KR102869619B1 - Insulator - Google Patents

Abstract

The present application can provide an insulating material that simultaneously maintains excellent insulation performance, semi-combustibility performance, and flame retardancy performance, and also has excellent handling properties, workability, lightness, cutting properties, and mechanical strength.

Description

Insulator

This application relates to insulating materials.

Insulation is a material used to prevent, delay, or mitigate heat loss or heat inflow. Its typical use is as a building material, but it can also be used for various other purposes that require heat preservation or cooling.

Representative examples of organic insulating materials include materials manufactured in the form of foam by foaming resin components such as phenol resin, polystyrene, polyurethane, and/or polyisocyanurate.

During the foaming process described above, so-called closed cells are formed within the foam, and these closed cells exert their insulating properties. In other words, the closed cell ratio and cell size of the closed cells formed during the foaming process described above are important factors in determining the performance of the insulation material.

Therefore, in the foaming process for manufacturing insulation materials, the conditions and materials of the foaming process are controlled so that independent cells that can exhibit optimal insulation performance are formed depending on the applied material.

Depending on the intended use, insulation materials are required to have so-called semi-fireproof or flame-retardant performance, and in particular, in the case of insulation materials for construction, the demand for the semi-fireproof or flame-retardant performance is growing due to the risk of fire, etc.

In order to secure semi-combustible or flame-retardant performance in insulation, one can simply consider mixing a flame-retardant into the insulation.

However, the mixed flame retardant affects the foaming process for forming the insulation, causing independent cells of a different shape or number than those designed for the insulation to be formed, and also reducing the stability of the inner walls of the formed independent cells.

Therefore, the mixing of flame retardants reduces the insulation's fundamental performance. In particular, when more flame retardants are added to achieve higher flame retardancy or semi-flame retardancy, the degree of degradation in the insulation's insulation performance becomes even greater.

This application relates to an insulating material. The purpose of this application is to provide an insulating material that simultaneously maintains excellent insulating performance, semi-combustibility, and flame retardancy. The application also aims to provide an insulating material that also exhibits excellent handleability, workability, lightness, cuttability, and mechanical strength.

Among the properties mentioned in this specification, if the measurement temperature and/or pressure affect the property value, the property refers to a property measured at room temperature and/or normal pressure, unless otherwise specifically stated.

In this application, the term room temperature means a natural temperature that is neither heated nor cooled, and may mean, for example, any temperature within the range of about 10°C to 30°C, or a temperature of about 25°C or 23°C.

In this application, the term atmospheric pressure refers to pressure when it is not specifically reduced or increased, and may mean a pressure of about 740 mmHg to 780 mmHg, which is the same as the normal atmospheric pressure.

In the case where the measured humidity affects the physical property value among the physical properties mentioned in this specification, unless otherwise specified, the physical property refers to the physical property measured at natural humidity that is not specifically controlled under the measurement temperature and pressure conditions.

The insulating material of the present application includes at least one organic layer. The term organic layer refers to a layer containing an organic material as a main component. In the present specification, the inclusion of a component as a main component may mean that the weight ratio of the component is about 55 wt% or more, about 60 wt% or more, about 65 wt% or more, about 70 wt% or more, about 75 wt% or more, about 80 wt% or more, about 85 wt% or more, or about 90 wt% or more. The upper limit of the weight ratio of the main component is not particularly limited, and for example, the weight ratio of the main component may be about 100 wt% or less, 99 wt% or less, 98 wt% or less, 97 wt% or less, 96 wt% or less, or about 95 wt% or less. The meaning of the term organic material in the present specification is as known in the art. Representatively, the organic material may be a cured resin as described below, and specifically, may be at least one selected from the group consisting of phenol resin, polystyrene, polyurethane, and polyisocyanurate, but is not limited thereto.

The organic layer may include so-called closed cells. Within the organic layer of the present application, the closed cells may be present so that the designed insulating performance can be stably implemented while ensuring excellent flame retardancy and near-fire resistance, as described below. Accordingly, the insulating material of the present application simultaneously secures excellent insulating performance, near-fire resistance, and flame retardancy.

The insulating material or the organic layer of the present application has excellent insulating performance.

Typically, insulation performance is confirmed by the thermal transmittance. The thermal transmittance is a physical quantity that divides the thermal conductivity by the thickness. The above-mentioned insulating material or organic layer may have a thermal transmittance of about 0.4 W/m ² ·K or less. In other examples, the thermal transmittance may be about 0.35 W/m ² ·K or less, 0.3 W/m ² ·K or less, 0.25 W/m ² ·K or less, or 0.2 W/m ² ·K or less. The lower the value of the thermal transmittance, the more advantageous the effect is, and there is no particular limitation on the lower limit. For example, the thermal transmittance may be about 0 W/m ² ·K or more, more than 0 W/m ² ·K, 0.05 W/m ² ·K or more, 0.1 W/m ² ·K or more, or 0.15 W/m ² ·K or more, in other examples.

The thermal transmittance of an insulating material or organic layer can be measured using the plate heat flow meter method based on the KS L 9016 standard for measuring the thermal conductivity of insulating materials. This method involves generating a temperature difference of 10 or greater on both sides of a test piece, electrically measuring the heat flow passing through the test piece, and then measuring the temperature difference across the test piece to determine the thermal conductivity.

