JP2016000523A - Manufacturing method of laminate and adhesive sheet used for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of drastically abbreviating a bonding operation of an adhesive sheet onto an adherend, the method enabling quick bonding of the adhesive sheet while reducing variation of adhesive strength and an adhesive sheet used for the method.SOLUTION: A method for manufacturing a laminate is configured to manufacture a laminate 100 including an adherend 5 and an adhesive sheet 10 bonded to the adherend 5. The method includes: a step of preparing the adhesive sheet 10 having an adhesion layer 2 to be cured by ionization radiation and a sign material 4 configured to display characters, figures or colors in accordance with exposure dose of the ionization radiation; a step of irradiating the adhesive sheet 10 with the ionization radiation; a step of stopping the irradiation of the ionization radiation after the sign material 4 has displayed the characters, figures or colors by the ionization radiation; and a step of bonding the adhesive sheet 10 onto a surface of the adherend 5.

Description

  The present invention relates to a laminate manufacturing method and an adhesive sheet used therefor. More specifically, a method capable of greatly omitting the operation of adhering the adhesive sheet to the adherend, and capable of adhering the adhesive sheet in a short time while reducing variations in adhesive strength, and an adhesive sheet used in the method I will provide a.

  Conventionally, various studies have been made on a method of manufacturing a laminate in which an adherend is laminated on an adherend and in which the adherend and the adhesive layer are firmly bonded. In recent years, such a method for producing a laminate is useful when repairing or reinforcing a so-called infrastructure facility such as a road, a railway, a water and sewage system, a port facility, a house, and a park. Moreover, the manufacturing method of the said laminated body can be widely used, for example for fixation of the concrete of a house, and a building member, or fixation of the metal component and resin part of a transport apparatus, etc.

When using the manufacturing method of a laminated body mentioned above for repair and reinforcement of an infrastructure installation, it is calculated | required to adhere | attach an adhesive layer firmly on the member containing a concrete material, a metal material, etc., for example. On the other hand, since concrete materials, metal materials, and the like are materials that are relatively difficult to obtain adhesiveness, there is a problem that it is difficult to perform strong adhesion to an adhesive sheet.
Moreover, when using the manufacturing method of the laminated body mentioned above for fixation of the concrete of a house, and a building member, or fixation of the metal component and resin part of a transport apparatus, a concrete material is included through an adhesive layer, for example. It is required to firmly bond the member and the member including the resin material, or to firmly bond the member including the metal material and the member including the resin material. On the other hand, concrete materials and resin materials, metal materials and resin materials, and the like are materials having different adhesive properties, and thus there is a problem that it is difficult to firmly bond a member containing them with an adhesive layer.

  For example, the following techniques have been proposed for such problems. That is, the adhesive layer forming the laminate is made of a layer containing a material that exhibits a curing reaction against ionizing radiation and heat, and the adhesive layer is cured on the surface of the adherend while the adhesive layer is placed on the surface of the adherend. Techniques to make progress are proposed. In this technique, since the curing reaction of the adhesive layer proceeds in a state where the adhesive layer is disposed on the surface of the adherend, the adhesive layer is cured so as to entrain the surface of the adherend. Accordingly, it is possible to firmly bond the adherend and the adhesive layer.

  For example, Patent Document 1 discloses an adhesive sheet in which a release layer having moisture or ultraviolet ray blocking properties is laminated on both surfaces of an adhesive layer. Patent Document 2 discloses an adhesive sheet in which a release layer is laminated on the surface of an adhesive layer containing an acrylic resin, a liquid epoxy resin, a solid epoxy resin, and a curing agent.

JP 2013-49844 A JP 2014-65889 A

  However, in the prior art, when a layer containing a material that exhibits a curing reaction against ionizing radiation or heat is used as the adhesive layer forming the laminate, the adhesive layer is disposed on the surface of the adherend. In order to cure the adhesive layer by applying ionizing radiation or heat, it is necessary to carry around the ionizing radiation irradiation device or heating device. There is a risk that the burden is large and dangerous. In the case where the first adherend and the second adherend are bonded via the adhesive layer and a layer having photocurability is used for the adhesive layer, the first adherend is used. Since the adhesive layer and the second adherend are stacked in this order and then the adhesive layer is irradiated with light to advance the curing reaction, at least one of the first adherend and the second adherend is light. There is a problem that it is necessary to have transparency.

  In the prior art, irradiation with ionizing radiation is performed after an adhesive layer is disposed on the surface of the adherend. On the other hand, in the step of irradiating with ionizing radiation, it is necessary to adjust the irradiation time and dose of ionizing radiation, but there is a problem that adjustment is required. If the irradiation time and dose of ionizing radiation applied to the adhesive layer are not constant, there will be variations in the curing of the adhesive layer, making it difficult to firmly bond the adhesive layer and the adherend. is there. Such a problem becomes more prominent as the adhesive layer becomes wider.

  The present invention provides a method capable of greatly omitting the bonding operation of the adhesive sheet to the adherend, and can perform the bonding of the adhesive sheet in a short time with reduced variation in the adhesive strength, and the adhesive sheet used in the method. Is to provide.

(1) A method for manufacturing a laminate according to the present invention for solving the above-described problems is a method for manufacturing a laminate that includes an adherend and a laminate having an adhesive sheet bonded to the adherend. Preparing the adhesive sheet comprising an adhesive layer that is cured by ionizing radiation, and a labeling material that displays characters, figures, or colors according to the irradiation amount of the ionizing radiation, and the ionizing radiation on the adhesive sheet. , The step of stopping the irradiation of the ionizing radiation after the marking material displays characters, figures or colors by the irradiation of the ionizing radiation, and the adhesive sheet is bonded to the surface of the adherend. And a process.

  In the method for producing a laminate according to the present invention, the labeling material is selected from a labeling compound contained in the adhesive layer, a labeling compound-containing seal constituting the adhesive sheet, and a labeling compound layer constituting the adhesive sheet. It can be configured to be any one or two or more.

  In the method for manufacturing a laminate according to the present invention, the step of irradiating the ionizing radiation is a step of irradiating the ionizing radiation to the adhesive sheet to start curing of the adhesive layer, and a step of bonding the adhesive sheet Is a step of bonding the adhesive layer to the adherend after curing is started in the step of irradiating the ionizing radiation, and the curing of the adhesive sheet after being bonded to the adherend is the step of It can be configured to proceed at the environmental temperature of the adherend.

  In the manufacturing method of the laminated body which concerns on this invention, the said adhesive sheet can be comprised so that a repair or a reinforcement member may be provided.

  In the manufacturing method of the laminated body which concerns on this invention, the said repair or reinforcement member can be comprised so that it may be contained in the inside of the said contact bonding layer, or provided in the one surface of the said contact bonding layer.

(2) An adhesive sheet according to the present invention for solving the above-described problems is used in the method according to the present invention.

(3) An adhesive sheet according to the present invention for solving the above-mentioned problems is an adhesive sheet that is bonded to an adherend to form a laminate, an adhesive layer that is cured by ionizing radiation, and irradiation of the ionizing radiation. It has a marking material for marking letters, figures or colors according to the quantity.

  In the adhesive sheet according to the present invention, the labeling material is any one selected from a labeling compound included in the adhesive layer, a labeling compound-containing seal constituting the adhesive sheet, and a labeling compound layer constituting the adhesive sheet. Or it can comprise so that it may be two or more.

  In the adhesive sheet according to the present invention, the adhesive layer contains a compound that releases the polymerization initiating substance upon receiving the ionizing radiation, and the compound releases the polymerization initiating substance after receiving the ionizing radiation. It can be configured to proceed at the normal ambient temperature of the adherend.

  The adhesive sheet which concerns on this invention WHEREIN: The said adhesive sheet can be comprised so that a repair or reinforcement member may be provided.

  In the adhesive sheet according to the present invention, the repair or reinforcement member may be included in the adhesive layer or provided on one surface of the adhesive layer.

  According to the present invention, a method of manufacturing a laminate that can greatly omit the bonding operation of the adhesive sheet to the adherend and can perform the bonding of the adhesive sheet in a short time with reduced variation in the adhesive strength, and An adhesive sheet used in the method can be provided.

