KR102370498B1 - Inorganic low viscosity aqueous adhesive coating composition and its use - Google Patents

Abstract

An embodiment of the present invention provides a composition for bonding and coating materials for inorganic water-based dissimilar materials.

Description

Inorganic low viscosity aqueous adhesive coating composition and its use

The present invention relates to a silicon oxide-based, low-viscosity, quick-drying, water-based adhesive coating agent. The same and different materials, such as styrofoam, polyurethane foam, polyurea foam, wood, etc., are cured at low temperature (100 ^o C or less) to adhere to iron plate, concrete, glass, etc. And it relates to a quick-drying water-based flame retardant / waterproof functional adhesive coating agent for coating.

In general, silicate materials such as sodium silicate and potassium silicate are well known as representative inorganic binders, and unlike organic adhesives obtained from petrochemicals, they have high thermal stability and are environmentally friendly, so they are widely used as heat-resistant, chemical-resistant, and waterproof coatings. In particular, as liquid sodium silicate decreases the amount of moisture, the viscosity of the solution increases rapidly and has adhesive strength. However, the applied and dried silicate is easily re-dissolved in moisture or water in the air, so unless it undergoes an insolubilization process, its use is inevitably limited. The easiest way to insolubilize liquid sodium silicate is to heat it slowly at a high temperature of 500°C or higher to remove the crystal water present therein, but the use is also limited due to the stability of the adherend and the limitation of the working environment, and the cost Also, the reality is that it takes a lot. Therefore, attempts are being made to solve these problems by adding an appropriate additive to liquid sodium silicate to proceed with the insolubilization reaction.

In the case of insolubilization of liquid sodium silicate, it is necessary to carefully control not only the type of additive but also the amount used. For example, in order to insolubilize silicate, there are many known methods of treating directly with an acid or a polyvalent metal ion (eg Zn+2, Cu+2, etc.). In this case, the reaction proceeds too quickly and the monolayer ) is insolubilized or the surface of the adhesive surface is cracked due to the rapid volume reduction of silicate due to too fast gelation. In order to make an adhesive that does not generate cracks or micropores at room temperature and does not dissolve well in water, it is important to find a raw material that reacts slowly to insolubilize it. Establishment of the process is also an important factor. Meanwhile, there is an example in which an insoluble binder has been developed using a conventional liquid sodium silicate, and examples thereof include Korean Patent Registration No. 10-0556902, Korean Patent Publication No. 10-2005-0056186, and Korean Patent Publication No. 10-2005-0056185. In these prior art, silicate is made by slowly reacting high concentrations of sulfuric acid, hydrochloric acid, phosphoric acid, and acetic acid with liquid sodium silicate as a binder and grouting agent, and 0.05-1.0 wt% of trace amounts of calcium carbonate (CaCO3), calcium nitrate (Ca(NO3)2 ), magnesium chloride (MgCl2), magnesium sulfate (MgSO4), and calcium hydroxide (Ca(OH)2) are added to provide a method for preparing an insoluble binder.

However, in the conventional manufacturing method, since a high concentration of acid is used, even when a small amount of high concentration of acid is added to the liquid sodium silicate in a rotating reactor, the liquid sodium silicate in contact with the acid is rapidly gelated, making it very difficult to stir, and It was confirmed that the gelled silicate and sodium salt were not easily dissolved even after adding and stirring for 3 hours or more, so that they remained in the form of fine lumps. These fine lumps can be a factor to lower the adhesive strength, and it was confirmed that the process control to control the constant viscosity as an adhesive is very difficult. Therefore, it is a reality that there are many difficulties in the preparation of so-called modified silicates that cause a complete insolubilization reaction with acids.

In addition, there is a characteristic of having water resistance after heating and drying at 100° C. or more, and there is a problem that it is difficult to expect the effect of water resistance expression at room temperature, so there is a limitation in applying it to adhesives for building materials that are commonly used. In addition, due to the decrease in the overall adhesive strength, it was possible to serve as a binder, but it was insufficient to play a role as an adhesive.

