WO2015159733A1 - 粘接着シートを用いた構造物の補修ないし補強方法、粘接着シートを用いて補修ないし補強された構造物を製造する方法、粘接着シート - Google Patents
粘接着シートを用いた構造物の補修ないし補強方法、粘接着シートを用いて補修ないし補強された構造物を製造する方法、粘接着シート Download PDFInfo
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- WO2015159733A1 WO2015159733A1 PCT/JP2015/060577 JP2015060577W WO2015159733A1 WO 2015159733 A1 WO2015159733 A1 WO 2015159733A1 JP 2015060577 W JP2015060577 W JP 2015060577W WO 2015159733 A1 WO2015159733 A1 WO 2015159733A1
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- adhesive layer
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- adhesive sheet
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- adhesive
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- UQYZZNBWUWLGRX-OUKQBFOZSA-N CCCCC(CC)COc1c(CC)cc(/C=C/C(N2CCCCC2)=O)c(O)c1 Chemical compound CCCCC(CC)COc1c(CC)cc(/C=C/C(N2CCCCC2)=O)c(O)c1 UQYZZNBWUWLGRX-OUKQBFOZSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
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- 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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
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- 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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
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- 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
- B29C73/00—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D
- B29C73/04—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D using preformed elements
- B29C73/10—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D using preformed elements using patches sealing on the surface of the article
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
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- 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
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- 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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0833—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using actinic light
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- 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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
- B29C2035/0872—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation using ion-radiation, e.g. alpha-rays
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0097—Glues or adhesives, e.g. hot melts or thermofusible adhesives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
- B29K2105/0809—Fabrics
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/776—Walls, e.g. building panels
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2453/00—Presence of block copolymer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2463/00—Presence of epoxy resin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2463/00—Presence of epoxy resin
- C09J2463/008—Presence of epoxy resin in the pretreated surface to be joined
Definitions
- the present invention relates to a method for repairing or reinforcing a structure using an adhesive sheet, a method for producing a structure repaired or reinforced using an adhesive sheet, and an adhesive sheet used for them.
- repair / reinforcement is an immediate task, particularly from the viewpoint of safety.
- infrastructure development such as the need for many expenses including labor costs.
- concrete repair or reinforcement is usually applied to parts that require repair and reinforcement. It is performed by applying adhesives or paints several times, or by adhering sheets for repair or reinforcement.
- the repair / reinforcement sheet prevents concrete deterioration factors such as water, oxygen, carbon dioxide, or chloride ions from entering the concrete and reinforces concrete that has deteriorated and has decreased strength.
- Various techniques for repairing or reinforcing concrete have been proposed.
- Patent Document 1 discloses an intermediate layer having a resin film and a surface layer made of a fabric material laminated on both sides with an adhesive resin.
- the construction time can be shortened without waiting for the construction adhesive to harden and applying the paint.
- the above technique has a problem in that workability is poor because a construction adhesive is applied to concrete or a concrete repair sheet during concrete repair work. Moreover, since the application amount of the construction adhesive cannot be made constant, there is a problem that the reproducibility of the repair work is lowered.
- Patent Document 2 adheres a protective layer and an adhesive coating layer to the adhesive surface of the adhesive coating layer to a concrete structure, or a hot-melt adhesive.
- a technique relating to a sheet for repairing, reinforcing, and preventing deterioration of a concrete structure in which an adhesive layer is formed has been proposed. According to this technology, this repair, reinforcement, and deterioration prevention sheet is affixed to parts that need repair on-site, thereby reducing, shortening, and improving the quality of repair and reinforcement work to prevent concrete peeling. It is possible to stabilize.
- the adhesive layer is a pressure-sensitive adhesive or a hot-melt adhesive
- the above-described technique has a problem that the adhesiveness is insufficient when the adhesive layer is a pressure-sensitive adhesive, for example.
- the adhesive layer is a hot melt adhesive
- the adhesive softens due to the heating during bonding. Therefore, if the concrete surface is a vertical surface or a ceiling surface, the sheet is adhered to the concrete surface. There is a problem that it is difficult.
- Patent Document 3 describes a method for repairing a concrete structure using a photocurable fiber reinforced resin (also referred to as FRP) sheet.
- FRP photocurable fiber reinforced resin
- JP 2010-144360 A Japanese Patent Laid-Open No. 2004-27718 JP 2009-052396 A International Publication No. 2014/007341 Pamphlet
- Patent Document 3 The concrete repair method described in Patent Document 3 is capable of immediate repair / repair of concrete, so it is effective when the repair location is specified, but the photocurable FRP sheet has initial adhesiveness. Therefore, it was necessary to repeat the sticking and curing of the sheet, and it was not suitable for repairing / reinforcing a wide range of concrete structures as a whole.
- the method proposed in Patent Document 4 is to repair and reinforce concrete by sticking a fiber reinforced sheet to an adhesive sheet. Since the fiber reinforced sheet is bonded to the sheet surface, the adhesive sheet does not directly touch the outside air. However, if the adhesive sheet is cured under conditions where it is exposed to the outside air, depending on the curing agent or curing catalyst used in the adhesive sheet, curing may be inhibited by oxygen in the air. The sheet sometimes did not harden. Moreover, by providing a release sheet or the like on the surface of the adhesive layer and preventing the direct contact with the outside air while the adhesive layer is cured, inhibition of curing can be suppressed. Since it is necessary to remove the release sheet after curing, there is also a problem that it takes a long time to complete the construction if it takes a long time for curing.
- an adjuvant is applied to the concrete surface.
- an adhesion aid mainly composed of an epoxyamine polymer is used for primer treatment, but depending on the curing agent or curing catalyst used for the adhesive sheet, the adhesion aid may be deteriorated. It was.
- the problem of the present invention is that even when the adhesive sheet is cured by ionizing radiation such as sunlight, the work load is small and the adhesion between the structure and the adhesive sheet is firmly maintained. It is to provide a method for repairing or reinforcing a possible structure.
- the present inventors have performed repair and reinforcement of a structure using an adhesive sheet containing a curable resin composition whose curing is accelerated by irradiation with ionizing radiation. Furthermore, it was found that by using a curing aid that generates a basic substance upon irradiation with ionizing radiation, inhibition of curing due to oxygen in the outside air can be suppressed.
- the present inventors can adhere to a primer treatment using an adhesive sheet containing a curing aid as described above, even when an adhesion aid mainly composed of an epoxyamine polymer is used for primer treatment. It was found that the adhesion between the structure and the adhesive sheet can be maintained firmly without deteriorating the auxiliary agent.
- the present invention has been made based on such knowledge.
- the structure repair or reinforcement method according to the first embodiment of the present invention is a structure repair or reinforcement method using an adhesive sheet having an adhesive layer, A step of preparing an adhesive sheet having an adhesive layer comprising at least a curable resin composition whose curing is accelerated by irradiation of ionizing radiation and a curing aid that generates a basic substance by irradiation of ionizing radiation When, Bonding the adhesive sheet to the surface of the structure; A step of curing the adhesive layer with the adhesive layer of the adhesive sheet exposed; and It is characterized by comprising.
- the structure repair or reinforcement method according to the second embodiment of the present invention is the structure repair or reinforcement method according to the first embodiment of the present invention.
- the adhesive sheet before being bonded to the surface of the structure has a release sheet provided on at least one side of the adhesive layer, After laminating the adhesive sheet to the surface of the structure, comprising the step of peeling the release sheet from the adhesive sheet, After peeling off the release sheet from the pressure-sensitive adhesive sheet, the adhesive layer of the pressure-sensitive adhesive sheet is cured.
- the method further includes a fifth step of performing primer treatment on the surface of the structure before the adhesive sheet is bonded to the surface of the structure.
- the primer treatment may be performed by applying a primer containing an epoxy resin and a polyamine curing agent to the structure surface.
- the repair or reinforcement method for a structure according to the third embodiment of the present invention is a repair or reinforcement method for a structure using an adhesive sheet provided with an adhesive layer, Applying a primer containing an epoxy resin and a polyamine curing agent to the surface of the structure, and performing a primer treatment;
- An adhesive layer comprising at least a curable resin composition whose curing is accelerated by irradiation with ionizing radiation and a curing auxiliary agent that generates a basic substance upon irradiation with ionizing radiation on the surface of the primer-treated structure. Bonding the adhesive layer of the adhesive sheet with Curing the adhesive layer; It is characterized by comprising.
- the adhesive layer before the adhesive layer is cured, it may further include a step of bonding a repair or reinforcing member on the adhesive layer.
- the adhesive layer may include a repair or reinforcing member containing a fiber material.
- the curable resin composition may include a curable compound having at least two epoxy groups in the molecule.
- the curing time of the adhesive layer may be at least 1 day.
- the adhesive layer may be cured by irradiation with sunlight.
- an adhesive sheet used for repairing or reinforcing a structure is also provided.
- seat provided with the adhesive layer is also provided.
- One way is A step of preparing an adhesive sheet having an adhesive layer comprising at least a curable resin composition whose curing is accelerated by irradiation of ionizing radiation and a curing aid that generates a basic substance by irradiation of ionizing radiation When, Bonding the adhesive sheet to the surface of the structure; A step of curing the adhesive layer with the adhesive layer of the adhesive sheet exposed; and It is characterized by comprising.
- Another way is Applying a primer containing an epoxy resin and a polyamine curing agent to the surface of the structure, and performing a primer treatment;
- An adhesive layer comprising at least a curable resin composition whose curing is accelerated by irradiation with ionizing radiation and a curing auxiliary agent that generates a basic substance upon irradiation with ionizing radiation on the surface of the primer-treated structure. Bonding the adhesive layer of the adhesive sheet with Curing the adhesive layer; It is characterized by comprising.
