MXPA97004814A - Granulated healing agent coated for a radically curable composition and composition of anchoring bolt comprising elmi - Google Patents

Abstract

The present invention relates to a coated granular curing agent characterized in that it is for use in the curing of at least one radically curable first compound selected from the group consisting of a radically curable resin and a radically polymerizable monomer, and comprising a granule of organic peroxide, wherein the organic peroxide granule has a complete surface thereof coated with a layer of a cured resin derived from at least one second radically curable compound selected from the group consisting of a radically curable resin and a radically polymerizable monomer , and wherein the first and second radically curable compounds are the same or different

Description

GRANULATED HEALING AGENT COATED FOR A COMPOUND RADICALLY CURABLE AND COMPOSITION OF BOLT FIXING ANCHOR THAT UNDERSTANDS THE SAME BACKGROUND OF THE INVENTION FIELD OF THE INVENTION The present invention relates to a coated granulation cure agent and an anchor bolt composition comprising the same. More particularly, the present invention relates to a coated granulation cure agent, which is to be used for the curing of a radically curable compound (hereinafter, often referred to as a "radically curable first compound") selected from the group consists of a radically curable resin and a radically polymerizable monomer, and comprising an organic peroxide granule, wherein the organic peroxide granule has a total surface thereof coated with a layer of a cured resin derived from another radically curable compound (from hereinafter, often referred to as a "radically curable second compound"), which is the same as or different from the first radically curable compound mentioned in the aforementioned above. The present invention also relates to an anchor bolt fixing composition comprising, (1) a curable composition comprising at least one radically curable compound selected from the group consisting of a radically curable resin and a radically polymerizable monomer, and a healing accelerator; and (2) a plurality of granules of the aforementioned coated granular curing agent. The coated granulation cure agent of the present invention is advantageous not only because the curing agent can be handled easily, but also because the curing agent can be uniformly dispersed in a radically curable compound, so that it exhibits excellent performance of healing. Therefore, the coated granulating curing agent of the present invention can be advantageously used as a cure agent for a radically curable resin and / or a radically polymerizable monomer, which is used in various fields, such as a resin mortar and pestle. transmission of water and a casting resin. Especially, the curing agent of the present invention can be advantageously used to provide an excellent anchor bolt fixing composition, which not only has a long life, but is also capable of fixing an anchor bolt to a base while there is a high resistance to fixation.

PREVIOUS TECHNIQUE Conventionally, as a curing agent for a radically curable resin, such as an unsaturated polyester resin, an acrylate epoxy resin or a polyester acrylate resin, various organic peroxides have been used. These organic peroxides are appropriately selected depending on various factors, such as the type of resin to be cured and the ambient temperature at the time of the cure of the resin. When trying to cure a resin at room temperature or below, the organic peroxide is often used in combination with a curing accelerator, such as an aromatic amine. Radically curable resins, which can be cured using an organic peroxide as a curing agent, have been used in various fields. For example, radically curable resins are used as a resin to provide a liner to prevent corrosion, as a resin to produce a molded article through the use of a metal mold and as a resin to be used as a principal agent for a anchor capsule. (The term "anchor capsule" used herein means a capsule used to fix an anchor bolt or an iron bar to a base, each of which is used in securing a machine or other structures to bases, such as a bedrock, concrete and masonry). When a resin is to be used as the main agent for an anchoring capsule, a radically curable resin, such as an unsaturated polyester resin or an acrylate epoxy resin, is generally used. Conventionally, the anchor capsule comprises a curable resin in a viscous liquid form, a curing agent, and optionally an aggregate. The operation of attaching an anchor bolt or an iron bar to a base using such an anchor capsule, is generally conducted through a method comprising inserting an anchor capsule into a bore hole in a base, and driving a bolt. of anchoring or an iron rod towards the hole, thus breaking the anchor capsule in the hole in order to allow the curing agent to be mixed with the curable resin in a viscous liquid form, so that the resin can be cured . Specific examples of methods for breaking an anchor capsule in a hole through an anchor bolt or iron bar include: a first method, wherein an anchor capsule in a hole is broken by driving the anchor bolt or bar of iron towards the hole through a hammer; and a second method, in which an anchor capsule in a hole is broken through the rotary percussion caused by the anchor bolt or the iron bar, which is driven towards the hole through a hammer driller or Similary. When the second method is employed, the anchor bolt can be fixed to the base while achieving a high resistance to fixation, compared to the resistance to fixation obtained by the first method. Therefore, the second method is advantageous especially for fixing an anchor bolt to a base located in the sea or water, or a base located on the shore, where a high resistance to fixation is required. In the second method mentioned in the foregoing, the type described in the following of an anchor capsule is generally used. That is, such an anchor capsule has a double-walled structure comprising outer and inner cylindrical shells, each of which can be broken through the action of an anchor bolt or an iron bar when the anchor bolt or anchor bolt The iron bar is applied to the anchor capsule, wherein a main agent comprising a curable resin in a viscous liquid form and an aggregate are arranged in a space defined by the inner wall of the outer shell and the outer wall of the shell. inner wrapper, and wherein the curing agent is dispersed in the inner wrapper (see European Patent No. 0 150 555).