The process of adding 0.05 to 1.0% by weight of alkaline earth metal to the primary result prepared in the above process adds a delicate mixing process of uniformly mixing by adding a small amount of additive, resulting in heterogeneity in the adhesive production process of the entire manufacturing process There is a possibility, and it is expected that the whitening phenomenon may occur by reacting with moisture in the air over time. The most important point is that the insolubility test and mechanical strength test do not meet the intended use of the adhesive at room temperature in that a binder, perlite, zeolite, carbon, etc. are mixed and tested by heat treatment at a temperature of 100 ° C or higher. .

In addition, Korean Patent Laid-Open Patent Nos. 10-2006-0043360 and 10-2006-0092783 disclose that water resistance, adhesion, sound absorption, heat insulation, shock absorption, ultra-lightness, low cost, complete non-combustibility, and complete pollution-free properties are required. It relates to construction and industrial foam moldings used in various industrial fields, and describes the preparation of inorganic binders used in manufacturing foam moldings. In detail, in addition to hydrochloric acid, sulfuric acid and phosphoric acid, potassium chloride, quicklime in liquid sodium silicate as in Korean Patent Registration Nos. 10-0556902, Patent Publication No. 10-2005-0056186, and Patent Publication No. 10-2005-0056185 already mentioned above. Acidic substances such as , ammonium chloride, alcohol (potassium chloride, quicklime, and ammonium chloride are basic substances, so there was an error.) Aluminum chloride, sodium aluminate, arsenic chloride, sodium arsenite, arsenic chloride, chromium (III) chloride, sodium chromite , zinc hydroxide, arsenic hydroxide, tin hydroxide, chromium (III) hydroxide, zinc acid, arsenic acid, ortho-tartaric acid, chromic acid, etc. by administering an amphoteric oxide or amphoteric hydroxide to incompletely gel the sodium silicate, resulting in incomplete gelation of silicic acid Describes how to make sodium.

In this technology, if the amount of acid input is increased to promote incomplete gelation excessively, the adhesive strength may increase, and if the amount of acid input is decreased, the adhesive strength will decrease. However, a method for dealing with excessive viscosity increase that occurs when incomplete gelation is excessively promoted has not been described. Also, there is no mention of the degree of insolubility during curing at room temperature as in the above-mentioned Korean Patent No. 10-0556902, Patent Publication No. 10-2005-0056186, and Patent Publication No. 10-2005-0056185, It is difficult to understand the physical properties of the binder because there is no mention of the mechanical strength of the foamed molding made by rapid drying at a high temperature of 150°C to 600°C using the prepared binder.

The above patent data mainly relates to the function as a binder, not the function as an adhesive, and is characterized by having a relatively low adhesive strength.

Liquid sodium silicate is a transparent or translucent solution showing viscous alkalinity, and the molar ratio of liquid sodium silicate determined by the Korean Industrial Standards (KS M 1415) is 1: 2.064 to 4.300 with respect to Na2O and SiO2 It has various compositions. This liquid sodium silicate has its own adhesive strength, so it is used in various ways, such as cement additives to improve adhesives and soft ground. is becoming In particular, unlike organic adhesives in the manufacturing process, it does not cause pollution, and liquid sodium silicate is not released from most organic adhesives. However, when liquid sodium silicate is used as an adhesive, sodium ions contained in sodium silicate easily react with moisture or water in the air to form a salt such as sodium hydroxide. There is a problem in that the strength is lowered and thus it cannot function as an adhesive. Because of these problems, some are adding raw materials such as carbon, zeolite, loess, and illite to liquid sodium silicate, but it is expensive compared to conventional organic adhesives or has lower adhesive strength, and it is still difficult to prevent the elution of the underlying sodium salt It is a reality that this exists.

However, there was no existing low-viscosity, high-strength, low-temperature (100 ^o C or less) curing type flame retardant/waterproof/corrosion prevention adhesive coating based on water glass.

US Patent Publication No. 6,642,338 (2003.11.04) US Patent Publication No. 7,285,592 (2007.10.23) US Patent Publication No. 6,777,549 (2004.08.17) Japanese Patent Laid-Open Publication JP 16,358,303 (2004.12.24) Japanese Patent Laid-Open Publication JP 4,248,457 (2009.01.23) Japanese Patent Laid-Open Publication JP 1,664,424 (2017.06.30) Japanese Patent Laid-Open Publication JP 6,048,913 (2016.12.02) Japanese Patent Laid-Open Publication JP 14,012,811 (2002.01.15) Japanese Patent Laid-Open Publication JP 14,146,260 (2002.05.22)

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The present invention is to solve the problems of the prior art described above, and an object of the present invention is to have excellent adhesive performance, cure at a low temperature of 100 ^o C or less, high adhesive strength, and economically advantageous low-temperature curing quick-drying adhesion due to a simple manufacturing process It's about coatings.

