JP5235290B2 - Epoxy resin composition - Google Patents

Description

  The present invention relates to an epoxy resin composition that can be suitably used as a primer for laminating a resin layer on the surface layer of a structure such as metal, concrete, natural stone, or ceramic. More specifically, the present invention relates to an epoxy resin composition that is excellent in adherence when laminating a reactive resin and can be suitably used as a primer.

  On the surface of a structure such as a metal structure such as steel, a concrete structure, a natural stone structure, or a ceramic structure, a resin layer may be formed for the purpose of waterproofing, corrosion prevention, prevention of peeling, and the like. As these resins, polyurea, polyurethane, epoxy resin, vinyl ester resin, unsaturated polyester resin, acrylic resin, acrylic urethane resin and the like are used. Among these, polyurea and polyurethane are tough and resistant to destruction at a wide range of environmental temperatures, and may be used alone in applications that require a reinforcing fiber sheet with other resins, and are attracting attention as high-performance coating resins. .

  When constructing a surface structure having such a resin layer, a primer is usually used for the purpose of ensuring adhesion and preventing pinhole formation. As the primer, in the case of using polyurea or polyurethane as a resin layer, a solvent-based urethane primer, a solvent-based epoxy primer, or the like is used.

  Since the solvent-based primer releases the solvent into the atmosphere, its use is restricted from the viewpoint of environmental problems. In addition, when the structure is a concrete structure, fine pores exist on the surface, so that it has been difficult to completely form a coating film on the concrete surface with a conventional solvent-based primer. Therefore, the present applicant has proposed a solvent-free epoxy resin primer that can be used for structures such as concrete (for example, Japanese Patent Application Laid-Open No. 2005-187683).

    In construction sites where a resin layer is formed on the surface of the structure, it is preferable that the primer can be applied in all seasons. However, when solvent-free epoxy resin is used as a primer for on-site construction, it should be used under conditions of low temperature and low humidity. When the primer is applied and the resin is laminated after curing, the adherence of the primer is not sufficient, and the necessary adhesion may not be obtained. Under winter weather conditions, there are many cases where the temperature is low and the humidity is low, and construction is restricted to ensure adhesion. Primers with excellent adhesive strength that can be laminated without problems under such weather conditions. It was sought after.

  The inventors of the present invention are sufficient to form a resin layer on the surface of a structure such as a metal structure such as steel, a concrete structure, a natural stone structure, or a ceramic structure even under low temperature and low humidity conditions. As a result of diligent efforts to develop an epoxy resin suitable for a primer having adhesive strength, the present invention has been achieved.

JP-A-2005-187683

The present invention provides an epoxy resin composition excellent in adhesiveness with a reactive resin layer.
The present invention provides an epoxy resin composition exhibiting sufficient adhesion with a reactive resin layer even under conditions of low temperature and low humidity.
The present invention provides an epoxy resin composition that can be suitably used as a primer for laminating a resin layer on the surface of a structure such as a metal structure, a concrete structure, a natural stone structure, or a ceramic structure.

By using a composition containing water as an ingredient in an epoxy resin as a primer, the present invention has sufficient adhesive strength in a wide range of environmental temperatures including low temperature and low humidity conditions of 0 to 40 ° C. and humidity of 10 to 100%. It is based on finding out that the laminated body which has can be obtained.
That is, this invention provides the epoxy resin composition which contains an epoxy resin and a hardening | curing agent, contains 0.1-20 weight% of water with respect to the weight of the whole epoxy resin, and contains a silane coupling agent .

  An epoxy resin composition obtained by mixing the epoxy resin composition with a curing agent containing an epoxy resin and water is a preferred embodiment of the present invention.

The epoxy resin is a bisphenol F type epoxy resin, and the curing agent is an alicyclic polyamine or an epoxy resin adduct thereof, an addition reaction product of ethylene oxide or propylene oxide, an addition reaction product of acrylonitrile, and a Mannich addition polyamine type curing agent. It is a modified product selected from .

The epoxy resin composition to the epoxy resin composition 100 parts by weight, it contains a silane coupling agent in a proportion of 0.1 to 5 parts by weight.

  The present invention provides a primer comprising the above-described epoxy resin composition that can be applied to the surface layer of a structure selected from a metal structure, a concrete structure, a natural stone structure, and a ceramic structure.

The present invention, metal structures, concrete structures, natural stone structures on the surface layer of the structure selected from ceramic structure, a step of forming a primer layer by supplying the epoxy resin composition, a primer layer It can be used in a method for constructing a surface structure including a step of supplying a curable resin composition to form a resin layer.

