TW438826B - Coated granular curing agent for radical-curable compounds and anchor bolt fixing composition prepared therefrom - Google Patents

Abstract

A coated granular curing agent for curing at least one first radical-curable compound selected from the group consisting of radical-curable resins and radical-polymerizable monomers, which is essentially composed of granules of an organic peroxide, the surfaces of which are completely covered with a coating layer made of a cured resin resulting from at least one second radical-curable compound selected from the group consisting of radical-curable resins and radical-polymerizable monomers, wherein the first and second radical-curable compounds may be the same or different from each other. This curing agent not only is excellent in handleability but also can be uniformly dispersed in the above first radical-curable compound to exhibit excellent curing properties. In particular, an anchor bolt fixing composition which contains the curing agent can fix anchor bolts into a base metal with high strength. Further, the curing agent makes it possible to produce a one-pack anchor bolt fixing composition which has a service life of at least one month at ordinary temperatures.

Description

438826 A7 B7 —One 丨 丨 丨 _ 丨 · ...... ~ * ............ 1 1 'V. Description of the invention (1) Consumer cooperation of the Central Standard Vehicle Bureau of the Ministry of Economic Affairs Du printed by mp—tf (please read the precautions on the back before filling out this page) The present invention relates to a coated granular hardener for a radical hardening compound, and a composition for fixing anchor bolts using the same . More specifically, the present invention relates to a coated granular hardener, which is a free radical hardening compound (selectable from a radical hardening resin and a radical polymerizable monomer group ( Hereinafter, it is often referred to as a first radical-curable compound), and its entire surface is covered with another radical-curable compound (hereinafter often referred to as the first radical-curable compound) An organic peroxide granular molded body of a cured resin layer composed of a second radical-curable compound). In addition, the present invention relates to a composition for fixing anchor bolts, characterized in that it comprises (1) at least one radical-hardening compound selected from a radical-curing resin and a group of radical-polymerizable monomers and a hardening accelerator And (2) a plurality of the coated granular hardener particles. In addition to being excellent in handleability, the coated granular hardening agent of the present invention can be uniformly dispersed in a radical hardening compound, and therefore can exhibit excellent hardening performance. Therefore, the coated granular hardener of the present invention is a hardener for radically curable resins and radically polymerizable monomers suitable for various applications such as water-permeable resin emulsions and living resins, and is particularly useful. When fixing the composition for anchor bolts, in addition to prolonging the life of the product, the anchor bolt can be fixed to the base material with a high-strength attitude, so an excellent composition for anchor bolts can be obtained. "Current unsaturated polyester resins" Various organic peroxides are often used as curing agents for radical curing resins such as epoxy acrylate resins and polyester acrylates. And these organic peroxides can be applied according to the type of resin that is hardened. The paper size is applicable to the Chinese national standard (CNS} A4 (2IOX297 mm). Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 4388 2 6 A7 B7 Note (2), the temperature and the like when curing the resin are appropriately selected. Also, when the resin is cured at room temperature or lower than normal temperature, organic peroxides can often be combined with aromatic amines and other hardening accelerators. Organic peroxides are used as hardeners to cure free-radical hardening resins. They are used in a wide range of resins for corrosion-resistant linings, resins for mold molding, and greases used as the main agent for fixing sachets. The term refers to a tube containing a hardened resin that is used to fix anchor bolts or steel bars to the base material in order to fix the machine, structure, etc. to the base material such as rock plate, mixed soil, and stone.) As for The resin used in the main agent of the fixed tube is generally a radical hardening resin such as an unsaturated polyester resin, an epoxy propylene resin, etc. At present, the fixed tube contains a viscous liquid hardening property. The two components of grease and hardener, or the three components of bone material. The method of fixing anchor bolts or steel bars to the base material using this fixing tube is generally to dig a hole in the base material, and then fix the fixing tube. Insert it into the hole, and then insert the anchor bolt or steel bar to break the fixing tube. • Mix the viscous liquid hardening resin and hardener to harden the anchor bolt or steel bar. Use the anchor bolt or steel bar to fix it. The method of crushing the tube is to use the mallet to punch the anchor bolt or steel bar into the hole to break the fixed tube bag, or use the gear of a rock drill to blow the anchor bolt or steel bar into the hole. In order to break the fixed pipe, the second method, etc. Because the second method can fix the anchor bolt to the base material with a higher strength than the first method, it is especially useful for fixing the anchor bolt in the sea. It is very advantageous for the base material in the water or its surroundings to require the fixing strength. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) --.-- ^ --- ^- --Install ------ order ------ 、 (read first read Note on the back, please fill out this page again) 43 88 2 6 A7 B7 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (3) In general, the fixed tube used in the second method is A double-walled structure consisting of a cylindrical outer container and an inner container that is broken by the action of anchor bolts or steel bars. The viscous liquid hardenability of the main agent is arranged in a certain space between the inner wall of the outer container and the outer wall of the inner container. Resin and bone, fixed tube with hardener placed in the inner container (refer to European Patent No. 0 1 5 0 5 5). In addition, Japanese National Patent Publication No. 4-1 160 It is characterized in that it has a double-wall structure composed of an outer container and an inner container that can be broken by the action of anchor bolts. One of viscous liquid hardening resin or solid particulate hardener and bone is placed in the inner container. Inside, while the other side is arranged in a certain space between the inner wall of the outer container and the outer wall of the inner container, the tube for the anchor bolt is fixed, and the solid granular hardener and the bone material therein can substantially Mix evenly Fixing anchor bolts Xiang tube. However, the above-mentioned pipe for anchor bolts needs to be separated by a double wall structure composed of an inner container and an outer container. The viscous liquid hardening resin and hardener disposed therein are not only complicated, but also have complicated manufacturing steps. When the dispersibility of the hardener to the resin is insufficient when applying 2, there is a disadvantage of uneven resin hardening. In addition, since the hardening agent used for viscous liquid hardening resin is powder or granular, it is filled into a tube with a double-walled structure as described above, especially in a very thin inner container. In addition to the complicated operation, the working environment is deteriorated due to the scattering of the hardener powder during filling, and the workability is deteriorated due to the blocking of the hardener in the filling hopper or container. Another proposal is that organic Binders, thinners, peroxides This paper is sized for China National Standards (CNS) A4 (2lOX2_97 mm) ~ — " (Please read the precautions on the back before filling this page) 438826 A7 B7 Ministry of Economic Affairs Central Standards Bureau Consumption and Work Cooperation Du Duan V. Invention Description (4) The rod-shaped formed body is formed by molding the mixture. The entire surface of the rod-shaped formed body is composed of a hardener with a resin coating layer and 'sticky' Mixture of liquid hardening resin and granular stone and bone material—-A tube for fixing bolts that is placed in an opaque cylindrical tube with an opening and is tightly embedded in the opening. Please refer to Japanese Patent Publication No. 63-13000) "Although this tube for fixing anchor bolts can solve the problems associated with the above-mentioned tube with a double wall structure, it is manufactured because its hardener is rod-shaped. Guan Xiang cannot be loaded together with the granular stone aggregate at the same time, that is, the rod-shaped hardener must be loaded first, and then the granular stone aggregate is loaded. Therefore, the operation complexity or the cylindrical tube and the The shortcomings of the rod-shaped hardening agent are that the granular granules and bones filled cannot be filled into the bottom of the tube. In addition, when the anchor bolt is buried