JP2006009461A - Filler - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide filler having fire resistance, excellent workability, and high strength. <P>SOLUTION: This filler for fixing a reinforcing bar is a component composed of main agent and harder. The main agent is a mixture of radical hardening type resin diluted by reactive monomer and inorganic filler. This filler contains a component which is produced by mixing inorganic filler having average grain size of 0.5 to 3.0 μm and inorganic filler having average grain size of 8 to 16 μm at mass ratio of 3:7 to 1:9 and in which endothermic discomposing is contained by 65 to 80 wt% in the main agent inorganic filler. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a filler for fixing reinforcing bars and concrete, reinforcing bars and reinforcing bars, etc. in civil engineering and construction.

  Conventionally, resin-based fillers have been used for injecting fillers into the couplers of reinforcing bar joints for fixing reinforcing bars and the like, and inserting and fixing reinforcing bars and the like into holes drilled in concrete. There are two types of fillers: on-site preparation type and cartridge type. In the on-site preparation type, the main agent and the curing agent contained in each container are mixed, refilled into a filling container, injected into the perforation, and the fixing member is fixed. For cartridge type, the main agent and curing agent in the cartridge are ejected in appropriate amounts by the force of hand gun or hydraulic pressure, etc., and the adhering agent mixed by the mixer such as static mixer is injected into the perforation, and the reinforcing bar A fixing member such as is fixed and used.

When the adhesive used for these fillers is used for a structure, fire resistance is required. Generally, an inorganic grout material is used instead of a resin system. However, this inorganic grout material is of the on-site formulation type, and it is mixed with water just before use, so it needs to be transferred to a filling container, and it is necessary to clean the agitator and container after use. However, it was troublesome. Moreover, although it is necessary to make water / grouting agent ratio small in order to make it high intensity | strength, there existed a limit in intensity | strength because filling property, intensity | strength, and fireproof performance conflicted.
In this way, an inorganic grout material is used in a portion where fire resistance is required. However, there has been a limit to the poor workability and handling, and the rebar, concrete, and the like that are used have a higher layer and become lighter and stronger. In addition, it was necessary to pay attention to weight management, weighing, etc. in the field preparation type.

  An object of this invention is to provide the high intensity | strength filler which is fireproof and excellent in workability | operativity.

  In order to solve the above problems, it is difficult to achieve both heat resistance and strength with inorganic grout materials, and as a result of intensive studies, investigation of resin-based fillers, especially the types and blends of resins and inorganic fullers, will be studied. This led to a solution. That is, the present invention is as follows.

1. It is a filler for fixing reinforcing bars and the like, and the filler is a composition comprising a main agent and a curing agent, and the mixture of a radical curable resin and an inorganic filler in which the main agent is diluted with a reactive monomer. Inorganic inorganic filler having an average particle size of 0.5 to 3.0 μm and 8 to 16 μm mixed at a mass ratio of 3: 7 to 1: 9 and undergoing an endothermic decomposition reaction A filler comprising 65 to 80% by mass of the above filler in the main agent.
2. The endothermic decomposition reaction absorbs heat by dehydration of an inorganic filler, and the dehydration temperature is 200 to 350 ° C. The filler described.
3. 1. The inorganic filler is aluminum hydroxide. Or 2. The filler described.
4). 1 to 5% by mass of at least one of an unsaturated polycarboxylic acid polymer and a polysiloxane copolymer, an unsaturated fatty acid polyamine amide, as a dispersant for an inorganic filler. . ~ 3. The filler according to any one of the above.
5. The radical curable resin has a molecular weight of 400 to 1500, contains two or more aromatic rings or alicyclic moieties, and the radical curable resin composition contains 50 to 80% by mass of a reactive monomer. 1. ~ 4. The filler according to any one of the above.

  According to the present invention, a composition comprising a main agent and a curing agent, wherein the main agent is a mixture of a radical curable resin diluted with a reactive monomer and an inorganic filler, the average of inorganic fillers A mixture of particles having a particle size of 0.5 to 3 μm and particles of 8 to 16 μm in a weight ratio of 3: 7 to 1: 9 and 65 to 80 wt% in which the inorganic filler undergoes endothermic decomposition reaction. By using a filler characterized by containing, providing high-strength adhesives that have fire resistance and excellent workability in adhesives that connect concrete and reinforcing bars, reinforcing bars and reinforcing bars, etc. in civil engineering and construction Make it possible. It is possible to provide a filler with fire resistance and excellent workability.