Further, Japanese Examined Patent Application Publication No. 4-1160 discloses an anchor bolt fixing capsule having a double wall structure comprising outer and inner shells, each of which can be broken through the action of an anchor bolt when the anchor bolt is applied to the capsule, comprising the outer and inner shells mentioned above, a curable resin in a viscous liquid form and a mixture of a solid granulated curing agent and an aggregate , where one of the curable resin and the mixture of healing agent - aggregate is disposed in the inner envelope, and the other is arranged in a space defined by the internal wall of the outer envelope and the outer wall of the inner envelope , and wherein the solid granulated curing agent and the aggregate are mixed uniformly. However, in the capsules mentioned in the foregoing for use in an anchor bolt fixing operation, it is a requirement that a curable resin in a viscous liquid form and a curing agent be disposed separately using a double wall structure. . Therefore, the capsule mentioned in the above is disadvantageous since not only is the production process for the capsules mentioned in the foregoing annoying, but also the dispersion of the curing agent in the curable resin in the bolt-fixing operation Anchoring probably becomes unsatisfactory and, therefore, the curing of the curable resin becomes non-uniform. Further, when a capsule to be used in an anchor bolt fixing operation has a double wall structure as mentioned in the above, problems arise, so that an operation wherein a curing agent in a powder or granular form it is packed in a wrap, especially the inner wrapper (which has a smaller diameter than the outer wrap), is extremely annoying and, in addition, the fine powder of the curing agent is inevitably diffused into the workspace during the packaging operation, thus degrading the work environment. Also, during the packing operation, a bridge of the curing agent occurs in the packing hopper, and in the wrapper that is being packaged with the curing agent, so that the efficiency of the operation becomes poor. An anchor bolt fixing capsule has been proposed, wherein a bar-shaped curing agent and a mixture of a curable resin in a viscous liquid form and an aggregate of granulated stone are arranged in a tubular wrap or cylindrical bale which it has an opening, which is fixedly closed by a transparent plastic lid, wherein the bar-shaped curing agent is a molded product obtained through the molding of a mixture of a peroxide, an organic binder and a diluent, and it has a total surface thereof coated with a cured resin layer (see Japanese Examined Patent Application Publication No. 63-13000). This capsule solves the problems of the capsule having a wall structure as mentioned in the above. However, this capsule is disadvantageous not only because, since the curing agent used therein in the form of a bar, the curing agent can not be packaged in the casing simultaneously with the packing of the granulated stone aggregate, and the granulated stone aggregate packing can only be conducted after the packing of the bar-shaped curing agent, thus making the packing operation difficult, but also during the packing of the granulated stone aggregate, a bridge of the aggregate of granulated stone between the inner wall of the tubular casing and the bar-shaped curing agent, so that the aggregate of granulated stone can not be completely packed into the bottom of the casing. further, this capsule also has the problem that, during the anchor bolt fixing operation, when the anchor bolt is driven towards the capsule by the rotary percussion caused by the hammer driller, the bar-shaped healing agent is breaks into pieces, and the pieces will sink to the bottom of the hole (where the anchor bolt will be fixed), so that the mixture between the curing agent and the curable resin in a viscous liquid form becomes non-uniform . Therefore, there is an enormous non-uniformity in the curing of the resin, so that an anchor bolt fixing performance can not be stably obtained. There is also the purpose of an anchor bolt fixing cartridge comprising a cylindrical cartridge having a plurality of macrocapsules disposed therein, wherein each macrocapsule is filled with a curable polymer, and wherein each of the macrocapsules is contact with other macrocapsules and / or the inner wall of the cartridge in order to be packaged in the cartridge in an immobilized form (see Public Open Specification of Japanese Patent Application Laid-Open No. 55-32814). According to the method described in this prior art document, the macrocapsules in the cartridge are broken and flaked through the action of an anchor bolt, and the resulting flakes function as a so-called "static agitator" for the curable polymer, so that the space between the anchor bolt and the inner wall of the hole is uniformly filled with the curable polymer. However, as can be seen from the above, the macrocapsules used in this technique must be those that can be broken into flakes through the action of an anchor bolt. As such macrocapsules, for example, hollow glass beads coated with a phenol resin, fragments of a clay tube (wherein the fragments have been sealed at both ends thereof), gelatin capsules and the like, are used, but the Materials that can be used for macrocapsules have been limited. Accordingly, methods for introducing a curable polymer into macrocapsules are also limited. As such methods, for example, there may be mentioned a method comprising immersing the macrocapsules in a curable liquid polymer, and degassing the macrocapsules in situ under vacuum, followed by an increase in pressure so that the macrocapsules are filled with the polymer curable liquid; and a method comprising injecting a liquid polymer curable to the macrocapsules through a syringe. These methods are, however, disadvantageous, due to the low productivity of the final macrocapsules containing a curable polymer liquid. Furthermore, in these methods, as can be clearly understood from the foregoing, it is absolutely necessary to use as a curable polymer, a curable liquid polymer and a curable solid polymer, such as a solid polymer in a granulated or powdered form, not They can be used.

There is also the purpose of a curative resin composition of equipment of a package usable as an adhesive, a sealant, a coating material, a molding material and the like, which is in the form of a dispersion of macrocapsules in a mixture. of a polymerizable polyfunctional acrylate compound (which is a monomer having at least two residues of acrylic acid) and / or a polymerizable polyfunctional methacrylate compound (which is, a monomer having at least two methacrylic acid residues) ) as a curing resin component with an organic peroxide as a curing agent, wherein the macrocapsules contain a curing accelerator which, when combined with the organic peroxide, is capable of forming a redox polymerization reaction system for the polyfunctional acrylate compound and / or the polyfunctional methacrylate compound, and is coated with a film comprising a composite or hydrocarbon capable of forming a coating (see Japanese Examined Patent Application Publication No. 54-32480). However, this single-pack type curing resin composition is disadvantageous since a gelatin formation of the resin component proceeds unfavorably and rapidly since the curing resin component is directly in contact with the curing agent in the resin. reaction system.

BRIEF DESCRIPTION OF THE INVENTION With a view towards the development of an excellent curing agent for a radically curable resin and / or a radically polymerizable monomer, which the curing agent is free from the problems mentioned in the foregoing, the inventors of the present have done extensive studies and intensive. As a result, it has unexpectedly been found that a coated granulation cure agent, which is for use in curing a radically curable first compound (i.e., a radically curable resin and / or a radically polymerizable monomer) and comprising a granules of organic peroxide, wherein the organic peroxide granule has a total surface thereof coated with a layer of a cured resin, derived from a radically curable compound secrum, which is the same as or different from the first radically curable compound, exhibits advantageous characteristics of so that the curing agent can be handled with ease, and the curing agent can be uniformly dispersed in the aforementioned first radically curable compound, so that the curing agent exhibits excellent curing performance. It has also unexpectedly been found that the curing agent mentioned in the above can be advantageously used to provide an anchor bolt fixing composition of a package type, which is not only capable of stably fixing an anchor bolt to a base while enjoying the high resistance to agitation, but also can be stored at room temperature for a period as long as a month or more without suffering any degradation. Based on these novel findings, the present invention has been completed. Accordingly, it is an object of the present invention to provide a coated granulation cure agent for use in curing a radically curable compound, which can be advantageously handled easily, and has excellent curing ability. It is another object of the present invention to provide an anchor bolt fastening composition, which can be stored for a prolonged period without suffering from any degradation, and is capable of stably fixing an anchor bolt to a base while enjoying a high resistance of fixation. It is a further object of the present invention to provide an anchor bolt fastening capsule comprising an anchor bolt fastening composition having the excellent properties mentioned above.

It is still another object of the present invention to provide a method for advantageously producing an anchor bolt fixing resin composition of one of the preferred embodiments of the anchor bolt fixing resin composition of the present invention. The above objects and other objects, features and advantages of the present invention will be apparent from the following detailed description and appended claims, taken in conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS In the accompanying drawings: Figure 1 is a diagrammatic cross-sectional view of an anchor bolt fixing capsule obtained in Examples 1, 3 and 5; Figure 2 is a diagrammatic cross-sectional view of an anchor bolt fixing capsule obtained in Example 4; and Figure 3 is a diagrammatic cross-sectional view of an anchor bolt fixing capsule obtained in Comparative Example 2.

In the Figure to Figure 3, similar parts or portions are designated with similar numbers. In Figure 1 to Figure 3, the reference numbers have the following meanings. 1: Wrap 2: Curable composition 3: Aggregate 4: Coated granulation curing agent of the present invention 4 ': Conventional bar-shaped curing agent 5: Sealed portion 6: First coating layer 7: Second coating layer 8: Top DETAILED DESCRIPTION OF THE INVENTION According to a basic embodiment of the present invention, a coated granular curing agent is provided, which is for use in the curing of at least one radically curable first compound selected from the group consisting of a radically curable resin and a monomer radically polymerizable, and comprising an organic peroxide granule, wherein the organic peroxide granule has a complete surface thereof coated with a layer of a cured resin derived from at least one second radically curable compound selected from the group consisting of a radically curable resin and a radically polymerizable monomer, and wherein the first and second radically curable compounds are the same or different. In order to easily understand the present invention, the essential aspects and representative embodiments of the present invention are listed below. The first representative embodiment of the present invention consists of: a coated granular curing agent, which is for use in the curing of at least one radically curable first component selected from the group consisting of a radically curable resin and a radically polymerizable monomer , and comprising a granule of organic peroxide, wherein the organic peroxide granule has a complete surface thereof coated with a layer of a cured resin derived from at least one second radically curable compound selected from the group consisting of a resin curable and a radically polymerizable monomer, and wherein the first and second radically curable compounds are the same or different.