A laminate (A) obtained by laminating an adhesive layer containing a labeling compound on the surface of the adherend, and an adhesive sheet provided with the adhesive layer and a labeling compound-containing seal provided on one side of the adhesive layer. Schematic showing the laminate (C) laminated on the surface of the adherend and the laminate (B) laminated with the adhesive sheet provided with the adhesive layer and the indicating compound layer provided on one side of the adhesive layer FIG. Adhesive layer (A) containing a repair or reinforcement member and an indicator compound, an adhesive layer containing a repair or reinforcement member, a release film provided on one side of the adhesive layer, and an indication compound-containing seal provided on the other side of the adhesive layer And an adhesive sheet including a repair or reinforcement member, a labeling compound layer provided on one side of the adhesive layer, and a release sheet provided so as to sandwich them from both sides It is typical sectional drawing which shows (C). Adhesive sheet (A) in which a release sheet, an adhesive layer containing a marking compound, and a repair or reinforcement member are sequentially laminated, and an adhesive sheet (B) in which a marking compound-containing seal, an adhesive layer, and a repair or reinforcement member are laminated in order It is a typical sectional view showing. It is typical sectional drawing which shows the other example of the adhesive sheet (A labeling material is included but abbreviate | omitted here for convenience) provided with the contact bonding layer and the repair or reinforcement member at least.

  The manufacturing method of the laminated body which concerns on this invention, and an adhesive sheet are demonstrated. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist thereof.

[Manufacturing method of laminate]
The manufacturing method of the laminated body which concerns on this invention is a method of manufacturing the laminated body 100 by laminating | stacking the adhesive sheet 10 and the to-be-adhered body 5 as shown in FIG. The characteristic is that a process (preparation process) of preparing an adhesive sheet 10 including an adhesive layer 2 that is cured by ionizing radiation and an indicator material (indicator) 4 that displays characters, figures, or colors according to the irradiation amount of ionizing radiation. And a step (irradiation step) of irradiating the adhesive sheet 10 with ionizing radiation, and a step (irradiation) of stopping the ionizing radiation after the marking material 4 displays the character, figure or color by the irradiation of the ionizing radiation. A stopping process) and a process of bonding the adhesive sheet 10 to the target structure (bonding process). Moreover, the manufacturing method of the laminated body which concerns on this invention may be equipped with the adhesive sheet repair or the reinforcement member 3, as shown in FIGS.

  According to this method, since the marking material (also referred to as an indicator or indicator) 4 for marking characters, figures, or colors according to the dose of ionizing radiation is provided, the ionizing radiation to the adhesive layer 2 cured by the ionizing radiation can be obtained. The dose can be made as constant as possible. As a result, variations in the curing time of each part can be suppressed, and variations in the adhesive strength and adhesive strength of the adhesive layer 2 after a certain period of time can be reduced. By such a method, it is possible to greatly omit the work of bonding the adhesive sheet 10 to the adherend 5 and to perform it in a short time.

  In addition, for example, the adhesive which does not completely cure immediately after irradiation with ionizing radiation but gradually cures at the ambient temperature around the adherend 5 to which the adhesive sheet 10 is bonded (this temperature is referred to as “normal ambient temperature”). In the case where the layer 2 is employed, the curing can be gradually advanced without applying a positive curing means thereafter. If the delayed-curing type adhesive layer 2 is adopted, the adhesive sheet 10 is cured and bonded to the adherend 5 while the adhesive sheet 10 is bonded to the target structure and the next work or setup is performed as it is. Can be glued to. As a result, the bonding work of the adhesive sheet 10 to the adherend 5 can be performed efficiently with good setup, and the total work time can be shortened.

  With the energy-saving methods described above, for example, in repair and reinforcement work for target structures such as tunnels and buildings, it is necessary to repair and reinforce in a short time with well-prepared places such as narrow places and high places. In constructions that must be controlled by traffic, tunnel construction at night, railway construction at night, etc., it is particularly important to perform adhesive sheet adhesion efficiently with reduced variations in adhesion strength, and the method according to the present invention. Can fully meet these requirements.

  Hereinafter, the manufacturing method of the laminated body using an adhesive sheet is demonstrated in detail.

(Adherent)
The adherend is a target to which the adhesive sheet is bonded, and is not particularly limited. Specific adherends include, for example, bridges, tunnels, road pavements, river management facilities, sabo dams, sabo floors, sewage pipes, sewage treatment plants, port facilities, public housing, collective housing, general housing, There are many social infrastructures such as city parks, coastal dikes, airports, airports, navigation signs, and government facilities. Hereinafter, a tunnel including a concrete material as an adherend will be described as an example.

[Preparation process]
The preparation step includes an adhesive sheet 10 including an adhesive layer 2 that is cured by ionizing radiation, and a marking material 4 that displays any one or two or more selected from characters, figures, and colors according to the dose of ionizing radiation. It is a process to prepare.

  The adhesive layer 2 may be a layer that becomes a cured adhesive layer by irradiation with ionizing radiation such as ultraviolet rays. The preferable adhesive layer 2 starts to be cured when it is exposed to ionizing radiation, but does not completely cure immediately after irradiation, and the ambient temperature around the adherend 5 to which the adhesive sheet 10 is bonded (this temperature is referred to as “normal ambient temperature”). It is a layer that hardens gradually. When the preferable adhesive layer 2 is applied, the adhesive sheet 10 can be provided with the delayed-curing type adhesive layer 2 that gradually cures and adheres without aggressive curing means thereafter. By using the adhesive sheet 10 having the delayed-curing type adhesive layer 2, it is possible to perform an efficient bonding operation and bonding operation to the adherend 5. Detailed description of the adhesive layer 2 will be described later.

  Moreover, the adhesive sheet 10 in the present invention may include a repair or reinforcement member 3 (hereinafter, abbreviated as a repair / reinforcement member 3) as necessary. As shown in FIG. 2, the repair / reinforcing member 3 may be one in which a delayed-curing adhesive is applied and impregnated in the adhesive, or as shown in FIG. 3 and FIG. It may be bonded to the adhesive layer 2. Detailed description of the repair / reinforcement member 3 will be described later.

  The marking material 4 is provided on the adhesive sheet 10 in various modes illustrated in FIG. 1 and is labeled according to the irradiation amount of ionizing radiation. When the marking material 4 receives ionizing radiation of a certain amount or more, the marking material 4 functions so that marking elements such as characters, figures, and colors appear. Since the labeling element appears during the irradiation of the ionizing radiation, it can be seen that the necessary ionizing radiation has been irradiated, so that the irradiation of the ionizing radiation can be stopped at that time. The irradiation amount of ionizing radiation until the marking element appears can be arbitrarily set according to the type of the marking material 4. Moreover, the marking material 4 can also be arbitrarily selected according to the kind and wavelength of ionizing radiation. Marking elements such as characters, figures, and colors may be used alone or in combination. Although the specific marking material 4 will be described later, it may be the marking compound 4a contained in the adhesive layer 2 as shown in FIG. 1 (A), or the adhesive layer as shown in FIG. 1 (B). It may be a labeling compound-containing seal 4b affixed to 2 or the like, or may be a labeling compound layer 4c provided on the adhesive sheet 10 as shown in FIG.

  The marking material 4 can indicate that the irradiation amount for curing the above-described adhesive layer 2 with ionizing radiation has been reached. In addition, when ionizing radiation is applied, curing starts, but the adhesive layer 2 that does not completely cure immediately after irradiation and gradually cures at the normal environmental temperature of the adherend 5 to which the adhesive sheet 10 is bonded is provided. The necessary or sufficient irradiation amount at which the adhesive layer 2 can be gradually cured at a normal ambient temperature after irradiation with ionizing radiation can be shown as a guideline for irradiation in advance. In this case, by irradiating with ionizing radiation until the marking material 4 provided in each part of the adhesive sheet 10 marks the marking elements (characters, figures, etc.), thereafter, it gradually cures at the normal environmental temperature of the adherend 5. It is possible to arrange time and the like, and work can be performed efficiently with good setup.

