JP5683302B2 - Adhesive and bonding method - Google Patents

Description

The present invention is an adhesive having excellent workability and curability, high adhesive strength and durability, and can be applied to various adhesive applications in the field of construction and civil engineering. Furthermore, it is a bonding method using the adhesive.

An organic adhesive is mainly used as an adhesive used for drilling a base material such as concrete or bedrock and fixing a fixing member such as an anchor bolt in the drill.

Examples of the organic adhesive include a two-component mixed resin adhesive composed of a main agent containing a thermosetting radical curable resin and a curing agent containing an organic peroxide as described in Patent Document 1. It is done. In use, the main agent and the curing agent are separately accommodated in each container, and are used by mixing them when used as an adhesive. The two-component injection type cartridge is made by combining the main agent and the curing agent separately in each container and combining them together, and when used, a mixing nozzle is attached to the cartridge, and the piston of the cartridge The main agent and the curing agent are discharged by pressurizing, the two components are mixed and discharged in the mixing nozzle, the resin composition is filled in the hole drilled in the base material such as concrete, and the anchor bolt is inserted. Then, it is cured and bonded and integrated.

However, organic adhesives have problems such as being easily ignited, having to dry the base material in advance, and having problems with durability.

JP 2002-338818 A JP 2004-244521 A JP 2008-169286 A

On the other hand, inorganic adhesives have been proposed, but there are cases where voids are easily generated in the gaps between the holes of the base material such as concrete and bedrock and anchor bolts, and sufficient adhesive strength may not be obtained.

JP 2006-335586 A JP 2009-114000 A

The adhesive of the present invention is characterized by the fact that the main component is an inorganic substance, so that it does not ignite, there is no need to dry the base material in advance, the durability is high, and the like, and the conventional inorganic adhesive Compared to the above, there is a feature that it easily penetrates into the gap between the hole of the base material such as the bedrock and the anchor bolt, and high adhesive strength is obtained.

The present invention is an adhesive comprising fine particle silica having an average particle size of 1.0 μm or less as a main agent and water, and a calcium compound having an average particle size of 1.0 μm or less, a dispersant, and water as a curing agent. And an adhesive further containing a polymer dispersion, which contains fine particle silica having an average particle diameter of 1.0 μm or less, a dispersant and water as a main agent, and an average particle diameter of 1.0 μm as a curing agent. It is an adhesive containing the following calcium compound, a dispersant and water, and further an adhesive containing a polymer dispersion, and the calcium compound is the adhesive that is calcium hydroxide, The fine particle silica and / or calcium compound is produced using one or more selected from the group consisting of a high-speed stirrer, a medium stirring mill and a pulverizer using high-pressure water. The adhesive is a high performance dispersant, the adhesive contains a polymer dispersion as a main ingredient, and further contains a curing time adjusting agent. This adhesive is a bonding method in which the main agent and curing agent of the adhesive are separately accommodated in respective containers, and two agents are mixed at the time of use.

By using the adhesive of the present invention, it is possible to provide an adhesive and a bonding method that are excellent in workability and curability, and further excellent in adhesive strength and durability.

Unless otherwise specified, parts and% in the present invention refer to parts by mass and% by mass.

Hereinafter, embodiments of the present invention will be specifically described.

The fine particle silica of the present invention can be produced by a method of oxidizing metal silicon or a method of collecting fumes (silica fume) generated from an electric furnace in the process of producing zirconia, in particular, by dispersing metal silicon powder. The fine particle silica powder produced by injecting the slurry into a flame, burning, and oxidizing is preferable in that it has little aggregation (structure) and high reactivity with the curing agent.

The fine particle silica of the present invention, for example, injects metal silicon or siliceous raw material powder into a high-temperature flame formed by a combustible gas and an auxiliary combustion gas to form a molten spheroid, and collects the spherical silica powder while cooling. Furthermore, fine particle spherical silica powder having an average particle diameter excellent in fluidity promoting effect can be collected by the classification treatment.

In the present invention, for example, a slurry having a metal silicon powder concentration of 5 to 70% in which metal silicon powder is dispersed in water in a high-temperature flame formed by combustible gas and auxiliary combustion gas is projected at least 10 m / second or more. Spherical silica powder is produced by spraying at a velocity to melt and spheronize and collect. Furthermore, fine particle spherical silica powder having an average particle diameter excellent in fluidity promoting effect can be collected by the classification treatment. For example, it can be manufactured according to Patent Document 6 and Patent Document 7.