in the hole by the turning and striking of the gear machine, the rod-shaped hardener may be broken and precipitated due to fragmentation, which makes the mixed state with the viscous liquid hardening resin not stable. It is difficult to obtain a stable high fixing performance due to the large variation in the hardness of the resin of the anchor bolt portion. Another proposal is to contain a plurality of thick tube-shaped cylindrical tubes containing a hardening polymer, and use the plurality of thick tube-shaped tubes and other thick tube capsules and / or the tube-shaped tubes. The thick tube sacs are accommodated in a cylindrical shape for fixing anchor bolts in a cylindrical shape in a state of being in contact with the inner wall surface (Japanese Patent Application Laid-Open No. 55-32814). This technology utilizes the role of the anchor bolt to break the thick tube capsules arranged as described above, and the sheet-like debris formed by the wall material of the thick tube is used as a "static mixer" to uniformly disperse the hardening polymer on the anchor. "Technology in the space between the bolt and the wall of the hole cut out on the base material" Therefore, it is technically necessary to use the anchor bolt work I —. „Attack ΐ -------- ^-(Please read the precautions on the back first (Fill in this education again) This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) ~ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 43 882 6 A7 _ B7 V. Description of the invention (5) When the tube is broken, a sheet is produced, so it is used on the hip. It is used to seal the gelatin tube at both ends of the clay tube with a glass ball covered with a phenol resin film. Therefore, the hardening polymer is filled into the thick tube capsule. The filling rule is limited. For example, the thick tube is immersed in a liquid hardening polymer, and the air in the thick tube capsule is removed under vacuum, and then the liquid hardening polymer is filled into the thick tube capsule under pressure. Or use a syringe to harden the liquid The polymer is filled into the thick tube sac, so it is a less productive method. In addition, the component filled in the thick tube must be a liquid component, so solid and powder components cannot be used. In addition, known proposals also Yes, a hardenable composition that can be used for adhesives, sealants, coating materials, molding materials, etc. It is a polymerizable polyfunctional acrylate (a monomer containing at least 2 acrylic residues) And / or a polyfunctional methacrylate (a monomer containing at least 2 methacrylic residues) and an organic peroxide, which is formed by containing a compound that can interact with this organic peroxide The microcapsules of the redox polymerization accelerator of polyacrylate and / or polymethacrylate are formed by the microcapsules formed by covering the dispersed outer surface with a film composed of a film-forming hydrogen blocking compound. The single-liquid curable composition (please refer to Japanese Patent Publication No. 54-32480) "However, this curable composition is a curable resin that directly contacts the curing agent. Therefore, the content of the resin is reduced due to rapid gelation. Disadvantages of product life " In order to develop excellent free radical hardening resins and / or hardeners for free radical polymerizable monomers without the above disadvantages, the inventors unexpectedly discovered a kind of Coated with hardened resin and / or radical polymerizable monomer (the first radical hardening compound) The paper size is applicable to China National Standard (CNS) A4 (2 丨 0X297 cm) 〇-8-^ ^ 1 I---—— II — ^ 1 ^^ 11 * ^ mm ml ml HI, 0¾ Ί (Please read the precautions on the back before filling out this page) 438826 A7 Member of the Central Standards Bureau of the Ministry of Economic Affairs M Consumer Cooperative Printed B7 _V. Description of the Invention (6) The granular hardener, and its surface is organically coated with a hardened resin layer composed of a second radical hardening compound that is the same as or different from the first radical hardening compound. Formed with a peroxide granular molded body. In addition to its excellent handleability, this hardener can be evenly dispersed in the first radical hardening compound, so it can exhibit excellent hardening performance. 'Especially when used in a composition for fixing anchors, it can be used at a high level. The strength bolt fixes the anchor bolt to the base material, and a single-liquid type fixed anchor bolt composition having a long product life of at least one month at room temperature can be obtained. The present invention has been completed on the basis of these findings. Therefore, a first object of the present invention is to provide a coated granular hardening agent for a radically curable compound that not only has excellent handling properties but also exhibits excellent hardening properties. Another object of the present invention is to provide a composition for a fixed anchor bolt that has a long product life and can fix the anchor bolt to a base material with a high-strength attitude. A third object of the present invention is to provide a product having the above-mentioned characteristics. A characteristic composition of a pipe for fixing an anchor bolt. A fourth object of the present invention is to provide a method for manufacturing a composition for fixing anchor bolts in a better form of the present invention. The above and other objects of the present invention, and various features and benefits thereof can be obtained by referring to the following chart. The detailed description and the scope of patent application are known * < simple description of the chart > Circle 1 is the tube for the fixed anchor bolt obtained in Examples 1, 3 and 5 The paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (210X2 ~ 7mm) (Please read the precautions on the back before filling out this page) 4388 2 6 A7 B7 Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Machining and Consumer Cooperatives 5. Description of the invention (7)-1 | 〇1 1 Figure 2 is a schematic cross-section of a tube for a fixed anchor bolt obtained in Example 4 1 1 Round surface 1 1 Please 1 I Figure 3 is a schematic of a tube for a fixed anchor bolt obtained in Comparative Example 2 Read first 4 read 1 side view β back I No. 1 and Fig. 1 1 WI Fig. 3 The same parts or parts are marked with the same number 1 Note 0 item * 1 Dan fill this pack I < Explanation of the number > Shell 1 1 1 Container 1 1 2 Hardenability Composition 1 I 3 Aggregate I 4 Covered granular hardener of the present invention 1 1 I 4 Known hardener formed into a rod 1 1 1 5 Sealing portion 1 1 6 First coating layer > 1 7 The second coating layer! I 8 Cover 1 The basic aspect of the present invention is to provide a coated granular hardener > 1 1 1 It is a radically curable resin and white polymerizable polymer Haplogroup 1 1 at least 1 species selected A 1 1 coated granular hardener hardened by a base-curing compound and its entire surface is covered with at least one selected from the group consisting of white-base hardening 1 1 resin and white-base polymerizable monomers. 1 1 This paper size applies to China National Standards (CNS) A4 specifications (210X297 mm) -10-438826 A7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ___B7 V. Description of the invention (8) Free radical hardening compound The formed organic peroxide granular molded body of the cured resin layer, and the first and second radical-curable compounds may be the same or different. In order to make the present invention easier to understand, the following first enumerates the present invention. The basic characteristics and main aspects. According to a first aspect of the present invention, there is provided a coated granular hardener, which is at least one selected from the group of a radical-curable resin and a radical polymerizable monomer. The coated granular hardener hardened by the first radical-hardening compound, and at least one of the second radicals selected from the group consisting of the radical-curing resin and the radical polymerizable monomers covering the entire surface. An organic peroxide granular molded body of a hardened resin layer composed of a hardened compound is formed. The first and second radical hardening compounds may be the same or different. The second main aspect of the present invention may be to provide a composition for fixing anchor bolts, which is characterized by including (1) at least one selected from the group consisting of a radically curable resin and a radical polymerizable monomer group. A hardening composition formed by a radical hardening compound and a hardening accelerator, and (2) the hardening composition (1) is coated with a granular hardening agent, and the entire surface thereof is covered by a radical hardening type An organic peroxide granular molded body of a hardened resin layer composed of at least one second radical-curable compound selected from a resin and a radical polymerizable monomer group is formed. Also, for this purpose, the first and second radicals are formed. The hardening compound may be the same or different plural coated hardener particles. The third main aspect of the present invention can be to provide a method for manufacturing the above (please read the precautions on the back before filling this page).

