KR101494305B1

KR101494305B1 - Urethane Foam Composition with Excellent Flame ersistance and Insulation Wall Construction Method Using the Same

Info

Publication number: KR101494305B1
Application number: KR20140113157A
Authority: KR
Inventors: 이완섭
Original assignee: 주식회사 원준하이테크; 모전산업 (주)
Priority date: 2014-08-28
Filing date: 2014-08-28
Publication date: 2015-02-24

Abstract

The present invention relates to a urethane foam composition that can realize physical properties similar to those of traditional urethane foam and can realize excellent performance in terms of flame retardancy, water resistance and adhesion; and to an insulation wall construction method using the same composition desirably. The self-extinguishing urethane foam composition with excellent flame retardancy according to the present invention comprises 5 to 35 wt% of isocyanate; 10 to 25 wt% of polyol; 1 to 10 wt% of a foaming accelerator; 1 to 15 wt% of cement; 25 to 40 wt% of a flame retardant; 0.1 to 3 wt% of a foam stabilizer; 0.1 to 1.5 wt% of a chain extender; and 10 to 20 wt% of solvent, wherein the flame retardant includes a flame retardant of low-solubility vinyl sodium silicate, wherein hydrophobically surface-treated sodium silicate powder is coated with polyvinyl alcohol (PVA), and a flame retardant of absorptive polymers. Moreover, the flame retardant may further include either or both of a layered mineral flame retardant and a metal oxide flame retardant. The method for constructing a self-extinguishing insulation wall with excellent flame retardancy according to the present invention is a method for constructing an insulation wall by using the urethane foam composition desirably, wherein the insulation wall is constructed by attaching masonry materials using the urethane foam composition and stacking the masonry materials, or the insulation wall is constructed by constructing a wall while forming empty space layers therein and inserting the urethane foam composition into the empty space layers to foam and mold the urethane foam composition.

Description

Technical Field [0001] The present invention relates to a self-extinguishing foamed urethane foam composition having excellent flame retardancy and a method of constructing a heat insulation wall using the foamed urethane foam composition.

The present invention relates to a novel foamed urethane foam composition capable of realizing physical properties similar to those of conventional urethane foam and capable of exhibiting excellent performance in flame retardance, water resistance, adhesion and the like, and a method of constructing a heat insulating wall using such a composition.

The general urethane foam is a hard urethane foam composed of organic materials. It is vulnerable to fire due to low ignition point in case of fire, the ignited fire is not turned off, it is spread to a bigger fire, and a fire burning space is created, Can occur. In order to improve the flame retardancy of urethane foam, it is necessary to increase the proportion of -NCO or -OH of the raw material resin. As one of the methods, the isocyanate can improve the thermal stability when forming a trimer. However, have.

Therefore, conventionally, the flame retardant performance of the urethane foam was improved by using a halogen-based flame retardant or a phosphorus flame retardant, a carbonization swelling agent, and a two-stage pyrolysis swelling agent in the production of urethane foam. However, the halogen-based flame retardant has a low degree of improvement in the flame retardant effect and a large burden of increasing the manufacturing cost, and the phosphorus flame retardant has a problem that the cured foam has a deteriorated flame retardancy in the long term. In order to secure the flame retardant performance, the foamed foam is turned off due to its own weight in the urethane foam foaming process when a large amount of mixture is applied in order to secure the flame retardant performance.

In order to secure the flame retardant property of the urethane foam, there is a method of adding a sodium silicate liquid phase. However, since it has a strong alkali property and a large amount of water, the foaming rate rapidly increases when the urethane foam is foamed due to the sodium silicate liquid phase, . Also, since the sodium silicate liquid phase has low water resistance even after drying and curing, there is a problem that the urethane foam foam has elution of strong alkali when exposed to moisture, thereby affecting the environment.

On the other hand, insulation walls are installed in buildings to prevent condensation and to save energy in heating and cooling. The heat insulating wall has a dry process in which a plate-like heat insulating material is installed and a wet process in which a wet heat insulating material is installed. The dry method has an advantage that it is easy to construct, and the wet method has an advantage that the wall can be integrated. Patent patents relating to a heat insulating wall by a wet process include patents 10-1085557 and 10-1268439.