The present invention will be specifically described below, particularly focusing on preferred forms thereof.
The radical curable resin that can be used in the present invention is an addition reaction of a vinyl ester resin derived from a polyhydric alcohol and an unsaturated monobasic acid, an epoxy resin and an unsaturated monobasic acid such as methacrylic acid or acrylic acid. Examples thereof include epoxy acrylate resins and urethane acrylate resins.
For example, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, dimethylol-tricyclodecane dimethacrylate, bisphenol A glycidyl ether methacrylic acid adduct, hydrogenated bisphenol A diglycidyl ether methacrylic acid adduct, tetrakis ( Glycidylphenyl) ethane methacrylic acid adduct, naphthalene-type diglycidyl ether methacrylic acid adduct, triglycidyl isocyanurate methacrylic acid adduct, and the like.

The radical curable resin is preferably used after being diluted with a reactive monomer, and is an ester of a carboxylic acid and an alcohol, which is a polyfunctional ester. In the present invention, a mixture of a radical curable resin and a reactive monomer is referred to as a radical curable resin composition.
For example, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, diallyl phthalate And esters with methacrylic acid and methallyl alcohol, which are excellent in alkali resistance, such as triallyl trimetate, triallyl isocyanurate, and phenylmaleimide. These reactive monomers may be used alone or in combination. Furthermore, monofunctional esters can be mixed in small amounts.

The mixing ratio of the reactive monomer to the radical curable resin is not particularly limited, but is preferably 60 to 80% by mass in the radical curable resin composition. Moreover, it is desirable to mix so that resin viscosity may be 0.1-5 poise (E-type viscosity meter, 25 degreeC).
Further, the radical curable resin preferably has a molecular weight of 400 to 1500, and preferably contains two or more aromatic rings or alicyclic moieties. Furthermore, it is preferable to contain 50-80 mass% of reactive monomers in the radical curable resin composition.

Curing agents that can be used in the present invention include diacyl peroxides, ketone peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, and peroxycarbonates. Examples thereof include benzoyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, dicumyl peroxide, cumene hydroperoxide, and the like, and most preferably benzoyl peroxide is used. Further, this curing agent is preferably diluted with a diluent.
Diluents of curing agents that can be used in the present invention are inorganic substances such as calcium sulfate and calcium carbonate, dimethyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, dioctyl phthalate, aliphatic hydrocarbons, aromatic hydrocarbons, silicone oil, liquid paraffin Polymerizable monomers, water and the like.

Accelerators that can be used in the present invention may be tertiary aromatic amines having a hydroxyl group in the nitrogen substituent, such as N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N N, N-dihydroxypropyl-p-toluidine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N, N-bishydroxybutyl-p-toluidine, etc. p-Toluidine is preferred. Further, the accelerator may be mixed with the main agent at the time of use separately from the main agent as long as avoiding direct contact with the curing agent, or may be previously mixed in the resin. The content is preferably 0.1 to 5% by mass, more preferably 0.5 to 1.5% by mass.
These accelerators may be used alone or in combination of two or more, and used in combination with accelerators such as N, N-dimethylaniline and cobalt naphthenate which have been generally used conventionally. May be used.

Furthermore, a polymerization inhibitor, a colorant, a pigment, an ultraviolet absorber, a surfactant, an aggregate, a filler, a thixotropic agent, and the like can be added to and mixed with the main component as necessary. Moreover, an aggregate, a filler, a thixotropic agent, a diluent, a plasticizer, etc. can be added and mixed with a hardening | curing agent component as needed.
Examples of the polymerization inhibitor used in the present invention include quinones, hydroquinones, phenols and the like. For example, benzoquinone, p-benzoquinone, p-toluquinone, p-xyloquinone, naphthoquinone, 2,6-dichloroquinone, hydroquinone, p- Necessary amount of t-butylcatechol, 2,5-di-t-butylhydroquinone, monomethylhydroquinone, p-methoxyphenol, 2,6-di-t-butyl-p-cresol, hydroquinone monomethyl ether can be added. However, quinones may react with amines and cause changes such as coloring, and it is preferable to add hydroquinones and phenols, and the most effective ones are cresols.