JP 2001-354409 A Japanese Patent Laid-Open No. 2002-2011

  In addition, the fine particle silica has an average value of sphericity of preferably 90% or more, more preferably 95% or more, and particularly preferably 97% or more in terms of permeability and compressive strength characteristics.

The sphericity can be measured using a scanning electron microscope (“JSM-T200 type” manufactured by JEOL Ltd.) and an image analyzer (manufactured by Nippon Avionics Co., Ltd.). For example, first, the projected area (A) and the perimeter (PM) of particles are measured from an SEM photograph of powder. When the area of a perfect circle corresponding to the perimeter (PM) is (B), the sphericity of the particle can be displayed as A / B × 100 (%). Therefore, assuming a perfect circle having the same circumference as the sample particle (PM), PM = 2πr and B = πr ² , so that B = π × (PM / 2π) ² , and each particle Can be calculated as sphericity = A / B × 100 (%) = A × 4π / (PM) ² × 100 (%), so the average value of 200 arbitrary particles is the sphere of the powder. It can be calculated as a degree.

  Furthermore, the amorphous ratio of the fine particle silica is preferably 95% or more, more preferably 98% or more, and particularly preferably 100%.

  The amorphous ratio is determined by X-ray diffraction analysis of the sample using a powder X-ray diffractometer (for example, “Mini Flex” manufactured by RIGAKU) in the range of 2θ of CuKα ray of 26 to 27.5 °. It can be measured from the intensity ratio of the peaks.

Examples of the fine particle silica include trade names “SFP-20M” and “SFP-30M” manufactured by Denki Kagaku Kogyo Co., Ltd., and trade names “Admafine” manufactured by Admatech.

The particle size of the fine particle silica of the present invention is not particularly limited as long as a desired effect is obtained, but an average particle size of 1.0 μm or less is preferable because of excellent permeability to mortar and concrete and adhesive strength, and 0.05 to 0.8 μm is more preferable.

Examples of the calcium compound of the present invention include inorganic substances such as calcium hydroxide, calcium chloride and gypsum, and calcium salts of organic acids such as calcium formate. Of these, calcium hydroxide is preferred because of its high reactivity with the main agent.

When the calcium compound is hardly soluble or insoluble alone, the calcium compound is preferably pulverized to an average particle size of 1.0 μm or less because of excellent permeability to mortar and concrete and adhesive strength. It is more preferable to grind to 1.0 μm. Alternatively, when the calcium compound is calcium hydroxide, the soluble calcium salt such as calcium chloride and the soluble alkali salt such as sodium hydroxide and potassium hydroxide are dissolved and mixed, respectively. Calcium hydroxide can be produced.

In the present invention, the fine particle silica and the calcium compound are further added with a dispersant as necessary and dispersed in water to produce a main agent and a curing agent.

The concentration of the fine particle silica in the main agent of the present invention is preferably 80% or less, more preferably 30 to 70%. If the concentration of fine particle silica exceeds 80%, workability may be poor. In the present invention, it is also possible to produce a high-concentration fine particle silica slurry in advance and dilute it with water during construction.

The amount of calcium compound used in the curing agent of the present invention is preferably from 20 to 200 parts, more preferably from 50 to 100 parts, based on 100 parts of fine particle silica. When the amount of the calcium compound is less than 20 parts or more than 200 parts, the reactivity with the main agent may be small. In the present invention, it is also possible to produce a calcium compound slurry having a high concentration in advance and dilute it with water at the time of construction.

The concentration of the calcium compound in the curing agent of the present invention is preferably 60% or less, more preferably 10 to 50%. If the concentration of the calcium compound exceeds 60%, workability may be poor. In the present invention, it is also possible to produce a calcium compound slurry having a high concentration in advance and dilute it with water at the time of construction.

In the present invention, a dispersant is used in combination with the curing agent. In the present invention, a dispersant is used in combination with the main agent depending on the use. When a dispersant is added only to the curing agent, the composition reacts at the moment of mixing with the liquid of the main agent, and the viscosity can be rapidly increased. Moreover, when a dispersing agent is used in combination with the main agent and the curing agent, an abrupt increase in viscosity can be prevented. Therefore, it is possible to secure an arbitrary working time by changing the amount of the main agent and the dispersant for the curing agent.

The dispersant used in the present invention is preferably a so-called high-performance dispersant such as a sulfonated melamine-based, naphthalenesulfonic acid-based, polycarboxylic acid-based, or polyether-based one, or a mixture of two or more of these. Used as.