- the repair or reinforcement method of the structure of the present invention even when the adhesive sheet is cured by ionizing radiation such as sunlight, it is necessary to prevent the inhibition of curing of the adhesive layer by a release sheet or the like. Therefore, the work burden can be reduced even if curing takes time. Moreover, even if it is a case where a primer process is given to a structure using an epoxyamine-type polymer, adhesiveness with an adhesive sheet
- FIG. 1 is a schematic cross-sectional view of an embodiment of an adhesive sheet used in a method for repairing or reinforcing a structure according to the present invention.
- the typical sectional view of another embodiment of the adhesive sheet used for the repair or reinforcement method of the structure by the present invention The typical sectional view of another embodiment of the adhesive sheet used for the repair or reinforcement method of the structure by the present invention.
- the structure repair or reinforcement method according to the first embodiment of the present invention includes: 1) a curable resin composition whose curing is accelerated by irradiation with ionizing radiation, and a curing aid that generates a basic substance by irradiation with ionizing radiation.
- the adhesive sheet used in the structure repair or reinforcement method according to the second embodiment of the present invention includes an adhesive layer and a release sheet provided on at least one side of the adhesive layer.
- the second embodiment of the present invention includes a step of peeling the release sheet from the adhesive sheet after the adhesive sheet is bonded to the surface of the structure.
- each step will be described.
- the adhesive sheet used in the structure repair or reinforcement method according to the first embodiment of the present invention includes an adhesive layer that can be cured by irradiation with ionizing radiation such as sunlight, and is adhesive.
- the layer includes at least a curable resin composition whose curing is accelerated by irradiation with ionizing radiation and a curing aid that generates a basic substance by irradiation with ionizing radiation.
- ionizing radiation means not only electromagnetic waves having wavelengths in the visible and non-visible regions, but also particle beams such as electron beams, and radiation that collectively refers to electromagnetic waves and particle beams. Specifically, microwaves, infrared rays, visible rays, ultraviolet rays, X-rays, ⁇ rays and the like can be mentioned.
- Examples of the curable resin composition whose curing is accelerated by irradiation with ionizing radiation constituting the adhesive layer include conventionally known ionizing radiation curable resins. In the present invention, at least two in the molecule.
- a curable compound having an epoxy group can be preferably used. Examples of such compounds include ionizing radiation curable epoxy resins.
- Various types of ionizing radiation curable epoxy resins can be used without limitation, but they cure when exposed to external light such as sunlight, but are adhesively bonded to structures as described later. It is preferable that the curable resin composition does not harden even when exposed to external light during the step of bonding the sheets. Therefore, in the present invention, it is preferable to use a curable resin composition containing a liquid ionizing radiation curable epoxy resin.
- the liquid epoxy resin is not particularly limited as long as it is a liquid epoxy resin at room temperature, and various epoxy resins can be used.
- various epoxy resins can be used.
- the liquid epoxy resin acts to impart a practical adhesive strength and a high adhesive strength to the adhesive layer. Therefore, even if the location where the structure is to be repaired / reinforced is a vertical surface or a ceiling surface, the adhesive work sheet can be bonded and temporarily fixed to the structure, thus facilitating construction work. Moreover, since an adhesive layer can be hardened slowly over time, the ultraviolet irradiation apparatus etc. for hardening an adhesive sheet in a short time are not required.
- bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin can improve mechanical strength, curability, heat resistance, adhesiveness, etc., and are preferably used. Can do.
- a bisphenol A type epoxy resin can be preferably used.
- those containing 1 or more and 3 or less of the bisphenol skeleton of the main chain are preferably used because they are liquid at room temperature.
- the liquid epoxy resin preferably has a mass average molecular weight (Mw) of 300 or more and 2000 or less. Liquid epoxy resins within this range have good compatibility with acrylic resins and can be preferably used. Further, the epoxy equivalent (g / eq.) Of the liquid epoxy resin is preferably 100 or more and less than 800. A liquid epoxy resin having an epoxy equivalent within this range can impart high durability to the cured adhesive layer. In addition, an epoxy equivalent is the gram number of resin containing the epoxy group of 1 gram equivalent measured by the method based on JISK7236.
- a solid epoxy resin may be included in addition to the liquid epoxy resin.
- a solid epoxy resin if it is a solid epoxy resin at normal temperature, it will not specifically limit, Various epoxy resins can be used.
- bisphenol A type epoxy resin bisphenol F type epoxy resin, orthocresol novolac type epoxy resin, phenol novolac type epoxy resin, modified phenol type epoxy resin, naphthalene type epoxy resin, triphenolmethane type epoxy resin, alkyl modified triphenolmethane Type epoxy resin, triazine nucleus-containing epoxy resin, dicyclopentadiene type epoxy resin, glycidylamine type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, hydrogenated bisphenol A type epoxy resin, aliphatic type epoxy resin, stilbene type One type or two or more types selected from an epoxy resin and a bisphenol A novolak type epoxy resin can be used.
- bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin can be more preferably used from the viewpoints of mechanical strength, curability, heat resistance, adhesiveness, and the like. Resins can be particularly preferably used.
- a bisphenol A type epoxy resin those having a main chain bisphenol skeleton of 2 or more and 10 or less are usually solid at room temperature.
- the solid epoxy resin preferably has a mass average molecular weight (Mw) of 300 or more and 8000 or less. Solid epoxy resins within this range have good compatibility with acrylic resins and can be preferably used. A more preferable range of the mass average molecular weight is 800 or more and 6000 or less, and high adhesive force and high durability can be imparted to the adhesive layer 2.
- the epoxy equivalent (g / eq.) Of the solid epoxy resin is preferably 100 or more and 5200 or less.
- the compounding quantity of an epoxy resin is 20 mass% or more and 90 mass% with respect to the total amount of the resin composition and hardening adjuvant which comprise an adhesive bond layer, 25 mass% or more and 85 mass% or less. It is more preferable that By making the compounding quantity of an epoxy resin into this range, the adhesive force suitable for practical use and high adhesive force can be provided to an adhesive layer. When there is too little content of an epoxy resin, the cohesive force of an adhesive layer will become low, and after hardening an adhesive layer, the adhesiveness of a structure and an adhesive layer may fall.
- compositions other than the above-described epoxy resin may be included in the curable resin composition constituting the adhesive layer, and in consideration of film-forming properties when forming the adhesive layer, acrylic System resin may be contained. Moreover, since the density
- acrylic resin the components used in conventionally known acrylic adhesives can be used without limitation.
- an acrylate ester copolymer having a monomer component of a compound having a polar group such as an epoxy group, amino group, hydroxyl group, carboxyl group or nitrile group as a functional group is preferable.
- This acrylate copolymer can further improve the adhesive force with a structure such as concrete.
- Specific examples include an ethyl acrylate-butyl acrylate-acrylonitrile copolymer, an ethyl acrylate-acrylonitrile copolymer, and a butyl acrylate-acrylonitrile copolymer.
- “acrylic acid” such as methyl acrylate and ethyl acrylate includes “methacrylic acid” such as methyl methacrylate and ethyl methacrylate.
- a block copolymer can be preferably exemplified, and among them, a methacrylate-acrylate-methacrylate block copolymer can be preferably exemplified.
- the block copolymer is preferably used from the viewpoint of imparting practical adhesive strength to concrete and improving the heat resistance of the adhesive layer 2.
- the methacrylate constituting the triblock copolymer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, and benzylid methacrylate. be able to.
- Examples of the acrylate constituting the triblock copolymer include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, and benzylid acrylate. Can be mentioned.
- Specific examples of the methacrylate-acrylate-methacrylate block copolymer include, for example, a methyl methacrylate-butyl acrylate-methyl methacrylate block copolymer.
- the acrylic resin preferably has a mass average molecular weight (Mw) in the range of 10,000 to 1,500,000, and more preferably in the range of 50,000 to 1,200,000.
- Mw mass average molecular weight
- the mass average molecular weight is a value in terms of polystyrene when measured by gel permeation chromatography (GPC).
- the content of the acrylic resin is preferably 4% by mass or more and 50% by mass or less with respect to the total amount of the acrylic resin, the liquid epoxy resin, and the solid epoxy resin. By setting the content within this range, it is possible to impart an adhesive force and high adhesive force suitable for practical use to the adhesive layer. Although depending on the content of the liquid epoxy resin, when the content of the acrylic resin is less than 4% by mass, the adhesive strength of the adhesive layer may be low. Moreover, the film-forming property at the time of forming an adhesive layer may fall. On the other hand, when content of acrylic resin exceeds 50 mass%, the adhesive force of the adhesive layer after hardening may fall. The more preferable content of the acrylic resin in the curable resin composition constituting the adhesive layer is 5% by mass or more and 34% by mass or less.
- stimulated by irradiation of ionizing radiation it is set as the adhesive sheet whose adhesive force of an adhesive layer is about 0.02N or more and 50N or less. Can do.
- the curable resin composition constituting the adhesive layer contains a compound that generates a basic substance upon irradiation with ionizing radiation as a curing aid for curing the ionizing radiation curable resin such as the epoxy resin described above. It is.
- a curing reaction proceeds by the action of a chemical species that releases a polymerization initiating substance upon irradiation with ionizing radiation.
- chemical species those that generate photo radicals, those that generate acidic substances, and those that generate basic substances by irradiation with ionizing radiation are known.
- a primer treatment for improving the adhesion between the structure and the adhesive sheet may be performed, but when using an epoxyamine polymer or the like as an adhesion aid used for this primer treatment, when a chemical species that generates an acidic substance by irradiation with ionizing radiation is used as a curing aid, the acidic substance may deteriorate the adhesion aid, and the adhesion between the structure and the adhesive sheet may be hindered. is there. In addition, since the chemical species that generate such an acidic substance corrodes the metal, it becomes impossible to repair or reinforce the portion where the metal is contained in the structure.
- an ionizing radiation curable resin can be cured without being affected by outside air by using a chemical species that generates a basic substance upon irradiation with ionizing radiation as a curing aid. Since it is no longer necessary to provide a release sheet to prevent the layer from being exposed to the outside air, the work burden is required even if it takes time to cure the adhesive layer, such as curing with ionizing radiation such as sunlight. Can be reduced. Moreover, even if it is a case where a primer process is given to a structure using an epoxyamine-type polymer, adhesiveness with an adhesive sheet
- aliphatic amines are formed by irradiation with ionizing radiation.