The insulating material or organic material of the present application may also exhibit a thermal conductivity of about 30 mW/m K or less. In other examples, the thermal conductivity may be about 28 mW/m K or less, about 26 mW/m K or less, about 24 mW/m K or less, about 22 mW/m K or less, about 20 mW/m K or less, or about 10 mW/m K or more, about 12 mW/m K or more, about 14 mW/m K or more, about 16 mW/m K or more, or about 18 mW/m K or more. This thermal conductivity can be measured using the HC-074 thermal conductivity measuring equipment of EKO, which adopts the thermal current measurement method among the thermal current measurement method specified in the ISO 8301 standard, the heat flow meter method according to the thermal conductivity measurement standard of insulating materials specified in the KS L 9016 standard, the plate direct method, the plate comparison method, or the heat current meter method.

The organic layer of the present application may have a density in the range of about 20 to 70 kg/m ³ . In insulating materials, density is functionally related to thermal conductivity characteristics. An insulating material containing an organic material having a density in the above range may exhibit excellent insulating characteristics. In addition, the density may be within an appropriate range in terms of securing light weight. In other examples, the density may be 21 kg/m ³ or more, 22 kg/m ³ or more, 23 kg/m ³ or more, 24 kg/m ³ or more, or 25 kg/m ³ or more, or 65 kg/m ³ or less, 60 kg/m ³ or less, 55 kg/m ³ or less, 50 kg/m ³ or less, 45 kg/m ³ or less, 40 kg/m ³ or less, or 36 kg/m ³ or less.

The density of these organic layers can be measured based on the JIS-K-7222 standard.

The organic layer may also have a weight per unit area within a range of 2 to 20 kg/m ² . The organic layer of the present application may exhibit advantageous effects in terms of lightness, etc., through the weight per unit area, while also exhibiting the insulating, semi-combustible, and flame-retardant performances. The weight per unit area may be, in other examples, 3 kg/m ² or more, 18 kg/m ² or less, 16 kg/m ² or less, 14 kg/m ² or less, 12 kg/m ² or less, 10 kg/m ² or less, or 8 kg/m ² or less.

The above insulating material or organic layer may exhibit excellent mechanical strength. For example, the insulating material or organic material may have a compressive strength of 90 kPa or more. In other examples, the compressive strength may be about 95 kPa or more, 100 kPa or more, 105 kPa or more, 110 kPa or more, 115 kPa or more, 120 kPa or more, or 125 kPa or more, or about 300 kPa or less, 280 kPa or less, 260 kPa or less, 240 kPa or less, 220 kPa or less, 200 kPa or less, 180 kPa or less, 160 kPa or less, 140 kPa or less, or 130 kPa or less.

The compressive strength of the insulation or organic layer can be measured using the compressive strength verification method specified in KS M ISO 844.

The insulating material or organic layer of the present application can simultaneously exhibit excellent insulating performance, semi-combustible performance, and flame retardant performance while being lightweight and having excellent mechanical strength.

These properties can be achieved by controlling the number and shape of independent bubbles within the organic layer, as well as the components present within the independent bubbles. In particular, in the present application, even when the composition is controlled to impart excellent flame retardancy and quasi-flammability performance to the insulating material and organic material, the number and shape of the independent bubbles can be stably maintained so that the desired performance can be achieved.

For example, the organic layer may have an independent cell ratio of 75% or more. In other examples, the independent cell ratio may be 77% or more, 79% or more, 81% or more, 83% or more, 85% or more, 87% or more, 89% or more, 91% or more, or 93% or more, or 95% or less, 93% or less, 91% or less, 89% or less, or 87% or less. An organic layer having an independent cell ratio within these ranges can effectively satisfy the above-mentioned characteristics.

The independent cell ratio of an organic layer can be measured using an appropriate measuring device (e.g., Quantachrome, ULTRAPYC 1200e) according to the KS M ISO 4590 standard, and a method for measuring the independent cell ratio of an organic layer used as an insulating material is known.

The independent bubbles present in the organic layer may have an average diameter in the range of 70 νm to 200 νm. An organic layer having independent bubbles with an average diameter in this range can effectively satisfy the above-mentioned characteristics. In other examples, the average diameter may be 75 νm or more, 80 νm or more, 85 νm or more, or 90 νm or more, or 190 νm or less, 180 νm or less, 170 νm or less, 160 νm or less, 150 νm or less, 140 νm or less, 130 νm or less, 120 νm or less, 110 νm or less, or 100 νm or less.

Methods for measuring the average diameter of independent bubbles in an organic layer are well known. For example, the average diameter can be measured using a standard electron microscope and the ImageJ program. Typically, the sample is first cut with a razor blade or similar device, peeled, photographed with an electron microscope, and then approximately 150 circular shapes are drawn. The average diameter can then be measured using the ImageJ program.

The insulating material and organic layer of the present application have independent cells of the above-mentioned type, and exhibit excellent insulating performance, light weight, mechanical strength, etc., and at the same time can exhibit excellent semi-combustible and flame-retardant performance.

For example, the insulating material or organic layer may have a 5-minute heat release rate (THR300s) of 11 MJ/m ² or less according to the KS F 5660-1 test method. The 5-minute heat release rate (THR300s) may be, in other examples, 10 MJ/m ² or less, 9 MJ/m ² or less, 8 MJ/m ² or less, 7 MJ/m ² or less, 6 MJ/m ² or less, 5 MJ/m ² or less, 4 MJ/m ² or less, 3 MJ/m ² or less, or 2.5 MJ/m ² or less. Since the 5-minute heat release rate (THR300s) represents superior flame retardancy and quasi-flame retardancy performance as the value is lower, the lower limit thereof is not particularly limited. In one example, the 5-minute heat release (THR300s) may be 0 MJ/m ² or more, 0.5 MJ/m ² or more, 1 MJ/m ² or more, or 1.5 MJ/m ² or more.

