Two-component adhesive, cured film, and method for producing the cured film

Abstract

To provide a two-pack adhesive capable of forming a cured film with low harmfulness of combustion gas.SOLUTION: A two-pack adhesive includes a first agent containing an epoxy compound and a second agent containing an amine-based curing agent. When a total amount of solids in the first agent and the second agent is 100 mass%, an amount of a nitrogen element in the solids is less than 4.9 mass% in the two-pack adhesive.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a two-component adhesive, a cured film, and a method for making the cured film. [Background technology]

[0002] Various measures have been taken to prevent materials from peeling off from structures such as tunnels and bridges. For example, Patent Document 1 describes a method for preventing concrete from peeling off, which is characterized by forming a high-strength coating film on the concrete surface. Furthermore, Patent Document 3 describes a reinforced coating method for reinforcing the surface of a concrete structure by forming a coating layer containing a continuous glass fiber sheet. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-15329 [Patent Document 2] Japanese Patent Application Laid-Open No. 2010-1707 Summary of the Invention [Problem to be solved by the invention]

[0004] When forming a resin film on a structure, it is desirable that the combustion gases produced are low in toxicity from the viewpoint of fire safety.

[0005] Therefore, an object of the present invention is to provide a two-component adhesive capable of forming a cured film with low harmful combustion gases. Another object of the present invention is to provide a cured film with low harmful combustion gases and a method for producing the cured film. [Means for solving the problem]

[0006] One aspect of the present invention relates to a two-component adhesive comprising a first component containing an epoxy compound and a second component containing an amine-based curing agent, wherein the amount of nitrogen element in the solid components is less than 4.9% by mass when the total amount of solid components in the first component and the second component is taken as 100% by mass.

[0007] In one embodiment, the epoxy equivalent weight of the epoxy compound may be greater than 190.

[0008] In one embodiment, the epoxy compound may include a glycidyl compound having a glycidyl group, and the amine-based curing agent may include an amine compound having a group selected from the group consisting of a primary amino group and a secondary amino group.

[0009] In one embodiment, the glycidyl compound may include a compound represented by formula (2-1). [ka] [In the formula, n and m each independently represent an integer of 1 or more, and R 1 and R 2 each independently represents a hydrogen atom or a methyl group, and R 3 and R 4 R each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 5 carbon atoms, or an optionally substituted phenyl group. 1 When there are multiple R 1 may be the same or different. 2 When there are multiple R 2 may be the same or different.]

[0010] In one embodiment, at least one of the first agent and the second agent may further contain a filler.

[0011] In one embodiment, the filler has a specific surface area of ​​70 g / m 2 The above fumed silica may be included.

[0012] In one embodiment, 90% by weight or more of the filler may be the fumed silica.

[0013] In one embodiment, when the total amount of solids in the first agent and the second agent is taken as 100% by mass, the content of the filler in the solids may be 0.1% by mass or more and 5.5% by mass or less.

[0014] In one embodiment, the mixture of the first agent and the second agent may exhibit a viscosity of 4000 mPa·s or more and 100,000 mPa·s or less, and a thixotropic index of 3.0 or more.

[0015] The two-component adhesive according to one embodiment may be an adhesive for forming a cured film on the surface of a structure.

[0016] In one embodiment, the structure surface may be a concrete surface or a mortar surface.

[0017] In one embodiment, the cured film may be composed of a composite of a cured mixture of the first agent and the second agent and a fiber material.

[0018] In one embodiment, the cured film may be used to prevent the constituent materials from peeling off from the surface of the structure.

[0019] Another aspect of the present invention relates to a cured film formed using the two-component adhesive, the cured film comprising a cured product of a mixture of the first component and the second component.

[0020] The cured film according to one embodiment may include a composite of the cured body and a fiber material.

[0021] The cured film according to one embodiment has a nitrogen element content of 39.3 g / m 2 It may be less than.

[0022] The cured film according to one embodiment may have a total light transmittance of 70% or more.

[0023] Yet another aspect of the present invention relates to a method for producing a cured film using the above-mentioned two-component adhesive, comprising: a coating step of placing a mixture of the above-mentioned first component and the above-mentioned second component on a surface of a structure to form a coating film; and a curing step of curing the coating film to obtain a cured film containing a cured product of the above-mentioned mixture.

[0024] In one aspect, the application process may be a process of placing the mixture and the fiber material on the surface of the structure to form a coating film containing the mixture and the fiber material, and the curing process may be a process of curing the coating film to obtain a cured film containing a complex of the cured product of the mixture and the fiber material.

[0025] In one embodiment, the structure surface may be a concrete surface or a mortar surface.

