JP6466058B2 - Concrete abnormality detection sheet and its construction method - Google Patents

Description

  The present invention relates to a concrete abnormality detection sheet, and more particularly, to a concrete abnormality detection sheet including a concrete abnormality detection member such as a crack sensor and an adhesive layer.

  In concrete structures, concrete is regularly inspected and inspected from the viewpoint of durability and safety, and repaired and reinforced as necessary. Until now, the inspection and inspection of concrete structures have generally been made by checking the occurrence of cracks or the like by visual observation. Moreover, the growth of the crack discovered by visual observation can be determined by measuring the crack width or the like with a dedicated device. However, since the discovery and measurement of cracks were performed by the operator for each crack, a huge concrete structure such as a tunnel or a bridge required a lot of time for inspection and inspection. In addition, it is necessary for an operator having specialized knowledge to perform inspection and inspection.

  From such a background, in recent years, the occurrence of cracks is also detected by a method of photographing a concrete surface and measuring the cracks by image processing or an optical method. Although the inspection and inspection time can be greatly shortened by such a method, there are problems that the measuring equipment is expensive and specialized knowledge is required for measurement and analysis.

  Attempts have also been made to use optical fibers and plastic films as crack sensors by utilizing the fact that signals change due to distortion of the optical fibers, and the property of whitening or discoloring when plastic films are deformed. The crack generation and growth can be monitored by pasting these crack sensors on the concrete surface and monitoring the sensors. For example, in Patent Documents 1 and 2, an optical fiber is attached to a concrete surface using an instantaneous adhesive or an epoxy adhesive, and a transmission loss of the optical fiber is monitored to confirm a crack position or to estimate a crack amount. Has been proposed. In Patent Document 3, a fiber-containing plastic sheet in which a fiber base material is embedded in a matrix made of an unsaturated polyester is attached to a concrete surface with an adhesive, and a portion where the fiber-containing plastic sheet is whitened or discolored is visually observed. Thus, it has been proposed to confirm the position of the crack or estimate the crack amount.

JP 2001-21336 A JP 2004-170397 A JP2013-213710A

  However, since the crack sensor as described above has been affixed on site, there is a problem that workability is poor when the concrete surface to which the crack sensor is affixed is vertical or a ceiling surface. Further, since an adhesive is required when the crack sensor is attached to the concrete, it is necessary to perform a preparatory process such as application of the adhesive at the construction site.

  As a result of intensive investigations in view of the above problems, the present inventors have used a concrete abnormality detection member such as a crack sensor in combination with an adhesive sheet using a specific adhesive, so that it can be used in a conventional field. The pre-preparation process can be omitted, the work time can be greatly reduced, and even if the concrete surface is vertical or the ceiling surface, the concrete abnormality detection member can be applied without burdening the operator. I found out that it was possible to work together. The present invention is based on this finding.

  Therefore, the object of the present invention is to eliminate the pre-preparation process in the field as in the prior art, greatly reducing the work time, and even when the concrete surface is vertical or ceiling surface. An object of the present invention is to provide a concrete abnormality detection sheet capable of performing a bonding operation of a concrete abnormality detection member without imposing a burden on an operator.

  Another object of the present invention is to provide a method for constructing a concrete abnormality detection sheet on concrete.

A concrete abnormality detection sheet according to the present invention includes a release sheet, an adhesive layer provided on one surface of the release sheet, and a concrete provided on a surface opposite to the release sheet side of the adhesive layer. A concrete anomaly detection sheet comprising an anomaly detection member,
The adhesive layer comprises a curable resin composition whose curing reaction is accelerated by irradiation with electromagnetic waves or heating after irradiation with electromagnetic waves.

In an aspect of the present invention, the curable resin composition is
A curable compound having at least two epoxy groups in the molecule;
As a curing agent, a compound having a mercapto group in the molecule,
As a curing catalyst, a base generating compound represented by the following formula (I) that generates a basic substance by irradiation with electromagnetic waves or heating after irradiation with electromagnetic waves;
May be included.
(Where
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 represent hydrogen or a monovalent substituent, and 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 electromagnetic waves. )

  In the aspect of the present invention, the adhesive layer may further include an acrylic resin.

  Moreover, in the aspect of this invention, the said concrete abnormality detection member may detect the crack, distortion, moisture concentration, or ion concentration of concrete.

Moreover, the construction method of the concrete abnormality detection sheet according to another aspect of the present invention,
To the above-mentioned concrete abnormality detection sheet, heat after electromagnetic wave irradiation or electromagnetic wave irradiation,
Peeling the release sheet from the concrete abnormality detection sheet to expose the adhesive layer,
Bonding the adhesive layer of the concrete abnormality detection sheet to the surface of the concrete;
Including things.

  According to the concrete anomaly detection sheet of the present invention, it is possible to omit the pre-preparation process in the field as in the past, greatly shortening the work time, and when the concrete surface is vertical or ceiling surface. Even if it exists, the bonding operation | work of a concrete abnormality detection member can be performed, without putting a burden on an operator.

The schematic cross section which shows the concrete abnormality detection sheet | seat by this invention. The schematic cross section at the time of constructing a concrete abnormality detection member to concrete using the concrete abnormality detection sheet | seat by this invention.

  Hereinafter, embodiments of the adhesive layer and the adhesive sheet according to the present invention will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist thereof.

<Concrete abnormality detection sheet>
FIG. 1 is a schematic cross-sectional view showing a concrete abnormality detection sheet according to the present invention. A concrete abnormality detection sheet 1 according to the present invention is provided on a release sheet 11, an adhesive layer 10 provided on one surface of the release sheet 11, and a surface opposite to the release sheet 11 side of the adhesive layer 10. The concrete abnormality detecting member 12 is provided.

  The concrete abnormality detection member 12 is a member that is affixed to concrete and can detect a change in the state of the concrete surface. For example, it is possible to detect the occurrence and growth of cracks on the concrete surface, or to detect changes in the ion concentration such as moisture concentration and salinity on the concrete surface. As such a concrete abnormality detection member, a conventionally known member can be used, and examples thereof include a conductive wire, an optical fiber, and a fiber-impregnated plastic film. Moreover, the concrete abnormality detection member may use a commercially available thing, for example, the crack detection sensor KZCA-A (made by Tokyo Sokki Kenkyujo Co., Ltd.) etc. are mentioned.

  The adhesive layer 10 constituting the concrete abnormality detection sheet includes a curable resin composition whose curing reaction is promoted by irradiation with electromagnetic waves or heating after irradiation with electromagnetic waves. As will be described later, the concrete abnormality detection sheet can be fixed to the concrete surface via the adhesive layer 10 by peeling the release sheet after being bonded to the concrete surface. At that time, if a curable resin composition whose curing reaction is accelerated by irradiation with electromagnetic waves or heating after irradiation with electromagnetic waves is used as an adhesive, before the irradiation with electromagnetic waves or heating after irradiation with electromagnetic waves (that is, concrete) Since the curing reaction of the curable resin composition does not proceed before use of the abnormality detection sheet, the storage stability is excellent. On the other hand, by using the electromagnetic wave irradiation or heating after the electromagnetic wave irradiation when using the concrete abnormality detection sheet, the curing reaction proceeds quickly and the curable resin composition is cured. Can be fixed on concrete surface. Moreover, since it is not necessary to attach an adhesive abnormality detection member after apply | coating an adhesive agent to a concrete surface like the past, the time of construction work in a field can be shortened significantly.