- a compound to be generated can be preferably used. Since the solubility is higher than that of a base generating compound that generates an aromatic amine and the concentration of the base generating compound can be relatively increased, the thermosetting property can be enhanced even at a low temperature.
- a base generating compound represented by the following general formula (I) can be preferably used.
- R 1 and R 2 each independently represent hydrogen or a linear or branched hydrocarbon group that may contain a substituent or an unsaturated bond, but R 1 and R 2 At least one of these is the hydrocarbon group, R 1 and R 2 may be bonded to form a cyclic structure; R 3 and R 4 each independently represent hydrogen or a monovalent substituent, R 5 to R 8 each independently represents hydrogen or a monovalent substituent, but two or more of R 5 to R 8 may be bonded to form a cyclic structure; R 9 represents a protecting group that can be deprotected by heating and / or irradiation with ionizing radiation. )
- the above-mentioned base generating compound does not show activity under normal conditions of normal temperature and pressure, but when exposed to ionizing radiation as an external stimulus, a (—CH ⁇ CH—C ( ⁇ O) —) moiety in the chemical formula Is isomerized to a cis form and further cyclized by heating to produce the base amine (NHR 1 R 2 ).
- a (—CH ⁇ CH—C ( ⁇ O) —) moiety in the chemical formula Is isomerized to a cis form and further cyclized by heating to produce the base amine (NHR 1 R 2 ).
- an amine is gradually generated by irradiation with ionizing radiation, so that the curing reaction of the ionizing radiation curable resin proceeds relatively slowly. Therefore, it also functions as a delayed curing means.
- R ⁇ 1 > and R ⁇ 2 > is a hydrocarbon group which may have an independent hydrogen or a monovalent substituent, and may also contain an unsaturated bond.
- R 1 and R 2 are monovalent substituents, the sensitivity of isomerization is improved, and the generated base becomes a secondary amine, so that the basicity becomes stronger than the primary amine, Even if the heating temperature is low, the catalytic activity is increased. In this respect, it is preferable that both R 1 and R 2 are monovalent substituents.
- R 1 and R 2 when at least one of R 1 and R 2 is a methyl group which may be substituted with a halogen atom, the steric size around the amide bond becomes small, and the photoisomerization reaction easily proceeds. Therefore, the sensitivity of isomerization is increased. Further, since the steric bulk of the generated basic substance is reduced, the generated amine is likely to react with a compound having a mercapto group, and as a result, the catalytic activity is improved. In this respect, it is more preferable that at least one of R 1 and R 2 is a methyl group which may be substituted with a halogen atom.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, etc., among which a fluorine atom or chlorine having a smaller atomic radius It is preferably an atom from the viewpoint of improving the catalytic activity, and the number of halogen atoms to be substituted is preferably smaller from the viewpoint of improving the catalytic activity, preferably 2 or less, and more preferably 1 or less. Is preferred.
- a methyl group that may be substituted with a halogen atom is preferably a methyl group from the viewpoint of improving catalytic activity.
- R 1 and R 2 are bonded to form a cyclic structure containing a nitrogen atom, the conjugated chain around the carbon-carbon double bond is easily expanded, and the sensitivity of isomerization is increased.
- the generated amine easily reacts with a compound having a mercapto group, the catalytic activity is improved.
- R 1 and R 2 are bonded to form a cyclic structure containing a nitrogen atom.
- the cyclic structure containing a nitrogen atom formed by combining R 1 and R 2 is a 5- to 7-membered ring from the viewpoint of increasing the sensitivity of isomerization.
- the hydrocarbon group may contain an unsaturated bond, and examples thereof include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. These hydrocarbon groups may contain a substituent in the hydrocarbon group, and even if they are linear or linear including a branched chain, they are bonded to form a cyclic structure. You may do it.
- the branched chain refers to a structure having a branched hydrocarbon group, and also refers to each branched hydrocarbon group included in the structure.
- a hydrocarbon group containing a substituent may be bonded to form a heterocyclic ring.
- the hydrocarbon group that may contain a substituent may be formed by bonding two or more branched chains contained in the hydrocarbon group to form a cyclic structure, and two or more branched chains containing a substituent are bonded. And a heterocycle containing a heteroatom may be formed.
- the cyclic structure is a combination of two or more selected from the group consisting of saturated or unsaturated alicyclic hydrocarbons, condensed rings, and heterocyclic rings, and the alicyclic hydrocarbons, condensed rings, and heterocyclic rings. The structure which becomes may be sufficient.
- the cyclic structure in this paragraph represents a cyclic structure in R 1 or R 2 such as, for example, R 1 is a cyclohexyl group, and is formed by combining R 1 and R 2 described above. It differs from a cyclic structure containing a nitrogen atom.
- hydrocarbon group examples include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group.
- these hydrocarbon groups include alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl and propyl groups, alkenyl groups having 1 to 20 carbon atoms such as vinyl and allyl groups, ethynyl groups, An alkynyl group having 1 to 20 carbon atoms such as a 2-propynyl group, a phenyl group, a naphthyl group, a biphenyl group, a tolyl group, a xylyl group and a fluorenyl group, an aryl group having 6 to 20 carbon atoms, a benzyl group, a phenethyl group, It has 4 to 23 carbon atoms such as aralkyl group having 7 to 20 carbon atoms such as 3-phenylpropyl group,
- the substituent means an atom or atomic group other than hydrogen that can be replaced with a hydrogen atom.
- the substituent is not particularly limited as long as it is an atom or atomic group other than hydrogen that can be replaced with a hydrogen atom, and examples thereof include an atomic group represented by —XR 10 .
- X is a direct bond or a divalent linking group
- —XR 12 is a combination of X and R 12 which is a hydrogen atom or an atom or atomic group other than hydrogen that can be replaced with a hydrogen atom.
- the X is not particularly limited as long as it is a direct bond or a divalent linking group.
- X is an oxy group, thio group, carbonyl group, oxycarbonyl group, thiocarbonyl group, oxythiocarbonyl group, carbonyloxy group, oxycarbonyloxy group, carbonylthio group, oxycarbonylthio group, imino group, oxyimino group, Examples include carbonylimino group, phosphono group, phosphonato group, sulfinyl group, and sulfonyl group.
- R 10 is not particularly limited as long as it is hydrogen or an atom or atomic group other than hydrogen that can replace hydrogen, and examples thereof include a halogen atom (—F, —Cl, —Br, —I), Hydrosyl group, mercapto group, cyano group, isocyano group, nitro group, nitroso group, carboxyl group, carboxylate group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group which may contain substituents, including substituents Examples thereof include a hydrocarbon group that may contain an unsaturated bond, a silyl group that may contain an unsaturated bond that may contain a substituent, and an amino group that may contain a substituent.
- halogen atom —F, —Cl, —Br, —I
- a preferable atom or atomic group as R 10 may have the above halogen atom, hydrosyl group, mercapto group, cyano group, isocyano group, nitro group, nitroso group, substituent, and an unsaturated bond.
- examples thereof include a hydrocarbon group which may be substituted, a silyl group which may have a substituent and which may contain an unsaturated bond, and an amino group which may contain a substituent.
- the hydrocarbon group which may contain the above-mentioned substituent or may contain an unsaturated bond may contain a branched chain, or two or more branched chains may be bonded to form a cyclic structure.
- the above branched chains may combine to form a heterocyclic ring.
- the heterocyclic ring may or may not have aromaticity, and examples thereof include cyclic ethers, lactones, lactams, and aromatic heterocyclic rings.
- Examples of the hydrocarbon group that may contain a substituent and may contain an unsaturated bond include, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, and a heterocyclic group.
- hydrocarbon groups examples include alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl and propyl groups, alkenyl groups having 1 to 20 carbon atoms such as vinyl and allyl groups, ethynyl groups, An alkynyl group having 1 to 20 carbon atoms such as a 2-propynyl group, a phenyl group, a naphthyl group, a biphenyl group, a tolyl group, a xylyl group and a fluorenyl group, an aryl group having 6 to 20 carbon atoms, a benzyl group, a phenethyl group, It has 4 to 23 carbon atoms such as aralkyl group having 7 to 20 carbon atoms such as 3-phenylpropyl group, cycloalkyl group having 4 to 23 carbon atoms such as cyclopentyl group and cyclohexyl group, cyclopentenyl group and cycl
- Cycloalkenyl group ethylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran, ⁇ -propiolactone ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -propiolactam, ⁇ -butyrolactam, ⁇ -valerolactam, ⁇ -caprolactam, furan ring, thiophene ring, 2H-pyran ring, 4H-thiopyran ring, benzofuran ring , 1-benzothiophene ring, 2H-chromene ring, 1H-2-benzopyran ring, xanthene ring, heterocyclic ring group in which one hydrogen is removed from a hetero ring, methoxymethyl group, ethoxymethyl group, propoxymethyl group And an aryloxyalkyl group having 7 to 26 carbon atoms such as an alkyloxyalkyl group having 2 to 20 carbon atoms, a
- Examples of the silyl group that may contain the above-mentioned substituent and may contain an unsaturated bond include trimethylsilyl group, triethylsilyl group, triisopropylsilyl group and other alkylsilyl groups, trimethoxysilyl group, dimethoxymethyl group, methoxydimethyl group And the like, and the like.
- the substituent which may be included may be the same as the substituent —XR 10 .
- Examples of an amino group (—NH (—R 11 ), —N (—R 12 ) (— R 13 )) that may contain a substituent and may contain a heteroatom bond in R 10 include R 11 , R 12 , and R 13 may include a hetero atom bond at the bond terminal with the nitrogen atom, and may include a hydrocarbon group that may include a substituent.
- the hydrocarbon group which may contain a heteroatom bond at the bond terminal with the nitrogen atom and may contain a substituent may be the same as the substituent —XR 10 as long as it can be bonded to the nitrogen atom.