The curable resin composition is a composition selected from polyurethane, polyurea, acrylic resin, acrylic urethane resin, epoxy resin, unsaturated polyester resin, vinyl ester resin, etc., and is a composition containing polyurethane or polyurea method for constructing a surface structure is a good preferable manner.

By this invention, the epoxy resin composition excellent in adhesiveness with the reactive resin layer is provided.
The present invention provides an epoxy resin composition exhibiting sufficient adhesiveness with a reactive resin layer even under low temperature and low humidity conditions.
ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin composition which can be used conveniently as a primer at the time of laminating | stacking a resin layer on structure surfaces, such as a metal structure, a concrete structure, a natural stone structure, and a ceramic structure, is provided.
Further, according to the present invention, the epoxy resin composition according to any one of claims 1 to 5 is supplied to a surface layer of a structure selected from a metal structure, a concrete structure, a natural stone structure, and a ceramic structure. There is provided a method for constructing a surface structure comprising a step of forming a primer layer and a step of forming a resin layer such as polyurethane or polyurea by supplying a curable resin composition onto the primer layer.

  This invention provides the epoxy resin composition which contains an epoxy resin and a hardening | curing agent, and contains 0.1-20 weight% of water with respect to the weight of the whole epoxy resin.

  The epoxy resin composition of the present invention can be suitably used as a primer applied to the surface layer of structures such as metal structures, concrete structures, natural stone structures, and ceramic structures. By using the epoxy resin of the present invention as a primer, it becomes possible to obtain a laminate having sufficient adhesive strength under conditions of a temperature of 0 ° C. to 40 ° C. and a humidity of 10 to 100%.

  The primer made of the epoxy resin composition of the present invention penetrates into the surface layer of a structure such as concrete and adheres firmly to the concrete base and the resin layer. Even when the concrete surface is in a wet state, similar performance can be achieved by using the epoxy resin primer of the present invention and a silane coupling agent in combination.

  The epoxy resin primer of the present invention is preferably a solventless type that does not use an organic solvent as a diluent. The agentless solvent epoxy resin primer refers to a primer that substantially does not contain an organic solvent used for viscosity adjustment. By using a solvent-free epoxy resin primer, there are few components diffused into the atmosphere, so there are fewer concerns about health and the environment due to organic solvents, and it is possible to work with peace of mind and to which the primer is applied Concerns about the environment itself can also be reduced.

The epoxy resin composition of this invention contains 0.1-20 weight% of water with respect to the weight of the whole epoxy resin, Preferably it is 0.2-7 weight%, More preferably, it contains 0.3-5 weight%. Water can be added to the main agent and / or curing agent, but is preferably added to the curing agent.
By mixing different components into the main agent and the curing agent, water can be generated by a chemical reaction when the two liquids are mixed, and the generated water can be contained in an amount of 0.1 to 20% by weight. A mode in which water is added to the curing agent is more preferable.

  Compatibilizers can be added when adding water. The compatibilizing agent may be a hydrophilic organic substance that does not react with the components of the curing agent. Examples of compatibilizers include glycerin, ethylene glycol, popylene glycol, polyethylene glycol, polypropylene glycol, triethanolamine, diethanolamine, triisopropanolamine, 2-amino-1-propanol, 2-amino-2-methyl-1- List propanol, N-methylethanolamine, N, N-dibutylethanolamine, N-methyl-N, N-diethanolamine, aminoethylethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, etc. Can do. Of these, triethanolamine is preferable. The amount of the compatibilizing agent is 0.1 to 20% by weight, preferably 0.2 to 7% by weight, more preferably 0.3 to 5% by weight, based on the total weight of the epoxy resin.

  Examples of the epoxy resin primer include a two-component type comprising a resin liquid mainly composed of an epoxy resin as a main agent (A liquid) and a curing agent liquid (B liquid) mainly composed of the curing agent. it can.

  Viscosity at 20 ° C. measured with a B-type viscometer in the composition after mixing both the resin liquid (A liquid) and the curing agent liquid (B liquid) from the viewpoint of workability and permeability to the concrete surface layer. However, the thing in the range of 20-5000 mPa * s, Preferably it is 50-3000 mPa * s is preferable.

  As A liquid, the reactive diluent, thixotropy imparting agent, surface tension reducing agent, coupling agent, etc. are mix | blended with the epoxy resin which is a main ingredient as needed.