As a curable resin composition whose curing reaction is accelerated by irradiation with electromagnetic waves as described above or heating after irradiation with electromagnetic waves, a curable compound having at least two epoxy groups in the molecule, a molecule as a curing agent, Curing comprising a compound having a mercapto group therein and a base generating compound that generates a basic substance by irradiation with electromagnetic waves represented by the following general formula (I) or heating after irradiation with electromagnetic waves as a curing catalyst: Resin composition.
(Where
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 represent hydrogen or a monovalent substituent, and 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 electromagnetic waves. )

  The curable compound having at least two epoxy groups in the molecule is not particularly limited, and examples thereof include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, and phenol novolac type epoxy resins. , Novolak type epoxy resin such as cresol novolac type epoxy resin, aliphatic epoxy resin, cycloaliphatic epoxy resin, polyfunctional epoxy resin, biphenyl type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type Examples include epoxy resins, alcohol-type epoxy resins such as hydrogenated bisphenol A-type epoxy resins, rubber-modified epoxy resins, urethane-modified epoxy resins, and epoxy group-containing acrylic resins. You may use these individually or in combination of 2 or more types. Among these, bisphenol-type epoxy resins such as bisphenol A-type epoxy resin and bisphenol F-type epoxy resin are widely available in grades with different molecular weights, and the adhesiveness and reactivity can be arbitrarily set. Is more preferable. In addition, the epoxy resin having a triazine nucleus in the skeleton forms a uniform film when applied (100 ° C., 10 minutes) after application of a coating liquid composed of a photosensitive resin composition containing the epoxy resin. When it becomes, it is preferable at the point of making peeling from mold release PET easy.

  The curable compound preferably has high reactivity and low epoxy equivalent in order to achieve curing in a short time. For example, the epoxy equivalent is 100 to 800 g / eq. It is preferable to be within the range. Here, the epoxy equivalent is the number of grams of a resin containing 1 gram equivalent of an epoxy group measured by a method according to JIS K7236.

  As a commercial item of the said sclerosing | hardenable compound, for example, "EPICLON EXA-835LV", "EPICLON 850S", "EPICLON N740", "EPICLON EXA-830CRP", "EPICLON EXA-830LVP", "EPICLON" by DIC Corporation “HP-820”, “jER 828”, “jER 806”, “jER 1001”, “jER 801N”, “jER 807”, “jER 152”, “jER 604”, “jER 630” manufactured by Mitsubishi Chemical Corporation , “JER 871”, “jER YX8000”, “jER YX8034”, “jER YX4000”, “Acryset BPA-328” manufactured by Nippon Shokubai Co., Ltd., “TEPIC SP” manufactured by Nissan Chemical Co., Ltd., manufactured by ADEKA Corporation EP4100 , EP4000 series, EPU series, Daicel Chemical Industries Co., Ltd. Celoxide series, Eporide series, EHPE series, Toto Kasei Co., Ltd. YD series, YDF series, YDCN series, YDB series, Nagase ChemteX Corporation Examples include the Denacol series manufactured by the company and the Epolite series manufactured by Kyoeisha Chemical Co., Ltd.

  The mass average molecular weight of the curable compound is preferably, for example, in the range of 100 to 5000, but in order to improve the adhesive strength, durability, and the like of the formed adhesive layer, the above range. Among them, it is more preferable to use a high molecular weight one. The curable compound can be used in a solid or liquid form.

  In addition to the above, a phenoxy resin capable of reacting with an epoxy resin with a relatively high molecular weight resin having an epoxy group at the terminal can be blended as the curable compound. Examples of the phenoxy resin include a phenoxy resin having a bisphenol A skeleton, a phenoxy resin having a bisphenol F skeleton, a phenoxy resin having a bisphenol S skeleton, and a bisphenol M skeleton (4,4 ′-(1,3-phenylenediisopridiene)). Phenoxy resin having bisphenol skeleton), phenoxy resin having bisphenol P skeleton (4,4 ′-(1,4-phenylenediisopridiene) bisphenol skeleton), bisphenol Z skeleton (4,4′-cyclohexyldiene bisphenol skeleton) Phenoxy resin having a bisphenol skeleton, phenoxy resin having a novolak skeleton, phenoxy resin having an anthracene skeleton, phenoxy resin having a fluorene skeleton, dicyclopentadiene Phenoxy resins having a rating, phenoxy resins having a norbornene skeleton, phenoxy resins having a naphthalene skeleton, phenoxy resins having a biphenyl skeleton include a phenoxy resin having an adamantane skeleton. The molecular weight of the phenoxy resin is not particularly limited, but the mass average molecular weight is preferably 5,000 to 100,000. More preferably, it is 10000-70000. If a mass average molecular weight is more than the said lower limit, the effect which improves film forming property can fully be acquired. On the other hand, if it is below the said upper limit, solubility can be maintained and it is suitable. In addition, in this specification, a mass average molecular weight means the value of polystyrene conversion at the time of measuring by gel permeation chromatography (GPC).

  The content of the curable compound described above needs to be appropriately set depending on the intended application, but is preferably 15 to 95 parts by mass when the entire curable resin composition is 100 parts by mass. By setting the content to 15 parts by mass or more, the elastic modulus at a high temperature can be improved, and by setting the content to 95 parts by mass or less, a thermal expansion relaxation effect can be obtained by increasing the linear expansion coefficient.

  It is preferable to use a compound having a mercapto group as a curing agent for curing the above-described curable compound. Conventionally known ones can be used as long as they have two or more mercapto groups in the molecule, but those having three or more mercapto groups in the molecule are 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.

  Among the compounds having a mercapto group, as 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-benzenedimethanethiol, 1,3 Benzenedimethanethiol, 1,4-benzenedimethanethiol, 4,4'-thiobisbenzenethiol, 2-di-n-butylamino-4,6-dimercapto-s-triazine, trimethylolpropane tris (β- Thiopropionate), 2,5-dimercapto-1,3,4-thiadiazole, 1,8-dimercapto-3,6-dioxaoctane, 1,5-dimercapto-3-thiapentane and the like are known.

  Examples of the trithiol 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.

  As tetrathiols, pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, 1,2,4,5-tetrakis (mercaptomethyl) benzene, tetramercaptobutane, and pentaerythritol are known.

  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 to 1.2 equivalents per 1 epoxy equivalent of the curable compound. It is preferable to be blended in The effect that the content of the compound having a mercapto group is 0.7 equivalent or more, the curability is good even at a relatively low temperature, and the adhesive strength after curing is remarkably exhibited. On the other hand, if the content of the compound having a mercapto group exceeds 1.2 equivalents, it is not preferable because there is a risk that the initial tackiness and the adhesiveness are lowered and the cost is increased.