* 1T This paper size applies to Chinese national standard (CNS) Α4 size (2 丨 0 × 297 mm) -11-^ 388 2 6 A7 ___B7 V. Description of the invention (9) The composition of the anchor bolts in two main forms The method is characterized by comprising a viscous liquid hardening composition composed of at least one selected from the group consisting of a radical hardening resin and a radical polymerizable monomer group and a hardening accelerator, and a plurality of organic The first step of forming a peroxide granular molded body on each of the entire surfaces of each granular molded body, and forming a hardened resin layer composed of the radical hardening compound contained in the hardenable composition. Method for producing a composition for fixing anchor bolts which is the same as the second radical-curing compound * The coated granular hardener of the present invention will be described in more detail below. The coated granular hardener of the present invention is used The organic peroxide may be hydroperoxides such as cumene hydroperoxide, dialkyl peroxides such as dicumyl peroxide, or difluorenyl peroxide such as phenylhydrazine peroxide. , Or ketone peroxides such as methyl ethyl ketone peroxide, or carboxy carbonates such as bis- (4-t-butylcyclohexyl) peroxycarbonate, or 1,1-di_t-butyl Peroxyketals such as cyclohexanone peroxide, or peroxyesters such as t-butyl peroxybenzoate. Among them, it is printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs-I- Ί-----------n--II — ^ 1 ^^ 1 ^ 1 —.1--C Please read the notes on the back before filling this page) Excellent performance at room temperature Phenylperoxide which has excellent hardening properties is preferred. The shape of the granular molded body of the organic peroxide used in the present invention is not limited, and may be a sphere or an object having an oval cross section or a plurality of irregularities on the surface Thing. The granular shaped body of the organic peroxide may be obtained by diluting the amount of the organic peroxide diluted with an inorganic substance such as calcium carbonate or calcium sulfate to a total weight of the granular shaped body and the organic peroxide of 1 to 95% by weight. The size of the paper obtained from the molding is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ~ ~ -1 FREE-4 3 88 2 6 A7 Printed by the Consumers' Cooperative of the Central Standardization Bureau of the Ministry of Economic Affairs B7 5. Invention Description (i 〇) to. In terms of handling safety, it is preferable to use a granular molded body in which peroxide has been diluted to 50% by weight or less. There is no particular limitation on the molding method for forming the granular molded body. For example, it may be (a) a method of molding organic peroxide powder diluted with an inorganic substance by mechanical pressure, or a method of molding a wet-solidified substance, or ( b) A method of adding a molding agent and water to the organic peroxide powder diluted with an inorganic substance to make it into a slurry and then drying, or (c) spraying the liquid molding agent in a spray form and diluting the inorganic substance The method of combining the organic peroxide powder with a powder to make it a block, or (d) adding water and a molding agent to the organic peroxide powder diluted with an inorganic substance to make it clay-like. Method for forming into a pellet shape by a pellet machine afterwards "The method of (a) is a method of forming an organic peroxide without using a molding agent into a pellet shape. Examples of the molding agent used in the methods (b), (c), and (d) include carboxymethyl fibers, methyl wovens, and microcrystalline fibers (trade names: Abischeru, Asahi Kasei, Japan) Industrial Co., Ltd.), acacia derivatives such as gum arabic, guar gum, and rocas gum, or gelatin, or PVA (polyvinyl alcohol), or starches such as amylose and amylopectin. Among them, carboxymethyl fiber, guar gum, rocas gum, amylose, and amylopectin are preferred in terms of a molded body that can exhibit excellent molding performance or obtain excellent shape retention when manufacturing a granular molded body. And other starches. In addition, a hardened composition (1) and a plurality of coated granular hardener particles of the present invention can form a granular molded body with sufficient strength that can maintain the shape of the hardener and has excellent handleability. Starch and amylopectin (please read the notes on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (2iOX297 mm) -13-Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs System 43 88 2 6 at B7 V. Invention description (11) is better. As for the use amount of the molding agent, the weight of the organic peroxide is preferably 0.1 to 20% by weight, and more preferably 1 to 15% by weight. The particle size (diameter) of the granular shaped body of the organic peroxide is preferably 0.5 mm to 15.0 mm, and if the particle size is less than 0.5 nm, it is difficult to stir and the like to make the coated granular hardener obtained. It is broken, so there is a concern that the radically curable resin and / or the radically polymerizable monomer may not be sufficiently cured. In addition, if the particle diameter is larger than 15 mm, it is disadvantageous for manufacturing the above-mentioned tube for a fixed anchor bolt. That is, in the process of manufacturing a pipe for fixing anchor bolts, a plurality of coated granular hardener particles are added to the above-mentioned hardening composition (1) filled in a container, and the container is obtained in the container. When the step of filling the container with a plurality of coated granular hardener particles in the operation of the composition for fixing anchor bolts is performed, or the composition for fixing anchor bolts composed of components (1) and (2) is first prepared In the step of filling the composition into the container after the object is filled into the container, the granular hardener or the granular hardener and the bone material may be suspended in the container and cannot be precipitated to the bottom. doubt. In order that the coated granular hardener particles (2) can be uniformly dispersed in the hardening composition (1), the particle diameter is preferably 1 to 10 mm. When the granular shaped body is a particle having an elliptical cross section, the particle diameter means the average value of the major and minor diameters of the cross section. The particle size of the granular shaped body having a plurality of irregularities on the surface is obtained by determining the volume of the granular shaped body by a known method, and then calculating the ball diameter of the same volume. The strength of the granular shaped body of the organic peroxide can be as follows: when the paper size of this issue applies the Chinese National Standard (CNS) A4 specification (2) 0X297 mm) m ^ n «« — ^ i ^^^ 1 — ^ Nm ^^ 4 0¾, T *, (Please read the notes on the back before filling this page) -14-438826 A7 B7 V. Description of the invention (l2) (Please read the notes on the back before filling this page) When the clear coated granular hardened material is used for fixing the anchor bolt composition, the hardening agent can be broken by a mechanical stirring method such as a hoisting machine during the construction of the anchor bolt, and there is no particular limitation. However, in order to prevent the above-mentioned coated granular hardener particles formed from a plurality of granular shaped bodies of organic peroxides from being separately dispersed or hardened in the hardening composition (1) containing a free hardening compound, When the aggregate is mixed with the agent and then filled into the hardening composition (1), the hardening agent is cracked. The soil breaking strength of the granular molded body is preferably 150 gf / cm2 or more, and 1 kgf / cm2 or more. For the better. If the damage strength is too high, the hardener cannot be broken by mechanical stirring during anchor bolt construction, so it is better not to exceed 200 k g f / c m 2. The Ministry of Economic Affairs, Central Bureau of Quarantine, Work and Consumption Cooperation Du printed at least one selected from the group consisting of radically curable resins and radically polymerizable monomers on the entire surface of the obtained granular shaped body of organic peroxide. (2) The method for curing the resin coating layer composed of a radical-hardening compound may be to immerse a granular molded body of an organic peroxide at a room temperature (about 20 to 30 ° C) with an organic peroxide. A method of forming a film by stirring a mixture of a second radical hardening compound and a hardening accelerator, which undergoes a hardening reaction. Thereafter, if necessary, it can be taken out of the mixture of a radical hardening compound and a hardening accelerator. The granular molded body coated with the entire surface of the cured resin layer (that is, the coated granular hardener of the present invention) is washed with acetone or the like to obtain the coated granular hardener of the present invention. As for the "first radical hardening compound" of the present invention, it means a radical hard paper sheet that can be hardened with the coated granular hardener of the present invention as described above, and uses the Chinese National Standard (CNS) Λ4 specification ( 2! 