KR20220091416A - Insulator - Google Patents

Abstract

The present application can provide an insulating material excellent in heat insulation performance, semi-incombustible performance and flame retardant performance at the same time, and excellent in handling, workability, lightness, cutability and mechanical strength.

Description

Insulator {Insulator}

This application relates to a heat insulating material.

Insulation is a material used for the purpose of preventing, delaying, or alleviating heat loss or inflow of heat, and a typical use is as a building material, but in addition, it can be used for various purposes requiring warmth or cooling.

As an organic heat insulating material, a material manufactured in the form of a foam by foaming a resin component such as phenol resin, polystyrene, polyurethane, and/or polyisocyanurate is known representatively.

In the above foaming process, so-called closed cells are formed in the foam, and thermal insulation performance may be exhibited by the formed closed cells. That is, the closed cell ratio due to the closed cells formed in the above foaming process or the size of the closed cells are important factors that determine the performance of the insulating material.

Therefore, in the foaming process for the manufacture of the heat insulating material, the conditions and materials of the foaming process are controlled so that closed cells capable of exhibiting the optimal heat insulation performance according to the applied material are formed.

Depending on the use, so-called semi-non-flammable performance or flame-retardant performance is required for a heat insulating material, and in particular, in the case of a building insulation material, the demand for the semi-non-flammable or flame-retardant performance is further increased due to fire risk.

In order to secure the semi-nonflammable or flame-retardant performance of the insulator, a method of simply mixing the flame retardant with the insulator can be considered.

However, the blended flame retardant affects the foaming process for the formation of the heat insulator to form closed cells of different shapes or numbers than those designed for the heat insulator, and also reduces the stability of the inner wall of the formed closed cells.

Therefore, the compounding of the flame retardant lowers the heat insulating property, which is the basic performance of the heat insulating material. In particular, when more flame retardants are applied to secure higher semi-incombustible or flame-retardant performance, the extent of deterioration of the thermal insulation performance of the insulator is further increased.

This application relates to a heat insulating material. An object of the present application is to provide an insulating material in which thermal insulation performance, semi-incombustible performance, and flame-retardant performance are maintained excellently at the same time. Another object of the present application is to provide an insulating material excellent in handleability, workability, lightness, cutability, mechanical strength, and the like.

Among the physical properties mentioned in this specification, when the measured temperature and/or pressure affect the physical properties, unless otherwise specified, the corresponding physical properties refer to properties measured at room temperature and/or pressure.

In the present application, the term room temperature is a natural temperature that is not heated or reduced, and for example, may mean any temperature within the range of about 10°C to 30°C, a temperature of about 25°C or 23°C.

In the present application, the term atmospheric pressure is a pressure when not particularly reduced or increased, and may refer to an atmospheric pressure of about 740 mmHg to 780 mmHg, such as atmospheric pressure.

Among the physical properties mentioned in the present specification, when the measured humidity affects the physical property, unless otherwise specified, the physical property means a property measured in natural humidity that is not specially adjusted in the measurement temperature and pressure state do.

The heat insulating material of the present application includes at least one organic material layer. The term organic layer is a layer containing an organic material as a main component. In the present specification, that a component is included as a main component means that the weight ratio of the component is about 55% by weight or more, about 60% by weight or more, about 65% by weight or more, about 70% by weight or more, about 75% by weight or more, about 80 It may mean a case of at least about 85 wt%, or at least about 90 wt% by weight. 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 is about 100% by weight or less, 99% by weight or less, 98% by weight or less, 97% by weight or less, 96% by weight or less, or about It may be about 95% by weight or less. The meaning of the term organic in this specification is as known in the art. Typically, the organic material may be a cured resin to be described later, 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. In the organic material layer of the present application, in a state in which excellent flame-retardant and semi-flammable performance to be described later are secured, the closed cells may exist so that the designed thermal insulation performance can be stably implemented. Accordingly, excellent thermal insulation performance, semi-incombustible performance, and flame-retardant performance are secured at the same time in the insulating material of the present application.