  The curable resin composition contains a base-generating compound that generates an aliphatic amine as a basic substance by irradiation with electromagnetic waves or heating after irradiation with electromagnetic waves in combination with the above-described curable compound and curing agent. Is preferred. In this specification, unless otherwise specified, the electromagnetic wave is not only an electromagnetic wave having a wavelength in the visible and invisible regions, but also a particle beam such as an electron beam, and a radiation that collectively refers to the electromagnetic wave and the particle beam. Or include ionizing radiation. The electromagnetic wave is not particularly limited, and includes not only electromagnetic waves having wavelengths in the visible and invisible regions, but also particle beams such as electron beams, and radiation or ionizing radiation that collectively refers to electromagnetic waves and particle beams. Specifically, microwaves, infrared rays, visible rays, ultraviolet rays, X-rays, γ rays, and the like can be given. Among these, ultraviolet rays that are particularly easy to handle and can obtain relatively high energy are more preferable.

As irradiation light, the light of the wavelength range of 200-450 nm is preferable, and the light of the wavelength range of 300-450 nm is more preferable. The light source is not particularly limited, and for example, a high pressure mercury lamp, an ultra high pressure mercury lamp, a carbon arc lamp, a mercury vapor arc, a fluorescent lamp, an argon glow lamp, a halogen lamp, an incandescent lamp, a low pressure mercury lamp, a flash UV lamp, deep UV A lamp, a xenon lamp, a tungsten filament lamp, sunlight, etc. are mentioned. The adhesive can be cured by using these light sources and irradiating light so that the integrated light quantity is in the range of 0.5 to 6 J / cm ² , preferably 1 to 6 J / cm ² . If the integrated light amount is less than 0.5 J / cm ² , curing may be insufficient, and if it is less than 6 J / cm ² , the working time may be long, which is not preferable.

  The base generating compound used as a curing catalyst is represented by the above general formula (I), and generates an aliphatic amine by irradiation with electromagnetic waves or heating after irradiation with electromagnetic waves. 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.

  The base generating compound represented by the general formula (I) can efficiently generate a base with a small irradiation dose by irradiation with electromagnetic waves or by combining irradiation with electromagnetic waves and heating. A base generating compound that generates a basic substance upon irradiation with electromagnetic waves refers to a compound that does not exhibit activity under normal conditions of normal temperature and pressure, but generates a base when electromagnetic waves are applied as an external stimulus. And

Since the base generating compound represented by the general formula (I) has the specific structure, (−CR ⁴ ═CR ³ —C (═O) in the general formula (I) is irradiated with an electromagnetic wave. The-) moiety isomerizes from the trans isomer to the cis isomer, and is further cyclized by heating to produce the basic substance, NHR ¹ R ² . And as shown below, this amine acts as a curing catalyst for a compound having a mercapto group.

  That is, if it is not heated after irradiation with electromagnetic waves, a base is not generated. Therefore, even if it coexists with a curable compound having at least one epoxy group in the molecule described later, the curing reaction does not proceed. Therefore, since the storage stability of the curable compound does not decrease, it is not necessary to adjust the progress of curing with a curing retarder as in the case of using a photoacid generator, for example. Since the curing retarder uses a hydrophilic material, the hydrophilic material remains in the cured product, causing the moisture permeability barrier property to deteriorate, but after irradiation with electromagnetic waves, if not heated, When a base-generating compound that does not generate a base is used, such a fear does not occur. In addition, curing by radicals or curing by cations proceeds immediately after the irradiation of electromagnetic waves, so that the pot life is short and the workability is inferior. However, if the curable resin composition used in the present invention is used, the electromagnetic waves Since a base-generating compound that generates a base by heating after irradiation is contained, the pot life can be adjusted by adjusting the heating after irradiation with electromagnetic waves, and workability is improved. Moreover, since it does not harden before irradiation with electromagnetic waves, it has excellent storage stability, and after the irradiation with electromagnetic waves, hardening proceeds rapidly at a low temperature of 100 ° C. or less. Can be fixed to.

  The heating temperature for generating the basic substance from the base generating compound may be heating at the temperature of the environment where the base generating compound is placed (for example, room temperature), and in this case, the base is gradually generated. . Further, since the base is also generated by heat generated as a by-product during irradiation with electromagnetic waves, heating may be performed substantially simultaneously with the heat generated as a by-product during irradiation with electromagnetic waves. The heating temperature for generating the base is preferably 30 ° C. or more, more preferably 60 ° C. from the viewpoint of increasing the reaction rate and generating the base efficiently, although it varies depending on the use conditions and desired physical properties. Above, still more preferably 100 ° C. or more, particularly preferably 120 ° C. or more. In order to efficiently generate a base, when a base generating compound is used, the base is generated by heating after exposure or simultaneously with exposure. Exposure and heating may be performed alternately. The most efficient method is a method of heating simultaneously with exposure.

  In the present invention, a base generating compound is used as a photolatent curing catalyst. The performance required when using a base-generating compound as a photolatent curing catalyst includes (a) adding to the resin and not precipitating when used (solubility), and (a) releasing the base efficiently. (Sensitivity of base generation), (c) releasing a basic substance having a structure that easily reacts with a compound having a mercapto group (catalytic activity). In the cinnamic amide type base-generating compound, these three performances can be controlled by the structure of the generated amine and the substituent introduced into the aromatic ring.

In the said general formula (I), 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. Among them, when both R ¹ and R ² are monovalent substituents, the sensitivity of isomerization is improved, and the generated base is a secondary amine, so that the basicity is stronger than the primary amine, Even if the heating temperature is low (for example, 120 ° C.), the catalytic activity is increased. In this respect, it is preferable that both R ¹ and R ² are monovalent substituents.

In particular, 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. In the methyl group in which at least one of R ^{1 and} R ² may be substituted with a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, etc. Among them, 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. Among these, a methyl group that may be substituted with a halogen atom is preferably a methyl group from the viewpoint of improving catalytic activity.

Furthermore, when 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. In addition, since the generated amine easily reacts with a compound having a mercapto group, the catalytic activity is improved. In this respect, it is preferable that R ¹ and R ² are bonded to form a cyclic structure containing a nitrogen atom. Moreover, it is more preferable that 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 isomerization sensitivity.

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. Here, 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. Note that the cyclic structure of the present paragraph, for example, like R1 is a cyclohexyl group, which shows a cyclic structure in the R ¹ or R ^2, described above, may be bonded to R ¹ and R ² It differs from a cyclic structure containing a nitrogen atom.

  Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. Examples of 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, cycloalkyl group having 4 to 23 carbon atoms such as cyclopentyl group and cyclohexyl group, cyclopentenyl group and cyclohexenyl group. A cycloalkenyl group etc. are mentioned.

In the present invention, 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 an atomic group other than hydrogen which can be replaced with a hydrogen atom, for example, an atomic group such as represented by -XR ^10. Here, X represents a direct bond or a divalent linking group, and —XR ¹² represents X and R ¹² which is an atom or atomic group other than hydrogen that can be replaced with a hydrogen atom or a hydrogen atom. There is no particular limitation as long as they are linked atomic groups. (However, the case where X is a direct bond and R ¹² is a hydrogen atom and -XR ¹⁰ is a hydrogen atom is excluded).