The amount of the dispersant used as the main agent is preferably 0.1 to 30 parts (in terms of solid content, the same applies hereinafter) or less, more preferably 1 to 10 parts, relative to 100 parts of the fine particle silica of the main agent. If it is less than 0.1 part, it may solidify by reaction at the moment when it is mixed with the curing agent liquid, and the working time may not be secured. If it exceeds 30 parts, the curing time may become long.

1-30 parts are preferable with respect to 100 parts of calcium compounds, and, as for the usage-amount of the dispersing agent of a hardening | curing agent, 5-20 parts are more preferable. If the amount is less than 1 part, the reaction solidifies at the moment of mixing with the main agent, and the working time may not be ensured. If the amount exceeds 30 parts, the curing time may become long. In order to increase the adhesive strength, the fine particle silica and the calcium compound are preferably pulverized or dispersed in advance by various wet pulverizers.

The reason why good permeability is obtained when the dispersant is used for both the main agent and the curing agent is unknown, but even if the dispersant reacts on the surface of the fine particle silica or calcium compound and the fine particle silica and the calcium compound come into contact with each other, This is thought to be due to the delay in curing so as not to cause a sum reaction.

The average particle size referred to here is an ultrasonic wave obtained by using a laser diffraction particle size distribution analyzer (for example, “LA-920 type” manufactured by HORIBA, Ltd.) as a normal pretreatment for a suspension that has been wet-dispersed. It is a value measured in a water medium without performing a dispersion treatment. In JIS R 1629, since the particle size is measured after applying an ultrasonic wave to disperse the aggregate, the permeability may be poor even if it is actually injected into the gap. Therefore, by measuring without performing ultrasonic dispersion processing, the result is close to the actual permeability to the gap. When the average particle size of the fine particle silica and the calcium compound measured without performing the ultrasonic dispersion treatment is 1.0 μm or less, the permeability is improved. Therefore, the adhesive strength can be increased.

The suspension subjected to wet dispersion treatment refers to, for example, a main agent obtained by wet dispersion treatment of fine particle silica and a curing agent obtained by wet dispersion treatment of calcium hydroxide.
Since the particle size of calcium hydroxide is affected by the pH value, the measurement is performed after the pH value of water is set to 12 or more with NaOH.

The wet pulverizer used in the present invention may be a method using any one of a high-speed stirrer, a medium stirring mill, a pulverizer using high-pressure water, etc., and is selected alone or in combination. Among the pulverizers, a pulverizer using high-pressure water is preferable in terms of pulverization efficiency.

The high-speed stirrer preferably has a structure that not only simply rotates the stirrer at a high speed but also a so-called turbulent state and a shear force acts on the particles. For example, trade names “Sharp Flow Mill” manufactured by Taiheiyo Kiko Co., Ltd., trade names “Homomixer”, “Homomic Line Mill”, “Homo Dispers” manufactured by Tokushu Kika Kogyo Co., Ltd., and the like. Further, the medium agitating mill is preferably pulverized using beads of 1 mm or less. As the media agitation mill for grinding using beads of 1 mm or less, the product name “Star Mill” manufactured by Ashizawa Finetech Co., Ltd., the product name “SC-Mill” manufactured by Mitsui Mining Co., Ltd., and the product name “Dual Apex Mill” manufactured by Kotobuki Industries Co., Ltd. Etc. A pulverizer using high-pressure water applies a high pressure of 50 to 400 MPa to the slurry, divides the slurry into two flow paths, and pulverizes them by colliding against each other at a portion where they rejoin. Examples of such a pulverizer include “Starburst” and “Ultimizer” manufactured by Sugino Machine, “Nanomizer” manufactured by Nanomizer, and “Microfluidizer” manufactured by Microfluidics. Among these, “starburst” is preferable in terms of permeability to the gap.

Furthermore, it is preferable to contain a polymer dispersion from the viewpoint of maintaining appropriate plasticity. The polymer dispersion is selected from the group consisting of a styrene acrylic copolymer, an acrylic copolymer, an epoxy resin, an ethylene-vinyl alcohol copolymer, an ethylene-acrylic acid copolymer, and an ethylene-acrylic acid ester copolymer. It is preferable to contain 1 type or 2 types or more. Among these, an ethylene-vinyl alcohol copolymer is more preferable because it is effective in a small amount.

The amount of polymer dispersion used (in terms of solid content, the same applies hereinafter) is preferably 10 parts or less, more preferably 0.1 to 5 parts, and most preferably 0.5 to 3 parts with respect to 100 parts of fine particle silica as the main component. . When the amount used exceeds 10 parts, the viscosity becomes high and workability may be poor.