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

Usually, the thermal insulation performance is confirmed by the thermal transmittance rate. Thermal transmittance is a physical quantity obtained by dividing thermal conductivity by thickness. The heat insulating material or the organic material layer may have a thermal transmittance of about 0.4 W/m ² ·K or less. In another example, 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. As for the thermal transmittance, the lower the value, the more advantageous the effect is, and the lower limit thereof is not particularly limited. For example, in another example, the thermal transmittance is 0 W/m ² ·K or more, 0 W/m ² ·K or more, 0.05 W/m ² ·K or more, 0.1 W/m ² ·K or more, or 0.15 W/m ² · It can be about K or more.

The thermal transmittance of the insulating material or the organic material layer can be measured by the flat plate heat flow meter method based on the method for measuring the thermal conductivity of the insulating material according to KS L 9016. In this method, a temperature difference of 10 or more is generated on both sides of the specimen, the amount of heat flow passing through the specimen is electrically measured, and the thermal conductivity is obtained by measuring the temperature difference of the specimen.

The heat insulating material or organic material of the present application may also exhibit a thermal conductivity of about 30 mW/m·K or less. In another example, the thermal conductivity is 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 is measured by the thermal ammeter method specified in the ISO 8301 standard or the thermal current measurement method according to the thermal conductivity measurement standard of the insulating material specified in the KS L 9016 standard, the direct plate method, the flat plate comparison method, or the thermal ammeter method of EKO, which employs the thermal ammeter method. It can be measured using HC-074 thermal conductivity measuring equipment.

The organic material layer of the present application may have a density in the range of about 20 to 70 Kg/m ³ . In insulation materials, density is a function of heat conduction properties. A heat insulating material including an organic material having a density within the above range may exhibit excellent heat insulating properties. Also, in terms of securing lightness, the density may be in an appropriate range. In another example, the density is 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 It may be about 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 such an organic material layer can be measured based on JIS-K-7222 standard.

The organic material layer may also have a weight per unit area of 2 to 20 Kg/m ² in the range. The organic material layer of the present application may exhibit the heat insulation, semi-incombustibility and flame-retardant performance while exhibiting advantageous effects such as lightness through the weight per unit area. In another example, the weight per unit area is 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 Alternatively, it may be about 8 Kg/m ² or less.

The heat insulating material or the organic material layer may exhibit excellent mechanical strength. For example, the heat insulating material or the organic material may have a compressive strength of 90 kPa or more. In another example, the compressive strength is 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 300 kPa or less, 280 kPa or less, 260 kPa or less, 240 It may be about 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 insulating material or organic layer can be measured by the method of confirming the compressive strength specified in KS M ISO 844.

The heat insulating material or organic material layer of the present application may simultaneously exhibit excellent thermal insulation performance, semi-incombustible performance and flame retardant performance even in a state of being lightweight and having excellent mechanical strength.

These characteristics can be achieved by controlling the number and shape of the closed cells present in the organic material layer and components present in the closed cells. In the present application, in particular, in order to impart excellent flame-retardant and quasi-non-flammable performance to the insulating material and organic material, the number and shape of the closed cells can be stably maintained so that the desired performance can be expressed even when the composition is controlled.

For example, the organic material layer may have a closed cell ratio of 75% or more. In another example, the closed cell rate is 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, It may be on the order of 93% or less, 91% or less, 89% or less, or 87% or less. The organic material layer having the closed cell ratio in this range can effectively satisfy the above-mentioned properties.

The closed cell rate of the organic material layer can be measured using an appropriate measuring device (ex. Quantachrome, ULTRAPYC 1200e) according to KS M ISO 4590 standard, and the method of measuring the closed cells of the organic material layer used as a heat insulator is known.