[0026] Yet another aspect of the present invention relates to an adhesive composition comprising an epoxy compound and an amine-based curing agent, wherein the amount of nitrogen element in the solid content is less than 4.9 mass% when the total amount of the solid content is taken as 100 mass%. [Effects of the Invention]

[0027] The present invention provides a two-component adhesive capable of forming a cured film with low harmful combustion gases. The present invention also provides a cured film with low harmful combustion gases and a method for producing the cured film. DETAILED DESCRIPTION OF THE INVENTION

[0028] Preferred embodiments of the present invention will be described in detail below.

[0029] <Two-component adhesive> The two-component adhesive of this embodiment includes a first component containing an epoxy compound and a second component containing an amine-based curing agent. Furthermore, in this embodiment, when the total amount of solids in the first and second components is taken as 100% by mass, the nitrogen content in the solids is less than 4.9% by mass.

[0030] From the viewpoint of further reducing the harmfulness of combustion gas, the nitrogen element content is preferably 4.7% by mass or less, more preferably 4.6% by mass or less, and even more preferably 4.5% by mass or less.

[0031] In the two-component adhesive of this embodiment, the first and second components each contain an epoxy compound and an amine-based curing agent, so that mixing the first and second components allows the formation of a strong cured film from the epoxy compound and the amine-based curing agent. That is, the adhesive composition, which is a mixture of the first and second components, can form a strong cured film. Furthermore, because the two-component adhesive of this embodiment has a low nitrogen element content in the solids, it is less likely to generate harmful components during combustion, and a cured film with low harmful combustion gases can be formed.

[0032] The two-component adhesive of this embodiment is capable of forming a cured film by mixing the first and second components. The two-component adhesive of this embodiment may be provided, for example, as a two-component adhesive kit including a first container containing the first components and the first component, and a second container containing the second components and the second component, or as a two-component adhesive kit including the first component, the second component, and containers containing the first component and the second component separately.

[0033] The two-component adhesive of this embodiment may be a room temperature curing type.

[0034] The two-component adhesive of this embodiment may contain a first component and a second component such that the epoxy compound and the amine-based curing agent are in equivalent amounts, or may contain the first component and the second component such that either the epoxy compound or the amine-based curing agent is in excess.

[0035] When using the two-component adhesive of this embodiment, it is preferable to mix the first and second components so that the epoxy compound and the amine-based curing agent are equivalent in weight, but the mixing ratio is not limited to this. For example, the first and second components may be mixed so that the amount of amine-based curing agent relative to the epoxy compound is 0.5 to 1.5 equivalents (preferably 0.8 to 1.2 equivalents).

[0036] The epoxy compound may be used alone or in combination of two or more. Examples of the epoxy compound include a compound having one epoxy group and a compound having two or more epoxy groups. The epoxy compound preferably contains at least a compound having two or more epoxy groups.

[0037] In this embodiment, the amount of amine-based curing agent is limited to reduce the amount of nitrogen element in the solid content. If the amount of amine-based curing agent is small, epoxy groups in the epoxy compound are likely to remain unreacted, which may cause problems such as reduced strength of the cured film and reduced reactivity of the adhesive. For this reason, the epoxy equivalent of the epoxy compound is preferably 160 or more, more preferably 180 or more, even more preferably more than 190, even more preferably 195 or more, and may even be 200 or more. This makes it less likely that the above problems will occur even when the amount of amine-based curing agent is small, and makes it easier to achieve a low nitrogen element content.

[0038] The epoxy equivalent of the epoxy compound is, for example, 700 or less, and from the viewpoint of providing a coating film with even better heat resistance and durability, it is preferably 510 or less, and more preferably 320 or less.

[0039] The epoxy equivalent of an epoxy compound indicates the mass (g) of the epoxy compound per mole of epoxy group. When two or more epoxy compounds are used in combination, the epoxy equivalent of the epoxy compound is calculated from the total amount of the epoxy compounds and the total number of epoxy groups.

[0040] The epoxy compound is preferably a compound having a glycidyl group as the epoxy group, that is, the epoxy compound preferably includes a glycidyl compound having a glycidyl group.

[0041] Examples of epoxy compounds include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol A bis(polypropylene glycol glycidyl ether) ethers, bisphenol A bis(polyethylene glycol glycidyl ether) ethers, hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol F type epoxy resins, biphenyl type epoxy resins, urethane-modified epoxy resins, rubber-modified epoxy resins, alkyl glycidyl ethers, cresyl glycidyl ethers, phenyl glycidyl ethers, alkyl diglycidyl ethers, polyethylene glycol diglycidyl ethers, polypropylene glycol diglycidyl ethers, glycerin triglycidyl ethers, and trimethylolpropane triglycidyl ethers.

[0042] The epoxy compound preferably contains a compound represented by formula (1-1). [ka]

[0043] In formula (1-1), p represents an integer of 0 or more, and R 11 and R 12 each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 5 carbon atoms, or an optionally substituted phenyl group.

[0044] R 11 and R 12 Examples of the substituent that the alkyl group having 1 to 5 carbon atoms may have in the formula include a fluorine atom and an alkoxy group (for example, an alkoxy group having 1 to 5 carbon atoms), and a fluorine atom is preferred.