  The epoxy resin is a glycidyl ether type epoxy resin, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin; glycidyl ester type epoxy resin, for example, hexahydrophthalic acid glycidyl ester, dimer acid glycidyl ester; Glycidylamine type epoxy resins such as triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane; linear aliphatic epoxides such as epoxidized polybutadiene, epoxidized soybean oil; alicyclic epoxy side such as 3,4-epoxy-6 -Methyl cyclohexyl methyl carboxylate, 3,4-epoxy cyclohexyl methyl carboxylate, etc. are mentioned. Preferably, it is a low-viscosity liquid epoxy resin such as bisphenol F type epoxy resin, and this resin is excellent in chemical resistance and is also used as an environmentally preferable one.

  As the reactive diluent that can be blended in the liquid A, mono- or polyglycidyl ethers of polyhydric alcohols are preferred, ethylene glycol mono- or diglycidyl ether, polyethylene glycol mono- or diglycidyl ether, neopentyl glycol mono- or di- Glycidyl ether, 1,6-hexanediol mono- or diglycidyl ether, mono- or diglycidyl ether of long-chain alkylene glycol having 8 or more carbon atoms, or even 10 or more, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, etc. Can be mentioned. Other reactive diluents include olefin oxides such as octylene oxide, butyl glycidyl ether, styrene oxide, phenyl glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 3- (pentadecyl) phenyl glycidyl ether, glycidyl. Mention may be made of low-viscosity mono- or polyepoxy compounds including monoepoxy compounds such as methacrylate, allyl glycidyl ether, cyclohexene vinyl monooxide, dipentene monooxide, α-pinene oxide and the like.

  Thixotropy imparting agents that can be used for liquid A include silicic acid-based (fine particulate silicic acid or fumed silica), hydrous silicon magnesium-based (sepiolite, chrysostyle, etc.), aluminum silicate-based (montmorillonite-based bentonite, zeolite, etc. ), Inorganic compounds such as organic bentonite with organic molecules adsorbed between layers, polyhydroxycarboxylic acid or its amides, polyacrylic acid soda, dibenzal sorbite, certain surfactants, etc. Examples of these organic compounds can be given.

  Examples of the surface tension reducing agent that can be used for the liquid A include polyhydroxycarboxylic acid amide, silicone-modified polyacrylate, polysiloxane, and the like. Since some of the thixotropic properties-imparting agents have a surface tension lowering effect, the thixotropic properties-imparting agent can also be used as a surface tension reducing agent.

  Examples of coupling agents that can be blended in the liquid A include titanium coupling agents, silane coupling agents, aluminum coupling agents, zirconium coupling agents, chromium coupling agents, and organic phosphate coupling agents. The use of a silane coupling agent is preferred. Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β-methoxyethoxy) silane, methacryloxytrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-glycine. Contains unsaturated groups or epoxy groups such as sidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane A silicon compound etc. can be mentioned. Among these, the use of a silane coupling agent having an epoxy group is preferable because a primer layer having excellent characteristics can be formed even when the concrete surface layer is in a wet state.

  For example, when the total amount of the epoxy resin and the reactive diluent is 100 parts by weight, the proportion of the epoxy resin is 60 to 100 parts by weight, preferably 65 to 90 parts by weight. The diluent is 40 to 0 parts by weight, preferably 35 to 10 parts by weight. The total amount of the epoxy resin and the reactive diluent is 100 parts by weight, and the thixotropic agent is 0 to 10 parts by weight. The ratio can be such that the tension reducing agent is 0 to 3 parts by weight and the coupling agent is 0.1 to 5 parts by weight.

The curing agent preferably used as the B liquid of the present invention is a curing agent that is liquid at room temperature, more preferably a room temperature curing type curing agent. Examples of liquid and room-temperature curable curing agents include aliphatic polyamines, alicyclic polyamines, polyamide polyamines, and polymercaptans. In the present invention, alicyclic polyamines and modified products thereof are particularly preferred. Is preferred. Specifically, alicyclic polyamines (so-called cycloaliphatic polyamines) such as N-aminoethylpiperazine, mensendiamine, and isophoronediamine, and modified compounds thereof. Examples of the modifying compound include addition reaction of an epoxy resin, addition reaction product of ethylene oxide / propylene oxide, addition reaction product of acrylonitrile, or Mannich addition polyamine type curing agent. These liquid polyamines may be used alone or in combination of two or more.
A solid aromatic polyamine or the like may be used in combination with the liquid polyamine as long as the effects of the present invention are not impaired.