  The X is not particularly limited as long as it is a direct bond or a divalent linking group. For example, a bond composed of an oxygen atom or a sulfur atom, a carbon atom, a silicon atom, an oxygen atom, a sulfur atom, or nitrogen Examples thereof include an atomic group containing an atom and / or a phosphorus atom and an atomic group containing a carbon atom. 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 an atom or an atomic group other than hydrogen that can be replaced with hydrogen or 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. A preferable atom or atomic group as R ¹⁰ may have the 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. Examples of 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, cycloalkyl group having 4 to 23 carbon atoms such as cyclopentyl group and cyclohexyl group, cyclopentenyl group and cyclohexenyl group. Cycloalkenyl group, ethylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran, β-propiolactone γ-butyrolactone, σ-valerolactone, ε-caprolactone, β-propiolactam, γ-butyrolactam, σ-valerolactam, ε-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, such as phenoxymethyl group, 2-phenoxyethyl group and 4-phenoxybutyl group. As the comprise substituents may be the same as the substituent -XR ^10.

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. As the comprise substituents 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 to 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 hetero atom 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 are mentioned.

Substituent: —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. For example, there is no particular limitation. Examples of —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. Group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a hydrocarbon group that may contain the above-described substituents or may contain an unsaturated bond (hereinafter, may be referred to as “the above-mentioned hydrocarbon group”), A silyl group which may contain the above-mentioned substituents or may contain an unsaturated bond, an amino group which may contain the above-mentioned substituents, a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, or ethyl Kishirokishi group, an alkoxy group having 1 to 20 carbon atoms such as cyclohexyl group ^{(-OR 14: R} 14 is above a hydrocarbon group), a benzyloxy group, naphthoquinone Aryloxy groups such as tiloxy group (-OAr: Ar is an aryl group which may have a substituent), acyloxy groups such as acetoxy group, benzoyloxy group (-OCOR ¹⁵ : R ¹⁵ is the above-mentioned hydrocarbon group) A carbamoyloxy group (-OCONR ¹⁶ R ¹⁷ : R ¹⁶ and R ¹⁷ are the same or different hydrocarbon groups as described above, which may be bonded to each other), a cyanooxy group (cyanato group) ( -OCN), a methylthio group, a thioalkoxy group having 1 to 20 carbon atoms such as an ethylthio group ^{(-SR 18: R} 18 is above a hydrocarbon group), benzylthio group, an arylthio group such as a naphthylthio group (-SAr: Ar is Aryl group optionally having substituent (s)), acylthio group such as acetylthio group, benzoylthio group (-SCOR ¹⁹ : R ¹⁹ is the above-mentioned hydrocarbon; Element), cyanothio group (thiocyanato group) (—SCN), formyl group (—COH), acyl group (—COR ²⁰ : R ²⁰ is the above-described hydrocarbon group), alkoxycarbonyl group (—COOR ²¹ : R ²¹ is The above-mentioned hydrocarbon group), aryloxycarbonyl groups such as benzyloxycarbonyl group (—COOAr: Ar is an aryl group which may have a substituent), carbamoyl groups (—CONR ²² R ²³ : R ²² , R ²³ are The above-described hydrocarbon groups which may be the same or different and may be bonded to each other, a thioacyl group (—CSR ²⁴ : R ²⁴ is the above-described hydrocarbon group), an alkoxythiocarbonyl group (—CSOR ²⁵ : R ²⁵ is the hydrocarbon group described above.

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. Utilizing amines containing these substituents leads to improved solubility.

NHR ¹ R ² is a base (in the present invention, “basic substance” is simply referred to as a base). By the way, when an amino group is contained in R ¹ and R ² , the base-generating compound itself becomes a base and reacts with an epoxy group, which may impair stability over time. In this respect, each of R ¹ and R ² is preferably an organic group not containing an amino group. On the other hand, 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 of 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.

The produced amine is NHR ¹ R ² , and R ¹ and R ² are each independently hydrogen or a hydrocarbon that may contain a substituent or may contain an unsaturated bond. Secondary amine. In addition, amines include aliphatic amines and aromatic amines, respectively, but aliphatic amines are preferred because of their high solubility and easy to obtain high concentration base generating compounds.

  Aliphatic primary amines include methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, pentylamine, isoamylamine, tert-pentylamine, cyclopentylamine, hexylamine, cyclohexylamine , Heptylamine, cycloheptaneamine, octylamine, 2-octaneamine, 2,4,4-trimethylpentan-2-amine, cyclooctylamine and the like.

  Examples of the aliphatic secondary amine include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, di-2-propanolamine, bis (2-methoxyethyl) amine; ethylmethylamine, N-methylpropylamine N-methylbutylamine, N-methylisobutylamine, N-tert-butylmethylamine, N-methylcyclohexylamine, N-isopropylcyclohexylamine, N-ethylcyclohexylamine, N-methyladamantan-1-amine, 3-methyl Amino-1,2-propanediol, methylaminoacetaldehyde dimethyl acetal, N-methyl-3-ethoxypropylamine, N-methyl-3-propoxypropylamine, N-methyl-3-butoxypropylamine Substitution with halogen atoms such as N-methyl-3-isopropoxypropylamine, N-methyl-3-heptyloxypropylamine, N-methyl-3- (2-ethylhexyloxy) propylamine, N-methyltetrahydrofurfurylamine An amine having a methyl group, which may be substituted; Tetramethylpyrrolidine, methylpiperidine, dimethylpiperidine, trimethylpiperidine, tetramethylpiperidine, pentamethylpiperidine, 4-hydroxypiperidine, 2-piperidinemethanol, 3 Piperidinemethanol, 4-piperidinemethanol, 4-piperidineethanol, 4-piperidine carboxylic acid ethyl 4-acetamide piperidine, aromatic amines such as morpholine may also be used. Among these, amines having a methyl group which may be substituted with a halogen atom and alicyclic amines are preferable because they have high isomerization sensitivity and high catalytic activity.

Further, the NHR ¹ R ^{2 to be} generated is not only a base such as monoamine having only one NH group capable of forming an amide bond, but also two or more NH groups capable of forming an amide bond such as diamine, triamine, and tetraamine. It may be a base.

When the generated NHR ¹ R ² is a base having two or more NH groups, it has an NH group capable of forming an amide bond at one or more terminals of R ¹ and / or R ^{2 in} the general formula (I). Examples include a structure in which a base is further bonded to an electromagnetic wave latent portion that is generated by irradiation of electromagnetic waves, or irradiation and heating of electromagnetic waves. The electromagnetic potential portion includes a residue excluding R ¹ and / or R ² of the general formula (I) at one or more terminals of R ¹ and / or R ² of the general formula (I). Furthermore, the structure which has couple | bonded is mentioned.

  Examples of the amine having two or more primary amino groups include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7- Linear aliphatic alkylenediamines such as heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine; 1-butyl-1,2-ethanediamine, 1,1-dimethyl-1 , 4-butanediamine, 1-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, 1,4-dimethyl-1 Branched aliphatic alkylenediamines such as 1,4-butanediamine and 2,3-dimethyl-1,4-butanediamine; cyclohexanediamine, methylcyclohexane Cyclohexane diamine, isophorone diamine, norbornane dimethyl amine, tricyclodecane dimethyl amine, mensen diamine, and other alicyclic diamines; p-phenylene diamine, m-phenylene diamine, p-xylylene diamine, m-xylylene diamine, 4, 4 Examples include aromatic diamines such as' -diaminodiphenylmethane; triamines such as benzenetriamine, melamine, and 2,4,6-triaminopyrimidine; tetraamines such as 2,4,5,6-tetraaminopyrimidine and the like.

