhesives, etc.
• concrete surfaces, undercoat layers, glass Epoxy-based adhesives are preferred from the viewpoint of superior adhesion to fiber sheets and the like.
• the form of the adhesive is not particularly limited, but may be, for example, a two-component adhesive. A preferred embodiment of the two-component adhesive will be described below.
• a two-component adhesive includes a first component containing an epoxy compound and a second component containing a curing agent.
• a two-component adhesive can form a cured product by mixing the first and second components. That is, when a two-part adhesive is used, the cured adhesive can be said to be a cured mixture of the first part and the second part.
• the two-component adhesive is, for example, a two-component adhesive comprising a first agent, a first container containing the first agent, a second agent, and a second container containing the second agent. It may be provided as a kit, and may be provided as a two-component adhesive kit comprising a first agent, a second agent, and a container in which the first agent and the second agent are individually accommodated.
• the two-component adhesive may be a room temperature curing type.
• the first component and the second component are mixed so that the ratio of the epoxy equivalent of the epoxy compound to the active hydrogen equivalent of the curing agent is 1:1.
• the ratio is not limited to this.
• the first agent and the second agent are mixed so that the ratio of the active hydrogen equivalent of the curing agent to the epoxy equivalent of the epoxy compound is 0.5 to 1.5 (preferably 0.8 to 1.2).
• the ratio of the active hydrogen equivalent of the curing agent to the epoxy equivalent of the epoxy compound is, for example, 0.5-1.5, 0.5-1.2, 0.8-1.5, or 0.8-1. can be two.
• Epoxy compounds may be used singly or in combination of two or more.
• Examples of epoxy compounds include compounds having one epoxy group and compounds having two or more epoxy groups.
• the epoxy compound preferably contains at least one compound having two or more epoxy groups.
• the epoxy compound a compound having a glycidyl group as an epoxy group is preferable. That is, the epoxy compound preferably contains a compound having a glycidyl group, and preferably contains a compound having two or more glycidyl groups.
• epoxy compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A bis (polypropylene glycol glycidyl ether) ether, bisphenol A bis (polyethylene glycol glycidyl ether) ether, hydrogenated bisphenol A type epoxy resin, water Bisphenol F type epoxy resin, biphenyl type epoxy resin, urethane-modified epoxy resin, rubber-modified epoxy resin, alkyl glycidyl ether, cresyl glycidyl ether, phenyl glycidyl ether, alkyl diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether and the like.
• a suitable example of the epoxy compound is a compound represented by the following formula (1-1).
• R 11 and R 12 each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 5 carbon atoms, or a substituent.
• the multiple R 11 may be the same or different.
• the multiple R 12 may be the same or different.
• Examples of the substituent that the alkyl group having 1 to 5 carbon atoms in R 11 and R 12 may have include a fluorine atom, an alkoxy group (eg, an alkoxy group having 1 to 5 carbon atoms), and the like. Atoms are preferred.
• substituents that the phenyl group in R 11 and R 12 may have include a fluorine atom, an alkyl group (eg, an alkyl group having 1 to 5 carbon atoms), an alkoxy group (eg, an alkoxy group having 1 to 5 carbon atoms). group) and the like.
• R 11 is preferably a group selected from the group consisting of a hydrogen atom, a methyl group, a phenyl group and a trifluoromethyl group, more preferably a group selected from the group consisting of a hydrogen atom and a methyl group, and further A methyl group is preferred.
• the plurality of R 11 may be the same or different, and are preferably the same.
• R 12 is preferably a group selected from the group consisting of a hydrogen atom, a methyl group, a phenyl group and a trifluoromethyl group, more preferably a group selected from the group consisting of a hydrogen atom and a methyl group, still more preferably is a methyl group.
• the plurality of R 12 may be the same or different, and are preferably the same.
• R 11 and R 12 may be the same or different, and are preferably the same.
• p is preferably 0-30, more preferably 0-20, still more preferably 0-2.
• Another suitable example of the epoxy compound is a compound represented by the following formula (2-1).
• n and m each independently represent an integer of 0 or more (preferably an integer of 1 or more)
• R 1 and R 2 each independently represent a hydrogen atom or a methyl group
• R 3 and Each R 4 independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 5 carbon atoms, or an optionally substituted phenyl group.
• R 1 is preferably a methyl group.
• the multiple R 1s may be the same or different, and are preferably the same.