The closed cells present in the organic layer may have an average diameter in the range of 70 νm to 200 νm. The organic material layer having closed cells having an average diameter in this range can effectively satisfy the above-mentioned properties. The average diameter is 75νm or more, 80νm or more, 85νm or more, or 90νm or more, or 190νm or less, 180νm or less, 170νm or less, 160νm or less, 150νm or less, 140νm or less, 130νm or less, 120νm or less, 110νm or less or 100νm or less in another example. may be

A method for measuring the average diameter of closed cells of the organic layer is known. For example, the average diameter may be measured using a general electron microscope and an image J program. Usually, a sample is first cut with a razor blade, etc. to be peeled, then photographed with an electron microscope, and circular shapes are drawn in about 150 sizes, and then the average diameter can be measured using the Image J program.

The heat insulating material and organic layer of the present application may exhibit excellent thermal insulation performance, light weight, mechanical strength, etc., while having closed cells of the above-mentioned form, and at the same time exhibit excellent semi-incombustible and flame retardant performance.

For example, the heat insulating material or the organic layer may have a heat release rate (THR300s) of 11 MJ/m ² or less in 5 minutes according to the KS F 5660-1 test method. The 5 minute heat release (THR300s) is 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. The lower limit of the 5-minute heat release (THR300s) is not particularly limited because the lower the value, the better the flame-retardant and semi-non-flammable performance. In one example, the five-minute heat release (THR300s) may be about 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 heat insulating material or the organic layer may have a heat release rate (THR600s) of 18 MJ/m ² or less in 10 minutes according to the KS F 5660-1 test method. The 10-minute heat release (THR600s) is 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 10-minute heat release (THR600s) is not particularly limited because the lower the value, the better the flame-retardant and semi-non-flammable performance. In one example, the 10-minute heat release (THR600s) is 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 It can be on the order of /m ² or more.

For example, the heat insulator or the organic layer may have a maximum heat release (peak HRR) of 55 kW/m ² or less according to the KS F 5660-1 test method. The maximum heat dissipation (peak HRR) is 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 or less, 23 kW/m ² or less, or 21 kW/m ² or less. The lower limit of the maximum heat release (peak HRR) is not particularly limited because the lower the value, the better the flame-retardant and quasi-non-flammable performance. In one example, the maximum heat release (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 insulating material or the organic material layer, according to the KS F 5660-1 test method, the reduction rate of the heat release amount (THR600s) in 10 minutes may be 25% or more. The reduction rate of the 10-minute heat release (THR600s) is 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, 70% or less, 68% or more, 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% or less, 34% or less, or 32% or less.

The insulating material or the organic material layer may also have a limiting oxygen index (LOI) of about 15% or more. The limiting oxygen index is, in another example, 20% or more, 25% or more, 30% or more, or 35% or more, 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 of the insulating material or organic material layer can be confirmed by calculating the minimum concentration of oxygen required to sustain combustion according to the test conditions specified in ASTM D2863/77 standard. The limiting oxygen index is usually given as a percentage by volume of oxygen in the oxygen and nitrogen mixture injected during the test.

A foaming gas may be present in the closed cells of the organic material layer. The foaming gas contributes to generating a desired shape and number of closed cells in the foaming process for producing the organic material layer, and is trapped in the closed cells generated in the foaming process, thereby contributing to the thermal insulation performance of the organic material layer.

There is no particular limitation on the type of the blowing gas, but, for example, hydrocarbons and/or halogenated hydrocarbons may 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, and 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 applied halogens (eg chlorine), but approximately 1 to 4 halogens may be applied. As the chlorinated aliphatic hydrocarbon, for example, chloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride and/or isopentyl chloride may be used.

The foaming gas may be in the range of about 1 to 25 parts by weight based on 100 parts by weight of the organic material (eg, phenol resin, polystyrene, polyurethane and/or polyisocyanurate, which will be described later) included in the organic material layer, but is limited thereto it is not

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

The organic layer may include a flame retardant or a flame retardant synergist in order to secure the semi-incombustible and flame retardant performance. Usually, such a flame retardant and/or a flame retardant synergist affects the foaming process for forming the organic material layer, thereby preventing the formation of a desired shape or number of closed cells, or lowering the stability of the inner wall of the already formed closed cells. Therefore, when a flame retardant and a flame retardant synergist are included, it is not easy to stably maintain the thermal insulation performance, mechanical properties, and lightness of the organic material layer and the insulating material including the same at a desired level.