Examples of amines having two or more secondary amino groups include N, N′-diethyl-1,6-diaminohexane, 1,3-di-4-piperidylpropane, N, N′-dimethylethylenediamine, N , N′-dimethyl-1,3-propanediamine, N, N′-dimethyl-1,4-butanediamine, N, N′-dimethyl-1,5-pentanediamine, N, N′-dimethyl-1, Aliphatic alkylenediamines such as 6-hexanediamine, N, N′-dimethyl-1,7-heptanediamine, N, N′-1,8-octanediamine; bis (2-methylaminoethyl) ether, 1,2 - represented by bis (2-methylamino-ethoxy) ethane, bis general formula _CH 3, such as [2- (2-methylamino) ethyl] ether _{NHCH 2 CH 2 O (CH 2} CH 2 NH) n CH 3 Aliphatic alkylenediamines such as containing oxy group.

In the above general formula (I), as R ³ and R ⁴ , the same hydrogen or substituent as R ¹ and R ² can be used. As R ³ and R ⁴ , both are preferably hydrogen from the viewpoint of easily achieving high sensitivity.

On the other hand, when at least one of R ³ and R ^{4 in} the general formula (I) is not hydrogen and is the above-mentioned specific substituent, compared with the case where both R ³ and R ⁴ are hydrogen, the organic solvent And the affinity with a polymer precursor is further improved. For example, when at least one of R ³ and R ⁴ is a hydrocarbon group that 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. For example, when at least one of R ³ and R ⁴ is a halogen such as fluorine, the affinity with a curable compound having two or more epoxy groups containing a halogen such as fluorine and a polythiol-based curing agent is improved. . As described above, R ³ and / or R ⁴ can be dissolved in a desired organic solvent by appropriately introducing a substituent in accordance with a desired organic solvent or a curable compound having two or more epoxy groups and a polythiol-based curing agent. And the affinity with a curable compound having two or more desired epoxy groups and a thiol-based curing agent is improved.

In the above general formula (I), 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. As the substituent for R ^{5 to} R ⁸ , those similar to the above-described —XR ¹⁰ can be used.

R ^{5 to} R ⁸ may have one or more monovalent substituents, or two or more of R ^{5 to} R ⁸ may be bonded to form a cyclic structure in order to achieve improved solubility and higher sensitivity. Is preferably formed. In 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 α carbon and β carbon located at the α-position and β-position of the carbonyl bond Yes, 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. The substituents R ⁵ to R ^8, by forming a cyclic structure two or more are combined to at least one introduced to or R ⁵ to R ⁸ substituents, the carbon - carbon double bonds around the conjugated chain Can be expanded and the sensitivity of base generation can be improved. Moreover, it is possible to adjust the wavelength of light to be absorbed by introducing at least one substituent to 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. Thereby, it is possible to improve the sensitivity of the curable resin composition in consideration of the absorption wavelength of the compound having two or more epoxy groups to be combined and the compound having two or more mercapto groups.

  Guidance on what substituents should be introduced in order to shift the absorption wavelength to the desired wavelength depends on the Interpretation of the Ultraviolet Natural Products (AI Scott 1964) and the spectrum of organic compounds. A table described in the identification method 5th edition (RM Silverstein 1993) is cited as a reference. By referring to these, it is possible to know a measure of how long the maximum absorption wavelength of the compound is increased.

Substituents introduced into the aromatic ring have different effects depending on the structure and position of introduction. For example, introduction of a substituent into R ⁶ is preferable because it can improve sensitivity efficiently and is suitable when a curable resin composition described later is used as a thick film. When a substituent is introduced into R ⁷ , the compound tends to be a compound having high sensitivity and good solvent solubility, and thus it is preferable in that the base generating compound is suitable when good solvent solubility is required.

Two or more of R ^{5 to} R ⁸ may be bonded to form a cyclic structure to form a cyclic structure. 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. It may be a structure. For example, R ⁵ to R ⁸ are formed by combining two or more of them, naphthalene share atoms of the benzene ring of R ⁵ to R ⁸ are attached, anthracene, phenanthrene, and fused ring indene You may do it. Two or more are bonded to R ⁵ to R ^8, naphthalene share atoms of the benzene ring of R ⁵ to R ⁸ are attached, anthracene, phenanthrene, when forming a fused ring indene etc. The conjugated chain around the carbon-carbon double bond is expanded and sensitivity is improved.

Cinnamic acid amide type base-generating compounds having cinnamic acid amide skeleton and having characteristic substituents are disclosed in JP 2011-89119 A and JP 2011-68888 A. Is mentioned. R ^{5 to} R ⁸ are preferable because the structures and solubility described in these two publications are likely to be high.

As a substituent in R ^{5 to} R ⁸ , Y which is a direct bond or a 2, 3, 4, pentavalent linking group, and R ²³ which is an atom or atomic group other than hydrogen that can be replaced with hydrogen or hydrogen; There is no particular limitation as long as it is an atomic group in which is connected. Examples of substituents in R ^{5 to} R ⁸ include 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, hydrocarbon group which may contain the unsaturated bond shown above, silyl group which may contain the unsaturated bond shown above, methoxy group, ethoxy group, isopropyloxy group, t-butoxyoxy, ethylhexyloxy Group, an alkoxy group having 1 to 20 carbon atoms such as a cyclohexyloxy group (—OR ²⁴ : R ²⁴ is the above-described hydrocarbon group), an aryloxy group such as a benzyloxy group or a naphthyloxy group (—OAr: Ar is an aryl group) ,), an acetoxy group, an acyloxy group such as a benzoyloxy group ^{(-OCOR 25: R} 25 is above Hydrocarbon group), Shianookishi group (cyanato group) (- OCN), a methylthio group, a thioalkoxy group having 1 to 20 carbon atoms such as an ethylthio group ^{(-SR 26: R 26} is above a hydrocarbon group), benzylthio group, naphthylthio arylthio group such (-SAr: Ar is an aryl group), acetylthio group, an acylthio group such as benzoylthio group ^{(-SCOR 27: R 27} is above a hydrocarbon group), Shianochio group (thiocyanato group) (- SCN), hydroxyamino group (—NHOR ²⁸ : R ²⁸ is hydrogen or the above-described hydrocarbon group), acylamino group (—NHCOR ²⁹ : R ²⁹ is hydrogen or the above-described hydrocarbon group), formyl group (—COH), acyl group ^{(-COR 30: R} 30 is above a hydrocarbon group), an alkoxycarbonyl group ^{(-COOR 31: R} 31 is above the coal Hydrogen group), an aryloxycarbonyl group such as benzyloxycarbonyl group (-COOAr: Ar is an aryl group), a carbamoyl group ^{(-CONR 32 R 33: R 32} , R 33 are each independently of the above hydrocarbon group, May be bonded), a thioacyl group (—CSR ³⁴ : R ³⁴ is the above-described hydrocarbon group), and an alkoxythiocarbonyl group (—CSOR ³⁵ : R ³⁵ is the above-described hydrocarbon group).