- Preferred examples of the amino group which may contain a substituent and may contain a heteroatom bond include an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, an N, N-diarylamino group, N-alkyl-N-arylamino group, acylamino group, N-alkylacylamino group, N-arylacylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N -Alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group.
- —XR 10 may be an atomic group obtained by linking X, which is a direct bond or a divalent linking group, and R 10 which is an atom or atomic group other than hydrogen that can be replaced with hydrogen or hydrogen.
- R 10 which is an atom or atomic group other than hydrogen that can be replaced with hydrogen or hydrogen.
- —XR 10 include halogen atoms (—F, —Cl, —Br, —I), hydrosyl groups, mercapto groups, cyano groups, isocyano groups, nitro groups, nitroso groups, carboxyl groups, carboxylate groups, sulfo groups.
- Particularly preferred —XR 10 includes a hydroxyl group, a mercapto group, a cyano group, an isocyano group, a hydrocarbon group that may contain the above substituent, a silyl group that may contain the above substituent, an alkoxy group, an aryloxy group, an acyloxy group, Carbamoyloxy group, cyanooxy group (cyanato group), thioalkoxy group, arylthio group, acetylthio group, acylthio group, cyanothio group (thiocyanato group), formyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, thioacyl Group, an alkoxythiocarbonyl group, and more preferable examples include a hydroxyl group, a mercapto group, an alkoxy group, an aryloxy group, a thioalkoxy group, and an arylthio group
- NHR 1 R 2 is a base (in the present invention, “basic substance” is simply referred to as a base).
- base-generating compound itself becomes a base and reacts with an epoxy group, which may impair stability over time.
- each of R 1 and R 2 is preferably an organic group not containing an amino group.
- not all amino groups impair the stability over time, and all amino groups are bonded to one or more terminals of R 1 and / or R 2 in the general formula (I). As long as the residues other than R 1 and / or R 2 are further bonded, even if R 1 or R 2 contains an amino group, stability over time will not be impaired.
- R 3 and R 4 the same hydrogen or substituent as R 1 and R 2 can be used.
- R 3 and R 4 both are preferably hydrogen from the viewpoint of easily achieving high sensitivity.
- R 3 and R 4 in the general formula (I) is not hydrogen and is the above-mentioned specific substituent, compared to the case where both R 3 and R 4 are hydrogen, the organic solvent And the affinity with a polymer precursor is further improved.
- R 3 and R 4 is a hydrocarbon group which may have a substituent such as an alkyl group or an aryl group and may contain an unsaturated bond, solubility in an organic solvent Will improve.
- R 5 to R 8 are each independently hydrogen or a monovalent substituent, which may be the same or different, and two or more of them are bonded to form a cyclic group. A structure may be formed.
- substituents for R 5 to R 8 those similar to the aforementioned —XR 10 can be used.
- R 5 to R 8 have one or more monovalent substituents, or two or more of R 5 to R 8 are bonded to form a cyclic structure in order to achieve improved solubility and higher sensitivity. Is preferably formed.
- the structure of the general formula (I) there are several factors that can effectively promote the isomerization reaction from the trans isomer to the cis isomer by the double bond between the ⁇ -carbon and the ⁇ -carbon located at the ⁇ -position and ⁇ -position of the carbonyl bond. For example, the size of steric hindrance around the carbon-carbon double bond, the electronic state of a conjugated chain extending around the carbon-carbon double bond, and the like can be mentioned.
- the substituents R 5 ⁇ R 8 by forming two or more ring structure by bonding with at least one introduction to or R 5 ⁇ R 8 substituents, the carbon - carbon double bonds around the conjugated chain Can be expanded and the sensitivity of base generation can be improved. Further, it is possible to adjust the wavelength of light to be absorbed by introducing at least one substituent into R 5 to R 8 , and to absorb a desired wavelength by introducing a substituent. You can also. The absorption wavelength can be shifted to a longer wavelength by introducing a substituent that extends the conjugated chain of the aromatic ring. It is also possible to improve the solubility and compatibility between the compound having two or more epoxy groups to be combined and the compound having a mercapto group.
- R 9 is a hydrogen atom or a protecting group that can be deprotected by irradiation with ionizing radiation, and is specifically described in WO2010 / 113814 International Publication.
- “deprotectable” refers to the possibility of changing from —OR 9 to —OH.
- R 9 is a hydrogen atom
- the base-generating compound contains a phenolic hydroxyl group, which may impair storage stability.
- R 9 when R 9 is the above protecting group, it is deprotected by irradiation with ionizing radiation to generate a hydroxyl group.
- the chlorine generator in which R 9 is the above protecting group has the advantage of having very high storage stability.
- the residue after the reaction may cause degassing, an extra process of deprotection may be required, and the cost for introducing a protecting group is high. Therefore, whether or not to introduce a protecting group into R 9 needs to be appropriately selected depending on the application to be used.
- R 9 is a protecting group of a phenolic hydroxyl group that can be deprotected by irradiation with ionizing radiation under the condition that the amide group present in the general formula (I) in the base generating compound used in the present invention is not decomposed, It can be used without being particularly limited.
- an amide bond is a strong acid such as boron tribromide or aluminum trichloride, a strong Lewis acid such as sulfuric acid, hydrochloric acid or nitric acid, or a strong base such as sodium hydroxide. Decomposes on heating under basic conditions.
- R 9 is appropriately selected depending on the type of compound used in combination with the base-generating compound, the application method of the base-generating compound, and the synthesis method for the purpose of improving solubility and compatibility or changing the reactivity during synthesis. It is what is done.
- the base generating compound represented by the above general formula (I) can take the chemical structure of a trans isomer and a cis isomer. However, in the present invention, only the trans isomer may be used, or the trans isomer and the cis isomer. Mixtures may be used.
- a base generating compound represented by the following general formula (II) is preferable.
- R 40 to R 49 are each independently hydrogen or a substituent.
- a method for synthesizing the base-generating compound represented by the general formula (II) will be described by taking the base-generating compound represented by the following formula (III) as an example.
- the method for synthesizing the base-generating compound represented by the general formula (II) is not limited to this, and it can be synthesized by a plurality of conventionally known methods.
- the base generating compound represented by the general formula (III) can be synthesized, for example, by the following method. First, ethoxycarbonylmethyl (triphenyl) phosphonium bromide and 2-hydroxy-4- (5-ethylhexyloxy) -5-ethylbenzaldehyde are dissolved in methanol, and a methanol solution of potassium carbonate is slowly added dropwise thereto and stirred. . After confirming the completion of the reaction by thin layer chromatography (hereinafter referred to as “TLC”), filtration is performed to remove potassium carbonate, and concentration is performed under reduced pressure. After concentration, an aqueous sodium hydroxide solution is added and stirred.
- TLC thin layer chromatography
- the reaction solution is concentrated and dissolved in water. Extraction with chloroform, washing with an aqueous hydrogen carbonate solution, hydrochloric acid and saturated saline, drying with sodium sulfate, and concentration are performed to obtain a base-generating compound represented by the above general formula (III). it can.
- the synthesized base generating compound represented by the general formula (III) generates piperidine as a base.
- a base-generating compound that generates a desired base can be easily synthesized.
- a base-generating compound in which R 44 is a hydroxyl group and R 45 is a hydrogen atom may be synthesized.
- 4-hydroxypiperidine may be added.
- the content of the base generating compound is 0.5% by mass or more and 10% by mass or less based on the ionizing radiation curable resin (for example, epoxy resin) when used in combination with a compound having a mercapto group described later. Is preferred.
- a base-generating compound As such a base-generating compound, a commercially available compound may be used.
- WPBG300, nonionic PBG, ionic PBG, WPBG018, WPBG140, and ADEKA sold by Wako Pure Chemical Industries, Ltd. are commercially available.
- PBG (oxime ester photobase generator), EIPBG commercially available from Ibitsu, and the like can be used.
- the adhesive layer may contain a curing agent for curing the ionizing radiation curable resin, for example, a compound having a mercapto group. .
- a curing agent for curing the ionizing radiation curable resin for example, a compound having a mercapto group.
- the ionizing radiation curable resin in the adhesive layer can be cured even in a relatively low temperature environment.
- a conventionally known compound can be used as long as it has two or more mercapto groups in the molecule, but a compound having three or more mercapto groups in the molecule is more preferable. When the number of mercapto groups is 1, the reaction point with the curable compound is lowered, and the adhesiveness and durability may be inferior.
- dithiols for example, 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, 1, 4-benzenedithiol, 1,10-decanedithiol, 1,2-ethanedithiol, 1,6-hexanedithiol, 1,9-nonanedithiol, 1,8-octanedithiol, 1,5-pentanedithiol, 1,2 -Propanedithiol, 1,3-propadithiol, toluene-3,4-dithiol, 3,6-dichloro-1,2-benzenedithiol, 1,3,5-triazine-2,4,6-trithiol (trimercapto -Triazine), 1,5-naphthalenedithiol, 1,2-benzenedimethanethi
- trithiols examples include trithioglycerin, 1,3,5-triazine-2,4,6-trithiol (trimercapto-triazine), trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 2,4,6-tris (mercaptomethyl) mesitylene, tris (mercaptomethyl) isocyanurate, tris (3 -Mercaptopropyl) isocyanurate, 2,4,5-tris (mercaptomethyl) -1,3-dithiolane is known.
- pentaerythritol tetrakisthioglycolate pentaerythritol tetrakisthiopropionate
- 1,2,4,5-tetrakis (mercaptomethyl) benzene 1,2,4,5-tetrakis (mercaptomethyl) benzene
- tetramercaptobutane pentaerythritol
- the content of the curing agent described above needs to be appropriately set depending on the intended use, but the active hydrogen equivalent is 0.7 equivalents or more and 1.2 equivalents or less with respect to 1 epoxy equivalent of the curable compound. It is preferable to mix
- the content of the compound having a mercapto group exceeds 1.2 equivalents, there is a possibility that inconveniences such as initial tackiness, lower adhesiveness and high cost may be caused.