• R 2 is preferably a methyl group. When a plurality of R 2 are present, the plurality of R 2 may be the same or different, and are preferably the same.
• Examples of the substituent that the alkyl group having 1 to 5 carbon atoms in R 3 and R 4 may have include a fluorine atom, an alkoxy group (eg, an alkoxy group having 1 to 5 carbon atoms), and the like. Atoms are preferred.
• substituents that the phenyl group in R 3 and R 4 may have include a fluorine atom, an alkyl group (eg, an alkyl group having 1 to 5 carbon atoms), an alkoxy group (eg, an alkoxy group having 1 to 5 carbon atoms). group) and the like.
• R 3 is preferably a group selected from the group consisting of a hydrogen atom, a methyl group, a phenyl group and a trifluoromethyl group, more preferably a group selected from the group consisting of a hydrogen atom and a methyl group, and further A methyl group is preferred.
• R 4 is preferably a group selected from the group consisting of a hydrogen atom, a methyl group, a phenyl group and a trifluoromethyl group, more preferably a group selected from the group consisting of a hydrogen atom and a methyl group, still more preferably is a methyl group.
• R 3 and R 4 may be the same or different, and are preferably the same.
• n+m is preferably 2 to 20, more preferably n+m is 2 to 11.
• the curing agent may be any component that can react with the epoxy compound and cure the mixture of the first and second agents.
• the curing agent may be, for example, a compound having two or more reaction points capable of reacting with epoxy groups in the epoxy compound.
• the curing agents may be used singly or in combination of two or more.
• Amine-based curing agents are preferred as curing agents.
• an amine compound having a group selected from the group consisting of primary amino groups and secondary amino groups is preferred.
• a primary amino group possessed by the amine compound is a group represented by —NH 2 .
• the secondary amino group possessed by the amine compound is a group represented by -NH-.
• the amine-based curing agent may be, for example, a compound having one or more primary amino groups, a compound having two or more secondary amino groups, or the like.
• Amine curing agent may be at least one selected from the group consisting of aliphatic amines, alicyclic amines, modified aliphatic polyamines, modified alicyclic amines and polyamidoamines, modified aliphatic polyamines, modified It is preferably at least one selected from the group consisting of alicyclic amines and polyamidoamines.
• the active hydrogen equivalent of the amine-based curing agent may be, for example, 20 or more, preferably 50 or more, more preferably 70 or more. This makes it easier to reduce the amount of elemental nitrogen in the adhesive, and makes it easier to obtain a cured product with a small amount of elemental nitrogen. Also, the active hydrogen equivalent of the amine-based curing agent may be, for example, 200 or less, preferably 150 or less, more preferably 120 or less, and may be 100 or less. This tends to form a denser crosslinked structure and further improve the heat resistance and durability of the cured product.
• the active hydrogen equivalent of the amine curing agent is, for example, 20 to 200, 20 to 150, 20 to 120, 20 to 100, 50 to 200, 50 to 150, 50 to 120, 50 to 100, 70 to 200, 70 ⁇ 150, 70-120, or 70-100.
• the active hydrogen equivalent of the amine-based curing agent indicates the mass (g) of the amine-based curing agent per 1 mol of active hydrogen.
• the amine equivalent of the amine-based curing agent is calculated from the total amount of the amine-based curing agents and the total number of active hydrogens.
• At least one of the first and second agents of the two-part adhesive may contain a filler.
• a filler By blending the filler, the viscosity of the mixture of the first agent and the second agent can be improved, and dripping during coating film formation can be suppressed.
• filler known fillers that are blended in two-component adhesives can be used without any particular restrictions.
• fillers include organic fillers and inorganic fillers.
• the filler may be obtained by subjecting these fillers to surface treatment such as hydrophobic treatment.
• the shape of the filler is not particularly limited, and may be, for example, granular, flaky, fibrous, emulsion, or the like.
• organic fillers include resin particles.
• the resin particles may be solid particles, porous particles, or hollow particles.
• examples of resin particles include (meth)acrylic acid ester particles and polystyrene particles.
• inorganic fillers examples include fumed silica, calcium carbonate, talc, clay, metal oxides, metal hydroxides, and silica.
• the inorganic filler may be these hollow particles, fibrous particles, solid particles, porous particles, or the like.
• an inorganic filler is preferable as the filler.
• inorganic fillers include fumed silica.