(Irradiation process)
An irradiation process is a process of irradiating the adhesive sheet 10 with ionizing radiation. Since the curing of the adhesive layer 2 is started by this irradiation, the irradiation process can also be called a curing start process. This irradiation process may be performed after (A) bonding the adhesive sheet 10 to the adherend 5 or (B) before bonding the adhesive sheet 10 to the adherend 5.

  As in (A) above, the adhesive layer 2 may be immediately cured by the ionizing radiation applied after the adhesive sheet 10 is bonded to the adherend 5, or the adhesive layer 2 may be cured slowly. When the ionizing radiation is irradiated after the adhesive sheet 10 is bonded to the adherend 5, a portable ionizing radiation device or the like can be used.

  As in (B) above, the adhesive layer 2 may be slowly cured by ionizing radiation that is irradiated before the adhesive sheet 10 is bonded to the adherend 5. In (B), the adhesive sheet 10 is bonded to the adherend 5 while the curing is not progressing so much, and the curing of the adhesive sheet 10 after the bonding is advanced at the environmental temperature of the adherend 5. Can be configured. When irradiating ionizing radiation before bonding the adhesive sheet 10 to the adherend 5, a portable ionizing radiation device may be used, or an installation type ionizing radiation device may be used. In particular, by using an installation type ionizing radiation apparatus, it is possible to irradiate ionizing radiation in a flat or wide area of the work place. For example, an installation type ionizing radiation irradiation apparatus can be placed in a work place, and the adhesive sheet 10 can be irradiated with ionizing radiation with a roll-to-roll. Alternatively, the adhesive sheet 10 may be placed in a work place, and the adhesive sheet 10 may be irradiated using, for example, a hand-held ionizing radiation irradiation apparatus. Moreover, when there is no specific ionizing radiation irradiation apparatus (for example, ultraviolet irradiation apparatus etc.), sunlight etc. may be sufficient, and ionizing radiations, such as an ultraviolet-ray contained in sunlight, are included in "ionizing radiation" in this application.

  In any of the above (A) and (B), among the irradiation conditions of ionizing radiation, the irradiation conditions when irradiating with ultraviolet rays differ depending on the type of the curing agent. For example, as in the examples described later, the wavelength is 300 nm. Irradiation conditions with an integrated light quantity of 50 mJ / cm 2 or more and 3000 mJ / cm 2 or less can be given in a region of ˜370 nm. Moreover, although the conditions in the case of irradiating an electron beam also change with kinds of hardening | curing agent, the irradiation conditions of the grade of 50 kGy or more and 100 kGy or less can be mentioned.

  In the above (B), it is necessary that the adhesive sheet 10 after being irradiated with ionizing radiation is rapidly cured and the adhesive sheet 10 does not lose its adhesiveness before being bonded. That is, while performing the operation | work which bonds the adhesive sheet 10 at the below-mentioned bonding process, it must have adhesiveness. Since the working time is usually about 30 seconds or more and 24 hours or less, it is preferable that the curing is completed at least within the time range and the tackiness is not lost.

  In the above (A) and (B), when the adhesiveness that can be bonded is evaluated by the adhesive strength against aluminum, the adhesive strength is at least 0.01 N / inch or more and 50 N / inch or less. Is preferred. "At least" means a range that is an adhesive force that can be bonded to the adherend 5 and maintain the bonded state if it has a minimum range of adhesive strength, and the upper limit is further It may be a large value. And by having adhesive force of this range, the adhesive sheet 10 can be preferably bonded to the adherend 5. For example, when pasting together before irradiating with ionizing radiation as in (A) above, it is desirable that the adhesive layer 2 has an adhesive strength within the above range, and ionizing radiation is applied as in (B) above. In the case of bonding after irradiation, it is desirable to bond to the adherend 5 while the adhesive layer 2 has an adhesive strength within the above range.

  In addition, in (B), since the change of the adhesive force of the adhesive layer 2 after irradiating the adherend 5 with ionizing radiation does not occur abruptly, the adhesive force within the above range is the same as before irradiating the ionizing radiation. It can be evaluated as the adhesive strength. Therefore, the adhesive sheet 10 subjected to the irradiation process has an adhesive strength before irradiation with ionizing radiation of at least 0.01 N / inch to 50 N / inch, and the adhesive strength is at least 30 seconds or more and 24 hours. It is desirable to keep within the following range. Using the adhesive sheet 10 having such adhesive properties and adhesive strength retention properties, it is possible to start curing by irradiating with ionizing radiation, and then perform an efficient laminating operation with good workability on the adherend 5. it can.

(Irradiation stop process)
The irradiation stopping process is a process of stopping the irradiation of ionizing radiation after the marking material 4 displays characters, figures or colors by irradiation of ionizing radiation. In this process, since the irradiation of ionizing radiation is stopped after the marking material 4 displays characters, figures, or colors, the dose of ionizing radiation can be adjusted within a predetermined range. As a result, it is possible to prevent partial irradiation or insufficient irradiation, and the adhesive layer 2 can be cured without variation.

  The marking material 4 is labeled according to the dose of ionizing radiation, and functions so that, for example, marking elements such as characters, figures, and colors appear when receiving a certain amount or more of ionizing radiation. When the marking element appears, it can be seen that the necessary ionizing radiation has been irradiated, so that the irradiation of the ionizing radiation can be stopped at that time. The irradiation amount of ionizing radiation until the marking element appears can be arbitrarily set according to the type of the marking material 4. The marking material 4 can be arbitrarily selected according to the type and wavelength of ionizing radiation. Marking elements such as characters, figures, and colors may be used alone or in combination.

  Although the specific marking material 4 will be described later, it may be the marking compound 4a contained in the adhesive layer 2 as shown in FIG. 1 (A), or the adhesive sheet as shown in FIG. 1 (B). It may be the labeling compound-containing seal 4b attached to the labeling material 10 or the labeling compound layer 4c provided on the adhesive sheet 10 as shown in FIG.

(Bonding process)
The bonding process is a process of bonding the adhesive sheet 10 to a target structure (not shown). As described above, this bonding step may be performed before the adhesive layer 2 is irradiated with ionizing radiation, or may be performed after the adhesive layer 2 is irradiated with ionizing radiation.

  Among the above, in the case of bonding after irradiation with ionizing radiation, it is possible to positively irradiate ionizing radiation or actively heat the adhesive sheet 10 bonded to the adherend 5. do not do. That is, no intentional curing work is performed. Therefore, the adhesive sheet 10 can be cured and adhered to the adherend 5 while the adhesive sheet 10 is bonded to the adherend 5 and the next operation or setup is performed as it is. As described above, the bonding time is usually in the range of 30 seconds to 24 hours. It is desirable that the adhesive strength of the adhesive sheet 10 that has been subjected to the curing start process does not decrease so much within the time of the bonding operation. It is desirable that the adhesive force retained during the bonding is an adhesive force within a range of 001 N / inch to 50 N / inch before irradiation with ionizing radiation. The adhesive sheet 10 having an adhesive strength within this range after the curing treatment can be well bonded to the adherend 5.

(Lamination of each adhesive sheet)
Each adhesive sheet 10 shown in FIGS. 1 to 4 may be irradiated with ionizing radiation after the adhesive sheet 10 is bonded to the adherend 5 as shown in (A) and (B) above. ) Ionizing radiation may be irradiated before the adhesive sheet 10 is bonded to the adherend 5. Below, although the aspect which irradiates ionizing radiation before bonding the adhesive sheet 10 to the to-be-adhered body 5 is demonstrated, it is not limited to this aspect.

  The adhesive sheet 10 shown in FIG. 1A is an adhesive sheet 10 in a mode in which the labeling compound 4 a is included in the adhesive layer 2. In the adhesive sheet 10 shown in FIG. 1 (A), ionizing radiation is irradiated until a labeling element such as the color of the labeling compound 4a appears, and then the surface S1 to be attached to the adherend 5 such as concrete is adhered to the adherend. 5 can be applied.

