KR930007349B1 - Process for the preparation of inorganic flame-resisting varnish - Google Patents

Abstract

The manufacturing method of the inorganic flame-resistant varnish comprises: uniformly mixing (a) an inorganic silicate resin, potassium silicate (the weight mole ratio of K2SiO3SiO2/ K2O= 3.2-5.3) or sodium silicate (the weight mole ratio Na2SiO3SiO2/ Na2O= 1.87-3.85), (b) an alkali component, potassium hydroxide or sodium hydroxide, and (c) silica powder; reacting them at 50-80 deg.C for 3-5 hours to yield a synthetic resin; partially reacting the obtained resin and a water-diluted mixture solution of H3PO4, H3BO3, ZnCl2, CaCl2, Na2SiF6, ZnSiF6, K2SiF6, Al2(SO4)3, ZnSO4, and AlH2(PO4)3 at a pH higher than 9 to give a liquid state varnish.

Description

Inorganic flame retardant varnish manufacturing method

The present invention relates to a foamable inorganic flame retardant varnish manufacturing method that is applied to wood as a building interior material to impart flame retardant performance in the event of fire.

Flame retardant is tested in accordance with KSF-22771 (Test method for flame retardancy of building materials and construction methods). ) And the inorganic flame retardant varnish of the present invention corresponds to flame retardant class 3 (flame retardant material).

In Korea, the building law uses the term non-combustible, semi-non-combustible, and flame-retardant materials for the interior materials of buildings. At present, the terms flame retardant and flame retardant are used in the same meaning, but since the institutions and laboratories regulated according to the purpose of use are different, it is preferable to use them separately because the contents of regulation and evaluation test methods are different. Flame retardant paints commonly used in Korea have been prepared by mixing organic resins with ammonium phosphate, melamine, urea, pentaerytritol, starch, and chlorinated paraffin. The flame retardant paint of the conventional flame retardant grade 3 has thermal properties by melting the organic resin in the fire and exhibiting thermoplastic properties to release the moisture and decomposition gas, and at the same time the carbon film is formed while the coating film is foamed to form a heat insulation layer. Let's do it.

In addition to the foaming of the coating film, a large amount of harmful gases such as hydrogen chloride gas (HCl), ammonia gas (NH ₃ ), carbon monoxide gas (CO), carbon dioxide gas (CO ₂ ), nitrogen gas (N ₂ ), hydrogen cyanide gas (HCN) Since the lamps are released to damage lives, it is necessary to consider countermeasures against toxic combustion gases generated by decomposition of organic substances in a fire. The worst conditions for protecting human life in the event of fire are not the same as flame burns. In most cases, aftereffect disorders occur. In terms of life-savings, in addition to the countermeasures for ignition, the occurrence of smoke and toxic combustion gases, which are the biggest obstacles to evacuation or extinguishing activities, occur frequently in high-rise buildings. Doing. To this end, fire-free materials, which are safe in case of fire, have been studied.

Inorganic flame retardant varnish of the present invention is composed of the main components of potassium oxide (Potassium Silicate, K ₂ SiO ₃ ), sodium oxide (Sodium Silicate Na ₂ SiO ₃ ), which is a safe inorganic silicate (Inorgarnic Silicate) resin during combustion in case of fire Water is generated to absorb heat and at the same time forms a strong foam coating to insulate heat and heat to prevent combustion and does not generate harmful gases to the human body. In addition, the existing paints with flame retardant class 3 performance according to KSF-2271 (Inner materials of building materials and the method of flame retardancy test of construction method) are in the form of varnishes that form transparent coating film because the raw materials themselves are made of opaque flame retardant materials and foam materials. Although not possible, the inorganic flame retardant varnish of the present invention is characterized by a transparent varnish showing the wood grain pattern by painting on the wood because the transparency of the dry coating film after coating is good. Intumescent Mechaism of inorganic flame retardant varnish is as follows.

Due to the heat, the hydroxyl groups (OH groups) of the inorganic silicate resin are condensed with each other to form an insoluble and insoluble gel phase, thereby generating water. At this time, the generated water absorbs heat while evaporating with water vapor, and serves to expand and foam the coating film, and the foamed coating film forms an insulating layer to prevent fire.

As such, the inorganic silicate resins, Potassium Silicate (K ₂ SiO ₃ ) and Sodium Silicate (Sodium Silicate, Na ₂ SiO ₃ ) are incombustible in a fire, and thus have excellent flame retardant performance and are also harmful as in a foaming mechanism. Although it has the characteristic that gas does not generate | occur | produce, it has a very difficult problem in making it into a film as a coating material.

First, there is no plasticity, so the coating film breaks shortly.

Second, during the curing process, the coating is shrunk and cracked or wrinkles are generated, resulting in poor appearance of the coating.

Third, when the surface of the coating film is exposed to the air for a long time, the whitening phenomenon tends to occur due to leaching of the alkaline component.

Fourth, water resistance is particularly poor.