The present invention relates to a novel foamed urethane foam composition which is developed to improve the conventional urethane foam and is capable of realizing physical characteristics similar to conventional urethane foam, but also exhibits excellent performance in flame retardance, water resistance and adhesiveness, There is a technical problem in providing a wall construction method.

In order to solve the above-described problems, the present invention provides a self-extinguishing foamed urethane foam composition having excellent flame retardancy and a method of constructing a heat insulating wall using the composition.

A self-extinguishing foamed urethane foam composition excellent in flame retardancy according to the present invention comprises 5 to 35% by weight of an isocyanate, 10 to 25% by weight of a polyol, 1 to 10% by weight of a foam accelerator, 1 to 15% by weight of a cement, 0.1 to 3% by weight of a foam stabilizer, 0.1 to 1.5% by weight of a chain extender, and 10 to 20% by weight of a solvent, wherein the flame retardant is a low-melting (PVA) A vinyl silicate soda flame retardant, and an absorbent polymer flame retardant. Further, the flame retardant may be composed of at least one of a layered mineral flame retardant and a metal oxide flame retardant.

The method for constructing a self-extinguishing heat insulating wall having excellent flame retardancy according to the present invention is a method for constructing a heat insulating wall by suitably using the above-mentioned foamed urethane foam composition, which comprises adhering a coarse material to a foamed urethane foam composition, Or a foamed urethane foam composition is injected into the hollow space layer after the wall is formed while forming an empty space layer in the hollow space layer, and then the insulation wall is formed while foaming and molding.

According to the present invention, the following effects can be expected.

First, it can provide a foamed urethane foam having improved flame retardancy, water resistance, adhesiveness, heat insulation and the like compared with conventional urethane foam.

Second, the foamed urethane foam molded from the composition according to the present invention can effectively prevent elution of strong alkaline characteristics due to securing of water resistance of the material imparting flame retardancy during moisture contact.

Thirdly, when a wall is constructed by attaching a masonry material such as a block or a block with the foamed urethane foam according to the present invention or filling the inner space layer of the wall, various kinds of condensation and thermal insulation deterioration phenomenon It can be completed with an insulating wall which can be shut off at the source. In particular, the foamed urethane foam according to the present invention exhibits excellent effects in flame retardancy, water resistance, adhesion, heat insulation, etc. Therefore, the finished heat insulating wall can be expected to have enhanced durability by strengthening flame retardancy, water resistance, adhesiveness, and heat insulation.

1 shows various embodiments of a heat insulating wall completed according to the present invention.

The present invention relates to a foamed urethane foam which exhibits excellent flame retardancy and water resistance. The foamed foam comprises 5 to 35% by weight of an isocyanate, 10 to 25% by weight of a polyol, 1 to 10% by weight of a foam accelerator, 1 to 15% by weight of a cement, 0.1 to 3 wt% of a foam stabilizer, 0.1 to 1.5 wt% of a chain extender, and 10 to 20 wt% of a solvent. Herein, isocyanate, polyol, foam accelerator, foam stabilizer, and chain extender are the same as the raw materials of general foamed urethane foam. In the present invention, a flame retardant is added to the foamed urethane foam raw material in order to preferably use the foamed urethane foam as a fireproofing building material. . In particular, it has been proposed that a low-solubility vinyl silicate soda flame retardant coated with PVA (polyvinyl alcohol) and an absorbent polymer flame retardant are further included in a hydrophobic surface-treated siliceous soda powder as a flame retardant, further comprising a layered mineral flame retardant and a metal oxide flame retardant . In addition, the present invention comprises cement to enhance flame retardancy and durability.

It is preferable to select at least one of 1MDI to 4MDI and most preferably 2MDI to use isocyanate. The isocyanate is used in an amount of from 5 to 35% by weight. When the amount is less than 5% by weight, foaming foam is difficult to form. When the amount is more than 35% by weight, the curing property of the foam is low.