〇Χ297mm〉 ~ -15-Listening to Shen Yuminqing on the 5th

3iHiS »4t Member of the Ministry of Economic Affairs X Consumer Cooperative Co., Ltd. Yincai 3, Description of the Invention (13) At least one type of radical hardening compound selected from the group of resins and radical polymerizable monomers, and" 2nd Freedom " "Base-hardening compound" means * at least one selected from the group of radical-curable resins and radical polymerizable monomers used when forming the cured resin layer of the coated particulate hardener of the present invention as described above. Base hardening compound. The first and second radical-curable compounds may be the same or different. Examples of the radical-curable resin of the present invention that can be used in both the first and second radical-curable compounds include epoxy acrylate resin, polyester acrylate resin, acrylic urethane resin, and unsaturated polyester resin. Wait. Among these, the "epoxy acrylate resin" can be referred to, for example, Japanese Patent Publication No. 6 2-0 3 7 0 7. For polyester acrylate resins, refer to, for example, Japanese National Publication No. 5-0 8 5 7 2. For acryl-based urethane resin, refer to, for example, Japanese National Publication No. 5-0 8 5 7 1 9. The unsaturated polyester resin can be referred to, for example, Japanese Patent Publication No. 3 8-12863. Examples of radical polymerizable monomers that can be used in the first and second radical curing compounds in the present invention are as follows. Polyfunctional carboxylic acid esters and the like. Specific examples of the radical polymerizable monomer include ethylene glycol dimethacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, book methacrylate, and phenoxyethyl methacrylate Ester, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,4 butanediol dimethacrylate, tricarboxymethylpropane trimethacrylate, dimethyl maleate , Isobornyl methacrylate, butanediol dimethacrylic acid vinegar, and 2,2-bis [4-mono (methacryloxydiethoxy) phenyl] The paper scale is applicable to Chinese national standards (CNS ) Λ4 specification (210X 297) {(Please read the precautions on the back before filling out this page) 袈. -Ϊ́έ-Printed by the staff of the Central Bureau of Standardization of the Ministry of Economic Affairs, '4388 2 6-^ __; _B7 Yan ^ ^ 63 Supplement V. Description of the invention (14) Propane and so on. As described above, the method for forming a hardened resin layer composed of a second radical-curable compound on the entire surface of the granular molded body of the organic peroxide may be performed at room temperature (about 20 to 30 ° C). A granular molded body of an organic peroxide is immersed in a mixture of a second radical hardening compound capable of reacting with the organic peroxide and a hardening accelerator, and is stirred to form a film. The amount of the second radical-curable compound to be used at this time is not particularly limited, but if the amount is too small, a hardened resin layer cannot be formed on the entire surface of the molded body. Therefore, its amount is smaller than the weight of the granular molded body. It is preferably 100% by weight or more. The hardening accelerator in the mixture of the second radical hardening compound and the hardening accelerator used when forming the hardening resin layer may be the same as the hardening property in the composition for fixing anchor bolts. A hardening accelerator used in the composition (1). The purpose of mixing the hardening accelerator with the second radical hardening compound is to promote the hardening of the second radical hardening compound on the surface of the granular molded body, and to form a hardened resin layer on the entire surface of the granular molded body. Examples of such hardening accelerators are 'Ν' Ν -dimethylaniline, Ν 'Ν-diethylaniline, Ν, Ν -dimethylρ -toluidine, Ν, Ν -dihydroxypropyl-ρ-methyl Aromatic anilines such as aniline, N, N-dihydroxyethyl-ρ-toluidine, or metal soaps such as cobalt naphthenate, or chelate compounds such as vanadylacetone acetone ligand. The amount is not particularly limited, and it is generally preferred to use a total amount of 0.1 to 5% by weight of the second radical curing compound and the hardening accelerator, and more preferably 0.2 to 3% by weight. {Please read the notes on the back before filling in this page. The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 0x 297 mm) 438826 A7 B7 V. Description of the invention (15) About the above-mentioned hardened resin layer The thickness is thin in order to increase the amount of the organic peroxide of the coated granular hardener and to easily break the granular hardener due to the action of the anchor bolt when it is used in the composition for fixing the anchor bolt. However, when it is too thin, there is a concern that the hardener is difficult to handle. Therefore, its thickness is preferably 0.3 to 40% of the particle diameter of the granular hardener, and 0.3 to 25% is better. Next, the composition for a fixed anchor bolt of the present invention will be described in detail. In the composition system for fixing anchor bolts of the present invention, a plurality of hardening compositions (1) formed by a first radical hardening compound and a hardening accelerator are mixed with a plurality of compounds that are the same as or different from the first radical hardening compound. The hardened resin layer formed of the second radical-curable compound of the present invention is obtained by coating the granular hardener particles (2) of the present invention. Also, the content of the plurality of granular hardener particles in the composition is preferably 0.5 to 20% by weight, and 2 to 15% by weight of the curable composition of the organic peroxide (1). % Is better. Printed I-J · —---I-m Hvt / 1 ^ 1 n ^ i (Please read the precautions on the back before filling this page) for the anchor bolt of the present invention The coated granular hardener in the composition has excellent mobility, and therefore, it is possible to uniformly disperse the plurality of coated hardener particles (2) in the hardenable composition (1) without previously dispersing the coated hardener particles (2). The granular hardener (2) is evenly diffused between the anchor bolt and the wall of the hole drilled in the base material by the stirring of the tooth rocker during the construction of the anchor bolt. However, it is better to improve the hardening performance of the composition. , The plurality of granular hardener particles (2) are uniformly dispersed in the hardenable composition (1) in advance * and the volume of the plurality of granular hardener particles (2) and the hardenable composition (1) in the composition This is easier to achieve than the approximate 1: 1 approach. This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) -18-Printed by the Men ’s Consumer Cooperatives of the Ministry of Economic Affairs, China Standards Bureau 438826 A7 _ _B7_ V. Description of the invention (16) as