The second representative embodiment of the present invention consists of: an anchor bolt fixing composition comprising: (1) a curable composition comprising at least a first radically curable compound selected from the group consisting of a radically curable resin and a radically polymerizable monomer, and a cure accelerator; and (2) a plurality of granules of a coated granular curing agent for the curable composition (1), the granulated curing agent comprising an organic peroxide granule, wherein the organic peroxide granule has a complete surface thereof coated with a layer of a cured resin derived from at least one second radically curable compound selected from the group consisting of a radically curable resin and a radically polymerizable monomer, wherein the first and second radically curable compounds are the same or different. The third representative embodiment of the present invention consists of: a method for producing an anchor bolt fixing composition as mentioned in the foregoing, as the second representative embodiment of the present invention, wherein the first and second radically curable compounds are same, comprising mixing a curable composition, which is in viscous liquid form and which comprises at least one radically curable compound selected from the group consisting of a radically curable resin and a radically polymerizable monomer, and a curing accelerator, with a plurality of organic peroxide granules, to thereby form a layer of a cured resin over the entire surface of each of the organic peroxide granules, wherein the cured resin is derived from the radically curable compound contained in the curable composition. Examples of organic peroxides used in the coated granulation cure agent of the present invention include hydroperoxides, such as eumeno hydroperoxide; dialkyl peroxide, such as dicumyl peroxide; diacyl peroxide, such as benzoyl peroxide; ketone peroxides, such as methyl ethyl ketone peroxide; oxycarbonates, such as bis (4-t-butylcyclohexyl) peroxycarbonate; peroxycetals, such as 1,1-di-t-butylperoxycyclohexanone; and peroxyesters, such as t-butyl peroxybenzoate. Among the organic peroxides mentioned in the foregoing, benzoyl peroxide is preferably used, since it can be handled with ease and exhibits excellent curing performance at room temperature.

With respect to the configuration of the organic peroxide granule used in the present invention, there is no particular limitation. The organic peroxide granule can be used in various forms, such as a sphere and an ellipsoid. Also, the organic peroxide granule can have a plurality of concave-convex portions on its surface. The organic peroxide granule can be obtained by a method which comprises diluting an organic peroxide with an inorganic compound (such as calcium carbonate, calcium sulfate or the like) in order that the concentration of organic peroxide in the resulting mixture be from 1 to 95% by weight, and configure the mixture to a granule. From the point of view of safety in handling, the concentration of the organic peroxide in the mixture is preferably 50% or less by weight, based on the weight of the mixture. With respect to the method for producing an organic peroxide granule, there is no particular limitation. An organic peroxide granule can be produced through, for example, (a) a method comprising applying a mechanical pressure to a powdered organic peroxide diluted with an inorganic compound or a wet mass of an organic peroxide powder diluted with an organic peroxide. inorganic compound, to form the organic peroxide powder; (b) a method comprising adding a configuration agent and water to a powdered organic peroxide diluted with an inorganic compound to obtain a sludge, and drying the obtained sludge; (c) a method comprising spraying a liquid configuration agent on an organic peroxide powder diluted with an inorganic compound to thereby cause the agglomeration of the peroxide; or (d) a method comprising adding water and a setting agent to a powdered organic peroxide diluted with an inorganic compound to obtain a clay-like mixture, and configuring the clay-like mixture obtained to spherical granules through a machine of granulation. In the method mentioned in the above (a), an organic peroxide is formed into granules without using a configuration agent. In the methods mentioned in the above (b), (c) and (d), a configuration agent is used. Examples of configuration agents that can be used in methods (b), (c) and (d) include cellulose derivatives, such as carboxymethylcellulose, methylcellulose, microcrystalline cellulose (manufactured and sold under the tradename "AVICEL"). Asahi Chemical Industry, Co., LTD, Japan), gum arabic, guar gum, and locust bean gum; jelly; polyvinyl alcohol (PVA); and starches such as amylose and amylopectin. Among the configuration agents mentioned in the foregoing, carboxymethylcellulose, guar gum, locust bean gum, starches (such as amylose and amylopectin) are preferred, because they have an excellent ability for configuration, and are capable of forming a organic peroxide granule with excellent configuration retention. Starches (such as amyloea and amylopectin) are especially preferred since they can be easily handled and are capable of imparting sufficient mechanical strength to an organic peroxide granule to maintain the granulated form in the anchor bolt fixing capsule mentioned in FIG. above, comprising an envelope and the anchor bolt fixation composition mentioned above disposed in the envelope, wherein the anchor bolt fixing composition comprises a curable composition (1) and a plurality of granules (2) of the coated granule curing agent of the present invention. With respect to the amount of the configuration agent used for the preparation of the organic peroxide granules, it is preferred that the configuration agent be used in an amount of 0.1% to 20% by weight, more preferably 1 to 15% by weight. weight, based on the weight of the organic peroxide. With respect to the diameter of organic peroxide granules, it is preferred that the organic peroxide granule have a diameter of 0.5 mm to 15.0 mm. When an organic peroxide granule having a diameter of less than 0.5 mm is used to obtain a coated granulating curing agent, it is difficult to break the obtained coated granulated curing agent, which also has a small diameter, by stirring or the like. Therefore, in this case, there is a danger that the radically curable resin and / or the radically polymerizable monomer can not be cured satisfactorily. On the other hand, when the organic peroxide granule having a diameter greater than 15 mm is used to obtain a coated granulating curing agent, disadvantages may be caused during the production process of the anchor bolt fixing capsule mentioned above. previous. Illustratively stated, when the production process of the anchor bolt fixing capsule includes an operation of adding a plurality of granules (2) of the coated granulation curative to the curable composition (1) which is contained in a shell, In order to obtain the anchor bolt fixation composition adapted in the shell, bridging may probably occur, during loading of the granules of the healing agent into the envelope, in the envelope in a position higher than the envelope. bottom of the shell through the agglomeration of the granules of the curing agent, or the agglomeration of a mixture of the granules of the curing agent and an aggregate, so that the granules of the curing agent or the mixture of the granules of the Curing agent and aggregate can not be completely packed in the bottom of the wrapper. Also, when the production process of the anchor bolt fastening capsule includes an operation of loading an anchor bolt fastening composition comprising the components (1) and (2) mentioned in the foregoing, which has been prepared previously, to an envelope, the same problem mentioned in the above can probably occur during the loading of the composition into the envelope. In addition, in order to uniformly disperse the granules of curing agent in the curing composition (1), it is preferred that the diameter of the organic peroxide granule is from 1 to 10 mm. In the present invention, when the organic peroxide granule has an elliptical cross section, the diameter of such a granule is defined as the average value of the long axis and the cutting axis of the cross section of the granule. When the organic granule has a plurality of concave-convex portions on its surface, the diameter of such a granule is defined as the diameter of a sphere having the same volume as that of the granule having a plurality of concave-convex portions, wherein the volume of the granule is calculated through a known method.