• fumed silica fumed silica having a specific surface area of 70 g/m 2 or more (preferably 80 to 400 g/m 2 ) is preferable.
• the said specific surface area means a BET specific surface area.
• the BET specific surface area is a value measured by a gas-phase adsorption method in which gas molecules (nitrogen molecules) having a known occupied area are adsorbed on the surface of the inorganic filler, and the specific surface area is determined from the adsorption amount of the gas molecules.
• hydrophilic silica can be suitably used as the inorganic filler.
• Hydrophilic silica is preferably hydrophilic fumed silica.
• the average particle size of hydrophilic silica may be, for example, 1 nm or more, preferably 5 nm or more, more preferably 7 nm or more, and may be 9 nm or more or 10 nm or more. Also, the average particle size of the hydrophilic silica may be, for example, 15 nm or less, or may be 14 nm or less.
• the average particle size of hydrophilic silica is, for example, 1 to 15 nm, 1 to 14 nm, 5 to 15 nm, 5 to 14 nm, 7 to 15 nm, 7 to 14 nm, 9 to 15 nm, 9 to 14 nm, 10 to 15 nm, or 10 It may be ⁇ 14 nm.
• the hydrophilic silica preferably has a hydrophobicity of 30 or less, more preferably 20 or less, and even more preferably 10 or less in terms of methanol wettability.
• the degree of hydrophobicity refers to the volume fraction of methanol in the methanol-water mixed solution at the time when silica is dispersed in water and methanol is added dropwise so that all of the floating silica sinks.
• the measurement can be performed, for example, by adding 0.2 g of silica to 50 ml of ion-exchanged water and adding dropwise methanol from a burette while stirring with a magnetic stirrer.
• the volume fraction of methanol in the methanol-water mixed solution at the end point at which the floating silica gradually settles down and all of it sinks is the degree of hydrophobicity.
• hydrophilic silica A commercially available product may be used as the hydrophilic silica.
• hydrophilic silica examples include AEROSIL 150, 200, 300, 380 (manufactured by Evonik), RHEOROSIL QS-10, QS-102, CP-102, QS-20, QS-20L, QS-30, QS-40 (manufactured by Tokuyama Corporation), WACKER HDK V15, N20, N20P, T30, T40 (manufactured by Asahi Kasei Wacker Silicone) and the like.
• the content of the filler in the two-component adhesive may be, for example, 0.1% by mass or more, preferably 0, when the total amount of solids in the first and second components is 100% by mass. 0.5% by mass or more, more preferably 1.0% by mass or more, and still more preferably 1.5% by mass or more. Thereby, the thickening effect which suppresses dripping is exhibited more notably.
• the content of the filler in the two-part adhesive may be, for example, 5.5% by mass or less, preferably 5.5% by mass or less, when the total amount of solids in the first and second parts is 100% by mass. is 5.0% by mass or less, more preferably 4.0% by mass or less. This tends to further improve the transparency of the cured body.
• the content of the filler in the two-component adhesive is, for example, 0.1 to 5.5% by mass, 0.1 to 5.5% by mass, when the total amount of solids in the first and second components is 100% by mass.
• At least a part of the first and second agents of the two-part adhesive contains a curing accelerator.
• the curability of the mixture of the first agent and the second agent may be further improved.
• any known curing accelerator can be used without any particular limitation as long as it can accelerate the reaction between the epoxy compound and the curing agent.
• a monophenol compound is preferably used.
• the monophenol compound 4-tert-butylphenol is preferred.
• the content of the curing accelerator in the two-component adhesive may be, for example, 0.1% by mass or more, preferably, when the total amount of solids in the first and second components is 100% by mass. is 0.5% by mass or more, more preferably 1.0% by mass or more. This tends to further improve the curability of the mixture of the first agent and the second agent. Further, the content of the curing accelerator in the two-component adhesive may be, for example, 5.5% by mass or less when the total amount of solids in the first and second components is 100% by mass. , preferably 5.0% by mass or less, more preferably 4.5% by mass or less. This tends to suppress residual non-reactants and improve durability.
• the content of the curing accelerator in the two-component adhesive is, for example, 0.1 to 5.5% by mass when the total amount of solids in the first and second components is 100% by mass, 0.1 to 5.0% by mass, 0.1 to 4.5% by mass, 0.5 to 5.5% by mass, 0.5 to 5.0% by mass, 0.5 to 4.5% by mass, It may be 1.0 to 5.5 wt%, 1.0 to 5.0 wt%, or 1.0 to 4.5 wt%.