above In general, the first radical-curable compound used in the curable composition (1) in the composition for fixing anchor bolts of the present invention is for curing the coated granular hardener with a resin layer, The second radical-curing compound used is the same or different, and the first radical-curing compound used is preferably epoxy acrylic acid that can obtain excellent anchoring properties and excellent low-temperature hardening properties and thorium resistance. Ester resin, polyester acrylate resin, or acrylic urethane resin "As described above, the hardening accelerator contained in the hardening composition (1) may be the same as the hardening resin layer of the coated granular hardener. A hardening accelerator in a mixture of a second radical hardening compound and a hardening accelerator used at the time. The purpose of containing a hardening accelerator in the hardening composition (1) is to adjust the hardening speed of the composition for fixing anchor bolts of the present invention. In addition, the content of this hardening accelerator is preferably 0.1 to 5% by weight to the weight of the hardenable composition (1), and more preferably 0.2 to 3% by weight. If the hardening accelerating amount is less than 0.1% by weight, the hardening rate of the free-radical hardening compound will be slowed down, especially if the hardening accelerator is used at a temperature lower than room temperature, and the hardening of the radical hardening compound may be insufficient. In addition, when it exceeds 5 wt%, the hardening speed of the radical hardening compound is too fast, and there is a problem that the hardening speed of the radical hardening compound is too fast to set the anchor bolt when the anchor bolt is installed. In addition, the hardening time of the radical hardening compound is such that the amount of hardening accelerator is adjusted to the above range so that the hardening time measured at 25 ° C of JIS-K 6901 (normal temperature hardening characteristics) is 2 ~ 60 minutes, even if it is used at a temperature lower than room temperature, it will not produce free radical hardening. The paper size is applicable to Chinese National Standard (CNS) A4 specification (2Ϊ0 × 297 mm) (please read the back first) Please note this page before filling in this page) -19 _438326 A7 __B7 V. Description of the invention (17) It is better if the compound is not hardened. In order to obtain high fixing strength, the curing time is preferably 2 to 45 minutes. The curable composition (1) of the present invention may contain a monofunctional reactive monomer. Examples thereof include styrene monomer, methyl methacrylate, ethyl methacrylate, and cyclohexyl acrylate. The content is preferably 1 to 70% by weight, and more preferably 1 to 60% by weight, based on the weight of the curable component (1). Printed by Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs-II--------I i-II-II _---Τ »、-& (Please read the precautions on the back before filling this page ) The hardening composition (1) in the composition for fixing anchor bolts of the present invention is preferably one containing an aggregate. The reason is that if the hardening composition (1) contains an aggregate, the anchor bolts During the construction, the aggregate hardening agent can be used to break up the granular hardener. Therefore, the organic peroxide and the hardening composition (1) can be efficiently mixed and the hardness of the hardened resin hardened material can be increased to achieve more "High fixation performance" The aggregates used are ordinary magnesia frit, artificial aggregates such as glass and ceramics, or inorganic substances such as natural stones such as silica and quartz. Hard plastics such as hard chlorinated vinyl can also be used. organic matters. In addition, the used aggregate may be a relatively large object that can be broken by turning and striking during the construction of the anchor bolt, but it is obtained by dispersing the hardening composition (1) and mixing it with a hardener. From the viewpoint of easy filling of the mixture, it is preferable to use a granular material. As for the particle size (diameter) of the aggregate, it can be appropriately selected according to the construction conditions (chisel hole diameter, anchor bolt size, etc.). The content of the aggregate to the weight of the sclerosing composition (1) is preferably 1 to 500% by weight, and more preferably 50 to 300% by weight. If necessary * Polymerization inhibitors, pigments, UV absorbers, surfactants, tackifiers, and fillers can be added to this hardening composition (1). The paper size applies to Chinese national standard {CNS) A4 specification (210X297 (Mm) -20-438826 A7 B7 5. Description of the invention (18) agent, thixotropic agent (fine powdered silicon dioxide, etc.) and coloring agent. The content of these additives can be used in the general industry. Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumer Cooperative (please read the precautions on the back before filling out this page). One of the advantageous methods for obtaining the composition for fixing anchor bolts of the present invention is as follows. The granular molded body is mixed with a viscous liquid-hardening composition formed of at least one radical-hardening compound selected from a radical-curing resin and a group of radical-polymerizable monomers and a hardening accelerator, and A hardened resin layer composed of a radical hardening compound contained in this hardening composition is formed on the entire surface of the shaped body, and it becomes a kind of coating which is contained in a viscous liquid hardening composition to form the coating of the present invention. The method of the step of the granular hardening agent is also characterized in that the aforementioned radical hardening compound is the same as the first radical hardening compound hardened by the coated granular hardening agent. * Because of the aforementioned method, In order to directly harden a granulated molded body of a plurality of organic peroxides with a radical hardening compound and a hardening accelerator In the composition, a composition in which a plurality of hardened composition (1) and the coated granular hardener particles (2) of the present invention are formed, that is, a first and a second radical hardening type can be obtained The method of the composition for fixing anchor bolts of the present invention with the same compound is therefore very advantageous from the viewpoint of productivity. The method for using the composition for fixing anchor bolts of the present invention is to fill the composition The method of breaking a plurality of coated granular hardener particles in this composition and mixing the hardening composition (1) at the same time before or after the drilling of the anchor bolt in the planned construction. Either method can be used Crushed hardener and mixed hardened composition (1), this paper size applies Chinese National Standard (CNS) A4 (2i × 297mm) '-21-Shellfish Consumption of Central Standards Bureau, Ministry of Economic Affairs Cooperative printed poly 438826 A7 _B7 V. Description of the invention (19) The hardening agent active part guaranteed by the hardened resin layer before crushing is brought into contact with the hardening composition (1) »As for a plurality of coated granular hardening agent particles The method of mixing the hardenable composition (1) while crushing includes the method of using a stirrer before filling into the hole, or the method of rotating and striking the anchor bolt after filling. The composition for fixing anchor bolts of the present invention It can be used to insert the anchor bolt into the hole after the container flows directly into the hole cut in the base material, or after it is filled into the hole by a piston pump, using the turning and striking of a rock drill, etc. to make the composition A method for fixing a plurality of coated granular hardener particles (2) in the material by mechanical stirring and simultaneously mixing the hardening composition (1) to harden the first radical hardening compound to fix the anchor bolt However, the method for using the