[0045] R 11 and R 12 Examples of the substituent that the phenyl group in the formula (I) may have include a fluorine atom, an alkyl group (for example, an alkyl group having 1 to 5 carbon atoms), and an alkoxy group (for example, an alkoxy group having 1 to 5 carbon atoms).

[0046] R 11is preferably a hydrogen atom, a methyl group, a phenyl group, or a trifluoromethyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a methyl group. 11 When there are multiple R 11 may be the same or different, and are preferably the same.

[0047] R 12 is preferably a hydrogen atom, a methyl group, a phenyl group, or a trifluoromethyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a methyl group. 12 When there are multiple R 12 may be the same or different, and are preferably the same.

[0048] R 11 and R 12 may be the same or different, and are preferably the same.

[0049] p is preferably 0 to 30.

[0050] The proportion of the compound represented by formula (1-1) in the epoxy compound may be, for example, 50% by mass or more, preferably 55% by mass or more, more preferably 60% by mass or more, and even more preferably 65% ​​by mass or more. The proportion of the compound represented by formula (1-1) in the epoxy compound may be, for example, 100% by mass or less, or may be 95% by mass or less, preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

[0051] The epoxy compound preferably includes a compound represented by formula (2-1). [ka]

[0052] In formula (2-1), n ​​and m each independently represent an integer of 1 or more, and R 1 and R 2 each independently represents a hydrogen atom or a methyl group, and R3 and R 4 each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 5 carbon atoms, or an optionally substituted phenyl group.

[0053] R 1 is preferably a methyl group. 1 When there are multiple R 1 may be the same or different, and are preferably the same.

[0054] R 2 is preferably a methyl group. 2 When there are multiple R 2 may be the same or different, and are preferably the same.

[0055] R 3 and R 4 Examples of the substituent that the alkyl group having 1 to 5 carbon atoms may have in the formula include a fluorine atom and an alkoxy group (for example, an alkoxy group having 1 to 5 carbon atoms), and a fluorine atom is preferred.

[0056] R 3 and R 4 Examples of the substituent that the phenyl group in the formula (I) may have include a fluorine atom, an alkyl group (for example, an alkyl group having 1 to 5 carbon atoms), and an alkoxy group (for example, an alkoxy group having 1 to 5 carbon atoms).

[0057] R 3 is preferably a hydrogen atom, a methyl group, a phenyl group or a trifluoromethyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a methyl group.

[0058] R 4 is preferably a hydrogen atom, a methyl group, a phenyl group or a trifluoromethyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a methyl group.

[0059] R 3 and R 4may be the same or different, and are preferably the same.

[0060] Regarding n and m, n+m is preferably 2-20, and more preferably 2-11.

[0061] The proportion of the compound represented by formula (2-1) in the epoxy compound may be, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. The proportion of the compound represented by formula (2-1) in the epoxy compound is, for example, 50% by mass or less, preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.

[0062] The amine-based curing agent may be any component capable of crosslinking the epoxy compound and curing the mixture of the first and second components. The amine-based curing agent may be, for example, a compound having two or more reactive sites capable of reacting with the epoxy group in the epoxy compound. The amine-based curing agent may be used alone or in combination of two or more.

[0063] The amine curing agent is preferably an amine compound having a group selected from the group consisting of a primary amino group and a secondary amino group. The primary amino group of the amine compound is a group represented by -NH2. The secondary amino group of the amine compound is a group represented by -NH-. The amine curing agent may be, for example, a compound having one or more primary amino groups, a compound having two or more secondary amino groups, or the like.

[0064] The amine-based curing agent may be, for example, at least one selected from the group consisting of an aliphatic amine, an alicyclic amine, a modified aliphatic polyamine, a modified alicyclic amine, and a polyamidoamine, and is preferably at least one selected from the group consisting of a modified aliphatic polyamine, a modified alicyclic amine, and a polyamidoamine.

[0065] The amount of nitrogen element in the amine curing agent may be, for example, 60% by mass or less based on the total amount of the amine curing agent, and from the viewpoint of further reducing the harmfulness of combustion gases, it is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0066] The active hydrogen equivalent of the amine curing agent may be, for example, 20 or more, preferably 50 or more, more preferably 70 or more. This tends to form a denser crosslinked structure and further improve the heat resistance and durability of the cured film. The active hydrogen equivalent of the amine curing agent may be, for example, 200 or less, preferably 120 or less, more preferably 100 or less. This makes it easier to reduce the amount of nitrogen element in the adhesive, and the above-mentioned effects are more pronounced.

[0067] The active hydrogen equivalent of an amine curing agent indicates the mass (g) of the amine curing agent per mole of active hydrogen. When two or more amine curing agents are used in combination, the amine equivalent of the amine curing agent is calculated from the total amount of the amine curing agent and the total number of active hydrogens.

