KR100778233B1 - Resin adhesion composition having hardening property in water - Google Patents

Abstract

The present invention relates to an underwater quickening resin fixing agent having a high curing speed in water. The present invention provides a polyurethane-acrylic resin obtained by adding an acrylic block copolymer represented by the following Scheme 1 to a polyurethane prepolymer; At least one filler selected from inorganic powders; It provides a resin fixing agent comprising; a curing agent for curing the polyurethane-acrylic resin.

 Scheme 1

(Wherein R ₁ is ethyl or butyl, R ₂ is methyl and x, y, z are one or more positive numbers.)

The resin fixing agent according to the present invention is rapidly cured even in water (including seawater), and has an effect of exerting excellent drawing force, adhesive force and fixing strength.

Construction, Civil Engineering, Resin, Binder, Urethane, Acrylic

Description

Underwater quenching resin fixing agent {RESIN ADHESION COMPOSITION HAVING HARDENING PROPERTY IN WATER}

The present invention relates to a resin fixing agent for construction and civil engineering, and more specifically, acryl and urethane as the main material, the urethane is synthesized in a water dispersion type, and by adding and polymerizing acrylic resin therein, water (including seawater) It also relates to a fastening resin fixing agent for underwater having excellent properties and fast curing speed.

In general, cement mortar or resin mortar is widely used in the construction and civil engineering fields as a fixing agent for cracking structures, connecting structures, and fixing reinforcing bars or anchor bolts in concrete, rock, especially tunnel ceiling rocks.

It is often necessary to fix reinforcing bars or anchor bolts on concrete floors in road construction, railway construction, tunnel construction, building construction, as well as in construction and civil construction sites where large signs are installed. At this time, a hole is drilled in the concrete floor, and then a reinforcing bar or anchor bolt is fixed by pouring and injecting a fixing agent such as cement mortar or resin mortar into the punched hole.

The cement mortar or resin mortar used as a fixing agent is required to have high adhesion and strength, and preferably a fast curing speed.

However, the cement mortar is inconvenient to make the mortar in the field, and above all, a considerable time is required due to curing curing, there is a problem that the pull-out force, adhesive strength and strength fall and cracks occur. Accordingly, in recent years, resin mortar compositions that excel in drawing force, adhesion strength, and strength after curing and are cured by properties have been frequently used.

Generally, the resin mortar composition includes a resin mortar made of a resin such as an epoxy resin and a filler such as calcium carbonate, silica sand, and silica; It consists of a curing agent for curing this, the compound of the amine is used as the curing agent.

In particular, NATM-Resin (New Austria Tunnel Method) is a resin fixing agent that is widely used in tunnel support-based processes, which is made of urethane, and is widely used for rock-bolt and front-side adhesion of rock-bolt. The urethane-type NATM-Resin currently produced and distributed is manufactured for each use (quicking, tipping, filling) by controlling foaming and drawing by chemical reaction of methylene diisocyanate (MDI) and polyol. In use, it has a significant pulling force (10 TON / EA per 500 g) and adhesion (six times the cement mortar). In addition, urethane type NATM-Resin is used for filling and repairing numerous cracks in concrete as well as for waterproofing.

As described above, the urethane-type resin fixing agent has many advantages over cement mortar. However, the conventional urethane type resin fixing agent has a weak problem in moisture.

In general, in the tunnel or underground, water is sprayed for the purpose of removing dust from the surrounding moisture or perforation, and a lot of moisture is present. A conventional urethane-type resin fixing agent has a problem in that physical properties are significantly lowered in the above water conditions. That is, under water (including seawater) conditions, there is a problem in that the magnetic capacity does not exhibit the pulling capacity, adhesion, weather resistance and strength.

The present invention has been invented to solve the conventional problems as described above. In constructing a resin fixing agent containing urethane as a main material, the urethane is synthesized in a water dispersion type, and by adding and polymerizing an acrylic resin therein, It is an object of the present invention to provide a fastening resin fixing agent for underwater having excellent physical properties and fast curing speed.

In order to achieve the above object, the present invention comprises a polyurethane-acrylic resin polymerized by adding an acrylic block copolymer synthesized from a three-component acrylic monomer to a water-dispersed polyurethane prepolymer in a building and civil engineering resin fixing agent; At least one filler selected from inorganic powders; It provides a resin fixing agent comprising; a curing agent for curing the polyurethane-acrylic resin.