In the present application, when a specific combination of flame-retardant components described later is applied, the flame-retardant component does not interfere with the formation of designed closed cells during the foaming process, and it has been confirmed that the desired flame-retardant and semi-non-flammable performance is secured even with a relatively small amount. Accordingly, the organic material layer including a combination of flame retardant components to be described later may exhibit the above-described properties such as thermal insulation performance, mechanical strength, and light weight characteristics together with excellent semi-nonflammable and flame retardant performance.

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

As the phosphorus compound, one selected from red, aromatic phosphoric acid esters, phosphoric acid esters such as aromatic condensed phosphoric acid esters or halogenated phosphoric acid esters, phosphazenes, and the like, or a combination of two or more may be used.

The phosphorus compound is a compound already known as a component capable of imparting flame retardancy or semi-incombustibility to the heat insulating material. Therefore, when only the phosphorus compound is used alone, it may be possible to secure the semi-incombustible and flame retardant performance, but it is impossible to secure the performance at the same time as the desired thermal insulation properties.

Accordingly, 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 phosphorus compound. In the above, the sulfenamide compound is a compound including a bond between one nitrogen atom and a sulfur atom (a bond of Formula 1 below), and the sulfenimide compound has a structure in which two sulfur atoms are bonded to one nitrogen atom (Formula 2 below) It is a compound containing the bond structure of). A sulfenimide compound may be included in the category of a sulfenamide compound in a broad sense, and in the present specification, a compound including a bond of Formula 1 or 2 may be collectively referred to as a sulfenamide compound.

[Formula 1]

[Formula 2]

It is not clear why such a compound is combined with a phosphorus compound to ensure semi-incombustible and flame-retardant performance along with thermal insulation performance and the like.

Presumably, the sulfenamide or sulfenimide compound generates an aminyl radical and a thiyl radical by thermal decomposition, and the generated radicals are self-extinguishing (self-extinguishment) in the ignited part or high-temperature region. ) function, the self-extinguishing function imparted by radicals generated by sulfenamide and/or sulfenimide and the synergistic effect by the combination of the flame retardant or semi-flammable performance of the phosphorus compound It seems that excellent flame-retardant and semi-flammable performance is secured even by a relatively small amount of flame-retardant components.

In addition, the viscosity characteristics of the mixture of the flame retardant component that can achieve a uniform dispersion state without adversely affecting the formation of closed cells designed in the manufacturing process including the foaming process for forming the organic layer is the phosphorus compound and sulfenamide and / or It appears to be achieved by an attractive interaction between sulfenimides.

Such a synergistic action is achieved only when the phosphorus compound is mixed with the sulfenamide and/or sulfenimide, and it seems difficult to achieve through mixing of other known flame retardant components.

As the sulfenamide or sulfenimide compound, if it is a compound including a structure in which one nitrogen atom and a sulfur atom are bonded (S-N) or a structure in which two sulfur atoms are bonded to one nitrogen atom (S-N-S), there is no particular limitation. of compounds can be applied.

For example, as the compound, a compound such as SF201, SF203, or SF205 from Songwon Industries may be used.

In one example, suitable compounds include a compound in which a heterocyclic structure such as benzothiazole is linked to a sulfur atom in Formula 1 or 2, or a compound in which a nitrogen atom in the structure of Formula 1 or 2 forms a phthalimide structure. may be used, but is not limited thereto.

The proportion of the flame-retardant components in the organic layer may be appropriately controlled according to a desired effect.