  The adhesive sheet 10 shown in FIG. 1 (B) is an adhesive sheet 10 in a mode in which the labeling compound-containing seal 4b is bonded to the adhesive sheet (preferably the adhesive layer 2). The adhesive sheet 10 is irradiated with ionizing radiation until a marking element such as characters, graphics, and colors of the marking compound-containing seal 4b appears, and then the surface S1 to be attached to the adherend 5 such as concrete is adhered to the adherend. 5 can be applied.

  The adhesive sheet 10 shown in FIG. 1C is an adhesive sheet 10 in an embodiment in which the marking compound layer 4c is provided on the adhesive sheet (preferably the adhesive layer 2). The adhesive sheet 10 is irradiated with ionizing radiation until a marking element such as characters, figures, and colors of the marking compound layer 4c appears, and then the surface S1 to be bonded to the adherend 5 is pasted to the adherend 5. Can be installed.

  An adhesive sheet 10 </ b> A shown in FIG. 2A is an adhesive sheet 10 in a mode in which the labeling compound 4 a is included in the adhesive layer 2 and the repair / reinforcing member 3 is impregnated in the adhesive layer 2. In the adhesive sheet 10A shown in FIG. 2 (A), ionizing radiation is irradiated until a labeling element such as the color of the labeling compound 4a appears, and then the surface S1 to be attached to the adherend such as concrete is attached to the adherend. Affixing and then peeling off the release film 1 provided on the opposite surface S2 can be applied.

  The adhesive sheet 10B shown in FIG. 2 (B) has a mode in which the labeling compound-containing seal 4b is bonded to the adhesive sheet (preferably the adhesive layer 2), and the repair / reinforcing member 3 is impregnated in the adhesive layer 2. It is an adhesive sheet. In this adhesive sheet 10B, ionizing radiation is irradiated until marking elements such as characters, figures, colors, etc. of the marking compound-containing seal 4b appear, and then the surface S1 to be attached to the adherend such as concrete is attached to the adherend. Affixing and then peeling off the release film 1 provided on the opposite surface S2 can be applied.

  The adhesive sheet 10C shown in FIG. 2C is an adhesive sheet in which the marking compound layer 4c is provided on the adhesive sheet (preferably the adhesive layer 2), and the repair / reinforcing member 3 is impregnated in the adhesive layer 2. is there. In this adhesive sheet 10C, irradiation with ionizing radiation is performed until marking elements such as characters, graphics, and colors of the marking compound layer 4c appear, and then the release film 1 ′ on the surface 1 to be attached to the adherend is peeled off and exposed. The applied adhesive layer 2 can be applied to the adherend, and then the release film 1 provided on the opposite surface S2 can be peeled off for application.

  In the adhesive sheets 10A, 10B, and 10C shown in FIGS. 2A, 2B, and 2C, other members such as a protective member, a cover member, and other repair / reinforcement members are attached to the exposed adhesive layer 2. Can do. Further, in the adhesive sheet 10C, the release film 1 on the surface S2 opposite to the surface S1 to be attached to the adherend is peeled off, and the other member is attached to the exposed adhesive layer 2, and in this state, the adherend 5 It is also possible to peel off the release film 1 ′ on the side S 1 to be attached to and adhere the exposed adhesive layer 2 to the adherend.

  An adhesive sheet 10 </ b> D shown in FIG. 3A is an adhesive sheet in which the labeling compound 4 a is included in the adhesive layer 2 and the repair / reinforcing member 3 is bonded to one surface S <b> 2 of the adhesive layer 2. In this adhesive sheet 10D, ionizing radiation is irradiated until a labeling element such as the color of the labeling compound 4a appears. Thereafter, the release film 1 on the surface S1 to be attached to the adherend is peeled off, and the exposed adhesive layer 2 is covered. Can be applied to the body. Since the repair / reinforcing member 3 sticks to the adhesive layer 2 in advance, the adhesive sheet 10D can be easily constructed.

  In the adhesive sheet 10E shown in FIG. 3B, the labeling compound-containing seal 4b is bonded to the adhesive sheet (preferably the adhesive layer 2), and the repair / reinforcing member 3 is bonded to one surface S2 of the adhesive layer 2. It is an adhesive sheet. In this adhesive sheet 10E, ionizing radiation is irradiated until marking elements such as characters, figures, colors, etc. of the marking compound-containing seal 4b appear, and then the surface S1 to be bonded to the adherend 5 is pasted to the adherend. Can be installed. Since the repair / reinforcing member 3 is adhered to the adhesive layer 2 in advance, the adhesive sheet 10E can be easily constructed.

  Although FIG. 4 (A)-(C) does not describe the marking material 4 for convenience, in order to compare the aspect of the peeling film with which the adhesive sheet 10 is provided, the marking material 4 is as shown in FIGS. It can be provided in various modes.

  An adhesive sheet 10 </ b> F illustrated in FIG. 4A is an adhesive sheet in which adhesive layers 2 and 2 ′ are bonded to both sides of the repair / reinforcing member 3. In this adhesive sheet 10F, similar to the above-described adhesive sheet 10D, the release film 1 provided on the surface S1 on the side to be attached to the adherend is peeled off, and the exposed adhesive layer 2 is attached to the adherend and applied. Can do. The adhesive sheet 10F can then be peeled off the release film 1 'as necessary, and a functional sheet or layer can be provided on the exposed adhesive layer 2'. On the other hand, the adhesive sheets 10G and 10H shown in FIGS. 3B and 3C are adhesive sheets in which the adhesive layers 2 and 2 ′ are bonded to both sides of the repair / reinforcing member 3. In the adhesive sheets 10G and 10H, similarly to the above-described adhesive sheet 1E, the surface S1 on the side to be attached to the adherend can be attached to the adherend and applied. Further, since the adhesive layer 2 ′ is provided similarly to the adhesive sheet 10 </ b> F shown in FIG. 3A, a functional film or layer can be provided on the adhesive layer 2 ′.

  In this way, the repair / reinforcement member 3 is adhered to the adherend using the adhesive sheets 10A to 10H. At that time, it is preferable that the adhesive layer 2 is pressure-bonded to the adherend with a roller or the like. When the adhesive layer 2 is irradiated with ionizing radiation in advance, since the curing of the adhesive layer 2 has already started, it is not necessary to apply the curing means more positively. The pressure bonding and the heat curing may be performed simultaneously, or the curing may be further promoted by blowing warm air after the roller pressure bonding.

  The repair / reinforcement member 3 shown in FIG. 2 is a repair / reinforcement member that can be impregnated in a delayed-curing adhesive that is not cured immediately after irradiation with ionizing radiation. Moreover, you may affix on the contact bonding layer 2 like the repair and reinforcement member 3 shown in FIG.3 and FIG.4. Examples of the repair / reinforcement member 3 include aramid fibers, carbon fibers, vinylon fibers, and PET fibers for reinforcement applications. Moreover, in the repair use which can provide a function, an advertising signboard, a coating film, a waterproof sheet, a water absorbing sheet, an ultraviolet resistant sheet, a water retaining sheet, a colored sheet, and the like can be given. In addition, reinforcement includes repairs that conceal cracks or erase unevenness, and further includes those that provide functions such as strength improvement, water retention, surface protection, and decoration.

  In addition, before bonding the adhesive sheet 10 to the adherend 5, a primer may be applied to the target structure. The primer applied at this time functions to adhere the adhesive layer 2 on the adherend 5 with good adhesion. Examples of the primer include Alpron 301 manufactured by Japan-US Resin Co., Ltd., Primer II for reinforced concrete manufactured by Mizutani Paint Co., Ltd., etc., and the primer is applied within a range of about 1 μm or more and 1 mm or less. Can be thick.

  As described above, by using the adhesive sheet 10 provided with the adhesive layer 2 that is cured by ionizing radiation and the marking material (indicator) 4 that displays characters, figures, or colors according to the irradiation amount of the ionizing radiation, The operation of adhering the adhesive sheet to the adherend 5 can be greatly omitted, and the adhesive sheet 10 can be adhered in a short time while reducing variations in adhesive strength. As a result, for example, of the problems related to social infrastructure development, repair or reinforcement work for many social infrastructures that require repair and reinforcement such as tunnels and buildings can be greatly omitted and performed in a short time. be able to.