The water-dispersed polyurethane prepolymer is a mixture of a polyol and a dimethylol propionic acid (DMPA; Dimethylol Propionic Acid) dissolved in a solvent, followed by mixing and isocyanate compound in the presence of a reaction catalyst to synthesize a prepolymer, Triethylamine (TEA) was added as a neutralizing agent to neutralize the COOH group of dimethylol propionic acid (DMPA), and then one or more monomers selected from epoxy and acryl were added as diluents to obtain a neutralized and diluted prepolymer. After that, the neutralized and diluted prepolymer is preferably obtained by adding water into the stirred water at high speed to perform a water dispersion process.

The resin fixing agent according to the present invention reacts instantaneously in water by mixing with a curing agent, but hardens by exothermic reaction, and has excellent drawing force, adhesive strength, and adhesive strength.

Hereinafter, the present invention will be described in more detail.

The resin fixing agent according to the present invention comprises a polyurethane-acrylic resin polymerized by adding an acrylic block copolymer to a water-dispersed polyurethane prepolymer; At least one filler selected from inorganic powders; It comprises; a curing agent for curing the polyurethane-acrylic resin. At this time, the polyurethane-acrylic resin and the filler are mixed and then packaged in one container, the curing agent is packaged in a separate container and spread to construction, civil works.

The polyurethane-acrylic resin is a resin in which acrylic block copolymer is polymerized to a polyurethane prepolymer emulsified in water, which is synthesized according to the present invention as follows.

First, a polyol is put in a reactor, and then heated to 80 ° C. to completely dissolve the polyol. Dimethylol propionic acid (DMPA) was dissolved in solvent N-methyl-2-pyrrolidone (NMP; N-methyl-2-pyrrolidone), put it in a reactor, and stirred at the same temperature for 30 minutes. Mix well. Next, a final NCO group intended to be obtained by adding dibutyltin dilaurate (DBTL; dibutyltin dilaurate) and an isocyanate compound as a tin catalyst (Sn) -based catalyst in a reactor and reacting at 80 ° C. for 150 minutes. Synthesis of a polyurethane (PU) prepolymer having a terminal group. As such, after the synthesis of the PU prepolymer having an NCO end group is completed, the temperature is lowered to 60 ° C. and triethylamine (TEA) is added as a neutralizing agent to form a carboxyl group (COOH group) group of the dimethylol propionic acid (DMPA). Neutralize After 20 minutes of neutralization, one or more monomers selected from epoxy and acryl are added as diluents and completely diluted for 10 minutes. At this time, the diluent lowers the viscosity of the PU prepolymer to improve the reaction temperature control and flow properties during synthesis, and enables the formation of an emulsion having excellent colloidal stability and water particle size of several tens of nanometers when dispersed.

Apart from the above, while adding water to another reactor and stirring at a high speed, the synthesis is completed, and the neutralized diluted PU prepolymer is gradually added to perform a water dispersion process to prepare a dispersed PU prepolymer. At this time, the reaction of the NCO group and water that did not react with the water dispersing process at the same time is avoided, and the chain extension reaction is performed by introducing the acrylic block copolymer to have strength reinforcement and excellent adhesion. The chain extension reaction was diluted with water at 25 ° C. in an acrylic block copolymer, and stirred for about 2 hours until the chain extension reaction was completely completed.

In the above reaction process, the polyol is preferably used after completely removing moisture of a low molecular weight polytetramethylene ether glycol (PTMG; poly-tetramethylene ether glycol) by using a vacuum oven. Preference is given to using isophorone diisocyanate (IPDI; Isophorone diisocyanate) as the isocyanate.

In addition, the acrylic block copolymer uses a reactant (the resultant) synthesized from Scheme 1 below according to the present invention. Specifically, as shown in Scheme 1 below, the acrylic block copolymer is used synthesized from a three-component acrylic monomer consisting of acrylate, methacrylate and acrylic acid, which has a rapid curing property and excellent adhesion strength after curing To have.

(Wherein R ₁ is ethyl or butyl, R ₂ is methyl and x, y, z are one or more positive numbers.)

In addition, in the reaction molar ratio of Scheme 1, y and z are small with respect to x, and the larger the amount of y, the better the fixing strength. That is, in Scheme 1, x> y> z is preferable.