For example, the phosphorus compound in the flame-retardant component may be present in the organic layer in a proportion in the range of about 0.5 to 20% by weight. The ratio is the ratio of the phosphorus compound based on the total weight of the organic layer. In another example, the ratio is 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 19 wt% or less, 18 wt% or more % 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 % 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 compound may be present in the organic layer in an amount ranging from about 0.01 to 15% by weight. The above ratio is the ratio of the sulfenimide and/or sulfenamide compound compound based on the total weight of the organic layer. In another example, the ratio is 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 more, or 14 wt% or less, 13 wt% or less, 12 wt% or less, 11 wt% or less, 10 wt% or less or less, 9 wt% or less, 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 It may be less than.

In another example, the phosphorus compound may be included in the organic material layer in a ratio of 1 to 20 parts by weight based on 100 parts by weight of the cured resin included in the organic material layer. The organic material layer usually applied to the insulating material is prepared by introducing a raw material blended with a cured resin with other additives (ex. foaming agent, etc.) in a foaming and curing process, etc. In this case, the cured resin is the phenol resin, polystyrene, polyurethane and / or polyisocyanurate or the like. In addition, in the present specification, the cured resin may mean a curable resin before curing or the cured curable resin. Based on the cured resin, the phosphorus compound may be included in an amount of 1 to 20 parts by weight based on 100 parts by weight of the cured resin. The ratio is 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, 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; It may be about 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.

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 material layer in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the cured resin. In another example, the ratio is 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 relative to 100 parts by weight of the cured resin. 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 or more or 0.95 parts by weight or less, 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 It may be about 1.5 parts by weight or less.

For example, in the organic layer, 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 is in the range of 0.5 to 20. can In another example, the ratio is 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 more. It may be about 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.

By controlling the ratio of the flame retardant component within the above range according to the purpose, it is possible to obtain an organic material layer or heat insulating material having a desired performance.

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

As described above, the flame-retardant component applied in the present application is a compound and sulfenamide and This is achieved by interaction between sulfenimides and/or sulfenimides by attraction, and thus an organic material layer having a desired shape can be effectively prepared.

Hereinafter, a method of manufacturing the organic material layer is exemplarily described based on the case where the organic material layer is a phenol resin foam layer made of a phenol resin, but the organic material layer applicable in the present application is not limited to the phenol resin foam layer. A method of forming an organic board including a desired closed cell according to the material applied to the formation of the organic layer is known, and for the production of the organic layer of the present application, a flame retardant component is appropriately included according to a desired ratio in such a known method you should do it

The phenol resin foam layer as an organic material layer can be prepared 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 added according to the desired ratio is blended with the above raw materials.

As the phenol resin, for example, a resin obtained by polymerizing the raw material by heating in a temperature range of about 40°C to 100°C with an alkali catalyst using phenols and aldehydes as raw materials can be used. If necessary, an additive such as urea may be added at the time of polymerization of the resol resin. When urea is added, urea previously methylolated with an alkali catalyst can be mixed with the resol resin. Since the synthesized phenolic resin usually contains excess water, a step of dehydrating to a water content capable of foaming may be added. The moisture content in the phenolic resin may be adjusted to, for example, 1 to 10% by weight, 1 to 7% by weight, 2 to 5% by weight, or 2 to 4.5% by weight, but is not limited thereto. The moisture content in the phenol resin may be controlled within an appropriate range in consideration of process efficiency such as productivity, or product quality such as dimensional stability.

In the phenol resin, the starting molar ratio of phenols to aldehydes can usually be in the range of 1:1 to 1:4.5 or 1:1.5 to 1:2.5.

As phenols used at the time of phenol resin synthesis|combination, a phenol or the compound which has a phenol skeleton is mentioned. Examples of the compound having a phenol skeleton include resorcinol, catechol, o-, m- and p-cresol, xylenols, ethylphenols, p-tert butylphenol, and the like, and dinuclear phenols may also be used. can

Examples of the aldehydes used in the production of the phenol resin include formaldehyde (formalin) or aldehyde compounds other than formaldehyde. As aldehyde compounds other than formaldehyde, glyoxal, acetaldehyde, chloral, furfural, benzaldehyde, etc. are mentioned. You may add urea, dicyandiamide, melamine, etc. to aldehydes as an additive. In addition, when adding these additives, a phenol resin refers to the thing after adding an additive.