With respect to the strength of the organic peroxide granule, there is no limitation as to whether the granule is breakable through mechanical agitation by a hammer drier or the like at the time of the anchor bolt fixing operation. However, the breakage of the coated granulation curing agent comprising the organic peroxide granule should be avoided at the time of the dispersion of the granules (2) of the coated granulation curative in the curable composition (1), or in the moment of loading a mixture of the granules (2) of the coated granulation curative and the granules of an aggregate into an envelope for an anchor bolt fixing capsule. Therefore, it is preferred that the organic peroxide granule have a breaking strength of 150 gf / cm 2 or more, more preferably 1 kgf / cm 2 or more. However, when the organic peroxide granule has an extremely high breaking strength, the coated granule curing agent obtained using such an organic peroxide granule, can not be broken through mechanical stirring at the time of the fixing operation of anchor bolt. Therefore, it is preferred that the breaking strength of the organic peroxide granule does not exceed 200 kgf / cm2. The formation of the layer of a cured resin on a whole surface of the organic peroxide granule, said cured resin is derived from at least one second radically curable compound selected from the group consisting of a radically curable resin and a radically polymerizable monomer, can be conducted through a method comprising: immersing the organic peroxide granule in a mixture of a second radically curable compound, which reacts with the organic peroxide to form a cured resin, with a curing accelerator at room temperature (approximately 20 ° C at about 30 ° C); and stir the resulting mixture. After the operation mentioned above, the organic peroxide granule having a complete surface thereof coated with the layer of a cured resin (i.e., the coated granular agent of the present invention), is taken from the mixture of the second radically curable compound with the healing accelerator. If desired, the coated granulated curing agent obtained from the mixture mentioned above can be washed with acetone or the like. In the present invention, as already mentioned above, a "radically curable first compound" means at least one radically curable compound selected from the group consisting of a radically curable resin and a radically polymerizable monomer, which will be cured using the coated granulating curing agent of the present invention, and as already mentioned above, a "radically curable second compound" means at least one radically curable compound selected from the group consisting of a radically curable resin and a radically monomer polymerizable, which is used to form the cured resin layer of the coated granular curing agent of the present invention. Furthermore, as mentioned in the above, the first and second radically curable compounds may be the same or different. Examples of radically curable resins, each of which can be independently used either as a first or a second radically curable compound, include an epoxy acrylate resin, a polyester acrylate resin, an acrylic urethane resin and a resin of unsaturated polyester. With respect to the acrylate epoxy resin, reference may be made to, for example, Examined Japanese Patent Application Publication No. 62-037076. With respect to the polyester acrylate resin, reference can be made to, for example, Japanese Examined Patent Application Publication No. 5-85720. With regard to acrylic urethane resin, reference may be made to, for example, Japanese Examined Patent Application Publication No. 5-085719. With respect to the unsaturated polyester resin, reference may be made to, for example, Examined Japanese Patent Application Publication No. 38-12863. Examples of radically polymerizable monomers, each of which can be independently used as either a first or second radically curable compound, include multifunctional carboxylic esters. Specific examples of radically polymerizable monomers include ethylene glycol dimethacrylate, n-butyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, dimethacrylate trimethylolpropane, dimethyl maleate, isobornyl methacrylate, butanediol dimethacrylate and 2,2-bis [4- (methacryloxydiethoxy) phenyl] -propane. As already mentioned in the foregoing, the formation of the layer of a cured resin over the entire surface of the organic peroxide granule, which the cured resin is derived from the second radically curable compound, can be conducted through a method comprising : immersing the organic peroxide granule in a mixture of the second radically curable compound with a curing accelerator at room temperature (from about 20 ° C to about 30 ° C); and stir the resulting mixture. With respect to the amount of the second radically curable compound used to immerse the organic peroxide granule in the second curable resin for the purpose of forming the cured resin layer, there is no particular limitation. However, when the amount of the second radically curable compound is too small, it becomes impossible to form the layer of a cured resin over the entire surface of the organic peroxide granule. Therefore, it is preferred that the second radically curable compound be used in an amount of 100% by weight or more, based on the weight of the organic peroxide granule. With respect to the cure accelerator used in the aforementioned mixture of the second radically curable compound with the curing accelerator, said mixture is used to form the layer of a cured resin, the same cure accelerator used in the curable composition (1). ) mentioned in the above of the anchor bolt fixing composition, can be used. The function of the curing accelerator, which is used in the aforementioned mixture to form the layer of a cured resin, is to facilitate the curing of the second, radically curable compound on the surface of the organic peroxide granule, to thereby form a layer of a cured resin over the entire surface of the organic peroxide granule. Examples of healing accelerators include aromatic anilines, such as N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, N, N-dihydroxypropyl-p-toluidine, N, N-dihydroxyethyl-p -toluidine; metal soaps, such as cobalt naphthenate; and chelate compounds, such as vanadyl acetylacetonate. With respect to the amount of the cure accelerator used in the mixture mentioned in the above, there is no particular limitation. However, it is preferred that the curing accelerator be used in an amount of 0.1 to 5% by weight, more preferably 0.2 to 3% by weight, based on the total weight of the second radically curable compound and the curing accelerator. With respect to the thickness of the aforementioned layer of a cured resin, it is preferred that the thickness of the layer be as small as possible so that the coated granulating curing agent is capable of having a high content of organic peroxide , and that, when the coated granulation cure agent is used in the anchor bolt fixing composition, the coated granulation cure agent can be easily broken by the action of an anchor bolt. However, when the thickness of the layer of a cured resin is too small, the handling of the coated granulation cure agent becomes disadvantageously problematic. Therefore, it is preferred that the thickness of the cured resin layer be from 0.3% to 40%, more preferably from 0.3% to 25%, based on the diameter of the coated granulation cure agent. Next, an explanation is presented with respect to the anchor bolt fixing composition of the present invention. The anchor bolt fixing composition of the present invention can be obtained by mixing the curable composition (1) comprising the first radically curable compound and the curing accelerator with a plurality of granules (2) of the granulated curing agent coated with the present invention, wherein the granulated curing agent has a layer of a cured resin derived from the second radically curable compound, which is the same as or different from the first radically curable compound. It is preferred that the anchor bolt fixing composition of the present invention contains the granules (2) of the coated granulation curative in an amount of 0.5 to 20% by weight, more preferably 2 to 15% by weight, in terms of the weight percentage of the organic peroxide, based on the weight of the curable composition (1). In the anchor bolt fixing composition of the present invention, the coated granulation cure agent exhibits excellent mobility. Therefore, when the anchor bolt fixing operation is conducted using the anchor bolt fixing composition of the present invention, even if the granules (2) of the coated granular coating agent have not been uniformly dispersed in the composition curable (1), the granules (2) are caused uniformly dispersed in the curable composition placed in a space between the anchor bolt and the wall of a hole drilled in a base by shaking with a similar hammer driller. However, in order to increase the curing performance of the curing agent, it is preferred that the granules (2) of the coated granulating curing agent (2) be uniformly dispersed in the curable composition (1). The uniform dispersion of the granules (2) in the curable composition (1) can be achieved by using the coated granulation curative and the curable composition (1) in respective amounts, so that the volume ratio of the granules (2) to the curable composition (1) becomes as close as possible to 1: 1. As already mentioned in the above, the first radically curable compound used in the curable composition (1) of the anchor bolt fixing composition of the present invention may be the same as or different from the second radically curable compound used to form the layer of a cured resin of the coated granulation cure agent. However, as a first radically curable compound, it is preferred to use an epoxy acrylate resin, a polyester acrylate resin and an acrylic urethane resin, since each of these compounds can not only be advantageously used to achieve excellent ability fixing the anchor bolt fixing composition, but also has: an excellent ability to cure at low temperature and excellent resistance to alkali. As mentioned in the above, as a cure accelerator used in the curable composition (1), the same cure accelerator as used in the mixture of the second, radically curable compound with the curing accelerator can be used, such mixture is used to form the layer of a cured resin of the coated granulation cure agent, it can be used. The cure accelerator is used in the curable composition (1) for the purpose of controlling the cure rate in the fixation composition of the anchor bolt of the present invention, with respect to the amount of the cure accelerator, it is preferred that the The curing accelerator is used in an amount of 0.1 to 5% by weight, more preferably 0.2 to 3% by weight, based on the weight of the curable composition (1). When the amount of the cure accelerator is less than 0.1% by weight, the cure rate of the radically curable compound becomes too low. In this