The adhesive of the present invention can contain a curing time adjusting agent in order to adjust the curing time. The curing time adjusting agent is not particularly limited, but examples thereof include known inorganic salts such as alkali metal sulfates, alkali metal carbonates, alkali metal bicarbonates, alkali metal phosphates, gluconic acid, tartaric acid, citric acid. One or two or more kinds selected from organic acids such as acid, malic acid and lactic acid, salts of the organic acids and the like can be mentioned. Among these, from the viewpoint of workability, alkali metal sulfates and / or alkali metal carbonates are preferable, and alkali metal sulfates are more preferable. Examples of the alkali metal sulfate include sodium sulfate and potassium sulfate.

The amount of the curing time adjuster used is preferably 30 parts or less, more preferably 0.1 to 30 parts, and most preferably 1 to 10 parts with respect to 100 parts of the calcium compound. If the curing time adjusting agent exceeds 30 parts, workability may be poor.

The adhesive of the present invention includes commonly used additives such as antifoaming agents, leveling agents, ultraviolet absorbers, viscosity modifiers, antioxidants, antifungal agents, etc., depending on the functions required for adhesion. It can be added as appropriate. Also, as fillers, quartz sand, cinnabar sand, aragonite powder, ceramic powder, lime sand, aluminum hydroxide, talc, clay, mica, volcanic ash, shirasu, concrete powder, glass flake, fly ash, carbon black, alumina, glass micro Balloons, silica balloons and the like can be added.

The mixing ratio of the main agent and the curing agent is preferably 5: 1 to 1: 5, and more preferably 2: 1 to 1: 2. The mixing method of the main agent and the curing agent is, for example, a method in which the main agent and the curing agent are put in a container and mixed with a stirring bar or a mixer, or the main agent and the curing agent are separately stored in each container, and two agents are used at the time of use. Although the method of mixing etc. is mentioned, the latter method is preferable from the point of workability | operativity. The container for storing the main agent or the curing agent may be any container that does not leak or break during transportation or storage, and examples of the material include glass, polyethylene, polyethylene terephthalate, polypropylene, polyamide, polycarbonate, and metal. Examples of the method of mixing the two agents include a method of mixing with an injection cartridge or a static mixer.

The adhesive of the present invention is a room temperature curing type, and is naturally cured by a hydration reaction at room temperature, but can be cured by heating at 100 ° C. or lower.

Although the application location of the adhesive of the present invention is not particularly limited, it can be used for fixing anchor bolts and the like, or for bonding concrete, mortar, slate, glass, enamel, metal, and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. Examples were performed at 20 ° C. unless otherwise specified.

Example 1

(Adhesive adjustment)
Mix 100 parts of fine particle silica with different particle sizes and types, 5 parts of dispersant (in terms of solid content), and 100 parts of water, wet-disperse with the product name “Starburst” manufactured by Sugino Machine Co., and add polymer dispersion. A main agent (agent A) was prepared. On the other hand, 100 parts of commercially available calcium hydroxide (average particle size 9.5 μm), 10 parts of a dispersant, and 150 parts of water are mixed, and similarly, wet dispersion is performed by changing the pulverization time using the product name “Starburst” manufactured by Sugino Machine. Then, a curing time adjusting agent was added to prepare a curing agent (B agent).
The pressure applied to the “Starburst” slurry was 245 MPa.
The main agent and the curing agent were mixed so that the amount of the calcium compound used was 75 parts with respect to 100 parts of the fine particle silica, and an adhesive was prepared with the formulation shown in Table 1.
The fine particle silica was produced by a method in which a metal silicon powder dispersed in water and having a metal silicon powder concentration of 5 to 70% is injected into a flame at a projection speed of at least 10 m / second, burned and oxidized.