The viscosity of the phenolic resin may be on the order of 5000 mPa·s to 100000 mPa·s at 40° C., which is a desired closed cell ratio, but can be adjusted from the viewpoint of manufacturing cost. The viscosity (40° C.) may be about 7000 to 50000 mPa·s or 10000 to 40000 mPa·s in another example.

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 easiness of adjustment of the phenol resin or securing of foamability. The ratio of the residual phenol may be adjusted in consideration of dimensional stability, strength, and closed cell ratio of the organic layer.

The phenol resin may contain an additive, for example, ethylene glycol, diethylene glycol, etc. which are phthalic acid esters and glycols generally used as a plasticizer can be used. Moreover, you may use an aliphatic hydrocarbon, a high boiling point alicyclic hydrocarbon, or a mixture thereof. When included, the content of the additive may be controlled within the range of 0.5 to 20 parts by weight based on 100 parts by weight of the phenol resin. The content of the additive may be controlled in consideration of the purpose of application of the additive and the viscosity of the material.

As the foaming gas contained in the raw material, the above-described foaming gas may be used. The amount of the blowing gas used may be, for example, in the range of 1 to 25 parts by weight or 1 to 15 parts by weight based on 100 parts by weight of the phenol resin.

Surfactants included in the raw materials may be those generally used for the production of the phenolic resin foam layer, and among them, nonionic surfactants are effective. As a nonionic surfactant, For example, alkylene oxide which is a copolymer of ethylene oxide and a propylene oxide; Condensate of alkylene oxide and castor oil; Condensates of alkylene oxide and alkylphenols such as nonylphenol and dodecylphenol; polyoxyethylene alkyl ether having 14 to 22 carbon atoms in the alkyl ether moiety; Furthermore, fatty acid esters, such as polyoxyethylene fatty acid ester; silicone compounds such as polydimethylsiloxane; polyalcohols and the like can be exemplified. Surfactant may be used independently and may be used in combination of 2 or more types. The amount of the surfactant used is not particularly limited, but is usually in the range of 0.3 to 10 parts by weight based on 100 parts by weight of the phenol resin.

As a curing catalyst, what is necessary is just a curing catalyst which can harden a phenol resin, for example, an acidic curing catalyst can be used. As the curing catalyst, an acid anhydride curing catalyst can be used. Examples of the acid 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, and naphthalenesulfonic acid. A curing catalyst may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, you may add resorcinol, cresol, saligenin (o-methylol phenol), p-methylol phenol, etc. as a hardening adjuvant. Moreover, you may dilute these curing catalysts with solvents, such as ethylene glycol and diethylene glycol. The amount of the curing agent to be used is not particularly limited, but is usually in the range of 3 to 30 parts by weight based on 100 parts by weight of the phenol resin.

The foamable phenol resin composition (raw material) can be obtained by mixing the said phenol resin, the said curing catalyst, the said foaming agent, and the said surfactant, and also mixing the said 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 the composition is maintained in a desired shape. Illustratively, when the heat insulating material includes the organic material layer as a core material, as described below, and a face material is included on one or both sides thereof, the foaming/curing process may be performed on the face material or between the face materials.

For example, the phenolic resin composition may be discharged onto a face material, and, if necessary, a surface opposite to the face in contact with the face of the phenolic resin composition may be coated with an additional face material, and foaming and curing processes may be performed.

This foaming process may be performed at a temperature of about 40° C. to 120° C., and if necessary, the foaming process and the like may be performed while changing the process temperature in multiple steps. Process conditions such as an appropriate foaming temperature depending on the type of raw material are known.

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

As the face material, a known configuration can be used without any particular limitation. For example, as the cotton material, synthetic fiber nonwoven fabric, synthetic fiber woven fabric, glass fiber paper, glass fiber woven fabric, glass fiber nonwoven fabric, glass fiber blended paper, paper, metal film, or a combination thereof may be used, and the cotton material is also flame retardant and A flame retardant may be contained in order to impart semi-flammable performance.