Particularly preferred substituents for R ^{5 to} R ⁸ include a hydroxyl group, a mercapto group, a cyano group, an isocyano group, a hydrocarbon group having 4 or more carbon atoms that may contain the above substituent, and a silyl that may contain the above substituent. Group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, cyanooxy group (cyanato group), thioalkoxy group, arylthio group, acetylthio group, acylthio group, cyanothio group (thiocyanato group), formyl group, acyl group, alkoxy Examples thereof include a carbonyl group, an aryloxycarbonyl group, a carbamoyl group, a thioacyl group, and an alkoxythiocarbonyl group.

At least one of R ^{5 to} R ⁸ is a linear or branched linear hydrocarbon group having 4 or more carbon atoms, which may contain a substituent and may contain an unsaturated bond, or oxygen More preferably, the substituent is bonded to the benzene ring via a bond containing an atom and a sulfur atom. Specific examples include a hydrocarbon group having 4 or more carbon atoms, an alkoxy group, an aryloxy group, a thioalkoxy group, and an arylthio group that may contain the above-described substituent. In addition, said "bond containing an oxygen atom and a sulfur atom" points out the case where an oxy group and a thio group are utilized as X. Use of these leads to improved solubility and improved base generation sensitivity.

In the above general formula (I), R ⁹ is a hydrogen atom or a protective group that can be deprotected by heating and / or irradiation with electromagnetic waves, and is specifically described in WO2010 / 113814 International Publication Pamphlet. ing. Here, “deprotectable” refers to the possibility of changing from —OR ⁹ to —OH. When R ⁹ is a hydrogen atom, the base-generating compound contains a phenolic hydroxyl group, which may impair storage stability.

On the other hand, when R ⁹ is the above protecting group, it is deprotected by heating and / or irradiation with electromagnetic waves to generate a hydroxyl group. By protecting the phenolic hydroxyl group with a protecting group that can be deprotected by heating and / or irradiation with electromagnetic waves, the chlorine generator in which R ⁹ is the protecting group has the advantage of having very high storage stability. There are also disadvantages that the residue after the deprotection 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 for a phenolic hydroxyl group that can be deprotected by heating and / or irradiation with electromagnetic waves under conditions where the amide group present in the general formula (I) in the base generating compound used in the present invention is not decomposed. If there is, it can be used without any particular limitation. For example, 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. Therefore, such a protecting group that can be deprotected only by heating under strongly acidic or strongly basic conditions is inappropriate as a protecting group for use in the base generating compound of the present invention. 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.

  The content of the base generating compound is preferably 1 to 20 parts by mass and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the curable compound described later. When the content of the base generating compound is less than 1 part by mass, the generated base is less than the equivalent, and curing may not proceed sufficiently, which is not preferable. When the amount exceeds 20 parts by mass, it is preferable because excessive bases are generated by irradiation of electromagnetic waves, and some of the bases may not react with the functional groups of the curable compound, or sufficient adhesive strength may not be obtained. Absent.

As an example of the base generating compound used in the present invention, a base generating compound represented by the following general formula (II) is preferable.
R ^{40 to} R ⁴⁹ in the formula 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. After completion of the reaction, triphenylphosphine oxide is removed by filtration, and then concentrated hydrochloric acid is added dropwise to make the reaction solution acidic. The precipitate is collected by filtration and washed with a small amount of chloroform to give 2-hydroxy-4- (5-ethylhexyloxy) -5-ethylcinnamic acid. Next, 2-hydroxy-4- (5-ethylhexyloxy) -5-ethylcinnamic acid obtained above was dissolved in dehydrated tetrahydrofuran under a nitrogen atmosphere, and 1-ethyl-3- (3- Add (dimethylaminopropyl) carbodiimide hydrochloride. Then piperidine is added and stirred overnight. After completion of the reaction, 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.

As described above, a base-generating compound that generates a desired base can be easily synthesized. For example, when 4-hydroxypiperidine is desired to be generated as a base, a base generating compound in which R ⁴⁴ is a hydroxyl group and R ⁴⁵ is a hydrogen atom may be synthesized. Instead of 4-hydroxypiperidine may be added.

  In addition to the above-described components, the curable resin composition used in the present invention may be used in combination with a photosensitizer in order to improve photosensitivity. Examples of the photosensitizer include anthracene, perylene, coronene, tetracene, benzanthracene, phenothiazine, flavin, acridine, ketocoumarin, thioxanthone derivatives, benzophenone, acetophenone, 2-chlorothioxanthone, and 2,4-dimethylthioxanthone. 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone and the like.

  Moreover, you may add an inorganic filler from the effect that heat conductivity and a flame retardance can be improved. The inorganic filler is not particularly limited. For example, silica, alumina, zirconium oxide, zinc oxide, antimony trioxide, antimony pentoxide, magnesium oxide, titanium oxide, iron oxide, cobalt oxide, chromium oxide, talc, etc. Metal oxide, aluminum, gold, silver, nickel, iron and other fine metal particles, carbon black, and glass. You may use these individually or in combination of 2 or more types. Although content of an inorganic filler needs to be set suitably according to the intended use, it is preferred that it is 0-1000 mass parts to 100 mass parts of the whole resin composition.

  The adhesive layer may add a silane coupling agent to the curable resin composition in order to improve the interfacial adhesion between the concrete and the concrete abnormality detecting member. For example, it is preferable to use a silane coupling agent having a functional group capable of reacting with an epoxy group such as an amino group, an epoxy group, a mercapto group, a phenolic hydroxyl group, or a carboxyl group. Examples of the functional group capable of reacting with the epoxy group include a primary amino group, a secondary amino group, a tertiary amino group, a mercapto group, an epoxy group, and a carboxyl group. Specifically, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-amino) Ethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane Amino group-containing silanes such as γ-anilinopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane Etc. Mercapto group-containing silanes, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Epoxy bond-containing silanes such as silane, β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (N-carboxymethylaminoethyl) -γ-aminopropyltri Examples thereof include carboxysilanes such as methoxysilane. You may use these individually or in combination of 2 or more types. The silane coupling agent is preferably added in an amount of 0.1 to 12 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the entire resin composition.

  Moreover, in order to obtain the molded object which was excellent in heat resistance, adhesiveness, resin strength, etc., the filler may be added to the curable resin composition. For example, calcium carbonate, silicon carbide, aluminum nitride, boron nitride, beryllium, zirconia, clay, aluminum hydroxide, organic fillers such as acrylic rubber and silicon rubber, silica, clay, glass balloon, alumina balloon, ceramic balloon, etc. Inorganic hollow bodies, organic spherical bodies such as nylon beads, acrylic beads and silicon beads, organic hollow bodies such as vinylidene chloride balloons and acrylic balloons, single fibers made of glass, polyester, rayon, nylon, cellulose, acetate, etc. Is mentioned.

  Furthermore, an adhesiveness-imparting agent, a viscosity-adjusting agent for adjusting the viscosity, and a thixotropic agent for imparting thixotropic properties (thixotropic properties) as necessary, as long as the object of the present invention is not impaired. Modification modifiers), physical property modifiers for improving tensile properties, etc., heat stabilizers, flame retardants, antistatic agents, colorants such as pigments, dyes, borate esters, phosphate esters, inorganic acids, organic acids An appropriate amount of additives such as preservability improvers such as polyimide resins, plasticizers, antioxidants and antifoaming agents may be blended.