• the two-component adhesive may further contain components other than those mentioned above.
• Other components include, for example, curing retarders, light stabilizers, light absorbers, antioxidants, antidegradants, pigments, dyes, silane coupling agents, antifoaming agents, leveling agents, dispersants, and rheology control agents. , wax, solvent, water, and the like. Among these, rheology control agents are preferred.
• the rheology control agent suppresses dripping and improves the workability of the two-component adhesive.
• Amides are preferred as rheology control agents. Amides include higher fatty acid amides, polyamides, oligomers of amides, and the like. Polyaminoamides are preferred as amides.
• the content of the rheology control agent in the two-component adhesive may be, for example, 0.01% by mass or more, preferably, when the total amount of solids in the first and second components is 100% by mass. is 0.05% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more. Thereby, the thickening effect which suppresses dripping is obtained more notably.
• the content of the rheology control agent may be, for example, 7.0% by mass or less, preferably 5.0% by mass or less, when the total amount of solids in the first agent and the second agent is 100% by mass. , more preferably 3.0% by mass or less. This tends to further improve the tensile properties.
• the content of the rheology control agent in the two-component adhesive is, for example, 0.01 to 7.0% by mass when the total amount of solids in the first and second components is 100% by mass. 0.01 to 5.0% by mass, 0.01 to 3.0% by mass, 0.05 to 7.0% by mass, 0.05 to 5.0% by mass, 0.05 to 3.0% by mass, 0.1 to 7.0% by mass, 0.1 to 5.0% by mass, 0.1 to 3.0% by mass, 0.5 to 7.0% by mass, 0.5 to 5.0% by mass, It may be 0.5 to 3.0 wt%, 1.0 to 7.0 wt%, 1.0 to 5.0 wt%, or 1.0 to 3.0 wt%.
• the first agent contains an epoxy compound, may contain a filler as necessary, and may further contain other components as necessary.
• the content of the epoxy compound in the first agent may be, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, It may be 100% by mass.
• the second agent contains an amine-based curing agent, may contain a filler as necessary, and may further contain other components as necessary.
• the content of the amine-based curing agent in the second agent may be, for example, 60% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total solid content of the second agent. Yes, and may be 100% by mass.
• the mixture of the first agent and the second agent is 2000 mPa s or more and 100000 mPa s or less (more preferably 4000 mPa s or more and 50000 mPa s or less, that is, for example, 2000 to 100000 mPa s, 2000 to 50000 mPa s, 4000 to 100000 mPa s, or 4000 to 50000 mPa s) and a viscosity of 2.0 or more (more preferably 3.0 to 8.0, that is, for example, 2.0 or more, 2.0 to It preferably exhibits a thixotropic index of 8.0 or 3.0-8.0).
• the mixture of the first agent and the second agent changes its viscosity and thixotropic index over time due to the reaction between the epoxy compound and the curing agent. That is, the above definition means that the mixture of the first part and the second part exhibits the above viscosity and thixotropic index for a certain period of time after mixing.
• the viscosity of the mixture of the first agent and the second agent indicates the viscosity at 23° C. and 20 rpm as measured by a cone-plate rotary viscometer.
• the thixotropic index indicates the ratio ( V2 / V1) of the viscosity V2 at 23°C and 2 rpm to the viscosity V1 at 23°C and 20 rpm, measured by a cone and plate rotary viscometer.
• the cured adhesive preferably has a spectral transmittance of 30% or more in the visible light region (380 to 780 nm) per 1 mm of thickness.
• the spectral transmittance of the cured product is measured using a UV-VIS-NIR spectrophotometer SolidSpec-3700i manufactured by Shimadzu Corporation. This makes it easier to obtain a peel-preventing layer with better base visibility.
• the cured adhesive has a tensile modulus of 150 MPa or more, preferably 300 MPa or more, more preferably 500 MPa or more, still more preferably 700 MPa or more, and still more preferably 1000 MPa or more. This tends to further improve the heat resistance of the cured product.
• the tensile elastic modulus of the cured adhesive is 2700 MPa or less, preferably 2500 MPa or less, and more preferably 2200 MPa or less.