As one embodiment, the present disclosure describes an inorganic aqueous adhesive coating composition including a silicate including at least one metal component, and an alkoxysilane (Alkoxysilane).

Preferably, the alkoxy silane may be tetramethoxysilane and/or tetraethoxysilane.

More preferably, the metal component is sodium (Na), potassium (K), lithium (Li), calcium (Ca), magnesium (Mg), aluminum (Al), zinc (Zn), iron (Fe), lead It may be at least one selected from the group consisting of (Pb), copper (Cu), and titanium (Ti).

More preferably, the inorganic aqueous adhesive coating composition is zinc (Zn), aluminum (Al), alumina (Al2O3), zinc oxide (ZnO), magnesium oxide (MgO), silicon oxide (SiO2), borax (B2O3), at least selected from the group consisting of boron (B), boric acid (B(OH)3), boron carbide (B4C), boron nitride (BN), aluminum nitride (AlN), silicon nitride (SiN), and titanium dioxide (TiO2) particles. It may further include one particle.

Even more preferably, the coating target of the inorganic water-based adhesive coating composition may include metals including iron, stainless steel, copper, aluminum and zinc, and alloys thereof, and concrete, glass, gypsum board, wood, and Styrofoam.

The inorganic aqueous adhesive coating composition as described above can be cured at low temperature by adhesive coating on metals including iron, stainless steel, copper, aluminum and zinc, and alloys thereof, and concrete, glass, gypsum board, wood, Styrofoam, etc. It can have excellent adhesion, anti-corrosion and waterproofing properties.

In addition, the coating composition containing boron element can be used for nuclear radiation shielding, such as neutron shielding.

(Figure 1) Adhesive strength measurement specimen
(Figure 2) Flame-retardant coating sandwich panel structure

Hereinafter, the present invention will be described with reference to the accompanying drawings 1 and 2 . However, the present invention may be embodied in several different forms, and thus is not limited to the embodiments described herein. And in order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification.

In addition, the water-based adhesive prepared by the present invention can be used for coating, and can be used for adhesion of dissimilar metal materials, anti-corrosion coating, and flame retardant, waterproof, and corrosion-resistant functions of concrete flooring.

Hereinafter, embodiments of the present invention will be described in detail.

Preparation Example 1

In a 1L round-bottom three-neck flask equipped with a reflux device, 35 wt% potassium silicate (SiO ₂ : K ₂ O molar ratio 3.2 to 4.8) aqueous solution and 40 wt% sodium silicate (SiO ₂ : Na ₂ O molar ratio 2.0 to 4.1) were each added to 10 g : 90g ~ 90g: Mix at a ratio of 10g, add about 350ml ~ 400ml of distilled water to make 9 20 wt% mixed silicate aqueous solutions, respectively, and then add 0.1g and 0.5 of alkoxysilane (tetramethoxysilane, tetraethoxysilane) g, 1g, and 3g were added and reacted at 50 ^o C to 60 ^o C for about 1 hour to prepare a total of 36 types of transparent low-viscosity water-based adhesive samples 1-1 to 9-4. At this time, when the alkoxysilane is added in excess of 3 g, the viscosity increases a lot, and when too little, the functionality decreases. The viscosity was measured using a Brockfield viscometer (DV2TLV) and the results are shown in Table 1.

division Viscosity (cps) Tetramethoxysilane (_1) Tetraethoxysilane (_2) 1-1 200 190 1-2 220 210 1-3 240 220 1-4 750 720 2-1 190 190 2-2 210 220 2-3 230 230 2-4 720 700 3-1 160 160 3-2 180 180 3-3 230 230 3-4 690 680 4-1 120 120 4-2 180 190 4-3 210 210 4-4 680 660 5-1 100 100 5-2 160 160 5-3 190 180 5-4 640 620 6-1 90 90 6-2 130 130 6-3 170 170 6-4 560 560 7-1 80 80 7-2 120 120 7-3 180 180 7-4 620 600 8-1 80 80 8-2 110 110 8-3 170 170 8-4 590 570 9-1 60 60 9-2 100 100 9-3 150 150 9-4 520 500