  The aforementioned thixotropy-imparting agent, surface tension reducing agent, coupling agent and the like can also be added to the B liquid of the curing agent liquid. For example, amino group-containing silicon compounds such as γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane as coupling agents Mercapto group-containing silicon compounds such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane can be blended.

  Further, one or both of the liquid A and the liquid B may contain additives for reducing viscosity or improving compatibility, including a plasticizer and a softening agent, as necessary. In addition, various additives used for the epoxy resin adhesive may be contained.

  The epoxy composition of the present invention constructs a surface structure in which a resin layer is laminated on the surface layer of a structure such as a metal structure such as steel, a concrete structure, a natural stone structure, or a ceramic structure. It is preferably used as a primer for this. By using the epoxy resin composition of the present invention as a primer, a laminate having sufficient adhesive force can be obtained even under conditions of 5 ° C. to 40 ° C. and humidity of 10 to 100%.

  Further, according to the present invention, the surface layer of a structure such as a metal structure such as steel, a concrete structure, a natural stone structure, or a ceramic structure is composed of a composition containing water as a component in the epoxy resin of the present invention. There is provided a method for constructing a surface structure comprising a step of forming a primer layer and a step of supplying a curable resin composition such as polyurethane or polyurea onto the primer layer to form a resin layer.

  There is no restriction | limiting in particular as the method of forming the primer layer which consists of an epoxy resin of this invention, and the method of forming a resin layer, A conventionally well-known method can be selected suitably and can be employ | adopted.

  In applying the epoxy resin primer to the surface of the concrete structure, liquid A and liquid B are mixed. The blending ratio of liquid A and liquid B depends on the type of epoxy resin and curing agent used and their content, but the optimum amount determined experimentally to the required amount based on the ratio of epoxy equivalent / active hydrogen equivalent. For example, it can be used at a ratio of 10 to 100 parts by weight, particularly 20 to 80 parts by weight with respect to 100 parts by weight of the A liquid.

  By appropriately selecting the type and blending amount of the epoxy resin, the curing agent, or other additives, the viscosity at 20 ° C. after mixing of the liquid A and the liquid B is 20 to 5000 mPa · s, preferably 50 to 3000 mPa · s. It is preferable to prepare as follows.

  When the construction of the surface structure of the present invention is applied to a concrete structure, the waterproofing of the rooftop, the waterproofing of the underground structure, the waterproofing of the floor of the bridge, the waterproofing of the end of the bridge girder, the waterproofing of the waterworks-related facilities, Suitable for anticorrosion, protection / repair of irrigation canal surface, protection / repair of intake dam tapping, salt damage prevention coating, alkali aggregate reaction suppression coating, frost damage prevention coating, surface peeling prevention, etc. This is the most preferred embodiment of the present invention because it exhibits a significant effect on prevention.

  The solvent-free epoxy resin primer of the present invention is also applied to the concrete structure surface layer in a wet state, in addition to the above-described method of using the silane coupling agent in combination with the epoxy resin and / or curing. It is preferable to use at least a part of the agent having a hydrophilic group such as a polyether skeleton. A primer layer having a desired tensile strength can be formed by applying such a mixed solution to the surface of the concrete structure by means of brushing or the like. The layer thickness of the primer layer is preferably about 0.02 to 0.4 mm. By having such a primer layer, the concrete structure and the polyurethane or polyurea layer can be firmly adhered, and by making a polyurethane or polyurea and a laminated structure to be described later, in the range of -20 to 60 ° C, A surface structure that can follow the displacement of the concrete piece and withstand the corresponding stress can be formed.

  Examples of the resin constituting the resin layer of the concrete surface structure of the present invention include polyurethane, polyurea, acrylic resin, acrylic urethane resin, epoxy resin, unsaturated polyester resin, and vinyl ester resin. In particular, the effect of the present invention is remarkable with respect to fast-curing polyurethane or polyurea.

  As the polyurethane or polyurea used in the present invention, those having an embrittlement temperature of −25 ° C. or lower, particularly −30 ° C. or lower are preferable. By using the above-mentioned properties as polyurethane or polyurea, it is possible to form a surface structure capable of following the displacement of the concrete piece and withstanding the corresponding stress in the range of -20 to 60 ° C. it can.

  Specifically, the polyurethane or polyurea can be formed by a polyurethane prepolymer having two or more isocyanate groups and a curing agent having two or more hydroxyl groups and / or amino groups.

  Such a urethane prepolymer can be obtained by reacting a polyisocyanate compound having two or more isocyanate groups in one molecule with a compound having two or more active hydrogens reacting with the isocyanate group in one molecule. it can. Particularly preferred as the active hydrogen compound is a urethane prepolymer formed by combining one or two or more polyol compounds having two or more alcoholic hydroxyl groups in one molecule, such as polyether polyol, polyester polyol or other polyols. It is.