Polyol is a raw material for urethane bonding reaction with isocyanate, and polyether polyol is preferable. The polyether polyol is prepared by adding propylene oxide (PO) or ethylene oxide (EO) to an initiator having two or more activated hydrogen (hydroxyl-OH, amine group -NH2). The polyol is used in an amount of from 10 to 25% by weight. When it is less than 10% by weight, foaming foam is difficult to form, and when it exceeds 25% by weight, micropores formation characteristics are deteriorated due to rapid foaming.

The foaming accelerator promotes the curing reaction of isocyanate and polyol. In the present invention, cyclopentane is used. The foaming promoter is used in an amount of from 1 to 10% by weight. When the amount is less than 1% by weight, the effect of promoting foaming is insignificant. When the amount exceeds 10% by weight, bubbles are combined with each other to form large bubbles.

Cement is used as an inorganic substance for durability of foamed urethane foam because it has excellent durability such as strength development and fire resistance. In addition, since the cement reacts with external moisture after the foaming process or the foamed urethane foam is formed, the physical properties of the foamed urethane foam can be improved, thereby contributing to the improvement of the flame retardancy of the foamed urethane foam, do. Cement is used in an amount of from 1 to 15% by weight, and if it is less than 1% by weight, it is difficult to expect performance based on cement. If it is more than 15% by weight, foamed urethane foam weight increases depending on the excess amount of powder, There is a falling problem.

The flame retardant is a raw material for adding flame retardancy to foamed urethane foam. In the present invention, it is proposed to use a low-melting vinylsilicate soda flame retardant, an water absorbent polymer flame retardant, a layered mineral flame retardant, and a metal oxide flame retardant.

Sodium silicate flame retardant with low solubility is PVA (polyvinyl alcohol) coated on hydrophobic surface treated siliceous soda powder. Sodium silicate dissolves and cures by fire or heat to form silicon-containing network structure in the event of fire, The foam structure is maintained even after the foamed resin is burned, thereby exhibiting flame retardant performance. On the other hand, when the PVA solution treated with the sodium silicate powder is dissolved in the water when the foamed urethane foam is stirred and foamed, the foamed urethane foam is present inside the cured foamed urethane foam The sodium silicate powder exhibits water resistance by preventing the elongation of the strong alkali even when the urethane foam is exposed to external moisture by the hydrophobic surface without any change in shape. In addition, polyvinyl alcohol (PVA) dissolved therein is excellent in adhesion properties as a polymer, thereby contributing to an increase in adhesion performance between the foamed urethane foam and the substrate surface (wall, masonry brick, etc.). The soda silicate flame retardant of low solubility is prepared by treating the siliceous sodium silicate powder with a hydrophobic coating agent and subjecting it to a hydrophobic surface treatment, mixing and stirring the alcohol solution with 5 to 10% by weight of PVA solution, applying PVA coating, And the like. When the content of the vinyl silicate soda flame retardant is less than 10% by weight, the flame retardant effect deteriorates due to a low network structure formation property. When the content is more than 15% by weight, the powdery content is excessive, It is easy to occur.

The water absorbent polymer flame retardant is dispersed in the urethane foam cured in a state of absorbing water, so that the absorbed water is vaporized at the time of the fire to be a raw material for realizing the flame retardant performance, and the silicate polyacrylate is preferably adopted. The water absorbing polymer flame retardant is used in an amount of 5 to 10% by weight, and less than 5% by weight is water absorbing amount so that the flame retarding effect is insufficient in case of fire. If it is more than 10% by weight, the foam has high viscosity, There is a possibility that an off phenomenon may occur.

The layered mineral flame retardant is employed in a range that does not affect the mechanical properties of foamed urethane foam such as a halogen-based or phosphorus-based material, and aluminum hydroxide or magnesium hydroxide is preferably employed. The layered mineral flame retardant is used in an amount of 8 to 10% by weight. If it is less than 8% by weight, the flame retardant effect is insignificant. If the amount is more than 10% by weight, the foam foam has a high weight and affects the physical properties of the foam.