As a method for solving this problem, zinc chloride (ZnCl ₂ ), calcium chloride (CaCl ₂ ), sodium fluoride (NaSiF ₆ ), phosphoric acid (H ₃ PO ₄ ), sulfuric acid (H ₂ SO ₄ ), and boric acid (H) ₃ BO ₃ ), aluminum sulfate (Al ₂ (SO ₄ ) ₃ ), zinc chloride (ZnSO ₄ ), aluminum phosphate (AlH ₂ (PO ₄ ) ₃ ), etc. are directly gelled at the same time It is not applicable as a paint. In addition, metal powders, metal oxides and metal hydrates such as zinc (Zn), zinc oxide (ZnO), magnesium oxide (MgO), calcium oxide (CaO), aluminum oxide (Al ₂ O ₃ ), auto aluminum phosphate (AlPO ₄ ), Baking hardening (100-150 ° C) when aluminum hydroxide (Al (OH ₃ )), zinc hydroxide (Zn (OH) ₂ ), magnesium hydroxide (Mg (OH) ₂ ) and calcium hydroxide Ca (OH) ₂ are used as curing agents Water resistance, shrinkage and cracking of the coating film can be solved to some extent, but the transparency of the coating film cannot be expected due to the added metal pigment.

In order to solve this problem, the inorganic flame retardant varnish of the present invention is prepared by the following method.

1) Resynthesis Resin

Potassium silicate, inorganic silicate resin (Potassium silicate, K ₂ SiO ₃ SiO ₂ / K ₂ O weight mole ratio = 3.2-5.3) or sodium silicon oxide (Sodium Silicate, Na ₂ SiO ₃ SiO ₂ / Na ₂ O weight mole ratio = 1.87 -3.85), add the alkali component and silica powder and resynthesize to use. As the film ratio of SiO ₂ / M ₂ O (M = Na or K) decreases, the coating film becomes soft but sticky and slows down, which tends to cause wrinkles.Since the hardness and water resistance become poor, the SiO ₂ / M ₂ O molar ratio Use to adjust properly. The resin resynthesis method slowly adds an alkali component (sodium hydroxide or potassium hydroxide) to the stainless container. At this time, the temperature increases while the alkali component self-heats. After completely dissolving the alkali component, water is added and the silica powder is slowly added and uniformly dispersed. The temperature is maintained at 50-80 ° C. and reacted for 3-5 hours while stirring at low speed, and then slowly cooled to room temperature. The fully reacted resin is converted from milky cloudy to transparent.

2) Immobilization of Soluble Na or K Group Soluble K and Na groups of potassium silicon oxide and sodium silicon oxide are immobilized with a curing agent to improve water resistance. While stirring the resynthesized resin at high speed, the curing agents zinc chloride (ZnCl ₂ ), calcium chloride (CaCl ₂ ), sodium fluoride (Na ₂ SiF ₆ ), potassium fluoride (K ₂ SiF ₆ ), phosphoric acid (H ₃ PO ₄ ), Boric acid (H ₃ BO ₃ ), sulfuric acid (H ₂ SO ₄ ), aluminum sulfate (Al ₂ (SO ₄ ) ₃ ), zinc sulfate (ZnSO ₄ ), aluminum phosphate (AlH ₂ (PO ₄ ) ₃ ), fluoride Zinc zinc (ZnSiF ₆ ), etc. is diluted with 5-30% in water and added slowly. Examples of the reaction of sulfuric acid and sodium fluoride are as follows.

When an excessive amount of the curing agent is added and reacted to a pH of 7-9, the resin-like property is lost and a pigment-like silica powder is formed. Therefore, partial substitution of Na or K group is performed above pH 9.

3) dehydration reaction

Alcohols (e.g. methanol, ethanol, n-propanol, isopropanol, butanol, ethylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, etc.) or amines (e.g. triethanol) Amine, triethylamine, diethanolamine, dimethylethanolamine, polyoxypropylenediamine, etc.) are added to polymerize the dehydration reaction. The immobilization reaction and dehydration reaction of the K and Na groups are carried out very quickly at room temperature, and when the dehydration reaction is completed, the gel state becomes a gel, so that the reaction is partially maintained. Resin prepared in this way can improve the water resistance to some extent, but there is a limit to expect complete water resistance, acrylic resin (Acrylic silicone) paint or acrylic urethane (Acrylic) excellent in water resistance, weather resistance, chemical resistance, impact resistance, etc. Xurethane) Paint is used as the top coat.

Example 1

848 parts of silicon oxide (or potassium oxide), 117 parts of sodium hydroxide (or potassium hydroxide), 229.9 parts of silica powder, and 138.3 parts of water are uniformly dispersed and maintained at a temperature of 50-80 ° C. for 3-5 hours. React. The resynthesized resin was slowly cooled to room temperature, and then stirred at high speed to dilute phosphate (Phosphoric Acid) with water in 8.9% to 106.7 parts, gamma-glycidoxy propyyl trimethoxy Silane 10 Parts, 40 parts of ethylene glycol, 40 parts of methanol diluted with 20% water, 533.3 parts of polyoxypropylene diamine, 60.7 parts of polyoxypropylene diamine, 6.7 parts of sodium phosphate, Manufactured in a state. When painting, 418.1 parts of water dispersion of polyurethane (34% solids) is used as a curing agent.