[0068] In the two-component adhesive of this embodiment, at least one of the first and second components preferably contains a filler. The inclusion of a filler increases the viscosity of the mixture of the first and second components, thereby preventing dripping when forming a coating on a wall, ceiling, or other surface.

[0069] The filler may be any known filler blended in two-component adhesives without any particular limitations. Examples of fillers include organic fillers and inorganic fillers. Furthermore, the filler may be one that has been subjected to a surface treatment such as hydrophobic treatment.

[0070] The shape of the filler is not particularly limited, and may be, for example, granular, flake, fibrous, emulsion, or the like.

[0071] Examples of organic fillers include resin particles. The resin particles may be solid particles, porous particles, or hollow particles. Examples of resin particles include (meth)acrylic acid ester particles, aramid fibers, polyester fibers, and polystyrene particles.

[0072] Examples of inorganic fillers include fumed silica, calcium carbonate, talc, clay, metal oxides, metal hydroxides, silica, etc. The inorganic fillers may be hollow particles, fibrous particles, solid particles, porous particles, etc.

[0073] The filler is preferably an inorganic filler. As the inorganic filler, fumed silica is preferred, and the specific surface area is 70 g / m 2 or more (preferably 80 to 400 g / m 2 ) is more preferred. The specific surface area refers to the BET specific surface area. The BET specific surface area is a value measured by a gas phase adsorption method in which gas molecules (nitrogen molecules) with a known occupied area are adsorbed onto the surface of an inorganic filler, and the specific surface area is determined from the amount of adsorbed gas molecules.

[0074] In this embodiment, the proportion of fumed silica in the filler may be, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, and may be 99% by mass or more, or even 100% by mass, which makes it possible to achieve both a thickening effect that sufficiently suppresses dripping and excellent optical transparency of the cured film.

[0075] The content of the filler in the two-component adhesive of this embodiment may be, for example, 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 1.0% by mass or more, when the total amount of solids in the first and second parts is taken as 100% by mass. This more significantly enhances the thickening effect that suppresses dripping. Furthermore, the content of the filler in the two-component adhesive of this embodiment may be, for example, 5.5% by mass or less, preferably 5.0% by mass or less, and more preferably 4.5% by mass or less, when the total amount of solids in the first and second parts is taken as 100% by mass. This tends to further improve the light transmittance of the cured film.

[0076] In the two-component adhesive of this embodiment, at least a portion of the first and second components preferably contains a curing accelerator, which improves the curing properties of the mixture of the first and second components.

[0077] The curing accelerator may be any known curing accelerator that can accelerate the reaction between the epoxy compound and the amine-based curing agent, and may be used without any particular limitation. For example, a monophenol compound is preferably used as the curing accelerator. As the monophenol compound, 4-tert-butylphenol is preferred.

[0078] The content of the curing accelerator in the two-component adhesive of this embodiment may be, for example, 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 1.0% by mass or more, when the total amount of solids in the first and second components is taken as 100% by mass. This tends to further improve the curing properties of the mixture of the first and second components. Furthermore, the content of the curing accelerator in the two-component adhesive of this embodiment may be, for example, 5.5% by mass or less, preferably 5.0% by mass or less, and more preferably 4.5% by mass or less, when the total amount of solids in the first and second components is taken as 100% by mass. This tends to further improve the curing properties of the mixture of the first and second components.

[0079] The two-component adhesive of this embodiment may further contain other components in addition to those described above, such as a cure retarder, a light stabilizer, a light absorber, an antioxidant, an anti-degradant, a pigment, a dye, a silane coupling agent, an antifoaming agent, a leveling agent, a dispersant, a rheology control agent, a wax, a solvent, and water.

[0080] The first agent contains an epoxy compound, and may contain a filler as needed, and may further contain other components as needed.

[0081] The content of the epoxy compound in the first agent may be, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, and may be 100% by mass, based on the total amount of solids in the first agent.

[0082] The second agent contains an amine-based curing agent, and may contain a filler as needed, and may further contain other components as needed.

[0083] The content of the amine-based curing agent in the second agent may be, for example, 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and may even be 100% by mass, based on the total amount of solids in the second agent.

[0084] In the two-component adhesive of this embodiment, the mixture of the first and second components preferably exhibits a viscosity of 4,000 mPa·s or more and 100,000 mPa·s or less (more preferably 8,000 mPa·s or more and 25,000 mPa·s or less) and a thixotropic index of 3.0 or more (more preferably 4.0 to 8.0). The viscosity and thixotropic index of the mixture of the first and second components change over time due to the reaction between the epoxy compound and the amine-based curing agent. In other words, the above definition means that the mixture of the first and second components exhibits the above viscosity and thixotropic index for a certain period of time after mixing.

[0085] In this specification, the viscosity of the mixture of the first and second agents refers to the viscosity measured at 23°C and 20 rpm using a cone-plate type rotational viscometer. The thixotropic index refers to the ratio (V2 / V1) of the viscosity V2 measured at 23°C and 2 rpm to the viscosity V1 measured at 23°C and 20 rpm using a cone-plate type rotational viscometer.