  In addition, before the adhesive layer (curable resin composition) is cured, by giving cohesive force to the adhesive layer and having tackiness, the concrete abnormality detection sheet can be temporarily fixed to the concrete surface, Workability is further improved. Examples of the resin that can impart cohesion to the adhesive layer include acrylic resin, polyester resin, urethane resin, polyamide resin, silicone resin, natural rubber, polyether, polycarbonate, polyvinyl ether, polyvinyl chloride, and ethylene-vinyl acetate. Copolymers, polyvinyl acetal resins such as polyvinyl acetate and polyvinyl butyral resins, styrene resins, saturated polyester resins, thermoplastic urethane resins, polyamide resins, thermoplastic polyimide resins, ketone resins, norbornene resins , Styrene-butadiene block copolymers and the like, and these may be used alone or in combination of two or more. By including the thermoplastic resin as described above in the curable resin composition, the construction work of the concrete abnormality detection sheet can be performed more quickly.

  The thermoplastic resin is preferably a polymer having a functional group that reacts with a curable compound having at least two epoxy groups in the molecule, and the functional group that reacts with the epoxy group is particularly It is not limited, For example, an epoxy group itself other than an amino group, a urethane group, an imide group, a hydroxyl group, and a carboxyl group is mentioned. Among these, a polymer having an epoxy group is preferable from the viewpoint of obtaining a cured product having excellent flexibility.

  The acrylic resin is not particularly limited, and examples thereof include polymers and copolymers of (meth) acrylic acid and / or various derivatives thereof. (Meth) acrylic acid derivatives include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic Aromatic groups such as (meth) acrylic acid alkyl esters such as lauryl acid, (meth) acrylic acid hydroxyl ethyl, (meth) acrylic acid hydroxyl alkyl esters such as hydroxyl propyl, and (meth) acrylic acid benzyl (Meth) acrylic acid ester containing, (meth) acrylic acid amide such as dimethyl (meth) acrylic acid amide, (meth) acrylic acid ester containing imide group such as imide acrylate TO-1492 (manufactured by Toagosei Co., Ltd.), Contains an epoxy group such as glycidyl (meth) acrylate ( Data), and acrylic acid esters. Moreover, the said copolymer also includes the copolymer of the said (meth) acrylic acid and / or its various derivatives, acrylonitrile, styrene, a butadiene, an allyl derivative, etc. Among these, those having an epoxy group are preferable from the viewpoint of adhesiveness. The introduction of the epoxy group can be performed by using a (meth) acryl compound containing an epoxy group. In addition, the mixture of the polymer which has an epoxy group, and the polymer which does not have may be sufficient.

  As a polyester resin, the polyester resin which consists of a reaction product of a polyhydric carboxylic acid component and a polyhydric alcohol component is mentioned, for example. Examples of the polyvalent carboxylic acid component include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, and paraphenylene dicarboxylic acid; and trivalent or higher aromatics such as trimellitic acid. Polyvalent carboxylic acid; cycloaliphatic polycarboxylic acid containing 5-membered or 6-membered ring such as cyclohexanedicarboxylic acid; aliphatic polycarboxylic acid such as succinic acid, glutaric acid, adipic acid, suberic acid, dodecanedioic acid Etc. You may use these individually or in combination of 2 or more types. Examples of the polyhydric alcohol component include aliphatic diols such as ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and neopentyl glycol; Trihydric or higher polyhydric alcohols such as trimethylolpropane and pentaerythritol; alicyclic diols such as 1,4-cyclohexanedimethanol; polyhydric alcohols having an ether structure such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol; Examples thereof include polyester polyol, polycarbonate polyol, polymer polyol, and rosinol. You may use these individually or in combination of 2 or more types.

  Among the above thermoplastic resins, the glass transition temperature (Tg) is preferably −40 ° C. to 30 ° C. If Tg is less than -40 ° C, the adhesive strength may be insufficient. Moreover, when Tg exceeds 30 degreeC, there exists a possibility that initial stage adhesive force may be insufficient.

  The content of the thermoplastic resin needs to be appropriately set depending on the intended use, but is preferably 5 parts by mass or more and 75 parts by mass or less when the entire resin composition is 100 parts by mass. By being 2 mass parts or more, it is excellent in stress relaxation property and shows an effect in thermal cycle resistance. Moreover, when it exceeds 75 mass parts, the adhesive strength and durability at the time of curing will be insufficient. In addition, "the whole resin composition" shows that it is the whole resin composition containing the above-mentioned other resin in addition to the above-mentioned "curable compound" and "thermoplastic resin".

  As the release sheet 11 used in the concrete abnormality detection sheet according to the present invention, conventionally known ones such as a release film, a separate paper, a separate film, a separate paper, a release film, and a release paper can be suitably used. Moreover, you may use what formed the release layer (not shown) in the single side | surface or both surfaces of base materials for release paper, such as quality paper, a coated paper, an impregnation paper, and a plastic film. The release layer is not particularly limited as long as it is a material having releasability. For example, silicone resin, organic resin-modified silicone resin, fluororesin, aminoalkyd resin, melamine resin, acrylic resin, polyester resin, etc. There is. These resins can be used in any of emulsion type, solvent type and solventless type.

  The release layer is formed by applying a coating liquid in which a release layer component is dispersed and / or dissolved on one side of a release paper base film, followed by heat drying and / or curing. As a coating method of the coating liquid, a known and arbitrary coating method can be applied, for example, roll coating, gravure coating, spray coating and the like. Moreover, you may form a release layer in the whole surface or a part of at least single side | surface of a base film as needed.

  Although the thickness of a release sheet is not specifically limited, For example, the thickness of 5 micrometers or more and 200 micrometers or less can be used conveniently.

  As such a release sheet, a commercially available sheet may be used. For example, a polyester film having a thickness of 38 μm that has been subjected to easy release treatment using a silicone-based release agent on one side (Mitsui Chemicals Tosero Co., Ltd., Trade name: SP-PET-01) and the like.

<Construction method for concrete abnormality detection sheet>
The above-described concrete abnormality detection sheet 1 is irradiated with electromagnetic waves or heated after irradiation with electromagnetic waves, and then the release sheet 11 is peeled off from the concrete abnormality detection sheet 1 to expose the adhesive layer 10. By adhering to the surface of 3, the concrete abnormality detecting member 12 can be fixed to the concrete 3 through the adhesive layer 10 as shown in FIG. 2. In the present invention, since the adhesive layer contains a curable resin composition whose curing reaction is accelerated by irradiation with electromagnetic waves or heating after irradiation with electromagnetic waves, before performing heating after irradiation with electromagnetic waves or irradiation with electromagnetic waves, The adhesive layer of the concrete abnormality detection sheet does not harden before use and has excellent storage stability. On the other hand, when the concrete abnormality detection sheet is used, the curing reaction proceeds rapidly and the curable resin composition is cured by performing irradiation of electromagnetic waves or heating after irradiation of electromagnetic waves. Can be fixed on the surface. Therefore, conventional preparation steps (preparation (measuring)), mixing, application, etc., such as conventional adhesives can be omitted, the work time can be greatly reduced, and the concrete surface is vertical or a ceiling surface. Even in such a case, it is possible to perform the work of bonding the concrete abnormality detecting member without imposing a burden on the operator.