case, especially when the anchor bolt fixing composition is used at a temperature lower than room temperature, there is a danger that the curing of the radically curable compound does not proceed at a satisfactory level. When the amount of the cure accelerator exceeds 5% by weight, the cure rate of the radically curable compound becomes too high. In this case, there is a danger that the anchor bolt fixing operation can not be finished due to the extremely rapid cure of the radically curable compound. In addition, to prevent the occurrence of an uncured portion remaining in the radically curable compound by conducting the anchor bolt fixing operation at a temperature lower than the ambient temperature, it is preferred to control the amount of the healing accelerator within the aforementioned range. in the above, so that the curing time of the radically curable compound as measured at 25 ° C in accordance with JIS-K6901 to determine the curing capacity at room temperature, it becomes from 2 to 60 minutes. In addition, to achieve a high resistance to fixation, it is highly preferable that the cure time be from 2 to 45 minutes. In the present invention, the curable composition (1) mentioned in the above, may further comprise a monofunctional reactive monomer. Examples of monofunctional reactive monomers include styrene, methyl methacrylate, ethyl methacrylate and cyclohexyl acrylate. Each of these monofunctional reactive monomers can be used in an amount of preferably 1 to 70% by weight, more preferably 1 to 60% by weight, based on the weight of the curable composition (1). In the anchor bolt fixing composition of the present invention, it is preferred that the curable composition (1) mentioned in the above further comprises an aggregate. The use of a curable composition (1) containing an aggregate is advantageous since, in the anchor bolt fixing operation, it becomes possible to break the granulated coating agent coated in fine particles through the aggregate, so that mixing of the organic peroxide contained in the granulated curing agent coated with the curable composition can be efficiently performed. As a result of such efficient mixing of the organic peroxide with the curable composition (1), it becomes possible to obtain a high hardness of the cured resin and a high fixing efficiency of the anchor bolt fixing composition. As an aggregate, an inorganic substance, such as an artificial aggregate (eg, magnesia slag, glass and ceramic) or a natural stone (eg, silica or marble), is generally used.; however, an organic substance such as a rigid polyvinyl chloride or a rigid plastic can also be used. In the present invention, an aggregate having a relatively large size can be employed, provided that it can be broken through the rotary percussion caused by the anchor bolt in the anchor bolt fixing operation; using a granulated aggregate from the point of view of dispersion capacity of the aggregate in the curable composition (1), and ease of operations, such as a mixing operation of aggregate with the curing agent and a loading operation of the resulting mixture The size (diameter) of an aggregate can be appropriately chosen depending on various conditions for the anchor bolt fixing operation (for example, the size of the hole where the anchor bolt is fixed and the size of the bolt of anchoring.) With respect to the amount of the aggregate, it is preferred that the aggregate be used in an amount of 1 to 500 weight percent, more preferably 50 to 300% by weight, based on the weight of the curable composition (1). In the present invention, if desired, an additive can be added to the curing composition (1). Examples of additives include a polymerization inhibitor, a pigment, an ultraviolet ray absorber, a surfactant, an adhesive imparting agent, a filler, a thixotropic agent (such as silica powder) and a coloring agent. These additives can be used in such amounts as are conventionally employed in the art. The anchor bolt fixing composition of the present invention can be advantageously produced through a method comprising mixing a curable composition, which is in a viscous liquid form and which comprises at least one radically curable compound selected from the group which consists of a radically curable resin and a radically polymerizable monomer, and a curing accelerator, with a plurality of organic peroxide granules, to form a layer of a cured resin over the entire surface of each of the organic peroxide granules, wherein the cured resin is derived from the radically curable compound obtained in the curable composition, thereby forming a coated granulating curing agent of the present invention in the curable composition. In this method, the same radically curable compound is used as the first radically curable compound which will be cured through the coated granulated curing agent. That is, through this method it becomes possible to obtain an anchor bolt fixing composition of the present invention, wherein a plurality of granules (2) of the coated granular curing agent of the present invention is formed in the curable composition. (1), wherein the first and second radically curable compounds are the same, simply by mixing the curable composition comprising a radically curable compound and a curing accelerator with a plurality of organic peroxide granules. Therefore, this method is very advantageous from the point of view of productivity. With respect to a method for conducting the anchor bolt fixing operation using the anchor bolt fixing composition of the present invention, wherein each of the granules (2) the coated granular healing agent is broken into pieces and , simultaneously with the breaking of each granule, the pieces of the granules are mixed with the curable composition (1), such method can be conducted either in a way in which the operation of breaking of granules (2) into pieces and, simultaneously with the breaking of the granules (2), mixing the obtained parts with the curing composition (1) is conducted before the anchor bolt fixing composition is charged to a hole where the anchor bolt intends to be fixed, or in such a way that the operation mentioned in the above is conducted after the anchor bolt fixing composition is charged to the hole mentioned in the above. In any of the above forms, through the breaking of the coated granulating curing agent into pieces and the mixing of the obtained parts with the curing composition (1) the active sites of the coated granulating coating agent, which are protected by the layer of the curing resin before the breakdown of the curing agent is brought into contact with the curable composition (1). When the operation mentioned in the above (which comprises breaking the granules (2) into pieces, and simultaneously with the breaking of the granules (2), mixing the obtained pieces with the curing composition) is intended to be conducted before the composition of fixing the anchor bolt is loaded into the hole, the operation mentioned in the above can be conducted, through, for example, a method where mixing is used. Alternatively, when the operation mentioned in the foregoing is intended to be conducted after the anchor bolt fastening composition has been loaded into the hole, the operation mentioned in the foregoing can be conducted through, for example, a method in which the rotating percussion that is going to be caused by the anchoring is used. Specifically, the anchor bolt fastening operation using the anchor bolt fastening composition of the present invention can be conducted through a method wherein the anchor bolt fastening composition as such is loaded into a hole. perforated in a base material by emptying from a container or through a piston pump and the anchor bolt is urged towards the hole through the rotary percussion caused by a hammer driller or the like, thus mechanically agitating the fixation composition of anchor bolt for breaking the granules (2) of the granulated curing elongate coated into pieces, and mixing the pieces obtained with the curable composition (1) simultaneously with the breaking of the granules (2), so that the radically curable compound is cured. However, it is preferred that the anchor bolt fixing composition of the present invention be used in an anchor bolt fixing capsule. With respect to such anchor bolt securing capsule, it is necessary that the anchor bolt securing capsule comprises an envelope, which has a sealed construction and can be broken through the action of an anchor bolt, and an Anchor bolt fixing composition of the present invention which is contained in the shell. Using such an anchor bolt fixing capsule containing the anchor bolt fixing composition of the present invention makes it possible to place an anchor bolt fixing composition having a desired composition of each component in the hole, so that an excellent resistance to fixation can be obtained stably. With respect to the aforementioned casing used in the anchor bolt fixing capsule, there is no particular limitation, provided that the casing can be torn or torn through the rotary percussion caused by the anchor bolt during the operation of fixing anchor bolt and being able to prevent penetration of the first radically curable compound, curing accelerator and / or monofunctional reactive monomer through the wall of the shell to escape out of the shell. However, a cylindrical envelope made of glass, synthetic resin, synthetic resin film, paper or the like, is generally used. The size of the envelope is eipropiadamente selected depending, for example, on the size of the hole drilled in the base.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below in detail with reference to the following Examples and Comparative Examples, which should not be construed as limiting the scope of the present invention. In the following Examples and Comparative Examples, evaluation is made with respect to the configured, coated curing agents and the anchor bolt fixing compositions according to the following methods. 1) The ease of handling of a configured, coated curing agent was evaluated as follows. 10 samples of a shaped, coated curing agent were dropped individually by gravity from a height of 1.1 m, and a visual observation was made to see if the samples broke or not. From the results of the observations, the evaluation of the ease of handling of the curing agent configured, made in accordance with the following criteria was made. 0: no samples broke between the 10 X samples: one or more samples were broken among the 10 samples 2) The storage life (at room temperature) of an anchor bolt fixing composition was determined by a method wherein the number of days taken for gelatin formation actually caused the composition at a temperature of 60 °. C, the storage life (months or years) of the anchor bolt fixation composition at room temperature was measured, and from this number of days, through the calculation according to the belief that the period of 28 days taken for gelatinization at 60 ° C is equivalent to a storage life of 2 years at room temperature.