  Examples of the polyisocyanate compound that can be used for the preparation of the urethane prepolymer include aliphatic polyisocyanates such as hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine methyl ester diisocyanate; 1,4-cyclohexane diisocyanate, isophorone Cycloaliphatic polyisocyanates such as diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hydrogenated tolylene diisocyanate, norbornane diisocyanate; p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 3,3 Aromatic diisocyanates such as' -dimethyldiphenyl-4,4'-diisocyanate, 4,4'-diphenylmethane diisocyanate Aromatic polyisocyanates and the like; such that each of the above-mentioned polyisocyanate and carbodiimide-modified or isocyanurate-modified, and these may be used alone or as a mixture of two or more. Preferably, aromatic polyisocyanates such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and 4,4'-diphenylmethane diisocyanate are used from the viewpoint of easy handling.

  Specific examples of polyether polyols that can be used for the preparation of urethane prepolymers include polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethyleneoxypropylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, and the like. , Low molecular weight active hydrogen compounds having two or more active hydrogens, for example, diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, 1,6-hexanediol; glycerin, trimethylolpropane, 1,2,6- Triols such as hexanetriol; propylene oxide and / or in the presence of one or more amines such as ammonia, methylamine, ethylamine, propylamine, butylamine, etc. It can be mentioned random copolymer obtained by the Chi alkylene oxide by ring-opening polymerization.

  Examples of polyester polyols that can be used to prepare urethane prepolymers include polymers obtained by dehydration condensation of polybasic acids and polyhydric alcohols; condensates of hydroxycarboxylic acids and polyhydric alcohols; ring-opening polymers of lactones, etc. Are preferably used. Examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, succinic acid, dimerized linolenic acid, maleic acid, and the like. Examples of the polyhydric alcohol include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, neo Diols such as pentyl glycol; triols such as glycerin, 1,1,1-trimethylolpropane, and 1,2,6-hexanetriol can be used. More specifically, polyethylene adipate, polytetramethylene adipate, polyhexamethylene adipate, polytetramethylene sebacate, poly (diethylene glycol adipate), poly (hexamethylene glycol-1,6-carbonate) whose both ends are diol components ), Polycaprolactone and the like.

  Other polyols that can be used to prepare the urethane prepolymer include, for example, acrylic polyols, hydrogenated polybutadiene polyols, castor oil derivatives, tall oil derivatives, polymer polyols, polycarbonate polyols, ethylene glycol, diethylene glycol, Low molecular polyols such as propylene glycol, dipropylene glycol, butanediol, pentanediol and hexanediol are also preferably used.

  These polyol compounds preferably have a number average molecular weight of 100 to 10,000, particularly 300 to 5,000, and can be used alone or in combination of two or more as desired.

  In the urethane prepolymer, the ratio of the isocyanate group contained in the polyisocyanate compound to more than 1 mole with respect to 1 mole of the hydroxyl group contained in the polyol compound, that is, the chemical equivalent ratio (NCO / OH) exceeds 1. As a formulation, the polyol compound and the polyisocyanate compound can be obtained by heating and reacting as necessary. Such urethane prepolymers usually have isocyanate groups at both molecular ends. As a urethane prepolymer, a polyol compound and a polyisocyanate compound are mixed at a ratio of 1.6 to 20 at a chemical equivalent ratio (NCO / OH) of a hydroxyl group contained in the polyol compound and an isocyanate group contained in the polyisocyanate compound. What reacts and exhibits liquid state at 23 degreeC is more preferable from points, such as workability | operativity and the physical property of cured | curing material.

  The polyurethane or polyurea forming the concrete surface structure of the present invention can be formed by curing the urethane prepolymer with a curing agent as a curable composition containing other additives as necessary.