In Table 1, the mixed silicate aqueous solution prepared by mixing the potassium silicate aqueous solution and the sodium silicate aqueous solution in a ratio of 10 g: 90 g is denoted as Preparation Example 1-# (in this case, # means the serial number of each Preparation Example), and , potassium silicate aqueous solution and sodium silicate aqueous solution were mixed in a ratio of 20 g: 80 g, and a mixed silicate aqueous solution prepared by mixing was denoted as Preparation Example 2-#, and potassium silicate aqueous solution and sodium silicate aqueous solution were mixed in a ratio of 10 g: 90 g. The mixed silicate aqueous solution was denoted as Preparation Example 9-#.

In addition, in Table 1, 0.1 g, 0.5 g, 1 g, and 3 g of tetramethoxysilane added to Preparation Example 1-# are denoted as Preparation Examples 1-1_1 to 1-4_1, respectively, and Preparation Example 1- 0.1g, 0.5g, 1g, and 3g of tetraethoxysilane added to 1 will be referred to as Preparation Examples 1-1_2 to 1-4_2, respectively. That is, for example, the addition of 1 g of tetramethoxysilane to the mixed silicate aqueous solution in which 35 wt% potassium silicate aqueous solution and 40 wt% sodium silicate aqueous solution are mixed in a ratio of 70 g: 30 g means Preparation Example 7-3_1, , 35 wt% potassium silicate aqueous solution and 40 wt% sodium silicate aqueous solution 70g: 1g of tetraethoxysilane was further added to the mixed silicate aqueous solution mixed in a ratio of 30g means Preparation Example 7-3_2.

Example 1

Using 36 types of water-based adhesives prepared according to Preparation Example 1 and Comparative Example (Ogong Bond), iron plate-iron plate, iron plate-stainless (SUS304) plate, iron plate-concrete brick, iron plate-glass, iron plate-Styrofoam, concrete-Styrofoam, As shown in Fig. 1, each specimen was made of iron plate-wooden board, concrete brick-wooden board, and each material was adhered, and the adhesive strength was measured using UTM (multi-testing machine) for 1-1-1 to 9-4-8 total of 288 pieces. Eight comparative examples were measured and shown in Table 2. At this time, 0.1ml of each adhesive was applied evenly to an adhesive area of 1 cm ² , and then cured in an oven at 80 ^o C for 30 minutes to adhere.