[0086] As described above, the two-component adhesive of this embodiment is capable of forming a cured film with low combustion gas toxicity, and therefore can be suitably used as an adhesive for forming a cured film on the surface of a structure.

[0087] The cured film may be used to prevent the constituent materials from peeling off from the surface of the structure. That is, the two-component adhesive of the present embodiment may be an adhesive for forming a cured film on the surface of the structure to prevent the constituent materials from peeling off.

[0088] The surface of the structure is not particularly limited, but a concrete surface or a mortar surface is preferred from the viewpoint of obtaining a significant effect of preventing the material from peeling off. That is, the two-component adhesive of the present embodiment may be an adhesive for forming a hardened film on a concrete surface or a mortar surface.

[0089] The cured film formed on the surface of the structure may include a composite of a fiber material and a cured product of the mixture of the first and second parts. That is, the two-part adhesive of the present embodiment may be an adhesive for forming a cured film on the surface of the structure, the cured film including a composite of a fiber material and a cured product of the mixture of the first and second parts.

[0090] The fiber material is not particularly limited, and any fiber material used for composites can be used without particular limitation. Examples of the fiber material include glass fiber, polyester fiber, polyethylene terephthalate fiber, vinylon fiber, acrylic fiber, nylon fiber, carbon fiber, and aramid fiber. Among these, glass fiber is particularly preferred from the viewpoints of the harmfulness of combustion gases and the visibility of the surface of the structure after curing.

[0091] <Cured film> The cured film of this embodiment is a cured film formed using the two-component adhesive described above, and includes a cured product of a mixture of the first and second components.

[0092] The mixture of the first and second parts may be one in which the amount of the amine-based curing agent relative to the epoxy compound is 0.5 to 1.5 equivalents (preferably 0.8 to 1.2 equivalents). The mixture of the first and second parts gradually cures at room temperature to form a cured product.

[0093] The cured film of the present embodiment may include a composite of a fiber material and a cured product of the mixture of the first and second agents. The composite may be formed by, for example, mixing the first and second agents with the fiber material, or by impregnating the fiber material with the mixture of the first and second agents.

[0094] The cured film of this embodiment may be composed of, for example, only a composite layer containing a cured body and a fiber material, or may be composed of a cured body layer containing a cured body and a composite layer containing a cured body and a fiber substrate.

[0095] The thickness of the cured film is not particularly limited, but may be, for example, 0.1 mm or more, preferably 0.4 mm or more, more preferably 0.6 mm or more, and may be, for example, 2.0 mm or less, preferably 1.2 mm or less, more preferably 1.0 mm or less.

[0096] The amount of the cured material in the cured film is, for example, 0.1 kg / m 2 or more, preferably 0.4 kg / m 2 More preferably, 0.6 kg / m 2 The amount of the cured material in the cured film is, for example, 2.0 kg / m 2 may be less than or equal to 1.2 kg / m 2 Less than or equal to 1.0 kg / m, more preferably 1.0 kg / m 2 The following is the result.

[0097] The cured film of this embodiment has a nitrogen element content of, for example, 50.0 g / m2 or less, preferably 45.0 g / m 2 or less, more preferably 40.0 g / m 2 More preferably, 39.3 g / m or less 2 less than 35.0 g / m 2 Below 33.5 g / m, particularly preferably 2 Such a cured film significantly suppresses the generation of harmful gases during combustion.

[0098] The cured film of the present embodiment preferably has a total light transmittance of 70% or more, more preferably 80% or more. Such a cured film allows the surface of the structure to be visually observed through the cured film, thereby providing advantages such as easy detection of cracks and the like on the surface of the structure and preventing peeling while maintaining the design of the surface of the structure.

[0099] In this specification, the total light transmittance of the cured film is measured using a UV-VIS-NIR spectrophotometer SolidSpec-3700i manufactured by Shimadzu Corporation in accordance with JIS K7136:2000 (Plastics: Determination of haze of transparent materials).

[0100] <Method of manufacturing the cured film> The cured film of this embodiment is produced by a production method including, for example, a coating step in which a mixture of the first agent and the second agent is placed on the surface of a structure to form a coating film, and a curing step in which the coating film is cured to obtain a cured film containing a cured product of the mixture.

[0101] In the coating step, the mixture and the fibrous material may be placed on the surface of a structure to form a coating film containing the mixture and the fibrous material. By forming such a coating film, a cured film containing a composite of the cured body and the fibrous material is formed.

[0102] The amount of the mixture applied to the surface of the structure is, for example, 0.1 kg / m as the amount of solids in the mixture. 2 or more, preferably 0.4 kg / m 2 More preferably, 0.6 kg / m 2The amount of the mixture applied to the surface of the structure is, for example, 2.0 kg / m in terms of the amount of solids in the mixture. 2 may be less than or equal to 1.2 kg / m 2 Less than or equal to 1.0 kg / m, more preferably 1.0 kg / m 2 The following is the result.