Example 2

848 parts of sodium oxide (potassium silicon oxide), 117 parts of sodium hydroxide (or potassium hydroxide), 229.9 parts of silica powder, and 138.3 parts of water are uniformly dispersed, and the temperature is maintained at 50-80 ° C. for 3-5 hours. Let's do it. The resynthesized resin was slowly cooled to room temperature, followed by stirring at high speed, and 171.6 parts of water was added, and 200 parts of phosphate (Phosphric Acid) was diluted with 8.9% in water and gamma-glycidoxy propyl trimethoxy silane (γ-Glycidoxy). propyl trimethoxy Silane) 71.7 parts, 7.3 parts of ammonia water was added slowly to prepare a uniform state. The curing agent is used by mixing 356.8 parts of the amine adduct epoxy resin (Amine Adduct Epoxy Resin). The method for preparing the curing agent is 14.7 parts of dimethyl ethanol amine, 14.7 parts of triethyl amine, and 83.6 parts of polyoxypropylene diamine, and mixed 108.4 parts of liquid epoxy resin in a uniform state. After reacting at a temperature of 60 ° C. for 20 minutes with stirring, 36.9 parts of ethylene glycol monomethyl ether and 98.5 parts of water were added and mixed uniformly to prepare an amine adduct epoxy resin.

Example 3

848 parts of silicon oxide (or potassium oxide), 117 parts of sodium hydroxide (or potassium hydroxide), 229.9 parts of silica powder, and 138.3 parts of water are uniformly dispersed with a stirrer and kept at a temperature of 50-80 ° C. to 3-5 Reaction is carried out for a time to resynthesize the resin in a transparent state. After slowly cooling to the resynthesized room temperature, 66.7 parts of water was added while stirring at high speed. Phosphoric Acid was diluted to 8.9% in water, 226.7 parts diluted to 20% methanol, and 66.7 parts were gradually added to water. It is prepared in a uniform state. When painting, 846.7 parts of curing agent is mixed and used. In the manufacturing method of curing agent, 521 parts of water-dispersed urethane (30% of solid content) and 130.3 parts of liquid epoxy resin (Epoxy Resin) are mixed in a uniform state and reacted for 30 minutes at a temperature of 60 ° C., followed by aluminum hydroxide (Al ( OH) ₃ ) 195.4 parts were prepared and mixed uniformly.

Claims (5)

Potassium Silicate, inorganic silicate resin (Potassium Silicate, K ₂ SiO ₃ SiO ₂ / K ₂ O weight molar ratio = 3.2-5.3) or Sodium Silicate (Na ₂ SiO ₃ SiO ₂ / Na ₂ O weight molar ratio = 1.87 -3.85), add potassium hydroxide (Potassium Hydroxide, KOH) or sodium hydroxide (Sodium Hydroxide, NaOH) and silica powder to the mixture, and then uniformly mix and keep the temperature at 50-80 ℃ to react for 3-5 hours Inorganic flame retardant varnish production method for resynthesizing the resin. Potassium oxide (Potassium Silicate, K ₂ SiO ₃ SiO ₂ / K ₂ O weight molar ratio = 3.2-5.3) or sodium oxide (Sodium Silicate, Na ₂ SiO ₃ ) including the resynthesized resin prepared by the method of claim ₁ SiO ₂ / Na ₂ O weight molar ratio = 1.87-3.85) phosphoric acid (H ₃ PO ₄ ), sulfuric acid (H ₂ SO ₄ ), boric acid (H ₃ BO ₃ ), zinc chloride (ZnCl ₂ ), calcium chloride (CaCl ₂ ) Sodium silicon fluoride (Na ₂ SiF ₆ ), silicon fluoride zinc (ZnSiF ₆ ), potassium fluoride silicon (K ₂ SiF ₆ ), aluminum sulfate (Al ₂ (SO ₄ ) ₃ ), zinc sulfate (ZnSO ₄ ), aluminum phosphate Method for producing an inorganic flame retardant varnish prepared by diluting (AlH ₂ (PO ₄ ) ₃ ) in water and partially reacting it to pH = 9 or more in a liquid state. A method for producing an inorganic flame retardant varnish prepared by the method of claim 2 in a liquid state by dehydration reaction with alcohol. A method for producing an inorganic flame retardant varnish prepared by dehydration reaction with amines prepared in the method of claim 2 in a liquid state. A method for preparing an inorganic flame retardant varnish prepared by mixing a water dispersible urethane (Water Dispersion of Polyurethane) prepared by the method of claim 2.