division
(Tetramethoxysilane) Adhesive strength by bonding material (kgf/cm ² ) iron plate - iron plate Steel plate - Stainless (SUS304) plate iron plate - concrete iron plate - glass iron plate - styrofoam iron-wood board Concrete - Styrofoam Concrete - wood planks comparative example <3 <3 <1 <3 <0.05 <1 <0.05 <1 1-1-1 300 350 150 300 0.2 < 300 0.2 < 5 < 1-2-1 450 450 200 400 0.2 < 450 0.2 < 5 < 1-3-1 600 800 300 600 < 0.2 < 800 0.2 < 5 < 1-4-1 800 850 600 600 < 0.2 < 1200 0.2 < 5 < 2-1-1 300 350 150 300 0.2 < 300 0.2 < 5 < 2-2-1 450 450 200 400 0.2 < 450 0.2 < 5 < 2-3-1 600 800 300 600 < 0.2 < 800 0.2 < 5 < 2-4-1 850 850 600 600 < 0.2 < 1200 0.2 < 5 < 3-1-1 300 350 150 300 0.2 < 300 0.2 < 5 < 3-2-1 450 450 200 400 0.2 < 450 0.2 < 5 < 3-3-1 600 800 300 600 < 0.2 < 800 0.2 < 5 < 3-4-1 900 850 700 600 < 0.2 < 1200 0.2 < 5 < 4-1-1 400 350 150 400 0.2 < 300 0.2 < 5 < 4-2-1 450 450 200 400 0.2 < 450 0.2 < 5 < 4-3-1 750 800 300 600 < 0.2 < 800 0.2 < 5 < 4-4-1 900 900 750 600 < 0.2 < 1200 0.2 < 5 < 5-1-1 450 500 300 300 0.2 < 300 0.2 < 5 < 5-2-1 550 550 450 450 0.2 < 450 0.2 < 5 < 5-3-1 1000 800 800 600 < 0.2 < 800 0.2 < 5 < 5-4-1 1200 1100 1000 600 < 0.2 < 1200 0.2 < 5 < 6-1-1 500 450 450 300 0.2 < 300 0.2 < 5 < 6-2-1 450 450 450 450 0.2 < 450 0.2 < 5 < 6-3-1 800 800 800 800 0.2 < 800 0.2 < 5 < 6-4-1 1200 1200 1200 1200 0.2 < 1200 0.2 < 5 < 7-1-1 300 300 300 300 0.2 < 300 0.2 < 5 < 7-2-1 450 450 450 450 0.2 < 450 0.2 < 5 < 7-3-1 800 800 800 800 0.2 < 800 0.2 < 5 < 7-4-1 1100 1200 1200 1200 0.2 < 1200 0.2 < 5 < 8-1-1 300 300 300 300 0.2 < 300 0.2 < 5 < 8-2-1 450 450 450 450 0.2 < 450 0.2 < 5 < 8-3-1 800 800 800 800 0.2 < 800 0.2 < 5 < 8-4-1 1100 1000 1300 1200 0.2 < 1200 0.2 < 5 < 9-1-1 400 400 450 300 0.2 < 300 0.2 < 5 < 9-2-1 450 450 450 450 0.2 < 450 0.2 < 5 < 9-3-1 800 800 800 600 < 0.2 < 800 0.2 < 5 < 9-4-1 1000 1100 1000 600 < 0.2 < 1200 0.2 < 5 <

- Styrofoam and plate materials are damaged.

division
(Tetraethoxysilane) Adhesive strength by bonding material (kgf/cm ² ) iron plate - iron plate Steel plate - Stainless (SUS304) plate iron plate - concrete iron plate - glass iron plate - styrofoam iron-wood board Concrete - Styrofoam Concrete - wood planks comparative example <3 <3 <1 <3 <0.05 <1 <0.05 <1 1-1-2 320 350 150 300 0.2 < 300 0.2 < 5 < 1-2-2 450 450 200 400 0.2 < 450 0.2 < 5 < 1-3-2 600 800 300 600 < 0.2 < 800 0.2 < 5 < 1-4-2 800 850 600 600 < 0.2 < 1200 0.2 < 5 < 2-1-2 300 350 150 300 0.2 < 300 0.2 < 5 < 2-2-2 450 450 200 400 0.2 < 450 0.2 < 5 < 2-3-2 600 800 300 600 < 0.2 < 800 0.2 < 5 < 2-4-2 800 850 600 600 < 0.2 < 1200 0.2 < 5 < 3-1-2 300 350 150 300 0.2 < 300 0.2 < 5 < 3-2-2 450 450 200 400 0.2 < 450 0.2 < 5 < 3-3-2 600 800 300 600 < 0.2 < 800 0.2 < 5 < 3-4-2 900 850 700 600 < 0.2 < 1200 0.2 < 5 < 4-1-2 400 350 150 400 0.2 < 300 0.2 < 5 < 4-2-2 450 450 200 400 0.2 < 450 0.2 < 5 < 4-3-2 750 800 300 600 < 0.2 < 800 0.2 < 5 < 4-4-2 900 850 800 600 < 0.2 < 1200 0.2 < 5 < 5-1-2 450 500 300 300 0.2 < 300 0.2 < 5 < 5-2-2 550 550 450 450 0.2 < 450 0.2 < 5 < 5-3-2 1000 800 800 600 < 0.2 < 800 0.2 < 5 < 5-4-2 1200 1100 1000 600 < 0.2 < 1200 0.2 < 5 < 6-1-2 500 450 450 300 0.2 < 300 0.2 < 5 < 6-2-2 450 450 450 450 0.2 < 450 0.2 < 5 < 6-3-2 800 800 800 800 0.2 < 800 0.2 < 5 < 6-4-2 1200 1200 1200 1200 0.2 < 1200 0.2 < 5 < 7-1-2 300 300 300 300 0.2 < 300 0.2 < 5 < 7-2-2 450 450 450 450 0.2 < 450 0.2 < 5 < 7-3-2 800 800 800 800 0.2 < 800 0.2 < 5 < 7-4-2 1100 1200 1200 1200 0.2 < 1200 0.2 < 5 < 8-1-2 300 300 300 300 0.2 < 300 0.2 < 5 < 8-2-2 450 450 450 450 0.2 < 450 0.2 < 5 < 8-3-2 800 800 800 800 0.2 < 800 0.2 < 5 < 8-4-2 1100 1000 1300 1200 0.2 < 1200 0.2 < 5 < 9-1-2 350 400 450 300 0.2 < 300 0.2 < 5 < 9-2-2 450 450 450 450 0.2 < 450 0.2 < 5 < 9-3-2 800 800 800 600 < 0.2 < 800 0.2 < 5 < 9-4-2 1000 1100 1000 600 < 0.2 < 1200 0.2 < 5 <