- the adhesive layer constituting the adhesive sheet may contain other components as necessary within the range not impairing the object of the present invention.
- the adhesiveness to the structure is improved.
- various additives such as a coupling agent and a leveling agent may be included.
- a tackifier may be included to increase the adhesive strength, and a filler or the like may be included to improve the shear strength.
- tackifier examples include 1 selected from rosin resin, modified rosin resin, terpene resin, terpene phenol resin, aromatic modified terpene resin, C5 or C9 petroleum resin, coumarone resin, and the like.
- species or 2 or more types can be mentioned.
- fillers examples include inorganic fillers such as silica, clay, glass balloons, alumina balloons, and ceramic balloons, organic fillers such as nylon beads, acrylic beads, and silicon beads, glass, polyester, rayon, nylon, cellulose, and acetate.
- inorganic fillers such as silica, clay, glass balloons, alumina balloons, and ceramic balloons
- organic fillers such as nylon beads, acrylic beads, and silicon beads, glass, polyester, rayon, nylon, cellulose, and acetate.
- the 1 type (s) or 2 or more types chosen from the single fiber etc. which can be mentioned can be mentioned.
- the thickness of the adhesive layer 2 is preferably 50 ⁇ m or more and 500 ⁇ m or less, and more preferably 100 ⁇ m or more and 300 ⁇ m or less. When it is less than 50 ⁇ m, the adhesive layer becomes thin, and the adhesive force and the adhesive force may be insufficient. On the other hand, if the thickness of the adhesive layer exceeds 500 ⁇ m, the curing reaction of the adhesive layer may not sufficiently proceed to the inside, or the curing time may be prolonged.
- the above-mentioned adhesive sheet 1 may be composed only of the adhesive layer 10, and, as shown in FIG. 2, on one side of the adhesive layer 10.
- a release sheet 20 may be provided, and release sheets 20 and 20 ′ may be provided on both surfaces of the adhesive layer 10.
- the release sheet is not particularly limited as long as it has strength and flexibility that can protect the adhesive layer 10, and various films can be used, for example, polyester resins, polypropylene resins, and the like.
- Resin polyvinyl chloride resin, fluorine resin, polystyrene resin, polyacrylic resin, cellulose resin, polycarbonate resin, polyamide resin, polyolefin resin, polyvinyl alcohol resin, polyimide resin, phenol resin, and A film or sheet containing a known resin such as polyurethane resin can be used.
- the above release sheet is preferably subjected to easy release treatment on the side in contact with the adhesive layer.
- an easy release layer (not shown) is preferably provided.
- the easy release layer is provided by applying a release agent.
- the release agent is not particularly limited, and various types can be applied. For example, water-soluble resins, hydrophilic resins, waxes, silicone resins, fluororesins, aminoalkyd resins, melamine resins, polyester resins, acrylic resins, and the like can be given.
- the application method of the release agent is not particularly limited, and examples thereof include application methods such as roll coating, gravure coating, and spray coating.
- the surface of the release sheet 20 on the side on which the easy release layer is formed has been subjected to an easy adhesion treatment for improving the adhesion of the easy release layer in advance.
- Such easy adhesion treatment is preferably a treatment that improves the wettability of the release agent. Examples of such treatment include corona discharge treatment, plasma treatment, ozone treatment, flame treatment, pre-heat treatment, dust removal treatment, vapor deposition treatment, and alkali treatment.
- the thickness of the release sheet 20 is not particularly limited, but is preferably 5 ⁇ m or more and 200 ⁇ m or less, for example.
- the adhesive sheet 1 may include a repair or reinforcing member 30 such as a fiber material in the adhesive layer 10.
- a repair or reinforcement member is not particularly limited, and examples thereof include one or more selected from woven fabric, knitted fabric, nonwoven fabric, laminated fabric, synthetic resin foam, paper, and the like. Can do.
- the constituent material of the fiber material layer include one or more selected from polyester fiber, polyamide fiber, aramid fiber, vinylon fiber, carbon fiber, glass fiber, polyolefin fiber, and the like.
- polyester fiber polyamide fiber, aramid fiber, vinylon fiber, and polyolefin fiber are preferably used because they are light and excellent in strength. These fibers may be blended, used separately for warp and weft, or laminated in multiple layers.
- the adhesive sheet 1 may be provided with two adhesive layers 10 via a repairing or reinforcing member 40 such as a resin film.
- repair or reinforcement members for resin films include polyester resins, polypropylene resins, polyvinyl chloride resins, fluorine resins, polystyrene resins, polyacrylic resins, cellulose resins, polycarbonate resins, polyamide resins.
- the sheet or film include a resin, a polyolefin resin, a polyvinyl alcohol resin, a polyimide resin, a phenol resin, and a polyurethane resin.
- the repair or reinforcement member 40 may be capable of providing a function at the same time, and examples thereof include an advertising signboard, a paint film, a waterproof sheet, a water absorbing sheet, an ultraviolet resistant sheet, a water retaining sheet, a colored sheet, and the like. it can.
- Such a repair or reinforcement member such as a resin film is appropriately selected according to the purpose of repair or reinforcement of the structure.
- the thickness of the repair or reinforcing member of the resin film or the like also varies depending on whether it is used for repair or for reinforcement, but is usually in the range of 0.01 mm or more and 1.0 mm or less.
- the surface of the structure may be subjected to a primer treatment before the step of pasting the adhesive sheet described later.
- the primer treatment By the primer treatment, the adhesion between the structure and the adhesive sheet can be made stronger.
- Structures to be primed are those that are subject to repair and reinforcement, such as bridges, tunnels, road pavements, river management facilities, sabo dams, sabo floors, sewage pipes, sewage treatment plants, port facilities,
- repair and reinforcement such as bridges, tunnels, road pavements, river management facilities, sabo dams, sabo floors, sewage pipes, sewage treatment plants, port facilities
- social infrastructures such as public housing, collective housing, general housing, city parks, coastal dikes, airports, airports, navigation signs, government facilities, etc., but most of them are concrete structures, so concrete (steel reinforced concrete) Will be described as an example of the structure.
- adhesion assistant used for the primer treatment various conventionally known urethane-based primers, epoxy-based primers, vinyl ester-based primers and the like can be used without limitation.
- ionizing radiation curing is used. Since a basic substance generating compound is used as a curing aid for a functional resin, an acidic substance generating compound is used as a curing aid even when a primer containing an epoxy resin and a polyamine-based curing agent is used as an adhesion aid. The adhesion aid is not deteriorated as it is used.
- the epoxy resin contained in the primer is a glycidyl ether type epoxy resin, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin; glycidyl ester type epoxy resin, for example, hexahydrophthalic acid glycidyl ester, dimer Acid glycidyl ester; glycidyl amine type epoxy resin such as triglycidyl isocyanurate, tetraglycidyl diaminodiphenyl methane; linear aliphatic epoxide such as epoxidized polybutadiene, epoxidized soybean oil; alicyclic epoxy side such as 3,4 -Epoxy-6-methylcyclohexylmethylcarboxylate, 3,4-epoxycyclohexylmethylcarboxylate and the like.
- glycidyl ether type epoxy resin for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol no
- a polyamine curing agent that is liquid at room temperature can be preferably used, and examples thereof include aliphatic polyamines, alicyclic polyamines, aromatic polyamines, polyamide polyamines, and polymercaptans.
- the primer may contain conventionally known additives such as a diluent, a thixotropic agent, and a coupling agent.
- epoxy amine primer commercially available ones may be used.
- Alpron W301 provided by Japan-US Resin Co., Ltd. or Primer II for reinforced concrete provided by Mizutani Paint Co., Ltd. It can be preferably used.
- the primer treatment can be performed by applying and drying the above-described primer on the surface of the concrete structure. For example, what is necessary is just to apply
- the layer thickness of the primer layer is preferably about 1 ⁇ m or more and 1 mm or less.
- the adhesive sheet After preparing the above-mentioned adhesive sheet, the adhesive sheet is bonded to the surface of the structure to adhere the structure and the adhesive layer.
- the adhesive sheet 1 is an embodiment as shown in FIG. 2, the surface of the adhesive layer 10 on which the release sheet 20 is not provided is bonded to the structure.
- one release sheet 20 ′ is peeled from the adhesive sheet, and the exposed surface of the adhesive layer 10 is bonded to the structure.
- the adhesive layer of the adhesive sheet has adhesive strength, it can be bonded and temporarily fixed to the surface of the structure. Therefore, it is not necessary to stick the adhesive sheet using an adhesive or the like.
- the adhesive sheet can be peeled off and pasted again after bonding, the workability is excellent. Furthermore, since the adhesive layer can be slowly cured after pasting and temporarily fixing the adhesive sheet, it is necessary to cure the adhesive layer using an ultraviolet irradiation device or the like as in the past. Absent.
- the adhesive layer is cured.
- the adhesive layer is cured by irradiation with ionizing radiation.
- the curing reaction of the ionizing radiation curable resin is performed by the basic substance-generating compound, so that the adhesive layer is exposed. It is characterized in that it is cured in a cured state. That is, when the adhesive sheet 1 includes the release sheet 20 as shown in FIG. 2, unlike the conventional repair / reinforcement method, the adhesive sheet is removed after the release sheet 20 is removed. 10 curing is performed. Therefore, according to the present invention, the step of removing the release sheet after curing, even when it takes time to cure the adhesive layer, such as when the adhesive layer is cured by ionizing radiation such as sunlight. This reduces the work burden during repair and reinforcement work.
- the ionizing radiation examples include microwaves, infrared rays, visible rays, ultraviolet rays, X-rays, ⁇ rays, etc.
- ultraviolet rays can be preferably used.
- a wavelength of 300 to ultraviolet integrated light quantity of 370nm is about 50 mJ / cm 2 or more, to cure the pressure-sensitive adhesive layer of about 3000 mJ / cm 2 or less it can. That is, the adhesive layer can be cured by light such as sunlight. In this case, the time until the adhesive layer is completely cured is about one day.