  Examples of the curing agent include compounds having two or more active hydrogens that react with isocyanate groups in one molecule. For example, water; ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, glycerin, trimethylolpropane, 1,2,4-trihydroxybutane 1,2,3,4-tetrahydroxybutane, 1,2,6-trihydroxyhexane, 1,1,1-trimethylolethane, pentaerythritol, polycaprolactone, fructose, xylitol, arabitol, sorbitol, mannitol, etc. Polyhydric alcohols; low molecular amino alcohols such as ethanolamine; ammonia, hydrazine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, m-phenylene Low molecular weight polyamine compounds such as amines, 2,4-tolylenediamine, 2,6-tolylenediamine, diethyltolylenediamine, 3,3'-dichloro-4,4'-diamino-diphenylmethane, and those mentioned above Polyols such as polyether polyols and polyester polyols that can be used in the preparation of urethane prepolymers; hydroxyl groups having polyether ends obtained by reacting alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; Examples thereof include polyether polyamines such as polyoxyethylene diamine, polyoxypropylene diamine, and polyoxybutylene diamine obtained by reacting with ammonia and substituting amino groups. Among these curing agents, it is preferable to use polyether polyol or polyether polyamine, but it is also possible to use polyether polyol or polyether polyamine in combination with one or more other low molecular polyols or low molecular polyamines. it can. When these curing agents are other than water, the active hydrogen in the low molecular weight compound is in a ratio of about 0.8 mol or more, preferably about 0.95 with respect to 1 mol of isocyanate group contained in the urethane prepolymer. It is preferable that it is -1.2 mol.

  For polyurethane, after construction on the target product, a one-pack type cured by reacting the terminal isocyanate group of the polyurethane prepolymer with moisture in the atmosphere, a main agent containing the polyurethane prepolymer, and a curing agent such as polyol, There are two-component types that are mixed and cured during construction. One-component polyurethane is an example of a polyurethane that can be suitably used because of its simple construction. In the present invention, a two-component polyurethane can also be preferably used.

  One-component polyurethane is said to be moisture curable, and reacts with polyisocyanate and moisture (water), and the amine produced by decarboxylation of the reaction product of isocyanate and water reacts with the remaining polyisocyanate and cures. It utilizes a reaction and is used as a moisture curable composition (see JP-A-4-279620). Further, a moisture curable composition comprising polyaldimine, polyketimine, polyenamine and the like and polyisocyanate as described in British Patent 1064841, German Patent 3607996A, JP-A-11-335650, etc. is used as a one-component polyurethane. You can also

  In addition to the urethane prepolymer and the curing agent, examples of additives that can be optionally blended include plasticizers, surfactants, pigments, dyes, fillers, curing accelerators, and anti-aging agents. .

  Plasticizers include phthalates, adipic esters, sebacic esters, azelaic esters, trimellitic esters, phosphate esters, normal paraffins, chlorinated paraffins, alkylbenzenes, or methyl stearates. Esters, palmitic acid methyl esters, lauric acid methyl esters, oleic acid methyl esters, tallow fatty acid methyl esters, nuka fatty acid methyl esters, vegetable fatty acid methyl esters, palmitic acid butyl esters and vegetable fatty acid butyl esters and other various liquid components These may be used alone or in combination of two or more.

  As the surfactant, various surfactants may be added singly or in combination of two or more according to properties such as an antifoaming agent, a wetting and dispersing agent for pigments and fillers, an emulsifier, and a viscosity modifier.

  In order to color the cured product, organic pigments such as azo pigments and copper phthalocyanine pigments, and various inorganic pigments such as carbon black, zinc oxide, zinc sulfide, chromium oxide, and bengara can be used as the pigment.

  Examples of the filler include calcium carbonate, magnesium oxide, clay, talc, silica, diatomaceous earth, and those treated with a surface treatment agent such as fatty acid or fatty acid ester.

  As a curing accelerating catalyst for accelerating the reaction between the urethane prepolymer and the curing agent, N-alkylbenzylamine, N-alkyl aliphatic polyamine, triethylenediamine, N-alkylpiperazine, N-alkylmorpholine, dimorpholinodiethyl ether, Examples thereof include organometallic compounds such as tin octenoate, dibutyltin dilaurate, organic acid lead salts, and organic acid bismuth salts, and these may be used alone or in combination of two or more. For the fast-curing polyurethane, it is preferable to use an organic acid lead salt or an organic acid bismuth salt, and it is more preferable to use an organic acid bismuth salt in consideration of environmental burden. Examples of the organic acid bismuth salt include alicyclic organic acids such as abietic acid, neoabietic acid, d-pimalic acid, iso-d-pimalic acid, podocarpic acid, and bismuth resin acid resin mainly composed of two or more of these. Bismuth salts, aromatic acid bismuth salts such as benzoic acid, cinnamic acid and p-oxycinnamic acid, and bismuth fatty acid bismuth salts such as octylic acid, neodecanoic acid and neododecanoic acid. Further, when using an organic acid bismuth salt, an organic acid exhibiting an effect such as a promoter may be added. Examples of the organic acid include aromatic carboxylic acids such as benzoic acid, phthalic acid, and o-chlorobenzoic acid, and aliphatic carboxylic acids such as 2-ethylhexanoic acid, octylic acid, stearic acid, oleic acid, and linoleic acid. . The curing accelerating catalyst and the cocatalyst are blended in the curing agent, and 2-ethylhexanoic acid is preferably excellent in compatibility with the polyol.