Example 2

Styrofoam (950mm*2100mm*30mm(T)) is applied with a spray gun on the entire surface of Styrofoam using 5-3 of the Sample Samples and adhered with color steel plates (1000mm*2100mm*0.5mm(T)) on both sides. Then, it was cured at 50 ^o C for 3 hours to prepare a sandwich panel, and the flame retardant properties were analyzed according to the Korean industrial standard KS F ISO 5660-1.

As a result of the analysis, it was analyzed as a semi-incombustible material.

Example 3

Among the inorganic aqueous adhesive coating compositions prepared according to Preparation Example 1, an iron plate was dipping using Preparation Example 9-3_1, followed by curing in an oven at 80° C. for 30 minutes to prepare Example 3.

Thereafter, a neutral salt spray test was performed on the coated specimen prepared according to Example 3 through ASTM B 117 (KS D6502), and the measurement results are shown in Table 4 below.

division Coated specimen neutral salt test (ASTM B 117) comparative example
(Iron material, 100×100×2T) - Elapsed time: 180hr elapsed
- Red rust is confirmed. Example 3
(Iron material, 100×100×2T) - Elapsed time: 1,200hr elapsed
- No red rust or deformation of the coating film

At this time, the heavy water salt spray test (ASTM B 117 (KS D6502)) is in a salt state 4.5 wt% to 5.5 wt% NaCl (3.5 to 7.5pH), salt concentration 1.0255 to 1.0400, spray pressure 0.7 to 1.8kg/cm2, and It was carried out under the test conditions of the chamber temperature of 33 ℃ to 37 ℃.

Accordingly, it was confirmed that the inorganic aqueous adhesive coating composition did not cause red rust or deformation on the coated film even after a long period of time.

The scope of the present invention is indicated by the following claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present invention.

1: iron plate
2: water-based adhesive
3: Styrofoam

Claims (5)

(i) the following conditions (a) and (b) and the ratio of the mixed silicate aqueous solution to the alkoxy silane
have,
(a) 35 wt% potassium silicate (SiO ₂ :K ₂ O molar ratio 3.2 to 4.8) aqueous solution and 40 wt% sodium silicate (SiO ₂ :Na ₂ O molar ratio 2.0 to 4.1) aqueous solution of 10 g: 90 g to 90 g: 10 g 20% by weight of a mixed silicate aqueous solution mixed in a proportion and to which 350ml to 400ml of distilled water is added;
(b) 0.1 to 3 g of alkoxysilane selected from tetramethoxysilane or tetraethoxysilane, which is added to the mixed silicate aqueous solution and reacted at 50° C. to 60° C. for 1 hour;
(ii) further comprising one or more particles selected from magnesium oxide (MgO), boron nitride (BN), aluminum nitride (AlN) and silicon nitride (SiN),
(iii) selected from iron, stainless, concrete, glass, styrofoam and wood;
applied to one material,
(iv) Red rusting and deformation of the coating film are not observed even after 1,200 hr in the neutral salt spray test according to ASTM B 117 (KS D6502) after being applied to a steel specimen;
Inorganic water-based adhesive coating composition. delete delete delete delete

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