[0103] Although preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments. For example, one aspect of the present invention may be a peeling prevention method for preventing peeling of a constituent material from a surface of a structure. Another aspect of the present invention may be a structure having a peeling-preventing cured film on at least a part of its surface. [Example]

[0104] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0105] The abbreviations for the components used in the examples and comparative examples and the test methods used in the examples and comparative examples are as follows:

[0106] <Epoxy compounds> jER828: Bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 190, glycidyl group-containing epoxy compound) jER806: Bisphenol F epoxy resin (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 165, glycidyl group-containing epoxy compound) ADEKA RESIN EP-4000 (referred to as "EP-4000" in the table): an epoxy compound having the structure of formula (2-2) (manufactured by ADEKA Corporation, epoxy equivalent weight 320) [ka] [In the formula, n and m each independently represent an integer of 1 or more.] ADEKA GLYCILOR ED-523T (referred to as "ED-523T" in the table): Diglycidyl ether (manufactured by ADEKA Corporation, epoxy equivalent weight 140)

[0107] <Amine-based curing agent> TEPA: Tetraethylenepentamine (manufactured by Tokyo Chemical Industry Co., Ltd., active hydrogen equivalent 23, nitrogen element content 53 mass%, amine-based curing agent with primary and secondary amino groups) jER Cure ST11: Modified aliphatic polyamine (manufactured by Mitsubishi Chemical Corporation, active hydrogen equivalent 114, nitrogen element content 9.2% by mass) TOMAID 235-A: Polyamidoamine (manufactured by T&K TOKA Corporation, active hydrogen equivalent 95, nitrogen element content 13.1% by mass)

[0108] <Filler> AEROSIL RY200S ("AEROSIL" in the table): Hydrophobic fumed silica (BET specific surface area 80 g / m 2 , manufactured by Evonik) Calcium carbonate (manufactured by Nitto Funka Kogyo Co., Ltd.)

[0109] <Other ingredients> 4-tert-butylphenol (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0110] <Fiber sheet> WL 230 140 BS6: Glass cloth (manufactured by Nittobo)

[0111] <Total nitrogen analysis of amine curing agents> Using Sumika Chemical Analysis Center's Sumigraph NC-220F, a calibration curve was created using aspartic acid (nitrogen content 10.52 mass%) as a standard sample, and the nitrogen content (mass%) of the amine curing agent was calculated.

[0112] <Viscosity measurement of two-component adhesive> A rotational viscometer TVB-25H manufactured by Toki Sangyo was used. A No. 5 rotor was used. The viscosity was measured 5 minutes after the specified amounts of the first and second agents were weighed and mixed. The amounts of the first and second agents were determined based on the epoxy equivalent and active hydrogen equivalent so that the epoxy group reacted with the active hydrogen derived from the amine in equivalent amounts. The cup temperature of the viscometer was set at 23°C, and the sample volume was 200 cm. 3The rotation speeds were 20 rpm and 2 rpm. The measurement result at 20 rpm was taken as the viscosity of the adhesive, and the ratio of the viscosity at 2 rpm to the viscosity at 20 rpm was taken as the thixotropic index. The results are shown in Table 1.

[0113] <Total light transmittance of cured film (1)> The first and second components were weighed out in specified amounts and mixed to obtain an adhesive composition. The amounts of the first and second components were determined based on the epoxy equivalent and active hydrogen equivalent so that the epoxy groups reacted with the active hydrogens derived from the amine in equivalent amounts. Next, a specified amount of coating (1.0 kg / m) was applied to the PET sheet. 2 The adhesive composition was applied to the substrate at 23°C for 7 days, and the PET film was then peeled off to obtain a cured film. The total light transmittance of the resulting cured film was measured using a Shimadzu SolidSpec-3700i UV-VIS-NIR spectrophotometer in accordance with JIS K7136:2000 (Plastics: Determination of haze for transparent materials).

[0114] <Total light transmittance of cured film (2)> The first and second components were weighed out in specified amounts and mixed to obtain an adhesive composition. The amounts of the first and second components were determined based on the epoxy equivalent and active hydrogen equivalent so that the epoxy groups reacted with the active hydrogens derived from the amine in equivalent amounts. Next, a specified amount of coating (1.0 kg / m) was applied to the PET sheet. 2 The adhesive composition was applied to the sheet using a roller. Immediately after application, a fiber sheet was placed on top of the sheet, and the adhesive composition was impregnated into the fiber sheet using a roller. After curing at 23°C for 7 days, the PET film was peeled off to obtain a cured film containing the composite. The total light transmittance of the resulting cured film was measured using a Shimadzu SolidSpec-3700i UV-VIS-NIR spectrophotometer in accordance with JIS K7136:2000 (Plastics: Determination of haze for transparent materials).