Example 1 [Preparation of the curable composition (Al)] 65% by weight of an epoxy resin of methacrylate type [which has been obtained by reacting an epoxy resin of bisphenol A type (weight average molecular weight: 836, manufactured and sold by Showa Highpolymer Co., Ltd., Japan) with methacrylic acid in a molar ratio of 1: 2] as a radically curable resin, 34% by weight of styrene monomer as a monofunctional reactive monomer, and 1% by weight of N, N-dimethylaniline as a curing accelerator were mixed together to obtain a curable composition (Al). The minimum cure time for the curable composition (A-1) was measured at 25 ° C according to JIS-6901 to determine the curing capacity at room temperature was about 7 minutes.

[Preparation of the coated granulation cure agent (Bl)] 100 parts by weight of benzoyl peroxide, which was diluted with calcium sulfate at a concentration of 40% by weight, 0.1 parts by weight of methylcellulose as a configuration agent, 2 parts by weight (in terms of solids content) of a styrene-butadiene latex (SB) and 45 parts by weight in water were mixed together to obtain a sludge. The sludge obtained was formed into granules having a diameter of 1.5 to 3.0 mm (average diameter: 2.4 mm) at room temperature through a MOHNO ROBO DISPENSER (manufactured and sold by Heishing Engineering &Equipment Co. Ltd., Japan). The obtained granules were dried at 60 ° C for 2 hours. Then, the dried granules were dipped between 300 cc of the curable composition (Al) in a 500 cc beaker and everything was stirred at 30 ° C for 30 minutes through a stirrer to form a layer of a cured resin derived of the curable composition (Al) on every surface of each of the granules, thus obtaining granules of coated granulation curing agent (Bl). The granules obtained from the coated granulating curing agent (B-1) were taken from the curable composition (A-1) and visually observed for each granule to have the cured resin layer on all its surface.

[Preparations of an anchor bolt fixing composition and an anchor bolt fixing capsule] 8.7 g of the curable composition (A-1) was charged in a glass envelope having an opening, and having an external diameter of 17.0 mm, a wall thickness of 0.7 mm and a length of 120 mm. Then, a mixture of 24 g of magnesia slag (as an aggregate) having a particle diameter of 1.5 to 3.0 mm and 2.0 g of the granules of the coated granulation cure agent (Bl) were loaded onto the glass wrap, so that an anchor bolt fixation composition was obtained in the wrapping. The opening of the glass envelope was sealed, thus obtaining an anchor bolt fixing capsule as shown in Figure 1. A concrete block having a size of 500 x 500 x 1,000 mm and having a compressive strength of 210 kg / cm2 was subjected to borer to make a hole with a diameter of 19.0 mm and a depth of 130 mm. The hole was cleaned through a blower and a nylon brush. Subsequently, the capsule obtained in the above was inserted into the hole of the concrete block. A fully threaded anchor bolt M16 (made of SNB7) having a diameter of 16 mm and having its tip end cut at 45 °, was securely connected at its rear end to an electric hammer driller, and the anchor bolt was activated at the bottom of the hole through the rotating percussion caused by the hammer driller. The resistance to fixation between the anchor bolt and the hole of the concrete block was measured one day after the anchor bolt was activated towards the bottom of the hole, through ANSER-5-III (manufactured and sold by Asahi Chemical Industry, Co., Ltd., Japan), which is a tension testing machine for an anchor bolt. The results are given in Table 1, together with the results of the evaluation of the coated granulation cure agent (B-1) with respect to ease of handling. The storage life of the anchor bolt fixation composition was 6 months.

Example 2 100 g of the curable composition (A-1) obtained in Example 1 was charged to a 300 cc polyethylene container having external diameters in its opening and bottom of 69 mm and 79 mm, respectively, and a length of 96 mm. Then, 18 g of the granules of the coated granulation cure agent (B-1) obtained in Example 1 was loaded into the envelope, so that an anchor bolt fixing composition was obtained in the container. A concrete block was subjected to drilling in substantially the same manner as in Example 1 to thereby make a hole in it, and 23 g of the anchor bolt fixing composition obtained in the above was emptied into the hole from the container. Then, the same operations were conducted substantially as in Example 1 to activate an anchor bolt at the bottom of the hole and to measure the fixing strength between the anchor bolt and the concrete block hole. The results are shown in Table 1, together with the results of the evaluation of the coated granulation cure agent (B-1) with respect to ease of handling.