• the tensile elastic modulus of the cured adhesive is, for example, 150 to 2700 MPa, 150 to 2500 MPa, 150 to 2200 MPa, 300 to 2700 MPa, 300 to 2500 MPa, 300 to 2200 MPa, 500 to 2700 MPa, 500 to 2500 MPa, 500 to 2200 MPa, It may be 700-2700 MPa, 700-2500 MPa, 700-2200 MPa, 1000-2700 MPa, 1000-2500 MPa, or 1000-2200 MPa.
• the tensile strength of the cured adhesive is not particularly limited, and may be, for example, 5 MPa or higher, preferably 10 MPa or higher, and more preferably 20 MPa or higher. This tends to further improve the heat resistance of the cured product.
• the tensile strength of the cured adhesive may be, for example, 80 MPa or less, 60 MPa or less, or 40 MPa or less. That is, the tensile strength of the cured adhesive is, for example, 5 to 80 MPa, 5 to 60 MPa, 5 to 40 MPa, 10 to 80 MPa, 10 to 60 MPa, 10 to 40 MPa, 20 to 80 MPa, 20 to 60 MPa, or 20 to 40 MPa. It's okay.
• the composite sheet of this embodiment includes a glass fiber sheet.
• the composition of the glass constituting the glass fiber sheet is not particularly limited, and may be, for example, E glass, AR glass, S glass, C glass, D glass, ECR glass, or the like.
• the fineness of the glass fiber sheet may be, for example, 50 tex or more, preferably 70 tex or more, more preferably 130 tex or more. This facilitates the formation of openings between fibers, facilitates impregnation of the adhesive, and improves workability during the production of the composite sheet. Further, the fineness of the glass fiber sheet may be, for example, 1500 tex or less, preferably 1000 tex or less, more preferably 500 tex or less. This increases the density of the fibers and improves the handleability.
• the fineness of the glass fiber sheet may be, for example, 50 to 1500 tex, 50 to 1000 tex, 50 to 500 tex, 70 to 1500 tex, 70 to 1000 tex, 70 to 500 tex, 130 to 1500 tex, 130 to 1000 tex, or 130 to 500 tex. .
• an adhesive for example, a mixture of a first agent and a second agent
• a glass fiber sheet for example, a glass fiber sheet is formed, and the coating film is cured. and a curing step.
• the composite sheet of the present embodiment can also be produced by a production method including, for example, an arrangement step of arranging a glass fiber sheet on an adhesive coating, and a curing step of curing the coating. .
• the coating step part or all of the adhesive may be impregnated into the glass fiber sheet.
• the applying step may be a step of applying an adhesive to a glass fiber sheet placed on the surface of the structure.
• the coating amount of the adhesive may be, for example, 200 g/m 2 or more, preferably 400 g/m 2 or more, and more preferably 500 g/m 2 or more. Also, the coating amount of the adhesive may be, for example, 1500 g/m 2 or less, preferably 1000 g/m 2 or less, more preferably 700 g/m 2 or less. This makes it easier to obtain a composite sheet in which the content of the cured adhesive is within the preferred range described below.
• the coating amount of the adhesive is, for example, 200 to 1500 g/m 2 , 200 to 1000 g/m 2 , 200 to 700 g/m 2 , 400 to 1500 g/m 2 , 400 to 1000 g/m 2 , 400 to 700 g/m 2 , 500-1500 g/m 2 , 500-1000 g/m 2 , or 500-700 g/m 2 .
• the placement step part or all of the adhesive may be impregnated into the glass fiber sheet.
• the placement step may be a step of placing a glass fiber sheet on the adhesive coating formed on the surface of the structure.
• the curing step may be, for example, a step of curing the coating film of the adhesive by heating.
• the heating temperature may be appropriately set according to the types of adhesive and curing agent.
• the glass fiber sheet has a basis weight of 150 g/m 2 or more, preferably 170 g/m 2 or more, and more preferably 200 g/m 2 or more. This makes it easier to obtain a peel-preventing layer that is more excellent in strength and elongation.
• the basis weight of the glass fiber sheet is 350 g/m 2 or less, preferably 300 g/m 2 or less, more preferably 250 g/m 2 or less. This makes it easier to obtain a peel-preventing layer with better base visibility.
• the basis weight of the glass fiber sheet is, for example, 150 to 350 g/m 2 , 150 to 300 g/m 2 , 150 to 250 g/m 2 , 170 to 350 g/m 2 , 170 to 300 g/m 2 , 170 to 250 g/m 2 , 200-350 g/m 2 , 200-300 g/m 2 , or 200-250 g/m 2 .