- the adhesive layer may be cured over a longer time, and the curing time may be shortened using an ultraviolet irradiation device or a heating device.
- the adhesive layer may be cured by irradiation with an electron beam. In that case, an irradiation dose of about 50 kGy or more and 100 kGy or less may be used.
- the structure repairing or reinforcing method according to the third embodiment of the present invention includes: 1) a step of applying a primer containing an epoxy resin and a polyamine curing agent to the surface of the structure and performing a primer treatment; 2) An adhesive layer comprising at least a curable resin composition whose curing is accelerated by irradiation with ionizing radiation and a curing auxiliary agent that generates a basic substance upon irradiation with ionizing radiation on the surface of the primer-treated structure. A step of laminating the adhesive layer of the provided adhesive sheet, and 3) a step of curing the adhesive layer.
- the difference between the first and second embodiments is that The adhesive layer is not cured when the adhesive layer is exposed.
- the adhesive or adhesive sheet 1 provided with the repair or reinforcement member 40 on one surface of the adhesive layer is used, and the repair or reinforcement member 40 is provided.
- the adhesive layer 10 on the surface side that is not bonded is bonded to the structure and the adhesive layer 10 is not exposed (that is, the adhesive layer 10 is covered with a repair or reinforcing member 40)
- the adhesive layer 10 is cured.
- an acidic substance generating compound or the like as a curing aid for the ionizing radiation curable resin. It is done.
- the adhesive layer 10 is cured before the adhesive layer 10 is cured.
- a repair or reinforcement member as described above may be provided on the surface.
- Example 1 ⁇ Production of adhesive sheet>
- a polyester film (trade name: SP-PET-03, film thickness: 38 ⁇ m, manufactured by Tosero Co., Ltd.) on which one side is subjected to a release treatment with a silicone-based release agent has the following adhesive properties:
- the coating solution 1 for forming a layer was applied using an applicator so that the thickness after coating was 200 ⁇ m, and dried at 80 ° C. for 2 minutes in a drying oven to form an adhesive layer.
- Two sheets of this were prepared, and carbon fiber (W-3101, manufactured by Toho Tenax Co., Ltd.) as a core material was embedded in one adhesive layer using a 2 kg roller at room temperature, and the other adhesive was adhered on it.
- the adhesive layers with the release sheets provided on both sides were produced by superimposing them so that the layers were facing each other and pressing on a hot plate at about 60 ° C. using a 2 kg roller.
- composition 1 composition for forming an adhesive layer Liquid epoxy resin 100 parts by mass (bisphenol A type epoxy resin, epoxy equivalent: 190 g / eq., Molecular weight: 380, manufactured by Mitsubishi Chemical Corporation, trade name: jER828) 7.0 parts by mass of a curing agent having a mercapto group (pentaerythritol tetrakis-3-mercaptopropionate, viscosity: 400 to 550 mPa.s / 25 ° C., mercaptan equivalent: 125 to 137 g / eq, manufactured by Mitsubishi Chemical Corporation, Product name: QX40) Acrylic resin 50 parts by mass (modified methyl methacrylate-butyl acrylate-methyl methacrylate block copolymer with amino group introduced, Tg: -42 ° C., manufactured by Arkema, Inc., trade name: M22N) -Photobase generator A 5 parts by mass-Diluent solvent (ethyl acetate
- the photobase generator A was synthesized as follows. First, 15 mL of methanol was placed in a 100 mL flask, and 2.00 g of potassium carbonate was added thereto. Next, 10 mL of methanol was put into a 50 mL flask, and 2.67 g (6.2 mmol) of ethoxycarbonylmethyl (triphenyl) phosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2-hydroxy-4- (5-ethylhexyloxy) After adding and dissolving 1.7 g (6.2 mmol) of -5-ethylbenzaldehyde, the well-stirred methanol solution of potassium carbonate was slowly added dropwise.
- Example 2 In Example 1, an adhesive sheet was produced in the same manner as in Example 1 except that the following adhesive layer forming coating solution 2 was used.
- ⁇ Adhesive layer forming coating solution 2 composition > -100 parts by mass of solid epoxy resin (bisphenol A type epoxy resin, molecular weight: 5000, manufactured by Mitsubishi Chemical Corporation, trade name: jER1009) 7.6 parts by mass of a curing agent having a mercapto group (pentaerythritol tetrakis-3-mercaptopropionate, viscosity: 400 to 550 mPa.s / 25 ° C., mercaptan equivalent: 125 to 137 g / eq, manufactured by Mitsubishi Chemical Corporation, Product name: QX40)
- Example 1 an adhesive sheet was produced in the same manner as in Example 1 except that the following adhesive layer forming coating solution 3 was used.
- Liquid epoxy resin 50 parts by mass bisphenol A type epoxy resin, epoxy equivalent: 190 g / eq., Molecular weight: 380, manufactured by Mitsubishi Chemical Corporation, trade name: jER828)
- curing agent photoacid generator, manufactured by Sanshin Chemical Industry Co., Ltd., trade name: Sun Aid SI60L
- Dilute solvent ethyl acetate, manufactured by DIC Graphics
- Example 2 an adhesive sheet was produced in the same manner as in Example 1 except that the following adhesive layer forming coating solution 4 was used.
- Comparative Example 3 In Comparative Example 1, the adhesive strength of the adhesive sheet was evaluated in the same manner as in Comparative Example 1 except that the other release sheet was not peeled off and natural light irradiation was performed without exposing the adhesive layer. went.
- Comparative Example 4 In Comparative Example 2, the adhesive strength of the adhesive sheet was evaluated in the same manner as in Comparative Example 2, except that the other release sheet was not peeled off and natural light irradiation was performed without exposing the adhesive layer. went.
- Comparative Example 5 In Comparative Example 3, the adhesive strength of the adhesive sheet was evaluated in the same manner as in Comparative Example 3, except that the adhesive sheet was bonded to the surface of the concrete piece without performing primer treatment.
- Comparative Example 6 In Comparative Example 4, the adhesive strength of the adhesive sheet was evaluated in the same manner as in Comparative Example 4 except that the adhesive sheet was bonded to the surface of the concrete piece without performing primer treatment.
- Comparative Example 7 In Comparative Example 1, the adhesive strength of the adhesive sheet was evaluated in the same manner as in Comparative Example 1, except that the adhesive sheet was bonded to the surface of the concrete piece without performing primer treatment.
- Comparative Example 8 In Comparative Example 2, the adhesive strength of the adhesive sheet was evaluated in the same manner as in Comparative Example 2, except that the adhesive sheet was bonded to the surface of the concrete piece without performing primer treatment.
- a concrete piece is prepared, and a primer (primary agent: bisphenol-based epoxy resin, curing agent: epoxy amine primer having a modified aliphatic polyamine, Alpron W301 manufactured by Nihon-US Resin Co., Ltd.) is applied on the surface after drying. It apply
- the adhesive sheet was peeled off the release sheet on one side, and the exposed adhesive layer was bonded to the surface of the primed concrete piece while being pressed with a hand roll in the same manner as above. The adhesive layer was cured. Subsequently, it cut
- a mortar piece (using ISO standard sand, manufactured by Yuko Trading Co., Ltd.) was prepared, and on its surface, a primer (main agent: bisphenol-based epoxy resin, curing agent: modified aliphatic polyamine, epoxyamine-based primer, Japan-US resin Alpron W301 manufactured by the company was applied so that the coating amount after drying was 200 g / m 2 and dried.
- a primer main agent: bisphenol-based epoxy resin, curing agent: modified aliphatic polyamine, epoxyamine-based primer, Japan-US resin Alpron W301 manufactured by the company was applied so that the coating amount after drying was 200 g / m 2 and dried.
- the adhesive sheet is peeled off from the release sheet on one side, and the exposed adhesive layer is bonded to the surface of the primed concrete piece while pressing with a hand roll, and the other release sheet is peeled off to the atmosphere.
- the adhesive layer was exposed inside.