composition for fixing anchor bolts of the present invention is preferably a tube for fixing anchor bolts. Such a tube needs to be a container having a closed structure that can be broken by the action of the anchor bolts. The tube containing the composition for fixing an anchor bolt of the present invention is housed therein. In the case where the method of using the composition of the present invention is the aforementioned pipe for fixing anchor bolts, since the composition for fixing anchor bolts having a desired composition can be arranged in the hole during the construction of the anchor bolt, stability can be achieved. High fixing power. As for the container used for the pipe, the container can be broken or cracked due to rotation, impact, etc. during the construction of the anchor bolt, and can block the ith radical hardening compound and hardening accelerator in the hardening composition (1). Permeation of monofunctional reactive monomers and the prevention of these components from diffusing to the container outside the container are not particularly limited. Generally, materials such as glass, synthetic resin, synthetic resin film, and paper are used. A tube formed. Its size can be appropriately selected according to the hole drilled in the base material of the anchor bolt, etc. The paper size is applicable to the Chinese national standard {〇 哪) from the specification (2! 0 乂 297 mm) -I ----. -I---- m -► (Please read the notes on the back before filling out this page) -22-Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4388 2 6 A7 _B7 V. Description of Invention (20) Options. Hereinafter, the present invention will be specifically described with examples and comparative examples, but it is not limited to this example. The method of evaluating the coated hardener molded body and the composition for fixing anchor bolts obtained in the examples and comparative examples is as follows: 1) The method of evaluating the handleability of the coated hardener molded body is to divide 10 samples from 1 The height of lm was dropped, and damage was visually observed. The evaluation criteria are as follows. Judgment criteria 〇: No damage was found in 10 samples "X: Damage was found in 10 samples. 2) The method of evaluating the shelf life of the composition for anchor bolts is to measure the number of days until gelation at 60 ° C, and then convert this number to the shelf life at room temperature (for example, 28 days) , Which corresponds to a storage life of 2 years at room temperature) Example 1 [Modified hardening composition (A-1)] Bisphenol A type epoxy resin with a weight average molecular weight of 8 3 6 (Showa Polymer, Japan) Co., Ltd.) and methacrylic acid methacrylic epoxy acrylate resins (radical curable resins) prepared at a molecular ratio of 1: 2 (65% by weight) The paper size of the reactive sheet is applicable to the Chinese national standard f CNS) A4 specification (2 丨 0X297 mm1 (please read the precautions on the back before filling this page),? Τ -23-Consumption by Employees of the Central Standards Bureau of the Ministry of Economic Affairs Cooperative printed bag 4 3 88 26 A7 _____B7_ V. Description of the invention (21) The styrene monomer of the body is 34% by weight, and the ratio of 1% by weight of N, N dimethylaniline of the hardening accelerator is compounded to obtain a hardenable composition ( A— 1). Based on JI S-6 9 of this hardening composition 0 1 (hardening characteristics at normal temperature) The minimum hardening time at 25 ° C was measured, and the result was about 7 minutes. [Preparation of the coated granular hardener (B-1)] Benzene diluted by mixing with calcium sulfate to 40% by weight醯 Peroxide 100 weight units, methylcellulose 0.1 weight unit of the molding agent, styrene-butadiene (SB) latex 2 weight units (solid content), and water 4 5 weight units to obtain a slurry. Next, at room temperature, the use of Morale Patisse manufactured by the Japanese National Weapon Equipment Co., Ltd. was formed to obtain a granular shaped body having a particle diameter of 1.5 to 3.0 mm (average particle diameter of 2. 4 mm). Thereafter, the molded body was dried at 60 ° C. for 2 hours, and then immersed in 300 cc of the above-mentioned hardening composition (A-1) in a beaker with a capacity of 500 cc, and then stirred with a mixer. Stir at 30 ° C for 30 minutes to form a hardened resin layer coated on the surface of the granular molded body to obtain a coated granular hardener (B-1). Next, take out the granular hardened material from the above composition Agent (B — 1), and visually check whether a hardened resin layer is formed on the entire surface of the granular molded body. Composition for Anchor Bolt and Tube for Fixing Anchor Bolt] The above-mentioned hardening composition (A-1) of 8. was incorporated into a glass having an opening of 17.0 mm in outer diameter, 0.7 mm in thickness, and 120 mm in length Second, the particle size of the aggregate is 1. 5 ~ This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) A 24-(Please read the precautions on the back before filling this page) Binding A7 4 3 88 2 6 B7 V. Description of the invention (22) 3. A mixture of 24 g of magnesium oxide frit of 0 mm and the coated granular hardener (B-1) 2.0 g, to obtain a composition for fixing anchor bolts »Seal the opening of this container again to make a tube with the structure of Figure 1.

Q. On a concrete block with a size of 500x500x1,000 mm and a compressive strength of 2 10 kg / cm2, drill a hole with a hole diameter of 19.0 mm and a hole length of 130 mm. Use a blower and a nylon brush to clean the hole. Insert the above-mentioned pipe grate into the hole, and then cut the full-screw bolt Ml 6 (material SNB 7) with a diameter of 45 degrees and an outer diameter of 16 mm at the tip, install it on the gear machine, and hit it by turning and hitting it. Enter the bottom of the hole and measure its fixing strength after a 1 day maintenance time. The measuring device was an anchor bolt tensile tester ANS ER — 5 -III (manufactured by Asahi Kasei Corporation, Japan). The obtained results are shown in Table 1 together with the evaluation results of the handleability of the coated granular hardener (B-1). The storage life of the above-mentioned composition for anchor bolts is 6 months. Example 2 100 g of the hardenable composition (A-1) obtained in Example 1 was placed in a polyethylene container (capacity 300 cc) having a bottom outer diameter of 69 mm, an opening outer diameter of 79 mm, and a height of 96 mm. Next, 18 g of the granular hardener (B-1) obtained in Example 1 was charged to obtain a composition for fixing an anchor bolt. Cut holes in the mixed soil block as in Example 1, and then apply the Chinese paper standard (CNS > A4 size (210X297 mm)) of the above paper size of 2 3 g (please read the precautions on the back before filling this page) ) Order printed by the Consumers 'Cooperatives of the Central Standards Bureau of the Ministry of Economics-25-Printed bags of the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economics 4388 26 A7 ______B7 V. Description of the invention (23) The components of the anchor bolts are included in the logistics. In Example 1, the anchor bolt was buried in the hole to measure the anchoring strength. The obtained results are shown in Table 1 together with the evaluation results of the granular hardener (B_1). Comparative Example 1 [Modified rod shape Hardener] 1.8 g of phenylhydrazone peroxide diluted to 40% by weight with calcium sulfate was molded using a mold to obtain a rod-shaped molded body having a length of 80 mm and a diameter of 4.2 mm. The resulting rod-shaped molded body was immersed in In a 40% ethanol solution of cellulose acetate, it was taken out and left at 40 ° C for 1 hour, so that a first coating layer made of cellulose acetate was formed on the surface of the rod-shaped molded body. Next, the rod-shaped body was formed. Body immersed in epoxy resin and amine series In the liquid mixture of the chemical agent, it is taken out and placed at 30 ° C for 24 hours to form a second coating layer, and a rod-shaped hardener having the first and second coating layers is obtained. The object] was used to make holes in the mixed soil block as in Example 1, and then 23 g of the resin composition (A-1) obtained in Example 1 was flowed into the holes. Next, the above-mentioned rod-shaped hardener was inserted into the holes, and the holes were A composition for fixing anchor bolts was obtained. Next, the anchor bolt was buried in the hole in the same manner as in Example 1 to measure the anchoring strength. The results obtained are shown in Table 1 together with the results of the rational evaluation of the rod-shaped hardener. Example 3 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the note on the back before filling in this page) Order -26-438826 A7 B7 Staff Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs Printed 5. Description of the invention (24). 