When the above reaction is completed, that is, when the water-dispersed PU prepolymer and the acrylic block copolymer are copolymerized, a polyurethane-acrylic resin is obtained as the water-soluble mixed water dispersion emulsion of the network structure.

And a filler is mixed in the polyurethane-acrylic resin as described above.

The filler is selected from fine powder inorganic materials, for example silicon oxide (SiO 2), aluminum oxide (Al 2 O 3), iron oxide (FeO, Fe 2 O 3), calcium oxide (CaO), magnesium carbonate (MgCO 3), calcium carbonate (CaCO 3), One or two or more selected from the group consisting of fume silica, magnesium oxide (MgO), fly ash (flyed ash), and ceramics (eg, rock, jade, etc.) may be used.

The curing agent may be a peroxide compound, specifically, dibenzoyl peroxide or methylethyl peroxide.

The resin fixing agent according to the present invention has excellent dispensing force, adhesive strength and adhesive strength while being rapidly hardened by mixing with a curing agent by being spread in construction and civil construction sites. Specifically, the polyurethane-acrylic resin is rapidly cured by causing an exothermic reaction by mixing a curing agent. In addition, it exhibits adhesion strength several times or more compared with the conventional cement mortar and several times or more compared with the conventional urethane resin adhesive, and has excellent quenching characteristics in water. In addition, according to the present invention, dimethylol propionic acid (DMPA) used in the synthesis of the water-dispersed PU prepolymer develops the network structure of the PU prepolymer to improve adhesion and at the same time have compatibility with water at high temperature Prevents the resin from gelling.

The polyurethane-acrylic resin is not particularly limited, but is copolymerized by mixing 30 to 80 parts by weight of the water-dispersed PU prepolymer with respect to 100 parts by weight of the acrylic block copolymer, but the water-dispersed PU prepolymer is based on 100 parts by weight of water. It is preferred that the emulsified PU prepoly 20 to 150 parts by weight.

In addition, the filler is preferably 50 to 200 parts by weight based on 100 parts by weight of the acrylic block copolymer. In addition, in mixing the curing agent at the construction site, it is preferable to mix the curing agent to 0.5 to 20 parts by weight based on 100 parts by weight of polyurethane-acrylic resin.

The resin fixing agent according to the present invention is usefully used as a fixing agent, a repairing agent to fill a crack, and a waterproofing agent in the same manner as usual in construction and civil engineering. More specifically, the resin fixing agent according to the present invention, construction, civil engineering, specifically NATM tunnel construction (road, railroad, subway, underground line), rock reinforcement and retaining wall reinforcement work, joint reinforcement construction of the joint, steel tower foundation For cracking structures, connecting structures, and for fixing reinforcing bars or anchor bolts in concrete, rock, especially in the rock masses of tunnels in construction, mountain bridge construction, waterway construction of dams, underground power plant arches and sidewall construction. Used as a fixing agent. And it is used for the use of the waterproofing agent apply | coated to the surface of concrete ground. In particular, it is useful in construction sites where moisture exists, such as tunnels, underground, and shorelines.

Hereinafter, specific test examples of the present invention will be described. The following examples are provided only to explain the present invention in more detail, whereby the technical scope of the present invention is not limited.

EXAMPLE

All reactions were conducted after purging with nitrogen (N ₂ ) gas and excluding other side reactions. Old reactors were used.

First, a polyol, that is, PTMG (Mw = 1000, OH number = 112) was added to a four-necked reactor, and the temperature was heated to 80 ° C. to completely dissolve the polyol. At this time, before the PTMG-1000 was introduced into the reactor, the vacuum oven was used for 6 hours at 120 ° C. to completely remove water. Dimethylol propionic acid (DMPA) was used to introduce a water-soluble group, but it was dried at 60 ° C. to completely remove water from DMPA, and then dissolved in NMP (using Aldrich's reagent grade). And the dissolved DMPA was put into the reactor and stirred for 30 minutes at the same temperature and mixed well.