- Adhesive sheet 10 Adhesive layer 20, 20 'Release sheet 30 Repair or reinforcement member containing fiber 40 Repair or reinforcement member
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Abstract
Description
電離放射線の照射により硬化が促進される硬化性樹脂組成物および電離放射線の照射により塩基性物質を発生する硬化助剤を少なくとも含んでなる粘接着層を備えた粘接着シートを準備する工程と、
前記粘接着シートを、構造物の表面に貼り合わせる工程と、
前記粘接着シートの粘接着層を露出させた状態で、該粘接着層を硬化させる工程と、
を含んでなることを特徴とするものである。
前記構造物の前記表面に貼り合わせる前の前記粘接着シートが、前記粘接着層の少なくとも一方の側に設けられた剥離シートを備えており、
前記粘接着シートを前記構造物の前記表面に張り合わせた後に、前記粘接着シートから前記剥離シートを剥離する工程を含んでなり、
前記粘着シートから前記剥離シートを剥がした後に、前記粘着シートの前記粘接着層を硬化させる、方法である。
前記プライマー処理が、エポキシ樹脂とポリアミン系硬化剤とを含むプライマーの構造物表面への塗布により行われてもよい。
構造物表面に、エポキシ樹脂とポリアミン系硬化剤とを含むプライマーを塗布して、プライマー処理を行う工程と、
前記プライマー処理された構造物の表面に、電離放射線の照射により硬化が促進される硬化性樹脂組成物および電離放射線の照射により塩基性物質を発生する硬化助剤を少なくとも含んでなる粘接着層を備えた粘接着シートの粘接着層を貼り合わせる工程と、
前記粘接着層を硬化させる工程と、
を含んでなることを特徴とするものである。
その一つの方法は、
電離放射線の照射により硬化が促進される硬化性樹脂組成物および電離放射線の照射により塩基性物質を発生する硬化助剤を少なくとも含んでなる粘接着層を備えた粘接着シートを準備する工程と、
前記粘接着シートを、構造物の表面に貼り合わせる工程と、
前記粘接着シートの粘接着層を露出させた状態で、該粘接着層を硬化させる工程と、
を含んでなることを特徴とするものである。
また、別の方法は、
構造物表面に、エポキシ樹脂とポリアミン系硬化剤とを含むプライマーを塗布して、プライマー処理を行う工程と、
前記プライマー処理された構造物の表面に、電離放射線の照射により硬化が促進される硬化性樹脂組成物および電離放射線の照射により塩基性物質を発生する硬化助剤を少なくとも含んでなる粘接着層を備えた粘接着シートの粘接着層を貼り合わせる工程と、
前記粘接着層を硬化させる工程と、
を含んでなることを特徴とするものである。
本発明の第1および第2の実施態様による構造物の補修ないし補強方法を、適宜図面を参照しながら説明する。本発明の第1の実施態様による構造物の補修ないし補強方法は、1)電離放射線の照射により硬化が促進される硬化性樹脂組成物および電離放射線の照射により塩基性物質を発生する硬化助剤を少なくとも含んでなる粘接着層を備えた粘接着シートを準備する工程と、2)前記粘接着シートを、構造物の表面に貼り合わせる工程と、3)前記粘接着シートの粘接着層を露出させた状態で、該粘接着層を硬化させる工程と、を含む。また、本発明の第2の実施態様による構造物の補修ないし補強方法において使用される粘接着シートは、粘接着層と粘接着層の少なくとも一方の側に設けられた剥離シートとを備えるものであり、本発明の第2の実施態様では、粘接着シートを構造物の表面に貼り合わせた後、粘接着シートから剥離シートを剥離する工程を含む。以下、各工程について説明する。
本発明の第1の実施態様による構造物の補修ないし補強方法に用いられる粘接着シートは、太陽光等の電離放射線の照射によって硬化し得る粘接着層を備えるものであり、粘接着層は、電離放射線の照射により硬化が促進される硬化性樹脂組成物および電離放射線の照射により塩基性物質を発生する硬化助剤を少なくとも含む。なお、本明細書中、「電離放射線」とは、可視および非可視領域の波長の電磁波だけでなく、電子線のような粒子線、および、電磁波と粒子線を総称する放射線を意味し、具体的には、マイクロ波、赤外線、可視光線、紫外線、X線、γ線等が挙げられる。
R1およびR2は、それぞれ独立して、水素、または、置換基を含んでもよく不飽和結合を含んでもよい、直鎖状または分岐鎖を有する炭化水素基を表すが、R1およびR2の少なくとも1つは該炭化水素基であり、R1およびR2は結合して環状構造を形成していてもよく、
R3およびR4は、それぞれ独立して、水素または1価の置換基を表し、
R5~R8は、それぞれ独立して、水素または1価の置換基を表すが、R5~R8の2つ以上が結合して環状構造を形成していてもよく、
R9は加熱および/または電離放射線の照射により脱保護可能な保護基を表す。)
本発明においては、後記する粘接着シートの貼合工程の前に、構造物の表面にプライマー処理を施しておいてもよい。プライマー処理により、構造物と粘接着シートとの密着性をより強固なものとすることができる。
上記した粘接着シートを準備した後、粘接着シートを構造物の表面に貼り合わせて、構造物と粘接着層とを密着させる。粘接着シート1が、図2に示すような実施形態の場合は、粘接着層10の剥離シート20が設けられていない面を構造物に貼り合わせる。また、図3に示したような実施形態の場合は、一方の剥離シート20’を粘接着シートから剥離し、露出した粘接着層10の面を構造物に貼り合わせる。本発明においては、上記したように、粘接着シートの粘接着層が粘着力を有するため、構造物の表面に貼り合わせて仮固定することができる。したがって、接着剤等を用いて粘接着シートを貼り合わせる必要がない。また、貼り合わせた後に粘接着シートを剥がして再度貼り直すこともできるため、作業性に優れている。さらに、粘接着シートを貼り合わせて仮固定した後、ゆっくりと粘接着層を硬化させることができるため、従来のように、紫外線照射装置等を用いて粘接着層を硬化させる必要がない。
構造物の表面に粘接着シートを貼り合わせた後、粘接着層の硬化を行う。粘接着層の硬化は電離放射線の照射により行われるが、本発明においては、上記したように、電離放射線硬化性樹脂の硬化反応を塩基性物質発生化合物により行うため、粘接着層を露出させた状態で硬化させる点が特徴である。即ち、粘接着シート1が、図2に示したような剥離シート20を備えている場合は、従来の補修・補強時の施工方法とは異なり、剥離シート20を除去した後に粘接着層10の硬化を行う。したがって、本発明によれば、太陽光のような電離放射線によって粘接着層を硬化させる場合等、粘接着層の硬化に時間を要する場合であっても、硬化後に剥離シートを除去する工程を省くことができるため、補修・補強施工時の作業負担を少なくできる。
本発明の第3の実施態様による構造物の補修ないし補強方法は、1)構造物表面に、エポキシ樹脂とポリアミン系硬化剤とを含むプライマーを塗布して、プライマー処理を行う工程、2)前記プライマー処理された構造物の表面に、電離放射線の照射により硬化が促進される硬化性樹脂組成物および電離放射線の照射により塩基性物質を発生する硬化助剤を少なくとも含んでなる粘接着層を備えた粘接着シートの粘接着層を貼り合わせる工程と、3)前記粘接着層を硬化させる工程と、を含むものであり、第1および第2の実施態様との違いは、粘接着層の硬化を、粘接着層が露出した状態では行わない点にある。第3の実施態様においては、図6に示すような、粘接着層の一方の面に補修ないし補強部材40が設けられた粘接着シート1を使用し、補修ないし補強部材40が設けられていない面側の粘接着層10を構造物に貼り合わせ、粘接着層10が露出していない状態(即ち、粘接着層10が補修ないし補強部材40で覆われた状態)で、粘接着層10を硬化させる。この場合、粘接着層が外気に曝されていないため、外気中の酸素による硬化阻害の影響が少ないため、電離放射線硬化性樹脂の硬化助剤として酸性物質発生化合物等を使用することも考えられる。しかしながら、本発明においては、上記したように、硬化助剤として塩基性物質発生化合物を使用するため、エポキシ樹脂とポリアミン系硬化剤とを含むプライマーを密着補助剤として使用した場合であっても、酸性物質発生化合物を硬化助剤として使用した場合のように、密着補助剤を劣化させることがない。
<粘接着シートの作製>
剥離シートとして片面にシリコーン系剥離剤による剥離処理が施されてなるポリエステルフィルム(商品名:SP-PET-03、膜厚:38μm、東セロ株式会社製)の剥離処理面上に、下記の粘接着層形成用塗工液1を、塗工後の厚さが200μmとなるようにアプリケーターを用いて塗布し、乾燥オーブンにて80℃で2分間乾燥させて粘接着層を形成した。これを2枚準備し、一方の粘接着層に芯材である炭素繊維(W-3101、東邦テナックス社製)を常温にて2kgのローラーを用いて埋設し、その上に他方の粘接着層が対向するように重ね合わせて、約60℃のホットプレート上にて2kgのローラーを用いて押圧することにより、両面に剥離シートが設けられた粘接着シートを作製した。
・液状エポキシ樹脂 100質量部
(ビスフェノールA型エポキシ樹脂、エポキシ当量:190g/eq.、分子量:380、三菱化学株式会社製、商品名:jER828)
・メルカプト基を有する硬化剤 7.0質量部
(ペンタエリスリトールテトラキス-3-メルカプトプロピオネート、粘度:400~550mPa.s/25℃、メルカプタン当量:125~137g/eq、三菱化学株式会社製、商品名:QX40)
・アクリル系樹脂 50質量部
(アミノ基が導入された変性メチルメタクリレート-ブチルアクリレート-メチルメタクリレートのブロック共重合体、Tg:-42℃、アルケマ社製、商品名:M22N)
・光塩基発生剤A 5質量部
・希釈溶剤(酢酸エチル、DICグラフィックス社製) 100質量部
実施例1において、以下の粘接着層形成用塗工液2を用いた以外は、実施例1と同様にして粘接着シートを作製した。
・固形エポキシ樹脂 100質量部
(ビスフェノールA型エポキシ樹脂、分子量:5000、三菱化学株式会社製、商品名:jER1009)
・メルカプト基を有する硬化剤 7.6質量部
(ペンタエリスリトールテトラキス-3-メルカプトプロピオネート、粘度:400~550mPa.s/25℃、メルカプタン当量:125~137g/eq、三菱化学株式会社製、商品名:QX40)
・アクリル系樹脂 50質量部
(アミノ基が導入された変性メチルメタクリレート-ブチルアクリレート-メチルメタクリレートのブロック共重合体、Tg:-42℃、アルケマ社製、商品名:M22N)
・光塩基発生剤A 5質量部
・希釈溶剤(酢酸エチル、DICグラフィックス社製) 100質量部
実施例1において、以下の粘接着層形成用塗工液3を用いた以外は、実施例1と同様にして粘接着シートを作製した。
・固形エポキシ樹脂 50質量部