  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
<Synthesis Example 1: Base-Generating Compound A>
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 placed in 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) ) -5-ethylbenzaldehyde (1.7 g, 6.2 mmol) was added and dissolved, and then 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 100 mL three-necked flask under a nitrogen atmosphere, and the solution was placed in an ice bath. 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (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 mixture 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 base generating compound A represented by the following formula (III).

<Synthesis Example 2: Base-Generating Compound B>
A synthesis example except that 1.5 g (6.2 mmol) of 2-hydroxy-5- (5-ethylhexyloxy) benzaldehyde was added instead of the above 2-hydroxy-4- (5-ethylhexyloxy) -5-ethylbenzaldehyde. By going through the same steps as 1, 0.8 g of the base generating compound B represented by the following formula (IV) was obtained.

In addition, the chemical structure of the produced base generating compound was confirmed by ¹ H NMR measurement. ¹ H NMR measurement was performed using a nuclear magnetic resonance apparatus JEOL JNM-LA400WB (manufactured by JEOL Ltd.).

Preparation of Concrete Abnormality Detection Sheet Epoxy resin (trade name “jER 828”, bisphenol A type epoxy resin, solid content: 100%, epoxy equivalent: 184 to 194 g / eq., Mass average molecular weight: 370, Mitsubishi 100 parts by mass of Chemical Co., Ltd. and PEMP (pentaerythritol tetrakis-3-mercaptopropionate, trade name “QX40”, a curing agent having a mercapto group, viscosity: 400 to 550 mPa · s / 25 ° C., mercaptan equivalent: 125 parts by mass (125 to 137 g / eq, manufactured by Mitsubishi Chemical Co., Ltd.) and 5 parts by mass of base generator A (generated base: piperidine) were mixed with a stirrer (product name “TK homodisper type 2.5”, After mixing and stirring using PRIMIX), defoaming was performed to obtain a curable resin composition used in Example 1.

  Subsequently, on the release treatment surface of the release sheet (trade name: SP-PET-03, polyester film having a release treatment with a silicone release agent on one side, film thickness: 38 μm, manufactured by Tosero). The adhesive layer was formed by applying the curable resin composition using an applicator so that the thickness after coating was 100 μm.

  By attaching a crack sensor (KZCA-A, manufactured by Tokyo Sokki Kenkyusha Co., Ltd.) as a concrete abnormality detection member to the surface of the adhesive layer, a concrete abnormality detection sheet was produced.

Construction of Concrete Abnormality Detection Sheet The concrete abnormality detection sheet obtained as described above was subjected to wavelength using an ultraviolet irradiation device (product name “DRE-10 / 12QN”, using an H bulb, manufactured by Fusion UV Systems Japan). Ultraviolet rays were irradiated so that the light intensity was 2000 mJ in the region of 300 to 370 nm. Subsequently, the release sheet was peeled off from the concrete abnormality detection sheet to expose the adhesive layer, and the surface of the adhesive layer of the concrete abnormality detection sheet was bonded to the primer-treated concrete plate. It took about 2 minutes to irradiate the concrete anomaly detection sheet with ultraviolet rays and paste it onto the concrete plate.

  After bonding the concrete abnormality detection sheet to the concrete plate, the adhesive layer was cured by curing for 3 days in an environment of 23 ° C. and 50% RH. One end of the crack sensor was fixed to Tensilon (Orientec RTA-1T), pulled at 90 °, 300 mm / min, and the adhesive strength was measured. did.

Example 2
In Example 1, as the concrete abnormality detection member, the crack sensor (KZCA-A, manufactured by Tokyo Sokki Kenkyujo Co., Ltd.) was changed to a concrete crack sensor (KK crack sensor, manufactured by Kurashiki Textile Co., Ltd.). Similarly, a concrete abnormality detection sheet was produced. Next, the obtained concrete abnormality detection sheet was bonded to a concrete plate in the same manner as in Example 1. It took about 2 minutes to irradiate the concrete abnormality detecting sheet during the construction work with ultraviolet rays and to bond it to the concrete plate. Moreover, when the adhesive strength at the time of peeling a concrete crack sensor from a concrete board was measured like Example 1, before the concrete crack sensor peeled from a concrete board, the crack sensor fractured | ruptured.

Comparative Example 1
Prepare a two-component epoxy adhesive (Quick 5, manufactured by Konishi Co., Ltd.), lighten the main agent and curing agent with a precision balance, and mix the main agent and curing agent to a predetermined ratio. Stir well for minutes. Next, the mixed two-component epoxy adhesive is applied to the primer-treated concrete board using a brush, and the crack sensor (KZCA-A, manufactured by Tokyo Sokki Kenkyujo Co., Ltd.) is applied to the concrete board via the adhesive. Pasted together. The time required from the preparation of the two-component epoxy adhesive to the bonding of the crack sensor to the concrete plate was about 15 minutes.

  Moreover, after bonding a crack sensor to a concrete board, when the adhesive strength was measured like Example 1, the crack sensor broke before the crack sensor peeled from the concrete board.

Comparative Example 2
In Comparative Example 1, as a concrete abnormality detecting member, except that the crack sensor (KZCA-A, manufactured by Tokyo Sokki Kenkyujo Co., Ltd.) is changed to a concrete crack sensor (KK crack sensor, manufactured by Kurashiki Textile Co., Ltd.), Comparative Example 1 and Similarly, a concrete abnormality detection sheet was produced. It took about 15 minutes to irradiate the concrete abnormality detecting sheet during the construction work with ultraviolet rays and to bond it to the concrete plate. Moreover, when the adhesive strength at the time of peeling a concrete crack sensor from a concrete board was measured like Example 1, before the concrete crack sensor peeled from a concrete board, the crack sensor fractured | ruptured.

1: Concrete abnormality detection sheet 3: Concrete 10: Adhesive layer 11: Release sheet 12: Concrete abnormality detection member

Claims (3)

Concrete comprising a release sheet, an adhesive layer provided on one surface of the release sheet, and a concrete abnormality detecting member provided on a surface of the adhesive layer opposite to the release sheet side An anomaly detection sheet,
The adhesive layer comprises a curable resin composition whose curing reaction is accelerated by heating after electromagnetic wave irradiation or electromagnetic wave irradiation ;
The curable resin composition is
A curable compound having at least two epoxy groups in the molecule;
As a curing agent, a compound having a mercapto group in the molecule,
As a curing catalyst, a base generating compound represented by the following formula (I) that generates a basic substance by irradiation with electromagnetic waves or heating after irradiation with electromagnetic waves;
A concrete anomaly detection sheet characterized by comprising:
(Where
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, and R ^{5 to} R ⁸ each independently represent hydrogen or a monovalent substituent, but R ^{5 to} R ⁸ Two or more of these may combine to form a cyclic structure,
R ⁹ represents a protecting group that can be deprotected by heating and / or irradiation with electromagnetic waves. ). The concrete abnormality detection sheet according to claim 1 , wherein the adhesive layer further includes an acrylic resin. The concrete abnormality detection sheet according to claim 1 or 2 , wherein the concrete abnormality detection member detects a crack, strain, moisture concentration, or ion concentration of concrete.