  Anti-aging agents are used to protect polyurethane or polyurea layers from light, oxygen, heat, etc., and those commonly used as anti-aging agents include light stabilizers and antioxidants, Examples of the agent include benzotriazole, benzophenone, benzoate, cyanoacrylate, hindered amine, and nickel. Antioxidants include hindered phenols, amines, sulfurs, phosphoruss and the like.

  A concrete surface structure which is a preferred embodiment of the present invention is a curable composition comprising the urethane prepolymer as described above, a curing agent and an additive optionally blended on an epoxy resin primer layer formed on a concrete structure. It is constructed by forming a 0.3 to 10 mm, preferably 0.5 to 3 mm layer of polyurethane or polyurea by applying and curing the object. The coating method can be performed by any method such as spray coating or brush coating, but spray coating is preferable because it can be applied in a short time. Lamination of fast-curing polyurethane or polyurea is usually preferably carried out using a tip impingement mixing gun with a dedicated sprayer.

  A curable composition comprising a urethane prepolymer, a curing agent, and an additive that is optionally blended, when considering application workability, is applied manually or by a method equivalent to this without using a spray device such as a trowel. It is preferable to adjust the viscosity appropriately. In addition, by selecting the molecular weight of the urethane prepolymer, the type of curing agent and curing accelerator, the amount added, etc., the touch drying time specified by JIS K5600-1-1 at 23 ° C. is a two-component collision mixed spray. When using an apparatus, it is preferable to prepare it so that it may be 1 to 120 seconds, and when it is applied manually or according to a method corresponding thereto, it is 10 to 200 minutes. Furthermore, the tensile strength, tensile breaking elongation, embrittlement temperature, and the like can be adjusted to desired values depending on the type of urethane prepolymer and curing agent and the type and amount of other additives.

  The concrete surface structure of the present invention can exhibit a sufficient peeling prevention effect without using a fiber sheet by using a laminated structure of the epoxy resin primer layer and the polyurethane or polyurea layer as described above. it can.

  For the purpose of imparting the weather resistance and other properties of the surface structure constructed as described above, a topcoat layer may be provided on the surface of the polyurethane or polyurea layer. As such a topcoat layer, a fluororesin, an acrylic silicon resin, an acrylic urethane resin, an acrylic resin, or a modified resin thereof can be used. For example, it is effective to form the top coat layer to a thickness of about 0.05 to 0.4 mm. For the purpose of protecting the polyurethane or polyurea layer, the thickness is about 2 mm or less, preferably about 1 to 2 mm, directly or via a primer layer on the surface of the polyurethane or polyurea layer or on the surface of the topcoat layer. A protective layer can be provided. The protective layer may be any material as long as it has good adhesion to the polyurethane or polyurea layer, does not deteriorate in a normal repair cycle, and serves the purpose of protecting the surface structure. The same material as polyurea can be used. In this case, when the protective layer is removed by refurbishment, it is preferable to color both of them in different colors so that the difference between the polyurethane or polyurea layer and the protective layer in the surface structure becomes clear. When such a protective layer is provided, a top coat layer as described above can be further provided thereon.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited at all by these examples.

Example 1
Preparation of epoxy primer Bisphenol F type epoxy resin (Epicoat 807: Japan Epoxy Resin Co., Ltd.) as liquid epoxy resin, Hexanediol diglycidyl ether (EX212: Nagase ChemteX Co., Ltd.), Silane cup as reactive diluent It was used as coupling agent γ- glycidoxypropyltrimethoxysilane (manufactured by Toray Dow coating silicone Co. product), and a main agent of the primer sufficiently stirred to at conductive dynamic stirrer.
As a curing agent, alicyclic hydrophilic polyamines was sufficiently stirred to primer curing agent of purified water and triethanolamine in electrostatic dynamic stirrer (DAITOCURAR X-5663H Daito Sangyo Co., Ltd. product).