The heat insulating material may include other necessary components in addition to the above components.

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

The present application may provide an insulating material in which thermal insulation performance, semi-incombustible performance, and flame retardant performance are maintained excellently at the same time. The heat insulating material, handleability, workability, lightness, cutability, mechanical strength, etc. may be excellently maintained.

Hereinafter, the present application will be described in detail through Examples, but the scope of the present application is not limited by the Examples below.

1. Thermal conductivity and thermal transmittance analysis method

The thermal conductivity of the organic material layer was measured using a measuring device (manufacturer: Eko Instruments Trading, product name: HC-704). The sample was mounted between the hot plates maintained at 10° C. and 30° C., respectively, and thermal conductivity was evaluated by checking the heat flow. The thermal conductivity was measured for samples having widths, lengths, and thicknesses of 300 mm, 300 mm and 50 mm, respectively. The thermal transmittance was obtained by dividing the measured thermal conductivity of the organic material layer by the thickness of the organic material layer (sample).

2. Evaluation of flame retardant and semi-flammable properties

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

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

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

[Formula A]

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

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

3. Measurement of Closed Cell Ratio and Average Diameter of Closed Cells

The closed cell rate was measured using a closed cell rate measuring device (Quantachrome, ULTRAPYC 1200e) according to KS M ISO 4590 standard. As a sample at the time of measurement, the length, width, and thickness of the organic material layer were cut to sizes of 2.5 cm, 2.5 cm and 2.5 cm, respectively, were used.

The average diameter of closed cells in the organic layer was measured using an electron microscope and an image J program. One side of the organic layer was cut with a razor blade and peeled, then pictures were taken using an electron microscope, and a circular shape was drawn in about 150 sizes, and then the average diameter was measured using the Image J program. This way of measuring the average diameter is known.

4. Measurement of compressive strength

Compressive strength was measured by the compressive strength measurement method specified in KS M ISO 844. Compressive strength was measured for a sample having 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. Determination 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 standard. It was measured by calculating the minimum concentration of oxygen required to sustain combustion of the organic layer.

Example 1.

An organic material layer (phenol resin foam layer) was prepared in the following manner.

3.5 parts by weight of a castor oil surfactant and 5 parts by weight of powdery urea were added to the resol phenol resin based on 100 parts by weight of the resin. In addition, as a flame retardant component, 5 parts by weight of red and 1 part by weight of a sulfenamide compound (Songwon Industrial Co., Ltd., SF201) were blended with respect to 100 parts by weight of the phenol resin. 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 based on 100 parts by weight of the phenol resin, and the mixture was sufficiently stirred for 3 minutes at a uniform speed of 1000 rpm to make a premix and left for 1 hour. All of the above processes were carried out at room temperature. Then, 10 parts by weight of a mixed foaming agent in a weight ratio of isopropyl chloride / isopentane 8:2 is added to the premix based on 100 parts by weight of the phenol resin, stirred at a uniform speed of 1000 rpm for 1 minute, and then put into a low temperature chamber to increase the temperature to 10 was lowered to °C. After that, 17 parts by weight of the liquid mixture containing para-toluenesulfonic acid (PTSA) was added based on 100 parts by weight of the phenol resin, and after high-speed stirring at 2000 rpm for 30 seconds, it was put into a mold at 70° C. at a density of 50 kg/m ³ and put into a mold for 7 minutes A phenol resin foam layer was prepared by foaming/curing. After taking out the prepared foam from the mold, it was cured in an oven at 80° C. for 24 hours.

Example 2.

An organic material layer (phenol resin foam layer) was prepared in the following manner.