• the content of the cured adhesive may be, for example, 200 g/m 2 or more, preferably 400 g/m 2 or more, and more preferably 500 g/m 2 or more.
• the content of the cured adhesive may be, for example, 1500 g/m 2 or less, preferably 1000 g/m 2 or less, more preferably 700 g/m 2 or less. This tends to reduce the amount of harmful components generated when the cured body is burned.
• the content of the cured adhesive is, for example, 200 to 1500 g/m 2 , 200 to 1000 g/m 2 , 200 to 700 g/m 2 , 400 to 1500 g/m 2 , 400 to 1000 g/m 2 , 400 to 1000 g/m 2 . It may be 700 g/m 2 , 500-1500 g/m 2 , 500-1000 g/m 2 , or 500-700 g/m 2 .
• the thickness of the composite sheet is not particularly limited, it may be, for example, 0.25 mm or more, preferably 0.4 mm or more, and more preferably 0.5 mm or more.
• the thickness of the composite sheet may be, for example, 1.6 mm or less, preferably 1.2 mm or less, and more preferably 0.8 mm or less. That is, the thickness of the composite sheet is, for example, 0.25 to 1.6 mm, 0.25 to 1.2 mm, 0.25 to 0.8 mm, 0.4 to 1.6 mm, 0.4 to 1.2 mm. , 0.4-0.8 mm, 0.5-1.6 mm, 0.5-1.2 mm, or 0.5-0.8 mm.
• the spectral transmittance of the composite sheet of the present embodiment in the visible light region is, for example, 30% or more, preferably 40% or more, more preferably 50% or more, and still more preferably 60% or more. Preferably it is 70% or more. This makes it easier to obtain a peel-preventing layer with better base visibility.
• the spectral transmittance of the composite sheet is measured using a UV-VIS-NIR spectrophotometer SolidSpec-3700i manufactured by Shimadzu Corporation.
• the composite sheet of this embodiment is placed on the surface of the structure in order to prevent concrete pieces and the like from falling off the surface of the structure.
• a layer other than the composite sheet may be further formed on the surface of the structure. That is, a laminate of the composite sheet and other layers may be formed on the surface of the structure.
• laminates examples include laminates containing an undercoat layer formed from a primer and a composite sheet.
• the primer may be, for example, a primer having a flexural strength of 2 N/mm 2 or more, measured according to the NEXCO test method for cracked impregnated materials.
• the viscosity of the primer is not particularly limited, it may be, for example, 100 mPa ⁇ s or more, preferably 200 mPa ⁇ s or more, more preferably 400 mPa ⁇ s or more. As a result, absorption into the substrate is prevented, and there is a tendency to facilitate coating film formation. Also, the viscosity of the primer may be, for example, 4000 mPa ⁇ s or less, preferably 2000 mPa ⁇ s or less, and more preferably 1000 mPa ⁇ s or less. This tends to further improve the impregnation of cracks on the surface of the structure.
• the viscosity of the primer is, for example, 100 to 4000 mPa s, 100 to 2000 mPa s, 100 to 1000 mPa s, 200 to 4000 mPa s, 200 to 2000 mPa s, 200 to 1000 mPa s, 400 to 4000 mPa s, It may be from 400 to 2000 mPa ⁇ s, or from 400 to 1000 mPa ⁇ s.
• primers examples include epoxy primers, urethane primers, and acrylic primers.
• an epoxy primer is preferable from the viewpoint of excellent adhesion to the surface of the structure.
• a layer formed of an impregnated reinforcing material, a cross-section repairing agent, an unevenness adjusting material, or the like may be further formed on the surface of the structure. That is, the laminate may further include a layer formed of an impregnated reinforcing material, a cross-section repairing agent, an unevenness adjusting material, or the like.
• the anti-peeling layer may be, for example, a layer made of the laminate.
• a method of preventing surface spalling of a structure may comprise a placement step of placing the composite sheet described above on the surface of the structure.
• the placement step includes a coating film forming step of forming a coating film containing an adhesive and a glass fiber sheet on the surface of the structure, and curing the coating film to form a composite sheet on the surface of the structure. and a sheet forming step.
• the coating film forming step may be, for example, a step of placing a glass fiber sheet on the surface of the structure and applying an adhesive to the glass fiber sheet to form a coating film.
• the coating film forming step may be a step of applying an adhesive on the surface of the structure and placing a glass fiber sheet on the applied adhesive to form a coating film.