For example, the insulating material or organic layer may have a 10-minute heat release rate (THR600s) of 18 MJ/m ² or less according to the KS F 5660-1 test method. The 10-minute heat release rate (THR600s) may be, in other examples, 17 MJ/m ² or less, 16 MJ/m ² or less, 15 MJ/m ² or less, 14 MJ/m ² or less, 13 MJ/m ² or less, 12 MJ/m ² or less, 11 MJ/m ² or less, 10 MJ/m ² or less, 9 MJ/m ² or less, 8 MJ/m ² or less, 7 MJ/m ² or less, 6 MJ/m ² or less, or 5.5 MJ/m ² or less. The lower limit of the above 10-minute heat release rate (THR600s) is not particularly limited because a lower value indicates better flame retardancy and semi-fire resistance. In one example, the above 10-minute heat release rate (THR600s) may be 0 MJ/m ² or more, 1 MJ/m ² or more, 2 MJ/m ² or more, 3 MJ/m ² or more, 4 MJ/m ² or more, or 5 MJ/m ² or more.

For example, the insulating material or organic layer may have a peak heat release rate (peak HRR) of 55 kW/m ² or less according to the KS F 5660-1 test method. The above peak heat release rate (peak HRR) may be ^, in other examples, 53 kW/m ² or less, 51 kW/m ² or less, 49 kW/m ² or less, 47 kW/m ² or less, 45 kW/m ² or less, 43 kW/m ² or less, 41 kW/m ² or less, 39 kW/m ² or less, 37 kW/m ² or less, 35 kW/m ² or less, 33 kW/m ² or less, 31 kW/m ² or less, 29 kW/m ² or less, 27 kW/m ² or less, 25 kW/m ² or less, 23 kW/m 2 or less, or 21 kW/m ² or less. The lower limit of the above peak heat release rate (peak HRR) is not particularly limited because a lower value represents better flame retardancy and semi-fireproof performance. In one example, the peak heat release rate (peak HRR) may be about 0 kW/m ² or more, 5 kW/m ² or more, 10 kW/m ² or more, or 15 kW/m ² or more.

The above insulating material or organic layer may have a reduction rate of 25% or more in the 10-minute heat release amount (THR600s) according to the KS F 5660-1 test method. The reduction rate of the above 10-minute heat release (THR600s) is, in other examples, 27% or more, 29% or more, 31% or more, 33% or more, 35% or more, 37% or more, 39% or more, 41% or more, 43% or more, 45% or more, 47% or more, 49% or more, 51% or more, 53% or more, 55% or more, 57% or more, 59% or more, 61% or more, or 63% or more, or 70% or less, 68% or less, 66% or less, 64% or less, 62% or less, 60% or less, 58% or less, 56% or less, 54% or less, 52% or less, 50% or less, 48% or less, 46% or less, 44% or less, 42% or less, 40% or less, 38% or less, 36% Below, it could be 34% or less, or 32% or less.

The insulating material or organic layer may also have a Limiting Oxygen Index (LOI) of about 15% or greater. The LOI may be, in other examples, 20% or greater, 25% or greater, 30% or greater, or 35% or greater, or 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, or 40% or less.

The limiting oxygen index (LOI) of an insulation or organic layer can be determined by calculating the minimum concentration of oxygen required to sustain combustion under test conditions specified in ASTM D2863/77. Typically, the LOI is given as the volume percent of oxygen in the oxygen and nitrogen mixture injected during the test.

Foaming gas may be present within the independent cells of the organic layer. The foaming gas contributes to the creation of independent cells of the desired shape and number during the foaming process for manufacturing the organic layer, and may be trapped within the independent cells created during the foaming process, thereby contributing to the insulating performance of the organic layer.

There is no particular limitation on the type of foaming gas, but for example, hydrocarbons and/or halogenated hydrocarbons can be applied.

As the hydrocarbon, for example, a cyclic, linear or branched alkane, alkene and/or alkyne having 3 to 7 carbon atoms can be used, and specifically, normal butane, isobutane, cyclobutane, normal pentane, isopentane, cyclopentane, neopentane, normal hexane, isohexane, 2,2-dimethylbutane, 2,3-dimethylbutane and/or cyclohexane can be used.

As the halogenated hydrocarbon, for example, a linear or branched chlorinated aliphatic hydrocarbon having 2 to 5 carbon atoms can be used. There is no particular limitation on the number of halogens (e.g., chlorine) applied, but approximately 1 to 4 halogens can be applied. As such chlorinated aliphatic hydrocarbons, for example, chloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and/or isopentyl chloride can be used.

The foaming gas may be present in an amount of about 1 to 25 parts by weight relative to 100 parts by weight of the organic material (e.g., phenol resin, polystyrene, polyurethane, and/or polyisocyanurate, etc., described below) included in the organic layer, but is not limited thereto.

The above organic layer may be a phenol resin foam layer, a polystyrene foam layer, a polyurethane foam layer, and/or a polyisocyanurate foam layer, or a foam layer of a material in which two or more of the above materials are mixed.