The metal oxide flame retardant is used as a raw material for adding flame retardancy, and it is used in the range of 2 to 5 wt% as 1 to 2 metal oxide powder such as AlO, BaO, and ZnO. If the amount is less than 2% by weight, the flame retardant effect is insufficient. If the amount is more than 5% by weight, the foam off is likely to occur due to an increase in the weight of the foam.

The foam stabilizer is used to adjust the structure of the foamed foam by lowering the surface tension to improve the miscibility and to uniformize the size of the foam produced. Non-water-soluble silicon based foam stabilizer is suitable. The foam stabilizer is used in an amount of from 0.1 to 3% by weight. When the foam stabilizer is less than 0.1% by weight, the foam tends to form due to a high surface tension during foaming. When the content exceeds 3% by weight, the residual rate of voids in the foam foam decreases, easy.

The chain extender is intended to be a chain or network structure with a chain of macromolecules, and it is appropriate to use one of the divalent alcohols. The embodiment of the present invention employs ethylene glycol. The chain extender is used in an amount of from 0.1 to 1.5% by weight. When it is less than 0.1% by weight, it is difficult to form a network structure. When the content of the chain extender exceeds 1.5% by weight, viscosity becomes high.

The solvent is used for mixing the powder raw materials and for decreasing the viscosity, and PC (propylene carbonate) is preferably used in the present invention. The solvent is used in an amount of 10 to 20% by weight. If the amount is less than 10% by weight, a smooth foam is not formed due to a high viscosity after mixing. If the amount is more than 20% by weight, the viscosity is lowered.

The foamed urethane foam composition as described above is classified into a liquid A composed of an isocyanate, a polyol, a layered mineral flame retardant and a solvent; and a liquid B composed of a foaming promoter, a low-melting vinyl silicate soda flame retardant, an absorbent polymer flame retardant, a foam stabilizer and a chain extender It is preferable to provide a two-component type. The cement may be mixed in any of the liquids A and B. In the following example, the cement is mixed in the liquid A. Such a two-component type material is prepared by mixing a liquid A and a liquid B to foam and form a foamed urethane foam. The foamed urethane foam thus produced can be advantageously utilized as a typical material for building materials for insulation purposes requiring flame retardant performance. Low-temperature warehouse walls, frozen / refrigerated warehouse walls, roof insulation materials such as slabs and factories.

In particular, the present invention proposes a method of constructing a heat insulating wall using a foamed urethane foam, wherein FIG. 1 shows various embodiments of the heat insulating wall completed according to the present invention. The insulation wall is formed by laminating a coarse material such as a brick or a block with a foamed urethane foam composition, or by laminating the foamed urethane foam composition, or by forming a hollow space layer in the interior of the wall, and then injecting the foamed urethane foam composition into a hollow space layer, Can be constructed. The foamed urethane foam according to the present invention exerts an improved effect on flame retardancy, water resistance, adhesiveness, heat insulation, etc. Therefore, when the wall is formed by using the foamed urethane foam, the durability is improved by securing the flame retardancy, water resistance, It is finished with an improved insulating wall.

Fig. 1 (a) shows an example of a heat insulating wall completed by foaming a foamed urethane foam 20 on a hollow space layer 10 between sandwich panels, which is a heat insulating wall of a sandwich structure integrated by a foamed urethane foam. Such an insulating wall can be advantageously applied to the inner partition wall of the building.

Fig. 1 (b) is a cross-sectional view of the foamed urethane foam 20 in which the foamed urethane foam 20 is laminated on the foamed urethane foam 20 to complete inner and outer walls with a masonry wall, Thereby making an example of the heat insulating wall integrally formed with the inner wall and the outer wall. In this case, since the foamed urethane foam 20 is filled in the space layer between the inner wall and the outer wall, the joints between the inner wall and the outer wall are filled with the reinforced insulation wall.