Next, a PU prepolymer having a terminal group of the final NCO group to be obtained by adding a reaction catalyst tin DBDB and IPDI (Isophorone diisocyanate: Bayer Co.) in a reactor for 150 minutes at 80 ° C. Was synthesized. The content of NCO groups in the synthesized PU prepolymer was measured using the di-n-butylamine back-titration (DBBT) method, and the theoretical amount of residual NCO groups was calculated based on the reaction with all OH groups. As described above, after the synthesis of the prepolymer having NCO end groups was completed, the temperature was lowered to 60 ° C. and TEA (produced by Junsei Chemical Co., Ltd.) was added as a neutralizing agent to neutralize the COOH group of DMPA. After 20 minutes of neutralization, acrylic monomer was added as a diluent and completely diluted for 10 minutes.

Water was added to another reactor and while stirring at a high speed, the synthesized PU prepolymer was slowly added to perform a water dispersion process. In this case, double-distilled deionized water (DDI water) was used as the dispersion water. At the same time as the water dispersion process was completed, an acryl block copolymer obtained by reacting ethyl acrylate, methyl methacrylate and acrylic acid in a molar ratio of 4: 3: 1 was added to the PU prepolymer to carry out a chain extension reaction. .

At this time, the chain extension reaction was prepared by diluting the acrylic block copolymer in water at 25 ° C. and further stirring for about 2 hours until the chain extension reaction was completed, thereby obtaining a water-dispersed polyurethane-acrylic emulsion. Next, silicon oxide (SiO 2), magnesium oxide (MgO), and silica were mixed with the copolymerized water-dispersed polyurethane-acrylic emulsion, followed by mixing with dibenzoyl peroxide. Then, the mixture was directly injected into a concrete base material having a hole of 20 mm in diameter and 50 mm in depth, and then a long rebar having a diameter of 10 mm and a length of 100 cm was erected. At this time, the hole of the base material was pre-injected with water, and the mixture was injected in a state where water was completely filled. After about 2 hours, the specimen was completely stuck.

With respect to the specimen, the pullout force, reinforcing bar adhesion force and fixing strength were measured in the same manner as in the following [Table 1], and the results are shown in [Table 1]. At this time, the pulling force was measured using a hydraulic drawing machine, the reinforcement adhesive strength and the bonding strength were measured using a universal testing machine UTM (Unversal test machine, Instron, USA).

[Comparative Example]

At present, a commercially available urethane-type resin fixing agent (Domestic, manufactured by S Company) was applied to this comparative example, and was injected into the hole of the concrete base material in the same manner as the above example to measure physical properties. At this time, the base material was injected with a product after spraying water, the results are as shown in Table 1 below.

Evaluation item Example Comparative example Assessment Methods Drawing force (ton) 23 11 Hydraulic drawing machine Rebar Adhesion (kg / cm3) 420 170 UTM Fixation strength (ton) 19 6 UTM Exam conditions After 2 hours at room temperature After 3 days at room temperature -

As shown in [Table 1], it can be seen that the embodiment of the present invention is superior to the pulling force, adhesive strength and adhesion strength than the conventional comparative example. In addition, in the case of the embodiment of the present invention, it was found that the reinforcing bar is completely fixed in about 2 hours after being injected into the hole of the base material, and the product of the comparative example was found to be fixed only after 3 days.

As described above, the resin fixing agent according to the present invention is rapidly cured by exothermic reaction in water, and has an effect of exerting excellent drawing force, adhesive force and fixing strength.

Claims (3)

In the resin fixing agent for construction, the civil engineering, Polyurethane-acrylic resin which superposed | polymerized by adding the acryl block copolymer obtained from following Reaction Formula 1 to the water-dispersed polyurethane prepolymer; A filler selected from inorganic powders; And a curing agent for curing the polyurethane-acrylic resin.  Scheme 1

(Wherein R ₁ is ethyl or butyl, R ₂ is methyl and x, y, z are one or more positive numbers.) The method of claim 1, The water-dispersed polyurethane prepolymer is a mixture of a polyol and a dimethylol propionic acid (DMPA) dissolved in a solvent, followed by mixing and stirring, and then mixing the isocyanate compound in the presence of a reaction catalyst to synthesize a prepolymer, a neutralizing agent Triethylamine (TEA) was used to neutralize the COOH group of dimethylol propionic acid (DMPA), and then one or more monomers selected from epoxy and acryl were added thereto to obtain a neutralized, diluted prepolymer. And a neutralizing and diluting prepolymer in a water being stirred at high speed to obtain a resin binder, which is obtained by performing a water dispersion process. The method according to claim 1 or 2, X, y, z of the reaction scheme 1 is x> y> z.