Comparative Example 1 [Preparation of a bar-shaped curing agent] 1.8 g of benzoyl peroxide, which had been diluted with calcium sulfate at a concentration of 40% by weight, was subjected to molding using a metal mold in an article configured in the form of a bar having a length of 80 mm and a diameter of 4.2 mm. The bar-shaped article obtained was immersed in a 40% solution of cellulose acetate in ethanol. Then, the bar-shaped article was taken from the solution and allowed to stand at 40 ° C for 1 hour, thereby forming a first coating layer of the cellulose acetate on a surface of the bar-shaped article. Then, the bar-shaped article having the first coating layer was immersed in a liquid mixture of an epoxy resin and an amine-type curing agent. Then, the bar-shaped article was taken from the liquid mixture, and allowed to stand at 30 ° C for 24 hours to form a second coating layer of the epoxy resin on the first coating layer of the bar-shaped article, thus obtaining a bar-shaped curing agent having the first and second coating layers.

[Preparation of an anchor bolt fixing composition] A concrete block was subjected to drilling in substantially the same manner as in Example 1, so as to make a hole in it, and 23 g of the curable composition were drained ( Al) obtained in Example 1 in hole. Then, the bar-shaped curing agent obtained in the above was inserted into the hole, thus obtaining an anchor bolt fixing composition in the hole. Then, the same operations were conducted substantially as in Example 1 to activate an anchor bolt at the bottom of the hole and to measure the fixing strength between the anchor bolt and the concrete block hole. The results are shown in Table 1, together with the results of the evaluation of the bar-shaped healing agent with respect to ease of handling.

Example 3 [Preparation of the curable composition (A-2)] 55% by weight of a methacrylate-type acrylate epoxy resin [which was obtained by reacting an epoxy resin of bisphenol A type (weight average molecular weight: 836 , manufactured and sold by Showa Highpolymer Co., Ltd., Japan) with methacrylic acid in a molar ratio of 1: 2], 44% by weight of diethylene glycol dimethacrylate as a radically polymerizable monomer, and 1% by weight of the N , N-dihydroxypropyl-p-toluidine as a curing accelerator were mixed together to obtain a curable composition (A-2). The minimum cure time for the curable composition (A-2) was measured at 25 ° C according to JIS-6901 to determine the curing capacity at room temperature, was approximately 13 minutes.

[Preparation of the coated granulation cure agent (B-2)] 100 parts by weight of benzoyl peroxide, which was diluted with calcium sulfate at a concentration of 40% by weight, 25 parts by weight of water and 10 parts by weight amylopectin weight as a configuration agent were mixed together to obtain a clay-like mixture. The clay-like mixture obtained was formed into spherical granules having an average diameter of 3 mm through a High Performance Pili-Making machine (manufactured and sold by Koike Iron Works, Ltd., Japan). The obtained granules were dried at room temperature for 3 hours and then at 60 ° C for 1 hour. The dried granules were immersed in 300 ce of the curable composition (A-2) in a 500 ce beaker, and everything was stirred at 30 ° C for 30 minutes through a stirrer to form a layer of a cured resin derived from IOL curable composition (A-2) over the entire surface of each of the granules, thus obtaining granules of coated granulating curing agent (B-2). The granules obtained from the coated granulating curing agent (B-2) were taken from the curable composition (A-2) and visually observed and it was seen that each granule had the cured resin layer over the entire surface thereof.

[Preparations of anchor bolt and anchor bolt fixing capsule fixation composition] An anchor bolt fixing composition and an anchor bolt securing capsule were obtained in substantially the same manner as in Example 1, except that 8.7 g of the curable composition (A-2), 2.0 g of the granules of the coated granular curing agent (B-2) and 16 g of the crushed silica rock (as an aggregate) having a diameter of 1.2 to 3.4 mm. Then, an anchor bolt was fixed in a hole using the obtained anchor bolt fixing capsule, and the resistance to fixation between the anchor bolt and the concrete block hole was measured, in substantially the same way as in Example 1. The results are shown in Table 1, together with the results of the evaluation of the coated granulation cure agent (B-2) with respect to ease of handling. The storage life of the anchor bolt fixation composition was 2 years.

Example 4 [Preparation of an anchor bolt fixing composition and preparation of an anchor bolt fixing capsule using the same] 100 parts by weight of benzoyl peroxide, which was diluted with calcium sulfate to a concentration of 40% by weight, 25 parts by weight of water, and 8 parts by weight of amylopectin as a configuration agent, were mixed together to obtain a clay type mixture. The clay type mixture obtained was formed into spherical granules having a diameter of 3 mm through a High Performance Pill-Making Machine (manufactured and sold by Koike Iron Works, Ltd., Japan). The obtained granules were dried at room temperature for 3 hours and then at 60 ° C for 1 hour. The dried granules were submerged in 8.7 g of the curable composition (A-2) obtained in Example 3, which was contained in a sheet film wrap having an opening (the wrap was obtained by twice folding a rectangular sheet film). polyethylene / polyethylene terephthalate / aluminum / polyethylene (length: 120 mm, width: 53.4 mm, thickness: 100 μm) along its longitudinal direction, and sealing a longitudinal opening extending along the long side of the rectangular film resulting twice folded, such side is placed opposite to the other side corresponding to the fold of the rectangular film, and one of the short side openings of the rectangular film twice folded), thus obtaining in the film wrapping of the laminate a Anchor bolt composition having granules of the coated granulation cure agent. After, some of the granules of the coated granulation cure agent were taken from the obtained composition and it was visually observed that each of the granules of the coated granulation cure agent had a layer of a cured resin over its entire surface. The opening of the sheet film casing containing the anchor bolt fastening composition was sealed, to thereby obtain an anchor bolt fastening capsule as shown in Figure 2. Afterwards, an anchor bolt was fixed to the anchor bolt. a hole in the concrete block, using the anchor bolt fixing capsule, and the fixing strength between the anchor bolt and the concrete block hole was measured in substantially the same way as in Example 1. The results were shown in Table 1, together with the results of the evaluation of the coated granulation cure agent with respect to ease of handling. The storage life of the anchor bolt fixation capsule was over 2 years.

Example 5 [Preparation of the coated granulation cure agent (B-3)] 100 parts by weight of benzoyl peroxide, which was diluted with calcium sulfate at a concentration of 40% by weight, 0.1 parts by weight of carboxymethylcellulose as a Configuration people, 5 parts by weight (in terms of solids content) of a styrene-butadiene latex (SB) and 45 parts by weight of water, were mixed together to obtain a sludge. The sludge obtained was configured to granules having a diameter of 0.1 to 0.4 mm (average diameter: 0.25 mm) at room temperature through a MOHNO ROBO DISPENSER (manufactured and sold by Haishin Engineering &Equipment Co., Ltd., Japan) . The obtained granules were dried at 60 ° C for 2 hours. Then, the dried granules were immersed in 300 cc of the curable composition (A-2) in a 500 cc beaker and everything was stirred at 30 ° C for 30 minutes through a stirrer to form a layer of a resin. Cured derivative of the curable composition (A-2) over the entire surface of each of the granules, thereby obtaining granules of the coated granulation cure agent (B-3). The granules obtained from the coated granular agent (B-3) were taken from the curable composition (A-2) and it was visually observed that each granule had the layer of the cured resin over its entire surface.