Accordingly, the organic layer may include at least one selected from the group consisting of phenol resin, polystyrene, polyurethane, and polyisocyanurate.

The organic layer may contain a flame retardant or flame retardant synergist to ensure the above-described semi-combustible and flame-retardant performance. Typically, such flame retardants and/or flame retardant synergists affect the foaming process for forming the organic layer, hindering the formation of independent cells of the desired shape or number, or reducing the stability of the inner walls of already formed independent cells. Therefore, when a flame retardant or flame retardant synergist is included, it is not easy to stably maintain the insulating performance, mechanical properties, lightweight, and other characteristics of the organic layer and the insulating material containing it at the desired level.

In this application, it was confirmed that the application of a specific combination of flame-retardant components, described below, secures the desired flame-retardant and quasi-flame-retardant properties even in relatively small amounts, without interfering with the formation of designed independent cells during the foaming process. Therefore, an organic layer comprising the combination of flame-retardant components described below can exhibit the aforementioned properties, such as insulation performance, mechanical strength, and lightweight characteristics, along with excellent quasi-flame-retardant and quasi-flame-retardant properties.

The organic layer of the present application may first include a phosphorus compound as a flame retardant component. As the phosphorus compound, any known component known to impart flame retardancy may be used without particular limitation.

As such phosphorus compounds, one or a combination of two or more selected from phosphorus esters such as phosphoric acid esters, aromatic condensed phosphoric acid esters, or halogenated phosphoric acid esters, or phosphazenes, etc. can be used.

The above-mentioned phosphorus compound is already known as a component capable of imparting flame retardancy or near-flammability to insulation materials. Therefore, when the above-mentioned phosphorus compound is used alone, it may be possible to secure near-flammability and flame retardancy properties, but it is not possible to simultaneously secure the desired properties, such as insulation.

Therefore, in the present application, one or more compounds selected from the group consisting of a sulfonamide compound and/or a sulfenimide compound are applied as a flame retardant component in combination with the above-described phosphorus compound. The sulfonamide compound is a compound containing a bond between one nitrogen atom and a sulfur atom (a bond represented by the following chemical formula 1), and the sulfenimide compound is a compound containing a structure in which two sulfur atoms are bonded to one nitrogen atom (a bond represented by the following chemical formula 2). In a broad sense, the sulfenimide compound can be included in the category of the sulfenamide compound, and in the present specification, compounds containing a bond represented by the following chemical formula 1 or 2 can be collectively referred to as sulfenamide compounds.

[Chemical Formula 1]

[Chemical Formula 2]

It is not clear why these compounds, when combined with phosphorus compounds, provide semi-combustible and flame-retardant properties along with insulating properties.

Assuming that the sulfenamide or sulfenimide compound generates an aminyl radical and a thiyl radical by thermal decomposition, and the generated radicals impart a self-extinguishing function to the ignition part or high-temperature area, it appears that excellent flame-retardant and semi-flame-retardant performance is secured even with a relatively small amount of flame-retardant components due to a synergistic effect resulting from the combination of the self-extinguishing function imparted by the radicals generated by the sulfenamide and/or sulfenimide and the flame-retardant or semi-flame-retardant performance of the phosphorus compound.

In addition, it appears that the viscosity characteristics of the mixture of flame retardant components, which can achieve a uniform dispersion state without adversely affecting the formation of designed independent cells during the manufacturing process including the foaming process for forming an organic layer, are achieved by the interaction by attraction between the above-mentioned compound and sulfenamide and/or sulfenimide.

This synergistic effect is achieved only when the phosphorus compound is mixed with the sulfenamide and/or sulfenimide, and appears to be difficult to achieve through mixing other known flame retardant ingredients.

As the above sulfenamide or sulfenimide compound, any known compound can be applied without any particular limitation, as long as it is a compound that includes a bonding structure of one nitrogen atom and a sulfur atom (S-N) or a structure in which two sulfur atoms are bonded to one nitrogen atom (S-N-S).

For example, compounds such as SF201, SF203 or SF205 from Songwon Industry can be used as the above compounds.

In one example, suitable compounds include, but are not limited to, compounds in which a heterocyclic structure such as benzothiazole is connected to a sulfur atom in the chemical formula 1 or 2, or compounds in which a nitrogen atom in the structure of the chemical formula 1 or 2 forms a phthalimide structure.

The ratio of the flame retardant components within the organic layer can be appropriately controlled depending on the desired effect.

For example, among the flame retardant components, the phosphorus compound may be present in the organic layer at a ratio of about 0.5 to 20 wt%. The ratio is the ratio of the phosphorus compound based on the total weight of the organic layer. In other examples, the ratio may be about 1 wt% or more, 1.5 wt% or more, 2 wt% or more, 2.5 wt% or more, 3 wt% or more, 3.5 wt% or more, or 4 wt% or more, or about 19 wt% or less, 18 wt% or less, 17 wt% or less, 16 wt% or less, 15 wt% or less, 14 wt% or less, 13 wt% or less, 12 wt% or less, 11 wt% or less, 10 wt% or less, 9 wt% or less, 8 wt% or less, 7 wt% or less, 6 wt% or less, or 5 wt% or less.