1 (c) is an example of a heat insulating wall completed by foaming a foamed urethane foam 20 on a hollow space layer 10 between a concrete wall and a finishing panel. As can be seen, the foamed urethane foam 20 integrates the concrete wall and the finish panel.

Hereinafter, the present invention will be described in detail based on examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

[Examples] Characteristics of foamed urethane foam

1. Foamed urethane foam composition

The foamed urethane foam composition was prepared in the same composition as shown in Table 1 below. In particular, low-boiling sodium silicate was prepared by treating sodium silicate powder with a hydrophobic coating agent, hydrophobic surface-treated, mixing and stirring the alcohol solution with 5 to 10 wt% solution of PVA, PVA coating treatment, powder filtering, Jet process.

Foamed urethane foam composition (% by weight) division ingredient Example 1 Example 2 Comparative Example Remarks Solution A Isocyanate 21 27 43 2MDI Polyether polyol 15 12 20 Number average molecular weight of 2000 to 4000, solidification point of 52 to 56 degrees, viscosity (75 degrees) of 620 to 700 mPa.s Usually portland cement 9 11 - 0.6% of ignition loss, 22% of SiO2, 65% of CaO, 2800cm2 / g or more of specific surface area Aluminum hydroxide 9 10 9 Al (OH) 3 content 99.5% or more, particle size (Dp50) 50micron, ignition loss (LOI) 34-35%, pH 9.3-9.7 PC 13 11 16 Number average molecular weight 60,000 ~ 65,000 Solution B Low solubility vinyl silicate 14 12 - Melting point 72 to 73 degrees, SiO2 content 27 to 29%, Na2O content 28 to 30%, pentahydrate, particle size 50 ± 15 micron Cyclopentane 7 6 6 Boiling point 49 ° C, Specific gravity 0.7 ~ 0.72, Water solubility 155mg / l at 25eh Silicic acid polyacrylate 6 5 - Viscoelastic 13N, density 1.22 g / cm3 Silicone foam stabilizer 1.4 2.0 1.6 Non-water-soluble silicone system, flash point 99 degree, viscosity 700 cp, specific gravity 1.05, water solubility Ethylene glycol One 0.8 1.1 Density 1.11 to 1.14 g / cc, freezing point -13 degrees, boiling point 197 degrees Barium oxide 3.6 3.2 1.3 Density 5.32 ~ 5.72g / cm3, Appearance White or light gray, Porous sub Total 100 100 100 -

2. Foamed urethane foam properties

The foamed urethane foam of [Table 1] was tested for compressive strength, tensile strength, flame retardancy, flammability, thermal conductivity, absorption and the like, and the results are shown in Table 2 below.

Foamed urethane foam properties characteristic Example 1 Example 2 Comparative Example Remarks Density (g / cm3) 0.048 0.051 0.050 KS M 3809 Compressive strength (N / cm2) 39 36 36 KS M 3809 Tensile strength (kg / cm 2) 18.8 19.6 15.2 KS M 3809 Flammability (-) Flame retardant grade 2 Flame retardant grade 2 Nonconformity KS F 2271 Flammable (self-extinguishing) 55mm combustion (burning for 15 seconds), digestion 35mm combustion (11sec combustion), digestion Continuous combustion (fire extinguishing after 70 seconds) B2-DIN-4102 Thermal conductivity (W / mK, average temperature 20 ± 5 ℃) 0.021 0.022 0.023 KS M 3809 Water resistance (absorption amount, g / 100㎠) 0.8 0.7 1.1 KS M 3809

As a result of the evaluation of the characteristics, it was confirmed that the physical properties, density and compressive strength, exhibited similar characteristics in Examples 1 and 2 and Comparative Example. The tensile strength (adhesion property) of Examples 1 and 2 was superior to that of Comparative Examples. The improvement in tensile strength (adhesion property) is attributed to low solubility of vinyl silicate and cement.