  Further, by using the adhesive sheet 10 having the delayed-curing type adhesive layer 2 that is not immediately cured even when irradiated with ionizing radiation, the irradiation of the ionizing radiation on the side of the adhesive sheet 10 to be bonded to the adherend 5 is performed. This can be performed on the adhesive layer 2. As a result, for example, even when the repair / reinforcement member 3 having no light transmittance is included, it can be easily attached. Further, since ionizing radiation such as ultraviolet rays can be applied to the adhesive sheet 10 with a roll-to-roll, there is an advantage that it is not necessary to perform ionizing radiation irradiation work in a high place or a narrow place as in the past.

[Adhesive sheet]
The adhesive sheet 10 used by said method is demonstrated. The adhesive sheet 10 is a sheet that is bonded to the adherend 5 and adhered to the adherend 5. And the characteristic has in having the adhesion layer 2 hardened | cured with ionizing radiation, and the marking material 4 which displays a character, a figure, or a color according to the irradiation amount of ionizing radiation. In addition, as shown in FIGS. 2-4, the adhesive sheet 10 may have the repair or the reinforcement member 3, as needed, and the peeling films 1 and 1 'are provided on the single side | surface or both surfaces of the contact bonding layer 2. You may have. Hereinafter, each component will be described.

(Adhesive layer)
The adhesive layer 2 is formed of a resin composition containing an ionizing radiation curable resin material and a curing agent for the ionizing radiation curable resin. The resin composition is not particularly limited as long as it is cured by irradiation with ionizing radiation, and various types of resin compositions can be applied. It may be cured immediately after irradiation with ionizing radiation, or may be cured slowly upon irradiation with ionizing radiation.

  Examples of the ionizing radiation curable resin material include an epoxy resin, an acrylic resin, and a urethane resin. Examples of the curing agent include a photo radical generator, a photo acid generator, a photo base generator, and the like.

  Hereinafter, the formation of the adhesive layer 2 that is delayed-cured will be mainly described.

  The adhesive layer 2 that does not cure immediately after being irradiated with ionizing radiation but is delayed cured comprises one or both of an ionizing radiation curable liquid epoxy resin and a solid epoxy resin, and a curing agent for the ionizing radiation curable resin. It is preferable to form with the resin composition containing. Since the adhesive layer 2 formed of a resin composition containing a resin component is an adhesive layer that is delayed-cured even when irradiated with ionizing radiation, it can be bonded to the adherend 5 with an adhesive force before irradiation with ionizing radiation. it can. As a result, the adhesive sheet 10 can be bonded to the adherend 5 through the adhesive layer 2 after irradiation with ionizing radiation. Further, since the adhesive layer 2 has not yet been sufficiently cured by delayed curing, after the adhesive sheet 10 is bonded to the adherend 5, the adhesive sheet 10 can be peeled off and bonded again. The adhesive layer 2 before irradiation with ionizing radiation has adhesive performance, and the adhesive layer 2 after irradiation with ionizing radiation has adhesive performance. Therefore, the surface of the adherend 5 is a vertical surface or a ceiling surface. Even if it exists, the adhesive sheet 10 can be bonded to the adherend 5 through the adhesive layer 2 in both cases before and after irradiation with ionizing radiation.

  The adhesive layer 2 before being irradiated with ionizing radiation is attached so that one surface thereof adheres to the adherend 5. In addition, other members (a protective member, a cover member, another repair / reinforcement member, etc.) are attached to the other surface. In the present application, “adhesion” means having adhesion performance and is used as a temporary adhesion phenomenon, whereas “adhesion” means having adhesion performance and is permanent. It can be distinguished in that it is used to mean a special adhesion phenomenon (Iwanami Shoten RIKEN Dictionary 5th edition).

  The adhesive layer 2 is a layered or sheet-shaped composition for forming an adhesive layer, and is usually provided on the release film 1 like an adhesive sheet 10 described later. The composition for forming an adhesive layer is a resin composition for forming the adhesive layer 2 by coating or the like. The adhesive layer composition can contain various resins, but can be composed of components for forming an adhesive layer. Examples of the component include an ionizing radiation curable acrylic resin, a liquid epoxy resin, an epoxy resin such as a solid epoxy resin, and a curing agent for the ionizing radiation curable resin.

  The adhesive layer 2 contains chemical species that enable delayed curing as delayed curing means. Although various means can be considered as the delayed curing means, in the present application, there can be mentioned the delayed curing means performed by a chemical species that receives ionizing radiation and releases a polymerization initiating substance.

  Among the delayed curing means, examples of the chemical species that release the polymerization initiating substance upon receiving ionizing radiation include chemical species in which a curing accelerating substance (for example, a base) is gradually generated by ionizing radiation, such as a photobase generator. it can.

  The photobase generator is a chemical species in which a base that is a curing accelerator is gradually generated by ionizing radiation. For example, it is preferable that the base be generated by irradiation with ionizing radiation such as ultraviolet rays or electron beams, which is represented by the following chemical formula.

  In the photobase generator, R1 and R2 are each independently hydrogen or a monovalent organic group, and may be the same or different. R1 and R2 may combine with each other to form a cyclic structure. However, at least one of R1 and R2 is a monovalent organic group. R3, R4, R5 and R6 are each hydrogen, halogen or a monovalent organic group, and may be the same or different. Two or more of R3, R4, R5 and R6 may be bonded to form a cyclic structure.

  The photobase generator generates a base when irradiated with ionizing radiation such as ultraviolet rays or an electron beam, and the generation of the base is promoted. Therefore, a base can be efficiently generated by irradiation with ionizing radiation. The photobase generator refers to an agent that does not exhibit activity under normal conditions of normal temperature and pressure, but generates a base when ionizing radiation is applied as an external stimulus. Since the photobase generator has the above specific structure, by irradiation with ionizing radiation, the (—CH═CHC (═O) —) moiety in the chemical formula is isomerized into a cis isomer, cyclized, It produces an amine, NHR1R2.

  The content in the case where the curing agent that cures the adhesive layer 2 by irradiating with ionizing radiation is a curing agent that initiates cationic polymerization by irradiation with ionizing radiation is, for example, 1% by mass or more with respect to the epoxy resin. It is preferable to be within the range of mass% or less. In addition, the content when using an epoxy resin and an equivalent reaction type curing agent such as a phenolic curing agent or an acid anhydride curing agent is, for example, 0.8 equivalent or more with respect to the epoxy equivalent of the epoxy resin, It is preferably within the range of 1.2 equivalents or less. In addition, the content when the curing catalyst in the equivalent reaction system of the epoxy resin of the photobase generator is used in combination is, for example, in the range of 0.5% by mass or more and 10% by mass or less for the epoxy resin. It is preferable.

  The adhesive layer 2 is, for example, a coupling agent for improving the adhesion between the adherend 5 and the adhesive layer 2 or a composition for forming an adhesive layer, as long as the object of the present invention is not impaired. Various additives such as a leveling agent for improving the coating properties of the film may be included. Further, a tackifier may be included to increase the adhesive strength, and a filler or the like may be included to improve the shear strength.

  The thickness of the adhesive layer 2 is preferably in the range of 150 μm or more and 500 μm or less, and more preferably in the range of 150 μm or more and 300 μm or less.

  The adhesive layer 2 is provided on the release film 1 that has been subjected to an easy release treatment. The release film 1 will be described in detail in the column of the form of the adhesive sheet described later.

  The composition for forming an adhesive layer is prepared by blending, stirring and dissolving the above-described raw materials. The stirrer used for stirring is not particularly limited, and a normal kneading disperser, for example, a two roll mill, a three roll mill, a pebble mill, a tron mill, a high speed impeller disperser, a high speed stone mill, a high speed impact mill, a disper, a high speed mixer, A ribbon blender, a kneader, an intensive mixer, a tumbler, a blender, a disperser, a homogenizer, an ultrasonic disperser, and the like can be applied.