Adhesion test A primer prepared by mixing the epoxy resin main agent prepared in 1) and the curing agent at a weight ratio of 2: 1 to a surface obtained by sanding a 30 cm concrete pavement plate specified in JIS A 5304 with a roller. The coating was performed at a rate of / m ² . It is kept for 24 hours at a constant temperature and humidity, and polyurethane (rim spray F1000: manufactured by Mitsui Chemicals, Inc.) is used as a resin layer on the primer-coated surface at a thickness of 2 mm with a gasmer H-2000 spraying machine. Applied.
After holding at a constant temperature for 7 days, a 4 × 4 cm metal jig was attached in accordance with JIS A 6209, and an adhesion test in the vertical direction was performed . Contact Chakukyodo showed 1.5 N / mm ^2, the underlying concrete layer or primer layer is broken. No peeling at the interface between the primer and polyurethane was observed.

(Example 2)
An adhesion test was conducted in the same manner as in Example 1 except that polyurea (Swaer A-100) was used as the resin layer instead of the polyurethane in Example 1 . Contact Chakukyodo showed 1.5 N / mm ^2, was peeled off in the underlying concrete layer or primer layer. No peeling at the interface between the primer and polyurethane was observed.

(Comparative Example 1)
In place of the curing agent of Example 1, an alicyclic hydrophilic polyamine (Ditocral X-5663H: manufactured by Daito Sangyo Co., Ltd.) was used, and an adhesion test was conducted in the same manner as in Example. At this time, the temperature when the epoxy resin is applied is 6 ° C., the humidity is 25%, the temperature is 1 to 8 ° C. and the humidity is 25 to 55% when held for 24 hours after the application, and the temperature when the polyurethane is applied is 5 ° C. and the humidity. Was 30%.
The adhesion test result was an adhesive strength of 0.8 N / mm ² and peeled at the interface between the primer and polyurethane.

According to the present invention, there is provided an epoxy resin composition that is excellent in adhesiveness with a reactive resin layer and exhibits sufficient adhesiveness with the reactive resin layer even under conditions of low temperature and low humidity.
ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin composition which can be used conveniently as a primer at the time of laminating | stacking a resin layer on structure surfaces, such as a metal structure, a concrete structure, a natural stone structure, and a ceramic structure, is provided.
Furthermore, according to the present invention, a step of forming a primer layer with a composition containing water as a component in an epoxy resin on the surface layer of a structure selected from a metal structure, a concrete structure, a natural stone structure, and a ceramic structure; There is provided a method for constructing a surface structure comprising a step of supplying a curable resin composition on a primer layer to form a resin layer such as polyurethane or polyurea.
By using a composition containing water as a component in the epoxy resin of the present invention as a primer, a laminate having sufficient adhesive strength in a wide range of environmental conditions including low temperature conditions such as 0 ° C. to 40 ° C. and humidity of 10 to 100%. Can be obtained.

Claims (6)

A curing agent which is a modified product selected from a bisphenol F type epoxy resin and an alicyclic polyamine or an epoxy resin adduct thereof, an addition reaction product of ethylene oxide or propylene oxide, an addition reaction product of acrylonitrile and a Mannich addition polyamine type curing agent. Epoxy resin containing 0.1 to 20% by weight of water with respect to the total weight of the epoxy resin, and 0.1 to 5 parts by weight of the silane coupling agent with respect to 100 parts by weight of the epoxy resin composition Composition.   The epoxy resin according to claim 1, obtained by mixing 100 parts by weight of the A liquid containing the epoxy resin and the silane coupling agent and 10 to 100 parts by weight of the B liquid containing the curing agent and the water at this ratio. Composition.   The epoxy resin composition according to claim 2, wherein the liquid A contains 60 to 100 parts by weight of an epoxy resin with respect to 100 parts by weight of the total amount of the epoxy resin and the reactive diluent.   The epoxy resin composition according to claim 1, wherein the silane coupling agent is a silane coupling agent having an epoxy group. Wherein the reactive diluent is a mono or polyglycidyl ethers of polyhydric alcohols, mono- or diglycidyl ether of a long chain alkylene glycol having the carbon number of the 8 or more, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, olefin oxide, Butyl glycidyl ether, styrene oxide, phenyl glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 3- (pentadecyl) phenyl glycidyl ether, glycidyl methacrylate, allyl glycidyl ether, cyclohexene vinyl monooxide, dipentene monooxide and α-pinene at least one mono- or polyepoxy compound selected from the oxide, the sum of the epoxy resin and the reactive diluent The epoxy resin composition according to claim 3 or 4 which is 40 to 0 parts by weight per 100 parts by weight.   The primer which consists of an epoxy resin composition in any one of Claims 1-5 applicable to the surface layer of the structure chosen from the metal structure, the concrete structure, the natural stone structure, and the ceramic structure.