For example, among the flame retardant components, the sulfenamide and/or sulfenimide compounds may be present in the organic layer at a ratio ranging from about 0.01 to 15 wt%. The ratio is the ratio of the sulfenimide and/or sulfenamide compound based on the total weight of the organic layer. The above ratio is, in other examples, 0.05 wt% or more, 0.1 wt% or more, 0.15 wt% or more, 0.2 wt% or more, 0.25 wt% or more, 0.3 wt% or more, 0.35 wt% or more, 0.4 wt% or more, 0.45 wt% or more, 0.5 wt% or more, 0.55 wt% or more, 0.6 wt% or more, 0.65 wt% or more, 0.7 wt% or more, 0.75 wt% or more, 0.8 wt% or more, 0.85 wt% or more, 0.9 wt% or more, 0.95 wt% or more, 1 wt% or more, 1.5 wt% or more, 2 wt% or more, 2.5 wt% or more, or 3 wt% or less, 14 wt% or less, 13 wt% or less, 12 wt% or less, 11 wt% or less, 10 wt% or less, 9 wt% or less, It may be 8 wt% or less, 7 wt% or less, 6 wt% or less, 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, 1.5 wt% or less, or 1 wt% or less.

In another example, the phosphorus compound may be included in the organic layer in a ratio of 1 to 20 parts by weight relative to 100 parts by weight of the cured resin included in the organic layer. The organic layer typically applied to insulation is manufactured by introducing a raw material in which a cured resin is mixed with other additives (e.g., a foaming agent, etc.) into a foaming and curing process, and the cured resin may be a phenol resin, polystyrene, polyurethane, and/or polyisocyanurate. In addition, the cured resin in the present specification may mean a curable resin before curing or a cured curable resin. When such a cured resin is used as a standard, the phosphorus compound may be included in a ratio of 1 to 20 parts by weight relative to 100 parts by weight of the cured resin. The above ratio may be, in other examples, about 1.5 parts by weight or more, 2 parts by weight or more, 2.5 parts by weight or more, 3 parts by weight or more, 3.5 parts by weight or more, 4 parts by weight or more, or 4.5 parts by weight or more, or 19 parts by weight or less, 18 parts by weight or less, 17 parts by weight or less, 16 parts by weight or less, 15 parts by weight or less, 14 parts by weight or less, 13 parts by weight or less, 12 parts by weight or less, 11 parts by weight or less, 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, 6 parts by weight or less, or 5.5 parts by weight or less, relative to 100 parts by weight of the cured resin.

In the case of the cured resin as described above, among the flame retardant components, the sulfenamide and/or sulfenimide compound may be included in the organic layer at a ratio of 0.01 to 10 parts by weight relative to 100 parts by weight of the cured resin. The above ratio may be, in other examples, about 0.05 parts by weight or more, 0.1 parts by weight or more, 0.15 parts by weight or more, 0.2 parts by weight or more, 0.25 parts by weight or more, 0.3 parts by weight or more, 0.35 parts by weight or more, 0.4 parts by weight or more, 0.45 parts by weight or more, 0.5 parts by weight or more, 0.55 parts by weight or more, 0.6 parts by weight or more, 0.65 parts by weight or more, 0.7 parts by weight or more, 0.75 parts by weight or more, 0.8 parts by weight or more, 0.85 parts by weight or more, 0.9 parts by weight or more, or 0.95 parts by weight or more, or 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, 6 parts by weight or less, 5 parts by weight or less, 4 parts by weight or less, 3 parts by weight or less, 2 parts by weight or less, or 1.5 parts by weight or less, relative to 100 parts by weight of the cured resin.

For example, the ratio (P/S) of the weight (P) of the phosphorus compound to the weight (S) of one or more compounds selected from the group consisting of sulfenimide compounds in the organic layer may be in the range of 0.5 to 20. The ratio may be 1 or more, 1.5 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, 4 or more, 4.5 or more, or 5 or more, or 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, 13 or less, 12 or less, 11 or less, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, or 5 or less in other examples.

By controlling the ratio of the flame retardant component within the above range according to the purpose, an organic layer or insulating material with the desired performance can be obtained.

The method for manufacturing the organic layer described above is not particularly limited, and can be manufactured, for example, according to a known method for manufacturing an organic foam board. Such an organic foam board can be manufactured by applying a raw material containing a phenol resin, polystyrene, polyurethane, and/or polyisocyanurate, or a precursor thereof, and other components such as a foaming agent (foaming gas) to a foaming process. During this process, the raw material may contain the aforementioned flame retardant component.

As described, the flame retardant component applied in the present application is achieved by the interaction between the compound and sulfenamide and/or sulfenimide, which has viscosity characteristics that enable a uniform dispersion state to be achieved without adversely affecting the formation of the desired independent bubbles during the manufacturing process of the organic layer, and thus, the organic layer of the desired shape can be effectively manufactured.

Hereinafter, a method for manufacturing an organic layer is described as an example based on the case where the organic layer is a phenol resin foam layer manufactured from phenol resin. However, the organic layer applicable to the present application is not limited to the phenol resin foam layer. Methods for forming an organic board including the desired independent cells depending on the material applied to form the organic layer are known, and for manufacturing the organic layer of the present application, it is sufficient to appropriately include a flame retardant component in the desired ratio in such known methods.

The phenol resin foam layer as an organic layer can be manufactured by foaming and curing a composition (raw material) containing a phenol resin, a curing catalyst, a foaming agent (foaming gas), and a surfactant, and in this process, the flame retardant component is additionally mixed into the raw material according to the intended ratio.