[0115] <Evaluation of the hazards of combustion gases> The first and second components were weighed out in specified amounts and mixed to obtain an adhesive composition. The amounts of the first and second components were determined based on the epoxy equivalent and active hydrogen equivalent so that the epoxy groups reacted with the active hydrogens derived from the amine in equivalent amounts. Next, the adhesive composition was applied to a calcium silicate board (220 mm x 220 mm x 10 mm) at a rate of 1.0 kg / m 2 Immediately after coating, a fiber sheet was placed on top of the adhesive composition, and the adhesive composition was impregnated into the fiber sheet using a roller. After curing at 23°C, a test specimen was obtained. The obtained test specimens were subjected to a gas toxicity test using mice as specified in the fire resistance performance test and evaluation procedure based on the Building Standards Act of Japan, and the average behavioral immobility time of the mice (X s The above fire resistance performance test and evaluation procedure manual is published by the Japan Testing Center for Construction Materials, a general incorporated foundation. s The larger the value, the less harmful the substance is. s For example, the time is preferably 6.8 minutes or more, and more preferably 7.0 minutes or more.

[0116] Example 1 70 parts by mass of jER828, 30 parts by mass of ADEKA RESIN EP-4000, and 3.5 parts by mass of AEROSIL RY200S were mixed to obtain a first part with an epoxy equivalent of 216. Next, Tomide 235-A was used as the second part. The first and second parts were mixed in a ratio of 100 parts by mass of the first part to 42 parts by mass of the second part to obtain an adhesive composition. When the total amount of solids in the adhesive composition was taken as 100% by mass, the nitrogen content in the solids was 3.8% by mass. The adhesive composition thus obtained was subjected to viscosity measurement, preparation of a cured film, preparation of a cured body including a composite, measurement of total light transmittance, and evaluation of the harmfulness of combustion gases, all using the methods described above. The results are shown in Table 1.

[0117] Example 2 An adhesive composition was prepared and evaluated in the same manner as in Example 1, except that ST11 was used as the second agent and the amount of the second agent was changed to 51 parts by mass per 100 parts by mass of the first agent. The results are shown in Table 1. When the total amount of solids in the adhesive composition was taken as 100% by mass, the amount of nitrogen element in the solids was 3.0% by mass.

[0118] Example 3 An adhesive composition was prepared and evaluated in the same manner as in Example 1, except that TEPA was used as the second agent and the amount of the second agent was changed to 10 parts by mass per 100 parts by mass of the first agent. The results are shown in Table 1. When the total amount of solids in the adhesive composition was taken as 100% by mass, the amount of nitrogen element in the solids was 4.7% by mass.

[0119] Example 4 100 parts by mass of jER828 and 3.5 parts by mass of AEROSIL RY200S were mixed to obtain a first agent with an epoxy equivalent of 190. Next, Tomide 235-A was used as a second agent. The first and second parts were mixed in a ratio of 100 parts by mass of the first part to 48 parts by mass of the second part to obtain an adhesive composition. When the total amount of solids in the adhesive composition was taken as 100% by mass, the nitrogen element content in the solids was 4.2% by mass. The obtained adhesive composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0120] Example 5 An adhesive composition was prepared and evaluated in the same manner as in Example 1, except that the second agent was a mixture of 43.9 parts by mass of Tomide 235-A and 3.0 parts by mass of 4-tert-butylphenol, and the amount of the second agent was 45 parts by mass per 100 parts by mass of the first agent. The results are shown in Table 1. When the total amount of solids in the adhesive composition was taken as 100% by mass, the amount of nitrogen element in the solids was 3.7% by mass.

[0121] Example 6 70 parts by mass of jER828, 30 parts by mass of ADEKA GLYCILOR ED-523T, and 3.5 parts by mass of AEROSIL RY200S were mixed to obtain a first agent with an epoxy equivalent of 172. Next, Tomide 235-A was used as the second agent. The first and second parts were mixed in a ratio of 100 parts by mass of the first part to 53 parts by mass of the second part to obtain an adhesive composition. When the total amount of solids in the adhesive composition was taken as 100% by mass, the nitrogen element content in the solids was 4.4% by mass. The obtained adhesive composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0122] Example 7 An adhesive composition was prepared and evaluated in the same manner as in Example 1, except that no filler was blended into the first agent and the blending amount of the second agent was 44 parts by mass per 100 parts by mass of the first agent. The results are shown in Table 1. When the total amount of solids in the adhesive composition was taken as 100% by mass, the amount of nitrogen element in the solids was 4.0% by mass.

[0123] Example 8 An adhesive composition was prepared and evaluated in the same manner as in Example 1, except that 3.5 parts by mass of calcium carbonate was used in place of AEROSIL RY200S in the first agent. The results are shown in Table 1. When the total amount of solids in the adhesive composition was taken as 100% by mass, the amount of nitrogen element in the solids was 3.8% by mass.