(ビスフェノールA型エポキシ樹脂、分子量:5000、三菱化学株式会社製、商品名:jER1009)
・液状エポキシ樹脂 50質量部
(ビスフェノールA型エポキシ樹脂、エポキシ当量:190g/eq.、分子量:380、三菱化学株式会社製、商品名:jER828)
・硬化剤 5質量部
(光酸発生剤、三新化学工業社製、商品名:サンエイドSI60L)
・希釈溶剤(酢酸エチル、DICグラフィックス社製) 100質量部
実施例1において、以下の粘接着層形成用塗工液4を用いた以外は、実施例1と同様にして粘接着シートを作製した。
・液状アクリル樹脂 100質量部
(アクリル酸混合物 日本合成社製 UVNS034)
・アクリル系樹脂 50質量部
(メチルメタクリレート-ブチルアクリレート-メチルメタクリレートのブロック共重合体、Tg:-42℃、アルケマ社製、商品名:M22)
・硬化剤 5質量部
(光ラジカル開始剤 BASF社製 商品名:イルガキュア184)
・希釈溶剤(酢酸エチル、DICグラフィックス社製) 100質量部
比較例1において、他方の剥離シートを剥がさずに粘接着層が露出していない状態で自然光の照射を行った以外は、比較例1と同様にして粘接着シートの接着強度の評価を行った。
比較例2において、他方の剥離シートを剥がさずに粘接着層が露出していない状態で自然光の照射を行った以外は、比較例2と同様にして粘接着シートの接着強度の評価を行った。
比較例3において、コンクリート片の表面にプライマー処理を行わずに粘接着シートを貼り合わせた以外は、比較例3と同様にして粘接着シートの接着強度の評価を行った。
比較例4において、コンクリート片の表面にプライマー処理を行わずに粘接着シートを貼り合わせた以外は、比較例4と同様にして粘接着シートの接着強度の評価を行った。
比較例1において、コンクリート片の表面にプライマー処理を行わずに粘接着シートを貼り合わせた以外は、比較例1と同様にして粘接着シートの接着強度の評価を行った。
比較例2において、コンクリート片の表面にプライマー処理を行わずに粘接着シートを貼り合わせた以外は、比較例2と同様にして粘接着シートの接着強度の評価を行った。
粘接着シートを硬化させる前の粘着力について、得られた各粘接着シートを縦25mm、横150mmに裁断して測定用試料とした。測定用試料の一方の面の剥離シートを剥がし、露出した粘接着層にアルミニウム合金(A6061、試料:25mm×150mm)を貼り合わせ、引張試験機(株式会社エー・アンド・デイ社製、型番:RTF-1150H)を用いて、JIS Z0237に準拠した条件(引張速度:300mm/分、剥離距離:150mm、剥離角:180°)にて、アルミニウム板面に対する粘着力(N/25mm)を測定した。
粘接着シートの一方の面の剥離シートを剥がし、露出した粘接着層をコンクリート壁にハンドロールで押圧しながら貼り合わせ、他方の剥離シートを剥がして大気中に粘接着層を露出させた。この状態で、自然光が照射される環境にて7日間放置した。7日間のうち、晴の日は4日、曇りの日は3日であった。また、7日間の外気温は18~25℃であった。7日間の放置後、粘接着シートとコンクリート壁との間に浮きがなかった場合を○、粘着性が弱くて貼れない場合や浮きが発生した場合を×として、施工性の評価を行った。
先ず、コンクリート片を準備し、その表面に、プライマー(主剤:ビスフェノール系エポキシ樹脂、硬化剤:変性脂肪族系ポリアミンとするエポキシアミン系プライマー、日米レジン社製のアルプロンW301)を乾燥後の塗布量が200g/m2となるように塗布し、乾燥させた。次いで、粘接着シートを一方の面の剥離シートを剥がし、露出した粘接着層を、プライマー処理されたコンクリート片の表面にハンドロールで押圧しながら貼り合わせた以外は、上記と同様にして粘接着層を硬化させた。次いで、コンクリートカッターを用いて40mm×40mmの大きさに切断し、はく落防止性能照査試験(JHS 424 2004)により評価した。
また、NEXCO試験法424-2004に準拠した押抜き試験により、コンクリート剥落防止性の評価を行った。5kN以上を示したものを○、5kN未満であったものを×とした。
先ず、モルタル片(ISO基準砂使用、ユーコウ商会社製)を準備し、その表面に、プライマー(主剤:ビスフェノール系エポキシ樹脂、硬化剤:変性脂肪族系ポリアミンとするエポキシアミン系プライマー、日米レジン社製のアルプロンW301)を乾燥後の塗布量が200g/m2となるように塗布し、乾燥させた。次いで、粘接着シートを一方の面の剥離シートを剥がし、露出した粘接着層を、プライマー処理されたコンクリート片の表面にハンドロールで押圧しながら貼り合わせ、他方の剥離シートを剥がして大気中に粘接着層を露出させた。この状態で、紫外線照射装置(アイグラフィックス社製のアイグランテージECS-4011GX)を用いて、波長300~370nmの領域で積算光量が800mJ/cm2となるように紫外線を照射した。その後、酢酸エチル(DICグラフィックス社製)をスポイトで1滴、粘接着シート表面に滴下し、表面が溶解するかどうかで硬化性を確認した。表面がとけなかったものを硬化性○、表面が溶解し食指でベタツキが増加したものを×とした。
10 粘接着層
20、20’ 剥離シート
30 繊維を含む補修ないし補強部材
40 補修ないし補強部材
Claims (18)
- 粘接着層を備えた粘接着シートを用いた構造物の補修ないし補強方法であって、
電離放射線の照射により硬化が促進される硬化性樹脂組成物および電離放射線の照射により塩基性物質を発生する硬化助剤を少なくとも含んでなる粘接着層を備えた粘接着シートを準備する工程と、
前記粘接着シートを、構造物の表面に貼り合わせる工程と、
前記粘接着シートの粘接着層を露出させた状態で、該粘接着層を硬化させる工程と、
を含んでなることを特徴とする、方法。 - 前記構造物の前記表面に貼り合わせる前の前記粘接着シートが、前記粘接着層の少なくとも一方の側に設けられた剥離シートを備えており、
前記粘接着シートを前記構造物の前記表面に張り合わせた後に、前記粘接着シートから前記剥離シートを剥離する工程を含んでなり、
前記粘着シートから前記剥離シートを剥がした後に、前記粘着シートの前記粘接着層を硬化させる、請求項1に記載の方法。 - 前記粘接着シートを前記構造物の前記表面に貼り合わせる前に、前記構造物の前記表面にプライマー処理を行う工程をさらに含んでなり、
前記プライマー処理が、エポキシ樹脂とポリアミン系硬化剤とを含むプライマーの前記構造物の前記表面への塗布により行われる、請求項1に記載の方法。 - 前記硬化性樹脂組成物が、分子中に少なくとも2個のエポキシ基を有する硬化性化合物を含んでなる、請求項1に記載の方法。
- 前記粘接着層を硬化させる前に、前記粘接着層上にさらに補修ないし補強部材を貼り合わせる工程を含む、請求項1に記載の方法。
- 前記粘接着層中に、繊維材料を含む補修ないし補強部材が含まれてなる、請求項1に記載の方法。
- 前記粘接着層の硬化時間が少なくとも1日以上である、請求項1に記載の方法。
- 前記粘接着層の硬化が太陽光の照射で行われる、請求項1に記載の方法。
- 請求項1に記載の構造物の補修ないし補強方法に使用される、粘接着シート。
- 粘接着層を備えた粘接着シートを用いて補修ないし補強された構造物を製造する方法であって、
電離放射線の照射により硬化が促進される硬化性樹脂組成物および電離放射線の照射により塩基性物質を発生する硬化助剤を少なくとも含んでなる粘接着層を備えた粘接着シートを準備する工程と、
前記粘接着シートを、構造物の表面に貼り合わせる工程と、
前記粘接着シートの粘接着層を露出させた状態で、該粘接着層を硬化させる工程と、
を含んでなることを特徴とする、方法。 - 粘接着層を備えた粘接着シートを用いた構造物の補修ないし補強方法であって、
構造物表面に、エポキシ樹脂とポリアミン系硬化剤とを含むプライマーを塗布して、プライマー処理を行う工程と、
前記プライマー処理された構造物の表面に、電離放射線の照射により硬化が促進される硬化性樹脂組成物および電離放射線の照射により塩基性物質を発生する硬化助剤を少なくとも含んでなる粘接着層を備えた粘接着シートの粘接着層を貼り合わせる工程と、
前記粘接着層を硬化させる工程と、
を含んでなることを特徴とする、方法。 - 前記粘接着層を硬化させる前に、前記粘接着層上にさらに補修ないし補強部材を貼り合わせる工程を含む、請求項11に記載の方法。
- 前記硬化性樹脂組成物が、分子中に少なくとも2個のエポキシ基を有する硬化性化合物を含んでなる、請求項11に記載の方法。
- 前記粘接着層中に、繊維材料を含む補修ないし補強部材が含まれてなる、請求項11に記載の方法。
- 前記粘接着層の硬化時間が少なくとも1日以上である、請求項11に記載の方法。
- 前記粘接着層の硬化が太陽光の照射で行われる、請求項11に記載の方法。
- 請求項11に記載の構造物の補修ないし補強方法に使用される、粘接着シート。
- 粘接着層を備えた粘接着シートを用いて補修ないし補強された構造物を製造する方法であって、
構造物表面に、エポキシ樹脂とポリアミン系硬化剤とを含むプライマーを塗布して、プライマー処理を行う工程と、
前記プライマー処理された構造物の表面に、電離放射線の照射により硬化が促進される硬化性樹脂組成物および電離放射線の照射により塩基性物質を発生する硬化助剤を少なくとも含んでなる粘接着層を備えた粘接着シートの粘接着層を貼り合わせる工程と、
前記粘接着層を硬化させる工程と、
を含んでなることを特徴とする、方法。
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CN106928873B (zh) * | 2017-04-25 | 2020-07-03 | 温州鸿越建设工程有限公司 | 一种混凝土构件粘钢加固施工方法 |
CN110643286B (zh) * | 2018-06-27 | 2021-11-19 | 3M创新有限公司 | Uv固化组合物及包含该组合物的胶膜、胶带和粘结构件 |
US20220356377A1 (en) * | 2019-10-02 | 2022-11-10 | Unmatched Bonding Company, Llc | Uv cured exothermic self-adhesive repair sheets |
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EP3133132A1 (en) | 2017-02-22 |
EP3133132A4 (en) | 2017-12-20 |
JP6337959B2 (ja) | 2018-06-06 |
US10597543B2 (en) | 2020-03-24 |
US20170120547A1 (en) | 2017-05-04 |
JPWO2015159733A1 (ja) | 2017-04-13 |
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