As a phenol resin, for example, a resin can be used that uses phenols and aldehydes as raw materials and polymerizes the raw materials by heating them in the temperature range of approximately 40°C to 100°C using an alkaline catalyst. If necessary, an additive such as urea may be added during the polymerization of the resole resin. When urea is added, urea that has been methylolated in advance with an alkaline catalyst can be mixed with the resole resin. Since the phenol resin after synthesis usually contains excess water, a dehydration process to a foamable moisture content may be added. The moisture content in the phenol resin can be adjusted to, for example, 1 to 10 wt%, 1 to 7 wt%, 2 to 5 wt%, or 2 to 4.5 wt%, but is not limited thereto. The moisture content in the phenol resin can be controlled within an appropriate range in consideration of the efficiency of the process, such as productivity, and the quality of the product, such as dimensional stability.

In phenol resins, the starting molar ratio of phenols to aldehydes can typically be within the range of 1:1 to 1:4.5 or 1:1.5 to 1:2.5.

Examples of phenols used in the synthesis of phenol resins include phenol or compounds having a phenol skeleton. Examples of compounds having a phenol skeleton include resorcinol, catechol, o-, m-, and p-cresol, xylenols, ethylphenols, p-tert butylphenol, etc., and dinuclear phenols can also be used.

Examples of aldehydes used in the production of phenol resins include formaldehyde (formalin) and aldehyde compounds other than formaldehyde. Examples of aldehyde compounds other than formaldehyde include glyoxal, acetaldehyde, chloral, furfural, and benzaldehyde. Additives such as urea, dicyandiamide, or melamine may be added to aldehydes. In addition, when these additives are added, the term "phenol resin" refers to the resin after the additives have been added.

The viscosity of the phenol resin may be approximately 5,000 mPa·s to 100,000 mPa·s at 40°C, and this may be controlled from the perspective of the desired independent cell ratio or manufacturing cost. The viscosity (40°C) may, in other examples, be approximately 7,000 to 50,000 mPa·s or 10,000 to 40,000 mPa·s.

The residual phenol contained in the phenol resin can be controlled to about 1.0 to 4.3 wt%, 2.3 to 4.25 wt%, or 2.7 to 4.2 wt% from the viewpoint of ease of adjustment of the phenol resin or securing foaming properties. The proportion of the residual phenol can be adjusted in consideration of the dimensional stability, strength, and independent cell rate of the organic layer.

The phenol resin may contain additives, and for example, phthalic acid esters or glycols such as ethylene glycol and diethylene glycol, which are commonly used as plasticizers, can be used. In addition, aliphatic hydrocarbons, high-boiling-point alicyclic hydrocarbons, or mixtures thereof may be used. When included, the content of the additives can be controlled within the range of 0.5 to 20 parts by weight per 100 parts by weight of the phenol resin. The content of the additives can be controlled in consideration of the application purpose of the additives and the viscosity of the material, etc.

As the foaming gas included in the raw material, the type of foaming gas described above can be used. The amount of foaming gas used can be, for example, in the range of 1 to 25 parts by weight or 1 to 15 parts by weight per 100 parts by weight of phenol resin.

The surfactant included in the raw materials can be one generally used in the production of a phenol resin foam layer, and among them, nonionic surfactants are effective. Examples of nonionic surfactants include alkylene oxides, which are copolymers of ethylene oxide and propylene oxide; condensates of alkylene oxides and castor oil; condensates of alkylene oxides and alkylphenols such as nonylphenol and dodecylphenol; polyoxyethylene alkyl ethers having 14 to 22 carbon atoms in the alkyl ether moiety; furthermore, fatty acid esters such as polyoxyethylene fatty acid esters; silicone compounds such as polydimethylsiloxane; and polyalcohols. Surfactants may be used singly or in combination of two or more. The amount of surfactant used is not particularly limited, but is usually in the range of 0.3 to 10 parts by weight per 100 parts by weight of the phenol resin.

As the curing catalyst, any curing catalyst capable of curing a phenol resin may be used. For example, an acidic curing catalyst may be used. As the curing catalyst, an anhydride curing catalyst may be used. Examples of the anhydride curing catalyst include phosphoric anhydride and arylsulfonic anhydride. Examples of the arylsulfonic anhydride include toluenesulfonic acid, xylenesulfonic acid, phenolsulfonic acid, substituted phenolsulfonic acid, xylenolsulfonic acid, substituted xylenolsulfonic acid, dodecylbenzenesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, etc. The curing catalyst may be used alone, or two or more types may be used in combination. In addition, resorcinol, cresol, saligenin (o-methylolphenol), p-methylolphenol, etc. may be added as a curing aid. In addition, these curing catalysts may be diluted with a solvent such as ethylene glycol or diethylene glycol. There is no particular limitation on the amount of hardener to be used, but it is usually in the range of 3 to 30 parts by weight per 100 parts by weight of phenol resin.

A foamable phenol resin composition (raw material) can be obtained by mixing the above phenol resin, the above curing catalyst, the above foaming agent, and the above surfactant, and also mixing the above flame retardant component. A phenol resin foam layer can be obtained by foaming and curing the obtained foamable phenol resin composition.

For example, the foaming/curing process may be performed while maintaining the composition in a desired shape. For example, when the insulation material comprises the organic layer as a core material and a face material on one or both sides thereof, as described below, the foaming/curing process may be performed on the face material or between the face materials.

For example, the phenol resin composition may be dispensed onto a cotton sheet, and if necessary, the side opposite to the side of the phenol resin composition that comes into contact with the cotton sheet may be covered with an additional cotton sheet, and a foaming and curing process may be performed.