It adds as needed as a coloring agent and a pigment which can be used for this invention. These additives include lake pigments, azo pigments, phthalocyanine pigments, higher organic pigments and inorganic pigments, single items thereof or mixtures thereof.
The surfactant that can be used in the present invention includes an anionic type, a cationic type, a nonionic type, and an amphoteric type, and an anionic type that is effective in stabilizing the tensile strength in water is preferable. Anionic surfactants include dialkylsulfosuccinates (Sanyo Kasei Co., Ltd.) such as alkyl ether carboxylates (for example, Sanyo Chemical Co., Ltd., trade name “Bulite EAC”) as carboxylates. ), Trade name “Sansepara 100”), alkyl allylsulfosuccinate, alkylsulfoacetate, α-olefin sulfonate, etc., sulfate ester salt, alkylallyl sulfate, alkyl ether sulfate, phosphate ester salt Examples include alkyl ether phosphates.

Particularly preferably, when a surfactant is added to the resin, it is desirable to use a dialkyl sulfosuccinate or alkyl allyl sulfosuccinate that does not promote gelation of the resin. These anionic surfactants are preferably monovalent or divalent metal salts or ammonium salts, and more preferably sodium salts.
These surfactants may be arranged anywhere, but are preferably mixed in the resin. The amount used is not particularly limited, but it is preferably suppressed to 30% by mass or less in terms of strength. Further, the surfactant may be used by dissolving in a reactive monomer or a solvent.
Examples of the dispersant used in the present invention include unsaturated polycarboxylic acid polymers and polysiloxane copolymer unsaturated fatty acid polyamine amides, and it is desirable to add about 0.5 to 10% by mass with respect to the inorganic filler.

The inorganic filler that can be used in the present invention is most preferably aluminum hydroxide having aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate or the like and having a dehydration temperature of 250 to 350 ° C. Moreover, the particle diameters of these fillers are 8 to 16 μm and 0.5 to 1.5 μm mixed at a mass ratio of 90:10 to 70:30. A compounding quantity is important in order to express fire resistance and intensity | strength by mix | blending 65-80 mass% with respect to a radical curable resin composition. It is preferable to mix a thixotropic agent in the main resin to prevent dripping.
In addition to the above inorganic fillers, soot powder, calcium carbonate, glass flakes, alumina and the like may be blended for the purpose of reinforcement. It is more effective to combine and blend those having a particle diameter of 0.5 to 1.5 μm.

The thixotropic agent that can be used in the present invention includes finely divided silica (Nippon Aerosil Co., Ltd., trade name, Erotic), powderless alumina, talc, asbestos, and colloidal hydrous aluminum silicate / organic composite (Shiraishi Kogyo Co., Ltd., Trade name, Orben), bentonite, castor oil derivatives and the like.
Further, an inorganic cement such as non-shrink mortar may be mixed on the main resin composition side, and water may be mixed with a curing agent to form a resin mortar. In this case, a mixture having good fluidity when added in combination with the same surfactant, dispersant, water reducing agent, fluidizing agent and the like as those used in the resin mortar so as to improve the mixing property of the main agent and the curing agent. Is obtained.
The main resin composition has a viscosity of 50 r.m. containing these inorganic fillers, thixotropic agents and the like. p. It is preferable to adjust so that the viscosity at m is 50 to 200 Pa · s (spiral viscometer, 25 ° C.).

Hereinafter, the present invention will be described by way of examples.
<Average particle size of inorganic filler (average particle size)>
A 50% weight by weight obtained from the particle size distribution measured by the laser diffraction scattering method is Seisin Kogyo, model number SKN-1000.

[Example 1]
Bisphenol A glycidyl ether methacrylic acid adduct (n = 1.2) 30% by weight, diethylene glycol dimethacrylate 70% by weight as a reactive monomer 500 g resin, accelerator N, N-dihydroxypropyl-p-toluidine 3 g and 0.4 g of 2,6-di-t-butyl-p-cresol (BHT) as a polymerization inhibitor were mixed. 200 g of aluminum hydroxide (average particle size: 12 μm) and 50 g of calcium carbonate (average particle size: 1 μm) were mixed with 100 g of this resin to prepare the main agent. The curing agent was prepared by mixing 40 g of aluminum hydroxide (average particle size 12 μm) and 3 g of Aerosil with 100 g of benzoyl peroxide paste (40% concentration, diluted silicone oil).
Each of the main agent and the curing agent prepared here was filled in a cartridge having a volume ratio of 10: 1 to make a prototype of the cartridge. A mixing nozzle for mixing and filling was installed at the discharge port, set in a suitable dispenser, and a test piece was made and evaluated using a resin in which the main agent and curing agent were discharged and mixed.
Evaluation produced the test piece of (PHI) 30x30mm, and it heated at 350, 400, 450 degreeC over 2 hours according to the heating curve of the fire test of JIS, and confirmed the decomposition state of the test piece. The results are shown in Table 1.