• the above method may further comprise a pretreatment step of applying a primer onto the surface of the structure to form an undercoat layer.
• the coating film forming step may be a step of forming a coating film on the undercoat layer.
• the above method may further comprise a top coating step of forming a top coating layer on the composite sheet.
• a top coating layer any overcoat layer used for a known anti-peeling layer can be used without particular limitation.
• the overcoat layer may be, for example, a protective coating, a topcoat layer, or the like.
• the surface of the structure is not particularly limited, but a concrete surface or a mortar surface is preferable from the viewpoint of obtaining a remarkable effect of preventing the material from peeling off.
• ADEKA RESIN EP-4100 an epoxy compound having the structure of formula (1-1) (manufactured by ADEKA CORPORATION, epoxy equivalent 190, R 11 and R 12 are methyl groups) - ADEKA RESIN EP-4005 (EP4005 in the table): an epoxy compound having a structure of formula (2-2) (manufactured by ADEKA CORPORATION, epoxy equivalent 510) - ADEKA RESIN EP-4000 (“EP4000" in the table): an epoxy compound having the structure of formula (2-2) (manufactured by ADEKA CORPORATION, epoxy equivalent: 320) ⁇ SY-OCG: ortho cresyl glycidyl ether (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., epoxy equivalent 180) [In the formula, n and m each independently represent an integer of 1 or more. ]
• ⁇ Filler> ⁇ AEROSIL 200 (AS200 in the table): hydrophilic fumed silica (primary particle diameter 12 nm, BET specific surface area 200 g/m 2 , degree of hydrophobicity 0%, manufactured by Evonik)
• BYK R607 polyaminoamide (rheology control agent (RC agent in the table), manufactured by BYK Chemie Co., Ltd.)
• U-shaped lid The center part of the upper lid type U-shaped side ditch (lid) specified in JISA5372 Annex E (400 x 600 x 60 mm) (hereinafter referred to as "U-shaped lid”) is ⁇ 100 mm in shape with a core drill for concrete. I pulled it out. Coring was performed at a depth of 55 ⁇ 3.0 mm from the surface opposite to the construction surface. In a 23 ° C environment, the construction surface is cleaned with a disc sander, after degreasing, the specified amount of the first agent and the second agent of the primer are weighed, mixed, and the prescribed application amount (0.15 kg / m 2 ) and cured for 1 day.
• the first agent and second agent of the adhesive are weighed in specified amounts, mixed, applied with a predetermined coating amount (0.60 kg / m 2 ) using a rubber spatula, immediately pasted with a fiber sheet, After impregnating with a roller and leveling the surface with a rubber spatula, curing was performed for 7 days. After curing, according to JSCE-K533, a load was applied to the center of the core at 1 mm/min, and after the core was broken, a load was applied at 5 mm/min, and the maximum load and the displacement at that time were measured.
• a crack scale simulating a crack with a width of 0.5 mm was pasted on mortar (70 ⁇ 150 ⁇ 10 mm) prepared according to JISR5201. Then, the first agent and the second agent of the primer were weighed in prescribed amounts, mixed, applied with a roller in a prescribed coating amount (0.15 kg/m 2 ), and cured for 1 day. After curing, the first agent and second agent of the adhesive are weighed in specified amounts, mixed, applied with a predetermined coating amount (0.60 kg / m 2 ) using a rubber spatula, immediately pasted with a fiber sheet, After impregnating with a roller and leveling the surface with a rubber spatula, curing was performed for 7 days. After curing, it was visually evaluated whether cracks in the crack scale were visible. A was given when it was visible, and B was given when it was not visible.
• Example 1 An adhesive composition was obtained by mixing the first agent and the second agent having the composition shown in Table 1. A tensile test was performed on the cured product of the obtained adhesive composition by the method described above. Next, using the glass fiber sheets shown in Table 1, composite sheets were produced and evaluated by the above method. Table 1 shows the results.
• Examples 2-12, Comparative Examples 1-2 An adhesive composition was prepared in the same manner as in Example 1, except that the compositions of the first agent and the second agent were changed as shown in Table 1, Table 2, or Table 3. did the test. Next, the composite sheet was prepared and evaluated in the same manner as in Example 1 except that the obtained adhesive composition was used and the glass fiber sheet and the primer shown in Table 1, Table 2 or Table 3 were used. did The results are shown in Table 1, Table 2 or Table 3.

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