This foaming process can typically be performed at a temperature of approximately 40°C to 120°C, and if necessary, the foaming process can be performed by changing the process temperature in multiple stages. The appropriate process conditions, such as the foaming temperature, depending on the type of raw material are known.

The insulation may additionally include other components in addition to the organic layer. For example, when the organic layer is used as a core material of the insulation, the insulation may additionally include a cotton material on one or both sides of the organic layer.

As the cotton material, any known composition can be used without special restrictions. For example, the cotton material can be a synthetic fiber nonwoven fabric, a synthetic fiber woven fabric, a glass fiber paper, a glass fiber woven fabric, a glass fiber nonwoven fabric, a glass fiber mixed paper, paper, a metal film, or a combination thereof. The cotton material can also contain a flame retardant to impart flame retardant and semi-flame retardant properties.

In addition to the above composition, the insulation may also include other compositions as required.

The insulating material of the present application can be used as a representative building material, but the use of the insulating material is not limited thereto.

The present application can provide an insulating material that simultaneously maintains excellent insulation performance, semi-combustibility, and flame retardancy. The insulating material can also maintain excellent handling, workability, lightness, cuttability, and mechanical strength.

The present application is specifically described through the following examples, but the scope of the present application is not limited by the following examples.

1. Method for analyzing thermal conductivity and thermal transmittance

The thermal conductivity of the organic layer was measured using a measuring device (Manufacturer: Eko Instruemts Trading, Product Name: HC-704). The sample was placed between hot plates maintained at 10°C and 30°C, respectively, and the heat flow was checked to evaluate the thermal conductivity. The thermal conductivity was measured for samples with a width, length, and thickness of 300 mm, 300 mm, and 50 mm, respectively. The thermal transmittance was obtained by dividing the measured thermal conductivity of the organic layer by the thickness of the organic layer (sample).

2. Evaluation of flame retardant and semi-flammable properties

The flame retardancy and semi-fire retardancy properties of the organic layer were evaluated by measuring the reduction rate of 5-minute heat release (THR300s), 10-minute heat release (THR600s), maximum heat release, and 10-minute heat release (THR600s) according to the KS F 5660-1 test method.

Specifically, the 5-minute heat release (THR300s), 10-minute heat release (THR600s) and maximum heat release were each evaluated by measuring the heat release for 10 minutes under 50 kW/m ² conditions for the sample (organic layer) using a cone calorimeter.

In addition, the reduction rate of the 10-minute heat release (THR600s) was evaluated by the following mathematical formula A.

[Formula A]

Decrease rate of 10-minute heat release (THR600s) = 100 - 100 × (H2/H1)

In the above formula A, H1 is the THR600 of the reference, and H2 is the THR600 of the sample.

3. Measurement of independent bubble ratio and average diameter of independent bubbles

The independent void ratio was measured using an independent void ratio measuring device (Quantachrome, ULTRAPYC 1200e) according to the KS M ISO 4590 standard. For the measurement, the organic layer was cut into sizes of 2.5 cm in length, 2.5 cm in width, and 2.5 cm in thickness, respectively, and used as a sample.

The average diameter of the independent bubbles in the organic layer was measured using an electron microscope and the ImageJ program. One side of the organic layer was cut with a razor blade, peeled, photographed using an electron microscope, and approximately 150 circular shapes were drawn on the surface. The average diameter was then measured using the ImageJ program. This method of measuring the average diameter is well known.

4. Measurement of compressive strength

Compressive strength was measured using the compressive strength measurement method specified in KS M ISO 844. The compressive strength was measured for samples with a width, length, and thickness of 50 mm, 50 mm, and 200 mm, respectively, and the compressive strength was measured while compressing the sample in the thickness direction at a load concentration rate of 20 mm/min.

5. Measurement of the limiting oxygen index (LOI)

The limiting oxygen index (LOI) of the organic layer was measured using a flammability tester (Stanton Redcroft, United Kingdom) according to ASTM D2863/77. It was determined by calculating the minimum concentration of oxygen required to sustain combustion of the organic layer.

Example 1.

The organic layer (phenol resin foam layer) was manufactured in the following manner.

To the resol phenol resin, 3.5 parts by weight of a castor oil surfactant and 5 parts by weight of powdered urea were added relative to 100 parts by weight of the resin. In addition, 5 parts by weight of red chromium and 1 part by weight of a sulfenamide compound (SF201, manufactured by Songwon Industrial Co., Ltd.) were blended relative to 100 parts by weight of the phenol resin as flame retardant components. The SF201 is N-(1,1-dimethylethyl)bis(2-benzothiazolesulfen)amide. In addition, 4 parts by weight of pentaerythritol and 1 part by weight of TEP (Triethyl phosphate) were added relative to 100 parts by weight of the phenol resin, and the mixture was sufficiently stirred at a uniform speed of 1000 rpm for 3 minutes to make a premix, which was then left to stand for 1 hour. All of the above processes were performed at room temperature. Next, 10 parts by weight of a mixed blowing agent of isopropyl chloride/isopentane in a weight ratio of 8:2 was added to the premix based on 100 parts by weight of the phenol resin, and the mixture was sufficiently stirred at a uniform speed of 1000 rpm for 1 minute, and then placed in a low-temperature chamber to lower the temperature to 10°C. Thereafter, 17 parts by weight of a liquid mixture containing paratoluenesulfonic acid (PTSA) was added based on 100 parts by weight of the phenol resin, and stirred at high speed at 2000 rpm for 30 seconds. Then, the mixture was placed in a 70°C mold at a density of 50 kg/m ³ and foamed/cured for 7 minutes to produce a phenol resin foam layer. The foam produced from the mold was taken out and cured in an oven at 80°C for 24 hours.