1 IC-modulated hardening composition (A-2)) 1 1 1 Bisphenol-A epoxy resin with weight average molecular weight 8 3 6 Made by subsidiary company) and methacrylic acid 1 to 2 1 1 Please make a methacrylic epoxy acrylate resin prepared by the molar ratio of 1 I. Read 1-k I (white hardened resin) ) 5 5 W t%, the back of white polymerizable monomers 1 '1 Diethylene glycol dimethacrylate 4 4 W t% of NT of hardening accelerator Note ί 事 N a dihydroxypropyl — P-toluidine (W t% ratio is combined to obtain a hardening item and then a 14 composition (A _ 2). 〇 Based on the JIS of this hardening composition—written% 6 9 0 1 (room temperature curing characteristics). Minimum hardening time at 5 ° C Page 1 1 1 The result is about 13 minutes. 0 1 1 1 C Prepare the coated granular hardener (B — 2) 1 Order 1 Mix benzene diluted with calcium sulfate to 40% by weight of benzene磕 Peroxide 1 I 1 0 0 weight unit, water 2 5 weight unit Λ molding agent of amylopectin 1 1 | 1 0 weight unit to obtain soil-like mixture D reuse pellets and (trade name 1 1; high-performance pellet machine called Koko Iron Works of Japan) Co., Ltd.) The mixed product was molded into a spherical granular molded body with an average particle diameter of 3 mm. Secondly, the granular molded body was dried at room temperature for 3 hours, and then dried at 60 ° C. J 1 Hour 0 After that, this granular molded body was immersed in the above-mentioned hardening composition (A-2) in a beaker with a capacity of 500 ICC, 3 0 0 1 ICC, and a mixer was used at 30 ° c. Stir for 30 minutes f to obtain a granulated molded 1 1 body. The coated granules on which the hardened resin coating is formed on the surface are tLK-like hardened 1 1 chemical agents (B-2). Then, 9 is taken out of the composition. Granular hardening 1 1 agent (B — 2) and confirm the granular formation by g measurement Over the entire surface of the sheet body 1 of a suitable scale Chinese National Standard Falcon (CNS) A4 size (21 OX297 mm) -27 4388 2 6 A7 B7 V. description of the invention (25) is formed with a hardening resin layer. [Preparing the composition for fixing anchor bolts and the tube for fixing anchor bolts] In addition to using the above-mentioned hardening composition (A-2) 8. 7 g 'The coated granular hardening agent (B-2) 2. Og ， The diameter of the aggregate is 1. 2 ~ 3. 4mm of silica other than 16g, the same as in Example 1, the composition for fixing the anchor bolt and the pipe for fixing the anchor bolt are prepared. Thereafter, the fixing strength of the obtained anchor pipe for anchor bolts was measured in the same manner as in Example 1. The results obtained are shown in Table 1 together with the rationality evaluation results of the granular hardener (B-2). The shelf life of this composition for fixing anchor bolts is 2 years. Window Example 4 [The composition for fixing anchor bolts and the pipe for fixing anchor bolts are prepared by adding a granular molded body of organic peroxide to the hardening composition (1)] Central Bureau of Standards, Ministry of Economic Affairs Printed by the employee consumer cooperative ί--^^ 1-I— —-H · I — ^ ϋ. {-Τ »• .¾ * τ (Please read the precautions on the back before filling this page) Mix with calcium sulfate Diluted to 40 weight percent of phenylhydrazone peroxide 100 weight units, water 25 weight units, and 8 weight units of amylopectin of the molding agent to obtain a clay-like mixture. The obtained clay-like mixture was shaped by a pellet machine (trade name: High-performance pellet machine; manufactured by Japan Koike Iron Works Co., Ltd.) to obtain spherical pellets having an average particle diameter of 3 mm. Next, the granular molded body was dried at room temperature for 3 hours, and then dried at 60 ° C for 1 hour. Put this granular shaped body 2. Og and ceramic bone material (brand name: Xue La Sade S; manufactured by Japan's Gomesu Kosan Co., Ltd.). The paper size is applicable to China National Standard (CNS) A4 (210X297) (Mm) -28-Printed by the Consumers' Cooperatives of the China Standards Bureau of the Ministry of Economic Affairs 4 3 88 2 6 a7 ____B7__ V. Description of the Invention (26) The gathering of the length 12010111111, the width 5 3.4mm, and the thickness 100mm Laminated film made of vinyl / polyethylene terephthalate / aluminum / polyethylene is folded in half along the long direction and heat-sealed one of the other long and short sides opposite to the fold The film-formed container at the opening was immersed in 8.7 g of the hardenable composition (A-2) obtained in Example 3 to form coated granular hardener particles to obtain a composition for fixing anchor bolts. "Next, From the obtained composition, 12 coated granular hardener particles were taken out, and it was confirmed visually whether or not a hardened resin coating layer was present on the entire surface of the hardened resin of the granular hardener. Next, the opening portion of the thin-film container in which the above-mentioned composition for fixing anchor bolts was placed was sealed to obtain a tube for fixing anchor bolts having a structure shown in Fig. 2. Thereafter, the fixation strength of this balloon was measured in the same manner as in Example 1. The results are reported in Table 1. The shelf life of this anchor bolt composition is 2 years or more. Window Example 5 [Preparing the coated granular hardener (B-3)] 100% by weight of phenylhydrazine peroxide diluted with calcium sulfate to 40% by weight, and carboxymethylcellulose of a molding agent. Weight unit, 5 weight units of SB latex (solid content), 45 weight units of water, you can get the pulp. ”Secondly, the obtained slurry was formed at room temperature by using Morapatisbanser made by the Japanese National Soldier Equipment Co., Ltd., A granular shaped body having a particle diameter of 0.1 to 0.4 mm (average particle diameter of 0.2 to 5 mm) was obtained. Then 'Dry this granular shaped body at 60 ° C for 2 hours, and then immerse it in this paper to apply Chinese National Standard (CNS) A4 specification (210 × 297 mm) (Please read the precautions on the back first (Fill in this page again)

1T -29 _ 438826 A7 _B7 V. Description of the invention (27) The above-mentioned hardening composition (A-2) in a beaker with a capacity of 50 0 cc in 30 cc, and stirred with a blender at 30 ° C for 30 minutes A coated granular hardener (B-3) was formed on the surface of the granular molded body with a hardened resin coating layer. Thereafter * the obtained granular hardener (B-3) particles were taken out of the above composition, and it was visually confirmed whether a hardened resin layer was formed on the entire surface of the granular molded body. [Modulation of composition for fixing anchor bolts and pipe for fixing anchor bolts] Except for using 2.0 g of the coated granular hardening agent described above, the composition for fixing anchor bolts and fixing anchor bolts were the same as in Example 1. Tube sac. Next, the results obtained by measuring the fixing strength of the composition for anchor bolts obtained in Example 1 are shown in Table 1 together with the handling evaluation results of the granular hardener described above. Comparative Example 2 Hardening composition (A_l) 8. 7 g Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Load 17mm in outer diameter, 0.8mm in wall thickness, and 13mm in length An opaque cylindrical tube made of phenol resin having an opening. Next, a rod-shaped hardener made in the same manner as in Example 1 was inserted into the tube to obtain a composition for fixing an anchor bolt. Next, 24 g of magnesia frit having a particle diameter of 1.5 to 3.0 mm (average particle diameter of 2.4 mm) was charged, and the opening was sealed with a polyethylene lid to obtain a structure having a structure shown in FIG. 3. Tube bag for fixing anchor bolts. Thereafter, the anchoring strength of this tube was measured in the same manner as in Example 1. The results obtained are shown in Table 1 together with the results of the rational evaluation of the hardener. In addition, the storage life of the composition for fixing anchor bolts is 4 months. Β This paper size applies the Chinese National Standard (CNS) A4 specification (2 丨 0 '乂 297 mm) -30-438826 V. Description of the invention (^)