  The application method of the composition for forming an adhesive layer is not particularly limited. Examples of the formation method by printing include a gravure printing method, a flexographic printing method, and an offset printing method. Examples of the coating method include roll coating, reverse coating, comma coating, knife coating, die coating, and gravure coating.

  Drying of the composition for forming an adhesive layer after being applied can sufficiently volatilize the solvent contained in the composition for forming an adhesive layer, and the curing of the ionizing radiation curable resin is excessively accelerated. It is preferable to carry out under conditions that do not deteriorate the adhesive performance. As drying conditions, it is usually carried out by holding at a temperature in the range of 50 ° C. or more and 100 ° C. or less for 2 minutes or more and 20 minutes or less.

(Adhesive sheet form)
The adhesive sheet 10 (10A, 10B, 10C, 10D) includes, for example, the above-described adhesive layer 2 and one side (S1) of the adhesive layer 2 as shown in FIGS. 2 (A) to (C) and FIG. 3 (A). Or it has the peeling film 1 provided in S2). This adhesive sheet 10 may be an adhesive sheet 10A, 10B, 10D in which the release film 1 is provided only on one side (S2 or S1), or the release films 1, 1 ′ are provided on both sides S1, S2. The adhesive sheet 10C may be used. Among these, the adhesive sheets 10A and B shown in FIGS. 2A to 2C include the repair / reinforcing member 3 in the adhesive layer 2, and the marking material 4 is included in the manner described above. Yes.

  Moreover, the adhesive sheet 10 (10D, 10E) includes, for example, the above-described adhesive layer 2 and the repair / reinforcing member 3 provided on one surface S2 of the adhesive layer 2 as shown in FIGS. Have This adhesive sheet 10 may be an adhesive sheet 10D in which the repair / reinforcing member 3 is provided on one side S2 of the adhesive layer 2 and the release film 1 is provided on the other side S1, or one side of the adhesive layer 2 The repair / reinforcement member 3 may be provided in S2, and the adhesive sheet 10E in which nothing is provided on the other surface S1 may be used. Note that the marking material 4 is included in the above-described manner.

  Further, the adhesive sheet 10 (10F, 10G, 10H) is repaired / configured to form the adhesive sheets 10D, 10E of FIGS. 3A and 3B, as shown in FIGS. 4A, 4B, and 4C, for example. In this embodiment, an adhesive layer 2 ′ is further provided on the reinforcing member 3. That is, the adhesive sheet 10 shown in FIG. 4 includes the adhesive layer 2 described above, the repair / reinforcement member 3 provided on one surface S2 of the adhesive layer 2, and the adhesive layer 2 provided on the repair / reinforcement member 3. 'And have. On the adhesive layer 2 ′, a release film 1 ′ may be provided as shown in FIGS. 4A and 4C, or no release film is provided as shown in FIG. 4B. Also good. “On the repair / reinforcement member 3” means on the opposite surface of the repair / reinforcement member 3 to the side where the adhesive layer 2 is provided. In FIG. 4, reference sign S <b> 2 ′ is a surface of the adhesive layer 2 ′ on the repair / reinforcement member side, and reference sign S <b> 1 ′ is a surface of the adhesive layer 2 ′ opposite to the repair / reinforcement member side. Note that the marking material 4 is included in the above-described manner.

  The adhesive layer 2 ′ may be composed of the same component as the adhesive layer 2 described above or may be composed of a different component, but the same component is desirable from the viewpoint of manufacturing cost.

(Repair and reinforcement members)
As shown in FIG. 2, the repair / reinforcing member 3 may be one in which a delayed-curing adhesive is applied and impregnated in the adhesive, or as shown in FIG. 3 and FIG. It may be bonded to the adhesive layer 2.

  Examples of the repair / reinforcing member 3 include one or more selected from polyester fiber, polyamide fiber, aramid fiber, vinylon fiber, carbon fiber, glass fiber, polyolefin fiber, and the like. Among these, 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. In addition, reinforcement includes repairs that conceal cracks or erase unevenness, and further includes those that provide functions such as strength improvement, water retention, surface protection, and decoration.

  In addition, a sheet-like member such as a waterproof sheet, a water-absorbing sheet, an ultraviolet-resistant sheet, a water-retaining sheet, or a colored sheet may be used as the repair / reinforcement member 3, or a sheet-like repair / reinforcement member and a fibrous repair / reinforcement member. May be combined.

  The repair / reinforcement member 3 can support the peeled adherend piece or the adherend piece that may be peeled off when a part of the adherend 5 peels off or when there is a risk of peeling. It is preferable to have strength (reinforcing strength). For example, the strength may be 1500 N or more when the displacement is 10 mm or more in the punching test specified by the former Japan Highway Public Corporation (East Japan Expressway Co., Ltd., Central Japan Expressway Co., Ltd., West Japan Expressway Co., Ltd.). preferable.

  The thickness of the repair / reinforcement member 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.

(Indication material)
The marking material 4 is labeled according to the dose of ionizing radiation, and functions so that, for example, marking elements such as characters, figures, and colors appear when receiving a certain amount or more of ionizing radiation. The marking material 4 can be arbitrarily selected according to the type and wavelength of ionizing radiation. Marking elements such as characters, figures, and colors may be used alone or in combination. Specifically, as shown in FIGS. 1 to 3, it may be a labeling compound 4 a included in the adhesive layer 2 or a labeling compound-containing seal 4 b attached to the adhesive sheet 10. The labeling compound layer 4c provided on the adhesive sheet 10 may be used.

  The indication compound 4a is a compound that develops color by receiving ionizing radiation (for example, ultraviolet rays), and examples thereof include a UV indicator pigment and a photochromic material. Such an indication compound 4a can be mixed in the resin composition constituting the adhesive layer 2 to constitute the adhesive layer 2 as shown in FIG. Although the content is not particularly limited, it can be within a range of 0.1 mass% or more and 99 mass% or less with respect to the total mass of the adhesive layer 2. Since the labeling compound 4a is contained in the adhesive layer 2, it is possible to irradiate the ionizing radiation with an appropriate dose over the entire range by confirming the labeling element such as the color.

  As shown in FIG. 1 (B) and FIG. 2 (B), the labeling compound-containing seal 4b is provided with the above-described labeling compound 4a on one side of the sealing substrate and a seal with an adhesive layer on the other side. Can be mentioned. Moreover, the seal | sticker which mixed the above-mentioned indication compound 4a with the adhesive and provided on the single side | surface of a sealing base material can be mentioned. As the indicating compound, the above-described indicating compound 4a can be applied. Similarly to the above, the content when the labeling compound is contained in the adhesive layer can be within the range of 0.1% by mass to 99% by mass with respect to the total mass of the adhesive layer. Unlike the following indication compound layer 4c, this indication compound containing seal | sticker 4b should just be affixed by the predetermined magnitude | size partially. The number of labeling compound-containing seals 4b may be one or a plurality. Since one or more labeling compound-containing seals 4b are provided, it is possible to irradiate ionizing radiation with an appropriate dose by confirming the labeling element of the seal.

  As shown in FIGS. 1C and 2C, the labeled compound layer 4c is formed by providing the above-described labeled compound in a layered form. As the indicating compound, the above-described indicating compound 4a can be applied. The labeling compound may be provided as it is in the form of a layer, or the labeling compound may be included in the adhesive layer. Similarly to the above, the content when the labeling compound is contained in the adhesive layer can be within the range of 0.1% by mass to 99% by mass with respect to the total mass of the adhesive layer. Since the marking compound layer 4c is provided, it is possible to irradiate ionizing radiation with an appropriate dose over the entire range by checking the marking element of the layer.

(Peeling film)
As shown in FIGS. 2 and 3, the release film 1 is provided on one side (S1 or S2) or both sides (S1 and S2) of the adhesive layer 2. The release film 1 covers one side (S1 or S2) or both sides (S1 and S2) of the adhesive layer 2 and acts to protect the adhesive layer 2 until use. As shown in FIGS. 2A and 2B, the release film 1 may be provided on the surface S <b> 2 opposite to the surface S <b> 1 on the side to be attached to the adherend among the surfaces S <b> 1 </ b> S <b> 2 of the adhesive layer 2. As shown in FIG. 2C, it may be provided on both the surface S2 and the surface 1 on the side to be attached to the adherend.