Example 2.

The organic layer (phenol resin foam layer) was manufactured in the following manner.

To the resol phenol resin, 3.5 parts by weight of a castor oil surfactant and 5 parts by weight of powdered urea were added relative to 100 parts by weight of the resin. In addition, 5 parts by weight of red cyanide and 1 part by weight of a sulfenamide compound (SF205, manufactured by Songwon Industrial Co., Ltd.) were blended as flame retardant components relative to 100 parts by weight of the phenol resin. The SF205 is N-(cyclohexylthio)phthalimide. In addition, 4 parts by weight of pentaerythritol and 1 part by weight of TEP (Triethyl phosphate) were added relative to 100 parts by weight of the phenol resin, and a premix was made by sufficiently stirring at a uniform speed of 1000 rpm for 3 minutes, and then left to stand for 1 hour. All of the above processes were performed at room temperature. Next, 10 parts by weight of a mixed blowing agent of isopropyl chloride/isopentane in a weight ratio of 8:2 was added to the premix based on 100 parts by weight of the phenol resin, and the mixture was sufficiently stirred at a uniform speed of 1000 rpm for 1 minute, and then placed in a low-temperature chamber to lower the temperature to 10°C. Thereafter, 17 parts by weight of a liquid mixture containing paratoluenesulfonic acid (PTSA) was added based on 100 parts by weight of the phenol resin, and stirred at high speed at 2000 rpm for 30 seconds. Then, the mixture was placed in a 70°C mold at a density of 50 kg/m ³ and foamed/cured for 7 minutes to produce a phenol resin foam layer. The foam produced from the mold was taken out and cured in an oven at 80°C for 24 hours.

Comparative Example 1.

An organic layer (phenolic resin foam layer) was manufactured in the same manner as in Example 1, except that the flame retardant component was not applied.

Comparative Example 2.

An organic layer (phenolic resin foam layer) was manufactured in the same manner as in Example 1, except that the flame retardant component was not applied.

The characteristics of each organic layer manufactured above are summarized and shown in Table 1 below.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Thermal conductivity (W/m·K) 0.01937 0.01937 0.01959 0.01902 Thermal transmittance (W/m ² ·K) 0.1937 0.1937 0.1959 0.1902 THR300s(MJ/m ² ) 2~5 2~4 5~8 13 THR600s(MJ/m ² ) 5~12 5~11 8~16 21.8 Peak HRR(kW/m ² ) 22.9 22.5 49.5 57.2 THR600s reduction rate 60 60 13 - Density (Kg/m ³ ) 38 38 37 36 Independent bubble rate (%) 90 90 88 91 Average diameter of independent bubbles (μm) 90 90 96 94 Compressive strength (kPa) 125 125 118 130 Limiting oxygen index (LOI) (%) 38 37 35 35

Claims (15)

It includes an organic layer containing independent bubbles with foaming gas inside, a thermal transmittance of 0.4 W/m ² ·K or less, and a 5-minute heat release rate of 11.0 MJ/m ² or less according to the KS F 5660-1 test method,
The organic layer further comprises a compound having one or more bonds selected from the group consisting of the following chemical formulas 1 and 2, including a phosphorus compound.
The ratio (P/S) of the weight of the compound (P) to the weight of the compound (S) having at least one bond selected from the group consisting of chemical formulas 1 and 2 is in the range of 0.5 to 10,
An insulating material in which the organic layer comprises a cured resin and the phosphorus compound is included in the organic layer in a ratio of 1 to 10 parts by weight relative to 100 parts by weight of the cured resin:
[Chemical Formula 1]

[Chemical Formula 2]
In the first paragraph, the foaming gas is an insulating material selected from the group consisting of hydrocarbons and halogenated hydrocarbons. In the first paragraph, an insulating material having an independent cell ratio of the organic layer of 75% or more. In the first paragraph, the organic layer is an insulating material having a density in the range of 20 to 70 Kg/m ³ . In the first paragraph, the organic layer is an insulating material having a compressive strength of 90 kPa or more. In the first paragraph, the organic layer is an insulating material having a limiting oxygen index of 35% or more. In the first paragraph, the organic layer is an insulating material having a 10-minute heat release rate of 18 MJ/m ² or less according to the KS F 5660-1 test method. In the first paragraph, the organic layer is an insulating material having a maximum heat release of 55 kW/m ² or less according to the KS F 5660-1 test method. In the first paragraph, the organic layer is an insulating material having a reduction rate of 60% or more in heat release after 10 minutes according to the KS F 5660-1 test method. In the first paragraph, the organic layer is an insulating material comprising at least one selected from the group consisting of phenol resin, polystyrene, polyurethane, and polyisocyanurate. delete In the first paragraph, the insulating material is at least one selected from the group consisting of phosphorus compounds, phosphazenes and phosphoric acid esters. delete In the first paragraph, an insulating material in which the organic layer comprises a cured resin, and a compound having at least one bond selected from the group consisting of chemical formulas 1 and 2 is included in the organic layer in a ratio of 0.01 to 10 parts by weight relative to 100 parts by weight of the cured resin. delete