[0124] Example 9 An adhesive composition was prepared and evaluated in the same manner as in Example 1, except that the amount of AEROSIL RY200S in the first agent was changed to 5.0 parts by mass. The results are shown in Table 1. When the total amount of solids in the adhesive composition was taken as 100% by mass, the amount of nitrogen element in the solids was 3.7% by mass.

[0125] Example 10 An adhesive composition was prepared and evaluated in the same manner as in Example 1, except that the second agent was a mixture of 8.8 parts by mass of Tomide 235-A and 8.4 parts by mass of TEPA, and the amount of the second agent was 17 parts by mass per 100 parts by mass of the first agent. The results are shown in Table 1. When the total amount of solids in the adhesive composition was taken as 100% by mass, the amount of nitrogen element in the solids was 4.6% by mass.

[0126] (Comparative Example 1) 100 parts by mass of jER828 and 3.5 parts by mass of AEROSIL RY200S were mixed to obtain a first agent with an epoxy compound epoxy equivalent of 190. Next, TEPA was used as a second agent. The first and second parts were mixed in a ratio of 100 parts by mass of the first part to 12 parts by mass of the second part to obtain an adhesive composition. When the total amount of solids in the adhesive composition was taken as 100% by mass, the amount of nitrogen element in the solids was 5.5% by mass. The obtained adhesive composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0127] (Comparative Example 2) 50 parts by mass of jER806, 50 parts by mass of ADEKA GLYCILOR ED-523T, and 3.5 parts by mass of AEROSIL RY200S were mixed to obtain a first agent with an epoxy equivalent of 151. Next, Tomide 235-A was used as a second agent. The first and second parts were mixed in a ratio of 100 parts by mass of the first part to 61 parts by mass of the second part to obtain an adhesive composition. When the total amount of solids in the adhesive composition was taken as 100% by mass, the nitrogen element content in the solids was 4.9% by mass. The obtained adhesive composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0128] [Table 1]

Claims

1. Contains an epoxy compound, an amine-based curing agent, and a filler, When the total amount of the solid content is 100% by mass, the amount of nitrogen element in the solid content is less than 4.9% by mass, The epoxy compound includes a compound represented by formula (2-1), an adhesive composition, wherein the content of the filler in the solid content is 0.1% by mass or more and 5.5% by mass or less, when the total amount of the solid content is 100% by mass. 【Chemical 1】 [In the formula, n and m each independently represent an integer of 1 or greater, R 1 and R 2 each independently represent a hydrogen atom or a methyl group, and R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms which may have a substituent, or a phenyl group which may have a substituent. When there are multiple R 1 s, the multiple R 1 s may be the same or different. When there are multiple R 2 s, the multiple R 2 s may be the same or different.]

2. The adhesive composition according to claim 1 , wherein the epoxy compound has an epoxy equivalent weight of greater than 190.

3. An adhesive composition as described in claim 1 or 2, wherein the amine-based curing agent comprises an amine compound having a group selected from the group consisting of a primary amino group and a secondary amino group.

4. The adhesive composition according to any one of claims 1 to 3, which exhibits a viscosity of 4000 mPa·s or more and 100,000 mPa·s or less, and a thixotropic index of 3.0 or more.

5. The adhesive composition according to any one of claims 1 to 4, which is an adhesive for forming a cured film on the surface of a structure.

6. The adhesive composition according to claim 5, wherein the surface of the structure is a concrete surface or a mortar surface.

7. The adhesive composition according to claim 5 or 6, wherein the cured film is composed of a composite of a cured product of the adhesive composition and a fiber material.

8. The adhesive composition according to any one of claims 5 to 7, wherein the cured film is used to prevent the component material from peeling off from the surface of the structure.

9. A cured film formed using the adhesive composition according to any one of claims 1 to 8, A cured film comprising a cured product of the adhesive composition.

10. The cured film according to claim 9 , comprising a composite of the cured body and a fibrous material.

11. Nitrogen element amount: 39.3 g / m ２ The cured film according to claim 9 or 10, wherein the cured film has a viscosity of less than 1000 MPa.

12. The cured film according to any one of claims 9 to 11, having a total light transmittance of 70% or more.

13. A method for producing a cured film using the adhesive composition according to any one of claims 1 to 8, comprising the steps of: a coating step of applying the adhesive composition to a surface of a structure to form a coating film; a curing step of curing the coating film to obtain a cured film containing a cured product of the adhesive composition; A method for producing a cured film, comprising:

14. the applying step is a step of placing the adhesive composition and a fiber material on a surface of the structure to form a coating film containing the adhesive composition and the fiber material, The manufacturing method according to claim 13 , wherein the curing step is a step of curing the coating film to obtain a cured film containing a composite of the cured product of the adhesive composition and the fiber material.

15. The manufacturing method according to claim 13 or 14, wherein the surface of the structure is a concrete surface or a mortar surface.

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