  Moreover, as shown in FIG. 3A and FIG. 4A, even if the release film 1 is provided on the surface S1 on the side to be adhered to the adherend among the surfaces S1 and S2 of the adhesive layer 2. Good. As shown in FIGS. 4A and 4C, when the adhesive layer 2 ′ is provided on the repair / reinforcing member 3, the release film 1 ′ may be provided on the adhesive layer 2 ′. Good.

  The surface on the adhesive layer side of the release film 1 is preferably subjected to an easy release treatment. The release film 1 subjected to the easy release treatment can be easily peeled off from the adhesive layer 2 after the adhesive layer 2 provided in the adhesive sheet 10 is attached to the adherend 5, for example.

  The release film 1 is not particularly limited as long as the release film 1 is provided on the surface of the adhesive layer 2 so as to be peelable, and has strength and flexibility that can protect the adhesive layer 2, and various films are used. Can do.

(Other)
Like the adhesive sheet 10 (10F, 10G, 10H), the adhesive layer (2, 2 ′) can be provided on both sides of the repair / reinforcing member 3, so that it can function like a double-sided tape. The adherend 5 can be attached to the surface S1 of the adhesive layer 2 of the adhesive sheet 10, and a functional sheet or layer to be described later can be attached to the surface S1 ′ of the adhesive layer 2 ′. The adhesive sheets 10F and 10H may be provided with functional sheets or layers instead of the release film 1 ′.

  Examples of the functional sheet or layer include one or more functions such as light resistance, water resistance, antifouling properties, weather resistance, impact resistance, scratch resistance, acid resistance, alkali resistance, and design properties. The sheet | seat or layer which has can be mentioned.

  As described above, the adhesive sheet 10 according to the present invention is a sheet that is bonded to the adherend 5 and adhered to the adherend 5, the adhesive layer 2 that is cured by ionizing radiation, and the irradiation of ionizing radiation. Since it has the marking material 4 for marking the character, figure or color according to the amount, the bonding work of the adhesive sheet 10 to the adherend 5 can be largely omitted, and the bonding strength of the adhesive sheet 10 can be varied. Can be performed in a short time.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  EXAMPLES The present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of the following examples unless it exceeds the gist.

[Example 1]
The concrete wall in the tunnel was used as the adherend 5, and the following adhesive sheet 10 was prepared on the adherend 5 in advance. Since the adhesive layer 2 of the prepared adhesive sheet 10 does not start to cure unless it receives ionizing radiation, it was stored in a light-shielding bag.

  In addition, the adhesive force of the adhesive layer 2 before the start of curing was about 17 N / inch when an aluminum hill was used as a bonding target. First, the prepared adhesive sheet 10 is cut into a length of 25 mm and a width of 150 mm, the release film of the adhesive sheet 10 is peeled off, and the exposed adhesive layer 2 is made of an aluminum alloy (A6061, sample: 25 mm × 150 mm). Then, the adhesive sheet 10 is peeled off by about 20 mm by hand, and using a tensile tester (manufactured by A & D Co., Ltd., model number: RTF-1150H), the conditions in conformity with JIS Z0237 (tensile speed: The adhesive force (N / 25 mm) to the aluminum plate surface was measured at 300 mm / min, peel distance: 150 mm, peel angle: 180 °.

  As the work, first, the adhesive sheet 10 was placed on the flat ground near the work place where light does not enter in the tunnel, and a portable ultraviolet irradiation device was held by hand to irradiate the adhesive sheet 10 with ultraviolet rays. Irradiation time was not concerned, and the ultraviolet light was irradiated until the color of the adhesive layer 2 became a predetermined color (blue in Example 1) by the indication compound 4a contained in the adhesive layer 2, and the irradiation was stopped after the entire surface was changed. . As the ultraviolet rays, ultraviolet rays having a wavelength of 300 nm to 370 nm were used. The indicating compound 4a changes at approximately 50 mJ / cm2 to 3000 mJ / cm2. When the adhesive force immediately after the irradiation was measured in the same manner as described above, it was the same as the adhesive strength before the irradiation.

  Next, the adhesive sheet 10 having a width of 1 m and a length of 1 m was cut from the wound irradiated roll. Carrying near the concrete wall in the tunnel to be constructed, peeling off the release film 1 provided on one side of the adhesive sheet 10, and pressing the exposed adhesive layer side with hand rolls from near the ground toward the ceiling Pasted. When the adhesive strength immediately after pasting was measured in the same manner as described above, it was the same as that before irradiation, and the adhesive strength was about 10 N / inch even when 24 hours had passed after irradiation with ionizing radiation. Was found to hold.

  After performing the bonding operation, no special curing treatment was performed, and no intentional curing operation was performed. And it was left as it was for 7 days at 18 to 25 degreeC which is the normal temperature of the construction place. After leaving, the workability was judged by checking that there was no floating. Good adhesion was confirmed when evaluated according to the evaluation criteria of “◯” when it adhered cleanly and did not float, and “x” when the adhesive was weak and could not be applied or when floating occurred.

  In addition, as the adhesion strength test, the same adhesive sheet 10 was bonded to the same concrete piece as described above under the same conditions as described above. It cut | disconnected to the magnitude | size of 40 mm x 40 mm using the concrete cutter, and evaluated by the peeling prevention performance verification test (JHS424 2004). As a result, it showed an adhesion strength of 2 N / mm 2, which was a practically acceptable level.

  Moreover, as peeling prevention property, it evaluated by the punching test (NEXCO test method, based on 424-2004). As a result, 5 kN or more was shown, and it was confirmed that there was no problem.

  In such a work, the adhesive sheet 10 can be cured and bonded to the adherend 5 while the bonded adhesive sheet 10 is left as it is and the next work or setup is performed. The bonding operation of the adhesive sheet 10 to the substrate can be performed efficiently with good setup, and the total operation time can be shortened. Therefore, for example, in repair and reinforcement work for tunnels and buildings, places where work is difficult such as narrow places and high places, construction that is performed with traffic regulation that must be repaired and reinforced in a short time with good setup, and nighttime It is particularly important to perform the tunnel construction, night railway construction, etc. efficiently, and the method according to the present invention can sufficiently meet such demands.

(Adhesive sheet)
The adhesive sheet 10 used is as follows. As release film 1, a polyester film (trade name: SP-PET-3, film thickness: 38 μm, manufactured by Tosero Co., Ltd.) having a release treatment with a silicone release agent on one side is prepared, and the release sheet is peeled off. On the treated surface, the following adhesive layer-forming coating solution was used and coated using an applicator so that the thickness after coating was 100 μm. Then, it was made to dry at 80 degreeC for 2 minute (s) in the drying oven, and the contact bonding layer 2 was formed. Two adhesive layers 2 were prepared. Next, carbon fiber (manufactured by Toho Tenax Co., Ltd., trade name: W-3101), which is a core material, is used on one surface of the two surfaces of the adhesive layer 2 obtained using a 2 kg roller at room temperature. The other side was stuck on a hot plate at about 60 ° C. using a 2 kg roller so as to come into contact with the aramid fiber. Thus, an adhesive sheet 10 of Example 1 was obtained.