As a result of confirming the flame retardant performance and the combustibility, Examples 1 and 2 showed characteristics similar to flame retardant grade 2 and confirmed that self-extinguishing property could be secured even in the combustibility, but Comparative Example was confirmed to be non-flame retardant and visa-proof. The low solubility vinyl silicate sulphate and silicate polyacrylate applied to the flame retardant performance were found to contribute to the self - extinguishing performance.

The thermal conductivity of Examples 1 and 2 was slightly lower than those of Comparative Examples. The results are shown in Table 1 below. In Examples 1 and 2, by applying the ordinary portland cement and the low-dissolving vinyl silicate, It is possible to have a finer pore distribution than the example and thus to have a lower thermal conductivity. It was confirmed that Examples 1 and 2 exhibited low water absorption in water resistance compared with Comparative Examples.

As described above, in Examples 1 and 2 according to the present invention, physical properties similar to those of conventional urethane foams can be realized, and it was confirmed that, among other things, excellent performance can be exhibited in terms of tensile strength (adhesion property), flame retardancy and water resistance. Accordingly, the foamed urethane foam according to the present invention can be advantageously used as a building material having excellent flame retardancy, water resistance, adhesiveness, and heat insulation, and can be advantageously used particularly in the construction of a heat insulation wall.

10: space layer
20: foamed urethane foam

Claims

5 to 35% by weight of isocyanate, 10 to 25% by weight of polyol, 1 to 10% by weight of a foaming accelerator, 1 to 15% by weight of a cement, 25 to 40% by weight of a flame retardant, 0.1 to 3% By weight, and 10 to 20% by weight of a solvent,
Wherein the flame retardant comprises a low melting vinyl silicate soda flame retardant and an absorbent polymer flame retardant,
The low-melting vinylsilicone soda flame retardant is prepared by treating a sodium silicate powder with a hydrophobic coating agent, subjecting it to a hydrophobic surface treatment, adding a solution of 5 to 10 wt% of PVA into the alcohol solution while mixing and stirring, By weight based on the total weight of the foamed urethane foam composition. The foamed self-extinguishing foamed urethane foam composition is excellent in flame retardancy.

The method of claim 1,
The self-extinguishing foamed urethane foam composition having excellent flame retardancy, wherein the flame retardant comprises at least one of a layered mineral flame retardant and a metal oxide flame retardant.

3. The method of claim 2,
Wherein 25 to 40% by weight of the flame retardant is composed of 10 to 15% by weight of a low-dissolving vinyl silicate flame retardant, 5 to 10% by weight of an absorbent polymer flame retardant, 8 to 10% by weight of a layered mineral flame retardant, and 2 to 5% Wherein the foamed urethane foam composition is a self-extinguishing foamed urethane foam composition having excellent flame retardancy.

4. The method of claim 3,
The polyol is a polyether polyol,
The foaming promoter is cyclopentane,
The flame retardant is composed of a low-dissolving vinyl silicate soda flame retardant, an absorbent polymer flame retardant by silicate polyacrylate, a layered mineral flame retardant by aluminum hydroxide or magnesium hydroxide, and a metal oxide flame retardant by barium oxide,
The foaming agent is a silicone foaming agent,
Wherein the chain extender is ethylene glycol,
The self-extinguishing foamed urethane foam composition is excellent in flame retardancy, wherein the solvent is PC (propylene carbonate).

5. The method according to any one of claims 2 to 4,
Liquid A consisting of isocyanate, polyol, layered mineral flame retardant, and solvent;
A liquid B consisting of a foaming accelerator, a low-melting vinyl silicate soda flame retardant, an water-absorbing polymer flame retardant, a foam stabilizer, and a chain extender;
, Wherein the cement is contained in the liquid A or the liquid B. The self-extinguishing foamed urethane foam composition is excellent in flame retardancy.

A method for constructing a heat insulating wall using the foamed urethane foam composition according to any one of claims 1 to 4, comprising the steps of applying a foamed urethane foam composition to the foamed material to form a heat insulating wall, Wherein the foamed urethane foam composition is injected into the hollow space layer after the wall is formed while forming the layer, and then the insulation wall is formed while the foamed urethane foam composition is foamed and molded.