(Materials used)
Fine particle silica S1: slurry having an average particle diameter of 0.05 μm after wet dispersion treatment, a sphericity of 97%, an amorphization rate of 100%, and a concentration of metal silicon powder in which metal silicon powder is dispersed in water is 30% Spherical silica fine particles produced by injecting, burning, oxidizing, and collecting at a protruding speed of 150 m / second or more onto silica: average particle size 0.1 μm, sphericity 97%, amorphous ratio 100%, metallic silicon Spherical silica fine particle silica S3 produced by a method in which a slurry in which a metal silicon powder concentration in which powder is dispersed in water is 30% is injected into a flame at a protruding speed of 120 m / sec or more, burned, oxidized and collected: wet A slurry having an average particle diameter of 0.6 μm after dispersion treatment, a sphericity of 97%, an amorphization rate of 100%, a metal silicon powder dispersed in water and a metal silicon powder concentration of 30% in a flame. Fine particle spherical silica fine particle silica S4 produced by a method of jetting, burning, oxidizing and collecting at a protrusion speed of 00 m / second or more: average particle size 1.0 μm after wet dispersion treatment, sphericity 96%, amorphous ratio Fine particle spheres produced by a method of injecting, burning, oxidizing, and collecting 100% slurry of metal silicon powder dispersed in water with a metal silicon powder concentration of 30% into a flame at a projection speed of 50 m / sec or more. Silica fine particle silica S5: flame with a mean particle size of 3.5 μm after wet dispersion treatment, a sphericity of 95%, an amorphization rate of 100%, and a metal silicon powder dispersed in water with a metal silicon powder concentration of 30% Fine particle spherical silica ferrosilicon by-product silica fume S6 produced by injecting, burning, oxidizing, and collecting at a protruding speed of 2 m / second or more: average particle diameter of 15.5 after wet dispersion treatment m (reference value: If sonicated 3.7 .mu.m), sphericity 86%
Silica sol S7: Average particle size after wet dispersion treatment of 10.1 μm, sphericity of 75% (reference value: average particle size of 9.8 μm when subjected to ultrasonic dispersion treatment)
Calcium compound C1: Average particle size after wet dispersion treatment 0.05 μm, Calcium hydroxide calcium compound C2: Average particle size after wet dispersion treatment 0.1 μm, Calcium hydroxide calcium compound C3: Average particle size after wet dispersion treatment 0.5 μm, calcium hydroxide calcium compound C4: average particle size 1.0 μm after wet dispersion treatment, calcium hydroxide calcium compound C5: average particle size 3.5 μm after wet dispersion treatment (reference value: in the case of ultrasonic treatment) Average particle size is 3.3 μm), calcium hydroxide dispersant: commercial product of naphthalenesulfonic acid, liquid, solid concentration 40%
Polymer dispersion: Polymer dispersion made of ethylene-vinyl alcohol copolymer, Commercial product curing time regulator: Sodium sulfate, Commercial product water: Tap water

(Test method)
Average particle diameter: A laser diffraction particle size distribution meter (“LA-920 type” manufactured by Horiba, Ltd.) was used.
Agent A and Agent B were measured in an aqueous medium without performing ultrasonic dispersion treatment.
Adhesive strength: The main agent and curing agent are each put in a polyethylene container, a mixing nozzle is attached to the cartridge, the piston of the cartridge is pressurized to discharge the main agent and the curing agent, and the two components are mixed and discharged in the mixing nozzle. In accordance with JIS A6909, the adhesion strength with mortar was measured.

The test results are shown in Table 1.

It can be seen that high adhesion strength is exhibited by using specific fine particle silica and specific calcium compound. Further, it can be seen that the performance is further improved by the combined use of a polymer dispersion and a curing time adjusting agent.

The adhesive of the present invention can be used for fixing anchor bolts and the like, and for bonding concrete, mortar, slate, glass, enamel, metal, and the like.

The present invention is an adhesive and a bonding method that are excellent in workability and curability, and further excellent in adhesive strength and durability since the average particle diameter of fine particle silica or calcium compound is as fine as 1.0 μm or less.

Claims (8)

An adhesive comprising fine particle silica having an average particle size of 1.0 μm or less as a main agent and water, a calcium compound having an average particle size of 1.0 μm or less, a dispersant, and water as a curing agent; and Further, an adhesive containing a polymer dispersion. An adhesive comprising fine particle silica having an average particle size of 1.0 μm or less as a main agent, a dispersant and water, and a calcium compound having an average particle size of 1.0 μm or less, a dispersant and water as a curing agent. And an adhesive further comprising a polymer dispersion. The adhesive according to claim 1, wherein the calcium compound is calcium hydroxide. The fine particle silica and / or calcium compound is produced by using one or more selected from the group consisting of a high-speed stirrer, a medium stirring mill, and a pulverizer using high-pressure water. The adhesive agent as described in any one of them. The adhesive according to any one of claims 1 to 4 , wherein the dispersant is a high-performance dispersant. The adhesive according to any one of claims 1 to 5 , wherein the main agent contains a polymer dispersion. Furthermore, the adhesive agent as described in any one of Claims 1-6 formed by containing a hardening time regulator. The adhesive construction method which mixes two agents at the time of using separately the main ingredient and hardening | curing agent of the adhesive agent as described in any one of Claims 1-7 in each container.