(Adhesive layer forming composition)
・ Liquid epoxy resin (bisphenol A type epoxy resin, epoxy equivalent: 190 g / eq., Molecular weight: 380, manufactured by Mitsubishi Chemical Co., Ltd., trade name: jER828) 100 parts by mass. -3 mercaptopropionate, viscosity: 400 to 550 mPa · s / 25 ° C., mercaptan equivalent: 125 to 137 g / eq., Manufactured by Mitsubishi Chemical Corporation, trade name: QX40) 70 parts by mass acrylic resin (polar group is Introduced modified methyl methacrylate-butyl acrylate-methyl methacrylate triblock copolymer, Tg: −42 ° C., manufactured by Arkema Co., Ltd., trade name: M22N, 50 parts by mass, photobase generator A (see synthesis method below) ) 5 parts by mass / diluting solvent (ethyl acetate, DIC graphics) Scan Co., Ltd.) 100 parts by mass · UV indicator pigment (trade name: Sani color die staff blue, Co., Ltd. For the record material manufactured by Research Institute) 10 parts by weight

  The photobase generator A used 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 2hydroxy-4- (5-ethylhexyloxy)- After 1.7 g (6.2 mmol) of 5-ethylbenzaldehyde was added and dissolved, the well-stirred methanol solution of potassium carbonate was slowly added dropwise. And after stirring for 3 hours, completion | finish of reaction was confirmed by TLC. Subsequently, potassium carbonate was removed by filtration, and the filtrate was concentrated under reduced pressure. After concentration, 50 mL of 1N aqueous sodium hydroxide solution was added and stirred for 1 hour. After completion of the reaction, triphenylphosphine oxide was removed by filtration, and concentrated hydrochloric acid was added dropwise to acidify the reaction solution. The precipitate was collected by filtration and washed with a small amount of chloroform to obtain 1.7 g of 2-hydroxy-4- (5-ethylhexyloxy) -5-ethylcinnamic acid. Subsequently, 1.0 g (3.19 mmol) of 2-hydroxy-4- (5-ethylhexyloxy) -5-ethylcinnamic acid was dissolved in 10 mL of dehydrated tetrahydrofuran in a 10 mL three-necked flask in a nitrogen atmosphere, and the solution was placed in an ice bath. 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.73 g (3.83 mmol, 1.2 eq.) Was added. After 30 minutes, 129 mg (1.52 mmol, 0.95 eq.) Of piperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as an amine, and the mixture was stirred overnight. After completion of the reaction, the reaction solution was concentrated and dissolved in water. After extraction with chloroform, the resultant was washed with an aqueous hydrogen carbonate solution, 1N hydrochloric acid and saturated brine, dried over sodium sulfate, and concentrated to obtain 1.0 g of a photobase generator A represented by the following formula (I). .

[Example 2]
In Example 1, the adhesive sheet 10 in which the adhesive layer 2 was formed with a composition obtained by removing the UV indicator pigment from the above-described adhesive layer forming composition was used. A seal-type UV indicator (UV label-M, length 18 mm, width 18 mm, thickness 0.1 mm, manufactured by NOF Corporation) was pasted at 30 cm intervals as the indicating compound-containing seal 4b. Also in this case, the adhesive sheet 10 was placed on the flat ground near the work place, and the portable ultraviolet irradiation device was held by hand to irradiate the adhesive sheet with ultraviolet rays. Irradiation time was not concerned, ultraviolet rays were irradiated until the label-shaped UV indicator became reddish brown, and the irradiation was stopped after all the UV indicators changed. As the ultraviolet rays, ultraviolet rays having a wavelength of 300 nm to 370 nm were used. The color of the UV indicator changes in a range of approximately 250 mJ / cm2 to 3000 mJ / cm2. When the adhesive force immediately after the irradiation was measured in the same manner as described above, it was the same as the adhesive strength before the irradiation. Other than that, it carried out on the same working conditions and working procedures as Example 1. Various tests were also performed in the same manner as in Example 1 and evaluated.

[Example 3]
In Example 1, the adhesive sheet 10 in which the adhesive layer 2 was formed with a composition obtained by removing the UV indicator pigment from the above-described adhesive layer forming composition was used. As the indication compound layer 4c, the same UV indicator pigment as in Example 1 was mixed with an adhesive (mixed in Example 1) to form a thickness of 50 μm on the adhesive layer 2. Also in this case, the adhesive sheet 10 was placed on the flat ground near the work place, and the portable ultraviolet irradiation device was held by hand to irradiate the adhesive sheet 10 with ultraviolet rays. Irradiation time was not concerned, ultraviolet rays were irradiated until the adhesive layer 2 containing the UV indicator pigment became blue, and the irradiation was stopped after the entire surface was changed. As the ultraviolet rays, ultraviolet rays having a wavelength of 00 nm to 370 nm were used. The color of the adhesive layer 2 containing the UV indicator pigment changes in a range of about 50 mJ / cm2 to 3000 mJ / cm2. Other than that, it carried out on the same working conditions and working procedures as Example 1. Various tests were also performed in the same manner as in Example 1 and evaluated.

[Comparative Example 1]
In Example 1, the adhesive sheet 10 in which the adhesive layer 2 was formed with a composition obtained by removing the UV indicator pigment from the above-described adhesive layer forming composition was used. Since there was no UV indicator, the entire surface of 1 m in length and 1 m in width was irradiated so that the irradiation time was about 15 seconds. Other than that was carried out similarly to Example 1, and obtained the adhesive sheet 10 of the comparative example 1. FIG. Various tests were also performed in the same manner as in Example 1 and evaluated.

[result]
The results are shown in Table 1. From the results shown in Table 1, the work of Example 1 was excellent in both workability and anti-peeling property, had high initial adhesive strength, high adhesion strength, and no variation.

DESCRIPTION OF SYMBOLS 1, 1 'Release film 2, 2' Adhesive layer 3 Repair or reinforcement member 4 Marking material 4a Marking compound 4b Marking compound containing sheet | seat 4c Marking compound layer 5 Adherent 10, 10A-10H Adhesive sheet S1, S2, S1 ', Surface of S2 'adhesive layer

Claims (11)

A method for producing a laminate, which produces a laminate having an adherend and an adhesive sheet adhered to the adherend,
A step of preparing the adhesive sheet comprising an adhesive layer that is cured by ionizing radiation, and a labeling material that displays characters, figures, or colors according to the irradiation amount of the ionizing radiation;
Irradiating the adhesive sheet with the ionizing radiation;
Stopping the irradiation of the ionizing radiation after the marking material has displayed characters, figures or colors by the irradiation of the ionizing radiation; and
And a step of attaching the adhesive sheet to the surface of the adherend.   The labeling material is any one or more selected from a labeling compound contained in the adhesive layer, a labeling compound-containing seal constituting the adhesive sheet, and a labeling compound layer constituting the adhesive sheet. The manufacturing method of the laminated body of 1. The step of irradiating the ionizing radiation is a step of starting the curing of the adhesive layer by irradiating the ionizing radiation to the adhesive sheet,
The step of laminating the adhesive sheet is a step of laminating the adhesive layer to the adherend after starting curing in the step of irradiating the ionizing radiation,
The manufacturing method of the laminated body of Claim 1 or 2 with which hardening of the said adhesive sheet after bonding to the said adherend advances at the environmental temperature of the said adherend.   The manufacturing method of the laminated body of any one of Claims 1-3 with which the said adhesive sheet is provided with repair or a reinforcement member.   The manufacturing method of the laminated body of Claim 4 with which the said repair or reinforcement member is contained in the inside of the said contact bonding layer, or is provided in one surface of the said contact bonding layer.   An adhesive sheet that is used in the method according to any one of claims 1 to 5.   It is an adhesive sheet that is bonded to an adherend to form a laminate, and has an adhesive layer that is cured by ionizing radiation, and a marking material that displays characters, figures, or colors according to the irradiation dose of the ionizing radiation. Adhesive sheet characterized by   The labeling material is any one or more selected from a labeling compound contained in the adhesive layer, a labeling compound-containing seal constituting the adhesive sheet, and a labeling compound layer constituting the adhesive sheet. 8. The adhesive sheet according to 7.   The adhesive layer contains a compound that releases the polymerization initiator upon receiving the ionizing radiation, and the compound releases the polymerization initiator after receiving the ionizing radiation at a normal environmental temperature of the adherend. The adhesive sheet according to claim 7 or 8, which proceeds.   The adhesive sheet according to any one of claims 7 to 9, wherein the adhesive sheet includes a repair or reinforcement member.   The adhesive sheet according to claim 10, wherein the repair or reinforcement member is included in the adhesive layer or provided on one surface of the adhesive layer.

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