[Example 2]
As an accelerator, 500 g of 2,2-bis [4- (methacryloxyethoxy) phenyl] propane 30% by mass, 40% by mass of diethylene glycol dimethacrylate as a reactive monomer, and 30% by mass of trimethylolpropane trimethacrylate 3 g of N, N-dihydroxypropyl-p-toluidine and 0.4 g of 2,6-di-t-butyl-p-cresol (BHT) were mixed as a polymerization inhibitor. 100 g of this resin was mixed with 250 g of aluminum hydroxide (average particle size: 12 μm) +50 g of calcium carbonate (average particle size: 1 μm) to prepare the main agent. The curing agent was prepared by mixing 40 g of aluminum hydroxide (average particle size 12 μm) and 3 g of Aerosil with 100 g of benzoyl peroxide paste (40% concentration, diluted silicone oil).
Each of the main agent and the curing agent prepared here was filled in a cartridge having a volume ratio of 10: 1 to make a prototype of the cartridge. A mixing nozzle for mixing and filling was installed at the discharge port, set in a suitable dispenser, and a test piece was made and evaluated using a resin in which the main agent and curing agent were discharged and mixed.
Evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1.

Example 3
Dimethylol-tricyclodecane dimethacrylate 50% by weight, diethylene glycol dimethacrylate 50% by weight as a reactive monomer, 500 g of resin, N, N-dihydroxypropyl-p-toluidine 3 g as an accelerator, and polymerization inhibitor 2, 0.4 g of 6-di-t-butyl-p-cresol (BHT) was mixed. 100 g of this resin was mixed with 300 g of aluminum hydroxide (average particle size of 12 μm) +50 g of calcium carbonate (average particle size of 1 μm) to prepare the main agent. The curing agent was prepared by mixing 40 g of aluminum hydroxide (average particle size 12 μm) and 3 g of Aerosil with 100 g of benzoyl peroxide paste (40 mass% concentration, diluted product of silicon oil).
Each of the main agent and the curing agent prepared here was filled in a cartridge having a volume ratio of 10: 1 to make a prototype of the cartridge. A mixing nozzle for mixing and filling was installed at the discharge port, set in a suitable dispenser, and a test piece was made and evaluated using a resin in which the main agent and curing agent were discharged and mixed.
Evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1.

Example 4
Bisphenol A glycidyl ether methacrylic acid adduct 30% by weight, 500 g of resin 70% by weight of diethylene glycol dimethacrylate as a reactive monomer, 3 g of N, N-dihydroxypropyl-p-toluidine as an accelerator, 2 as a polymerization inhibitor , 6-Di-t-butyl-p-cresol (BHT) 0.4 g was mixed. 200 g of magnesium hydroxide (average particle size: 12 μm) and 50 g of aluminum hydroxide (average particle size: 1 μm) were mixed with 100 g of this resin to prepare a main agent. The curing agent was prepared by mixing 40 g of aluminum hydroxide (average particle size 12 μm) and 3 g of Aerosil with 100 g of benzoyl peroxide paste (40 mass% concentration, diluted product of silicon oil).
The main agent and the curing agent prepared here were each filled in a cartridge with a ratio of 10: 1 to make a prototype of the cartridge. A mixing nozzle for mixing and filling was installed at the discharge port, set in a suitable dispenser, and a test piece was made and evaluated using a resin in which the main agent and curing agent were discharged and mixed.
Evaluation produced the test piece of (PHI) 30x30mm, and it heated at 350, 400, 450 degreeC with the electric furnace over 2 hours according to the heating curve of the JIS fire resistance test, and confirmed the decomposition state of the test piece. The results are shown in Table 1.