[Preparations of an anchor bolt fastening composition and an anchor bolt fixing capsule] An anchor bolt fastening composition and an anchor bolt fastening capsule are obtained in substantially the same shape as in Example 1 except that 2.0 g of the granules of the coated granulation cure agent (B-3) was used. Then, an anchor bolt was fixed in a hole of the concrete block, using the fixing capsule of the obtained anchor bolt, and the fixing strength between an anchor bolt and the hole of the concrete block, substantially of the anchor bolt, was measured. same as in Example 1. The results are shown in Table 1, together with the results of the evaluation of the coated granulation cure agent (B-3) with respect to ease of handling.

Comparative Example 2 8.7 g of IOL curable composition (Al) obtained in Example 1 was charged into a cylindrical phenol resin tube having an opening, and having an external diameter of 17.0 mm, a wall thickness of 0.8 mm and a length of 130 mm. Then, a bar-shaped curing agent obtained in substantially the same manner as in Comparative Example 1 was inserted into the tube mentioned in the above. Subsequently, 24 g of a magnesia slag having a diameter of 1.5 mm to 3.0 mm (average diameter: 2.4 mm) were added as an aggregate to the tube mentioned above and then the tube opening was sealed through a polyethylene cap, so as to obtain an anchor bolt fixing capsule as shown in Figure 3. Next, an anchor bolt was fixed in the hole of the concrete block, using the obtained anchor bolt fixing capsule, and the fixing strength between the anchor bolt and the hole of the concrete block was measured, in substantially the same way as in Example 1. The results are shown in Table 1, together with the results of the evaluation of the Bar-shaped cure (Al) with respect to ease of handling. The storage life of the anchor bolt fixation capsule was 4 months.

Table 1 INDUSTRIAL APPLICABILITY The coated granulating curing agent of the present invention is advantageous not only because the curing agent can be handled with ease, but also because the curing agent can be uniformly dispersed in a radically curable compound, so that it exhibits excellent curing performance . Therefore, the coated granulation cure agent of the present invention can be advantageously used as a curing agent for a radically curable resin and / or a radically polymerizable monomer, which is used in various fields, such as a water transfer resin mortar and a casting resin. Especially, the curing agent of the present invention can be advantageously used to provide an excellent anchor bolt fixing composition which not only has a long life, but is also capable of fixing an anchor bolt to a base while They enjoy a high resistance to fixation.

Claims (14)

1. A coated granular curing agent, characterized in that it is for use in the curing of at least one radically curable first compound selected from the group consisting of a radically curable resin and a radically polymerizable monomer, and comprising an organic peroxide granule, in wherein the organic peroxide granule has a complete surface thereof coated with a layer of a cured resin derived from at least one second radically curable compound selected from the group consisting of a radically curable resin and a radically polymerizable monomer, and wherein the first and second radically curable compounds are the same or different.

2. The curing agent according to claim 1, characterized in that each of the first and second radically curable compounds are independently selected from the group consisting of: an acrylate epoxy resin, a polyester acrylate resin, an acrylic urethane resin, an unsaturated polyester resin, a multifunctional carboxylic ester and mixtures thereof.

3. The curing agent according to claim 1, characterized in that the organic peroxide granule comprises at least one organic peroxide selected from the group consisting of a hydroperoxide, a dialkyl peroxide, a diacyl peroxide, a ketone peroxide, a oxycarbonate, a peroxy etal and a peroxyester.

4. The curing agent according to claim 1, characterized in that the curing agent has a diameter of 0.5 to 15.0 mm and the thickness of the cured resin layer is from 0.3 to 40%, based on the diameter of the curing agent .

5. An anchor bolt fixing composition, characterized in that it comprises: (I) a curable composition comprising at least one radically curable first compound selected from the group consisting of a radically curable resin and a radically polymerizable monomer, and a curing accelerator; and (II) a plurality of granules of a coated granular curing agent for the curable composition (I), the granulated curing agent comprising an organic peroxide granule, wherein the organic peroxide granule has a complete surface thereof coated with a layer of a cured resin derived from at least one second radically curable compound selected from the group consisting of a radically curable resin and a radically polymerizable monomer, wherein the first and second radically curable compounds are the same or different.

6. The composition according to claim 5, characterized in that the plurality of the granules are present in an amount of 0.5 to 20% by weight, based on the weight of the curable composition.

7. The composition according to claim 5 or 6, characterized in that each of the first and second radically curable compounds are independently selected from the group consisting of an epoxy acrylate resin, a polyester acrylate resin, an acrylic urethane resin, a unsaturated polyester resin, a multifunctional carboxylic ester and mixtures thereof.

8. The composition according to any of claims 5 to 7, characterized in that the first and second radically curable compounds are the same.

9. The composition according to any of claims 5 to 8, characterized in that the organic peroxide granule comprises at least one organic peroxide selected from the group consisting of a hydroperoxide, a dialkyl peroxide, a diacyl peroxide, a peroxide of ketone, an oxycarbonate, a peroxyketal and a peroxyester.

10. The composition according to any of claims 5 to 9, characterized in that each of the granules independently have a diameter of 0.5 to 15.0 mm and wherein the layer of the cured resin of each of the granules independently have a thickness of 0.3 to 40%, based on the diameter of each granule.

11. The composition according to any of claims 5 to 10, characterized in that the curable composition further comprises an aggregate.

12. An anchor bolt fixing capsule characterized in that it comprises a shell having a sealed construction and an anchor bolt fixing composition according to any of claims 5 to 11, which is contained in the shell, the shell can be Break through through the action of an anchor bolt when the anchor bolt is applied to the capsule.

13. A method for producing an anchor bolt fixing composition according to claim 8, characterized in that it comprises mixing a curable composition, which is in a viscous liquid form and which comprises at least one radically curable compound selected from the group that consists of a radically curable resin and a radically polymerizable monomer, and a curing accelerator, with a plurality of organic peroxide granules, to thereby form a layer of a cured resin over the entire surface of each of the organic peroxide granules, wherein the cured resin is derived from the radically curable compound contained in the curable composition.

14. The method according to claim 13, characterized in that the curable composition further comprises an aggregate. SUMMARY A coated granular curing agent is disclosed, which is for use in the curing of at least one radically curable first compound selected from the group consisting of a radically curable resin and a radically polymerizable monomer, and which comprises a peroxide granule. organic, wherein the organic peroxide granule has a complete surface thereof coated with a layer of a cured resin derived from at least one second radically curable compound selected from the group consisting of a radically curable resin and a radically polymerizable monomer, and wherein the first and second radically curable compounds are the same or different. The coated granulation cure agent of the present invention is advantageous not only because the curing agent can be handled easily, but also because the curing agent can be uniformly dispersed in a radically curable compound, so that it exhibits excellent performance of healing. Therefore, the coated granulation cure agent of the present invention can be advantageously used to provide an anchor bolt fixing composition of a package type, which is not only capable of stably fixing an anchor bolt to a base while enjoying such a resistance to fixation, but also can be stored at room temperature for a period as long as 1 ra.s or longer without suffering any degradation.