3.5 parts by weight of a castor oil surfactant and 5 parts by weight of powdery urea were added to the resol phenol resin based on 100 parts by weight of the resin. In addition, as a flame retardant component, 5 parts by weight of red and 1 part by weight of a sulfenamide compound (Songwon Industrial Co., Ltd., SF205) were blended with respect 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 based on 100 parts by weight of the phenol resin, and the mixture was sufficiently stirred for 3 minutes at a uniform speed of 1000 rpm to make a premix and left for 1 hour. All of the above processes were carried out at room temperature. Then, 10 parts by weight of a mixed foaming agent in a weight ratio of isopropyl chloride / isopentane 8:2 is added to the premix based on 100 parts by weight of the phenol resin, and the mixture is stirred at a uniform speed of 1000 rpm for 1 minute and then put into a low temperature chamber to increase the temperature to 10 was lowered to °C. After that, 17 parts by weight of the liquid mixture containing para-toluenesulfonic acid (PTSA) was added based on 100 parts by weight of the phenol resin, and after high-speed stirring at 2000 rpm for 30 seconds, it was put into a mold at 70° C. at a density of 50 kg/m ³ and put into a mold for 7 minutes A phenol resin foam layer was prepared by foaming/curing. After taking out the prepared foam from the mold, it was cured in an oven at 80° C. for 24 hours.

Comparative Example 1.

An organic material layer (phenolic resin foam layer) was prepared in the same manner as in Example 1 except that red from among the flame retardant components was not applied.

Comparative Example 2.

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

The characteristics of each of the prepared organic material layers 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 Closed cell rate (%) 90 90 88 91 Average diameter of closed cells (μm) 90 90 96 94 Compressive strength (kPa) 125 125 118 130 Limiting Oxygen Index (LOI) (%) 38 37 35 35

Claims (15)

Insulation material containing closed cells with foaming gas inside, thermal transmittance of 0.4 W/m ² ·K or less, and an organic material layer with a heat release rate of 11.0 MJ/m ² or less for 5 minutes according to KS F 5660-1 test method . The insulating material of claim 1, wherein the foaming gas is at least one selected from the group consisting of hydrocarbons and halogenated hydrocarbons. The heat insulating material according to claim 1, wherein the closed cell ratio of the organic material layer is 75% or more. The heat insulating material according to claim 1, wherein the organic material layer has a density in the range of 20 to 70 Kg/m ³ . The heat insulating material according to claim 1, wherein the organic material layer has a compressive strength of 90 kPa or more. The insulating material according to claim 1, wherein the organic material layer has a limiting oxygen index of 35% or more. According to claim 1, wherein the organic material layer, 10 minutes according to the KS F 5660-1 test method, the heat release amount is less than 18 MJ/m ² Insulation material. According to claim 1, wherein the organic material layer, the maximum heat release according to the KS F 5660-1 test method is 55 kW / m ² or less of the insulating material. According to claim 1, wherein the organic material layer, in accordance with the KS F 5660-1 test method, a 10 minute reduction in the amount of heat release is 60% or more heat insulating material. According to claim 1, wherein the organic material layer, phenolic resin, polystyrene, polyurethane, and the insulating material comprising at least one selected from the group consisting of polyisocyanurate. The insulating material according to claim 1, wherein the organic material layer comprises a phosphorus compound and further comprises a compound having one or more bonds selected from the group consisting of the following Chemical Formulas 1 and 2:
[Formula 1]

[Formula 2]

The insulating material according to claim 11, wherein the phosphorus compound is at least one selected from the group consisting of red, phosphazene, and phosphoric acid esters. The insulating material according to claim 11, wherein the organic material layer includes a cured resin, and the phosphorus compound is included in the organic material layer in a ratio of 1 to 20 parts by weight based on 100 parts by weight of the cured resin. The organic material layer according to claim 11, wherein the organic material layer includes a cured resin, and the compound having one or more bonds selected from the group consisting of Chemical Formulas 1 and 2 is contained in the organic material layer in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the cured resin. insulator. 12. The method according to claim 11, wherein the ratio (P/S) of the weight (P) of the phosphorus compound to the weight (S) of the compound having one or more bonds selected from the group consisting of formulas 1 and 2 is in the range of 0.5 to 30. insulator.