[Comparative Example 1]
Bisphenol A glycidyl ether methacrylic acid adduct (n = 1.2) 30% by weight, diethylene glycol dimethacrylate 70% by weight as a reactive monomer, 500 g of resin, N, N-dihydroxypropyl-p-toluidine as an accelerator 3 g and 0.4 g of 2,6-di-t-butyl-p-cresol (BHT) as a polymerization inhibitor were mixed. 200 g of calcium carbonate (average particle size of 15 μm) and 50 g of calcium carbonate (average particle size of 1 μm) were mixed with 100 g of this resin to prepare a main agent. The curing agent was prepared by mixing 40 g of aluminum hydroxide (average particle size 12 μm) and 3 g of Aerosil with 100 g of benzoyl peroxide paste (40% concentration, diluted silicone oil).
Each of the main agent and the curing agent prepared here was filled in a cartridge having a volume ratio of 10: 1 to make a prototype of the cartridge. A mixing nozzle for mixing and filling was installed at the discharge port, set in a suitable dispenser, and a test piece was made and evaluated using a resin in which the main agent and curing agent were discharged and mixed.
Evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 2]
Bisphenol A glycidyl ether methacrylic acid adduct 30% by weight, 500 g of resin 70% by weight of diethylene glycol dimethacrylate as a reactive monomer, 3 g of N, N-dihydroxypropyl-p-toluidine as an accelerator, 2 as a polymerization inhibitor , 6-Di-t-butyl-p-cresol (BHT) 0.4 g was mixed. 150 g of aluminum hydroxide (average particle size 4 μm) was mixed with 100 g of this resin to prepare a main agent. The curing agent was prepared by mixing 40 g of aluminum hydroxide (average particle size 12 μm) and 3 g of Aerosil with 100 g of benzoyl peroxide paste (40% concentration, diluted silicone oil).
Each of the main agent and the curing agent prepared here was filled in a cartridge having a volume ratio of 10: 1 to make a prototype of the cartridge. A mixing nozzle for mixing and filling was installed at the discharge port, set in a suitable dispenser, and a test piece was made and evaluated using a resin in which the main agent and curing agent were discharged and mixed.
Evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 3]
Bisphenol A glycidyl ether methacrylic acid adduct 30% by weight, 500 g of resin 70% by weight of diethylene glycol dimethacrylate as a reactive monomer, 3 g of N, N-dihydroxypropyl-p-toluidine as an accelerator, 2 as a polymerization inhibitor , 6-Di-t-butyl-p-cresol (BHT) 0.4 g was mixed. 200 g of talc (average particle diameter of 11 μm) and 50 g of talc (average particle diameter of 1.1 μm) were mixed with 100 g of this resin to prepare a main agent. The curing agent was prepared by mixing 40 g of aluminum hydroxide (average particle size 12 μm) and 3 g of Aerosil with 100 g of benzoyl peroxide paste (40% concentration, diluted silicone oil).

Each of the main agent and the curing agent prepared here was filled in a cartridge having a volume ratio of 10: 1 to make a prototype of the cartridge. A mixing nozzle for mixing and filling was installed at the discharge port, set in a suitable dispenser, and a test piece was made and evaluated using a resin in which the main agent and curing agent were discharged and mixed.
Evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1.
As a result, as can be seen from Table 1, it can be seen that the carbonization of the resin in the high temperature region is remarkably improved. By using the present invention, it is possible to provide a high-strength adhesive having fire resistance and excellent workability.

  The filler of the present invention can be suitably used in the field of adhesives for bonding concrete and reinforcing bars, reinforcing bars and reinforcing bars in civil engineering and construction. It is possible to provide a high-strength adhesive having fire resistance and excellent workability.

Claims (5)

  It is a filler for fixing reinforcing bars and the like, and the filler is a composition comprising a main agent and a curing agent, and the mixture of a radical curable resin and an inorganic filler in which the main agent is diluted with a reactive monomer. Inorganic inorganic filler having an average particle size of 0.5 to 3.0 μm and 8 to 16 μm mixed at a mass ratio of 3: 7 to 1: 9 and undergoing an endothermic decomposition reaction A filler comprising 65 to 80% by mass of the above filler in the main agent.   The filler according to claim 1, wherein the endothermic decomposition reaction absorbs heat by dehydration of an inorganic filler, and the dehydration temperature is 200 to 350 ° C.   The filler according to claim 1 or 2, wherein the inorganic filler is aluminum hydroxide.   It is characterized by containing at least one of unsaturated polycarboxylic acid polymer and polysiloxane copolymer unsaturated fatty acid polyamine amide as an inorganic filler dispersant in an amount of 0.5 to 10% by mass based on the inorganic filler. Item 5. The filler according to any one of Items 1 to 4.   The radical curable resin has a molecular weight of 400 to 1500, contains two or more aromatic rings or alicyclic moieties, and the radical curable resin composition contains 50 to 80% by mass of a reactive monomer. The filler according to any one of claims 1 to 5.