Ministry of Economic Affairs_Central Bureau of Standards, Printed by Employee Consumer Cooperatives, Table 1 Fixing Strength (ton) Covered Hardener Molded Body, Rational Construction Test Number, Measured Value, Average Example 1 1 11.5 11.5 〇2 11.2 3 11.8 Example 2 1 7.6 7.7 〇2 8. 0 3 7.5 Comparative Example 1 1 6.5 5. 5 X 2 3. 2 3 5.8 Example 3 1 12.1 11.7 〇2 11.4 3 11.5 Example 4 1 11.8 11.8 〇2 11.9 3 11.8 Example 5 1 11.0 10.5 〇2 10.1 3 10.4 Comparative Example 2 1 10.8 9.5 X 2 8. 6 3 9.2 (Please read the precautions on the back before filling this page)

This paper size applies the Chinese National Standard (CNS) A4 specification (2 丨 OX 297 mm) _3 |-438826 A7 B7 V. Description of the invention (29) From the above, it is known that the coated granular hardener of the present invention has In addition to excellent handleability, it can exhibit excellent hardening properties because it can be uniformly dispersed in a radical hardening compound. Therefore, the coated granular hardener of the present invention is suitable for use in a water-permeable resin emulsion or Radical curable resins for various applications such as injection molding resins, and hardeners for radical polymerizable monomers, especially when used in compositions for anchor bolts, which not only prolongs product life, but also enables high-strength attitude. The anchor bolt is fixed on the base material, so an excellent composition for fixing the anchor bolt can be obtained. ^ 1 ^ — · —a ^ ia Influ— — · ϋ n I * .¾-6 · (Please read the notes on the back before filling out this page) Printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Consumer Cooperatives Paper size applicable to China National Standards (29 Women in the Remuneration Department)

Claims (1)

438826 Patent Application No. 8 5 1 1 5 2 3 No. 1 Chinese Patent Application Amendment Revision April 1989 1. A granular hardener for coated fixed anchor bolts, characterized in that it is a kind of A coated granular hardening agent that cures at least one selected from the group consisting of a radically curable resin and a group of radically polymerizable monomers. The entire surface is covered with a radically curable resin. The resin and the radical polymerizable monomer group are composed of an organic peroxide granular molded body of a hardened resin layer formed of at least one second radical hardening compound selected from the group of the first and second free radicals. The base-hardening compounds may be the same or different. 2. For example, the hardening agent in the first item of the patent application * wherein the first and second radical curing compounds are independently composed of epoxy acrylate resin, polyester acrylate resin, acrylic urethane resin, and unsaturated Polyester resins, polyfunctional carboxylic acid esters, and mixtures selected from them. 3. If the hardener for item 1 of the scope of application is applied, where the organic peroxide granular molding system consists of hydroperoxides and dioxane Formed by at least one organic peroxide selected from the group consisting of a base peroxide, a dimethyl peroxide, a ketone peroxide, a hydroxycarbonate, a ketal peroxide, and a peroxide ester group. 3〜40% · 5. Kind of fixing anchors, wherein the particle size of the hardener is 0, 5 ~ 15 · 0mm, and the thickness of the hardening resin layer is preferably 0.3 to 40% · 5. The composition for bolts includes the following features: (1. Degree applicable to China National Standard (CNS) A4 specification (210x297 mm) ------------- ^ --- i-.1t · —------- (Please read the note on the back? Matters before filling out this page) Printed by Sakusha 438826 A8B8C8D8 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 6. Scope of patent application. At least one of the first free radical hardening type and hardening selected from the group of free radical hardening resin and free radical polymerizable monomer A hardening composition formed by an accelerator and (2) the hardening composition (1) a coated hardening agent, and the surface of the hardening composition is covered with a radical curing resin and a radical polymerizable monomer group An organic peroxide granular molded body of a hardened resin layer formed of at least one second radical-curable compound selected from the above, and the first and second radical-curable compounds may be the same or different A plurality of granular hardener particles that are finally coated. 6. The composition according to item 5 of the scope of patent application, wherein the content of the plurality of particles (2) is preferably 0.5 to 20% by weight based on the weight of the curable composition (1). 7. The composition according to item 5 of the scope of patent application, wherein the first and second radical-curing compounds are independently composed of epoxy acrylate resin, polyester acrylate, acrylic urethane resin, and unsaturated polyester. Resin, polyfunctional carboxylic acid esters and mixtures thereof are selected from the group "8. For example, the composition of item 5 of the patent application, wherein the first radical hardening compound and the second radical hardening compound are the same. 9. The composition according to item 5 of the application scope, wherein the organic peroxide granular molding system is composed of hydroperoxide, dialkyl peroxide, difluorenyl peroxide, ketone peroxide 1 hydroxycarbonic acid. It is formed by at least one organic peroxide selected from the group of esters, ketal peroxides, and peroxide esters. For example, the composition of claim 5 in the scope of the application, wherein the particles (2) are each independent 〇5 ～ 15. 0mm particle size, and this paper size applies the Chinese national standard (CNSU4 specification (210 X 297 mm) — — — — — — — — — III — I I--I-^ --- --III I (Please read the notes on the mouth first, then fill in this page) -2-438826 A8 BS C8 D8 6. The scope of patent application, the hardening resin layer has its own independent particle size of each particle is 0 Thickness of 3 to 40% · 1 1. Aggregate may also be included in the composition of the scope of application for patent No. 5 1 2 types of pipes for fixing anchor bolts, containers with extremely closed structures, and containers It contains the composition of any one of the items of Shin ~ 11, and this container is used for management The effect of the anchor bolt is broken. 1 3 .—A method as described in the eighth application of the application of Li Fanfan, which is characterized by including at least one radical hardening accelerator selected from a mixed radical hardening tree single population. Step of forming a viscous liquid curable composition and a granular molded body of the compound, and then forming a cured resin layer cured by the radical containing the curable composition on each of the granular molded bodies. The viscous liquid sclerosing composition (1) made in item 13 also contains bones. Among them, the sclerosing characteristic is that it has the patent application No. 5 which can be used for the manufacture of the composition and the radical polymerization of anchor bolts. Type compound and hardening multiple organic peroxy compound on the whole surface. Compound method, among which, please read the material β. Note on the back, then fill in 5 packs. Printed paper sizes are applicable to the Chinese Standard SCN (A4) (210 X 297 mm)