KR102220943B1 - Thermosetting foam, method of producing the same, and insulating material - Google Patents

Abstract

It provides a thermosetting foam which is a thermosetting product of a foamable composition comprising a thermosetting resin, a foaming agent, _{a siloxane compound having a C 2} to C ₁₅ alkyl group, and a surfactant, a method for producing the same, and a heat insulating material including the same.

Description

Thermosetting foam, its manufacturing method, and insulation material including the same {THERMOSETTING FOAM, METHOD OF PRODUCING THE SAME, AND INSULATING MATERIAL}

It relates to a thermosetting foam, a method of manufacturing the same, and a heat insulating material comprising the same.

The insulation material contains thermosetting foam, and the insulation material is attached to the wall of the building to prevent heat transfer, thereby reducing the effect of external temperature changes on the internal temperature of the building, and maintaining a constant indoor temperature with less energy. have.

On the other hand, when the heat insulating material absorbs moisture, the heat insulating property of the heat insulating material significantly deteriorates due to the high thermal conductivity of the water. In addition, when the insulation material absorbs moisture and contains moisture, it undergoes a freeze-thaw process according to a sudden temperature change from the outside, and deformation and dropping of the insulation material and thermosetting foam can easily occur. There is a problem that is further reduced accordingly.

One embodiment of the present invention provides a thermosetting foam that maintains thermal conductivity at an ideal level and at the same time realizes excellent moisture resistance and long-term weather resistance.

Another embodiment of the present invention provides a method of manufacturing the thermosetting foam.

Another embodiment of the present invention provides an insulating material comprising the thermosetting foam.

In one embodiment of the present invention, there is provided a thermosetting foam, which is a thermosetting resin, a foaming agent, a thermosetting foam of a foamable composition comprising a siloxane compound having a _{C 2} to C _{15 alkyl group, and a surfactant.}

In another embodiment of the present invention, preparing a foamable composition comprising a _{thermosetting resin, a foaming agent, a siloxane compound having a C 2} to C _{15 alkyl group, and a surfactant;} And foaming and curing by applying heat to the foamable composition.

In another embodiment of the present invention, it provides a heat insulating material comprising the thermosetting foam.

The thermosetting foam may exhibit excellent moisture resistance and long-term weather resistance while maintaining the thermal conductivity at a level above a certain level.

1 is a schematic diagram briefly showing a method of measuring the water absorption rate of the thermosetting foam of the present invention.

Advantages and features of the present invention, and a method of achieving them will become apparent with reference to the embodiments to be described later. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various different forms, However, these embodiments are provided to complete the disclosure of the present invention, and to fully inform the scope of the invention to those of ordinary skill in the art to which the present invention pertains, and the present invention is defined by the scope of the claims. It just becomes.

In the drawings, the thicknesses are enlarged to clearly express various layers and regions. And in the drawings, for convenience of description, the thickness of some layers and regions is exaggerated. The same reference numerals refer to the same elements throughout the specification.

In addition, in the present specification, when a part such as a layer, film, region, plate, etc. is said to be "on" or "on" another part, it is not only "directly above" another part, but also when another part is in the middle. Also includes. Conversely, when one part is "directly above" another part, it means that there is no other part in the middle. In addition, when a part such as a layer, film, region, or plate is said to be "below" or "under" another part, it is not only "directly below" another part, but also if there is another part in the middle. Include. Conversely, when one part is "right under" another part, it means that there is no other part in the middle.

In one embodiment of the present invention, there is provided a thermosetting foam, which is a thermosetting resin, a foaming agent, a thermosetting foam of a foamable composition comprising a siloxane compound having a _{C 2} to C _{15 alkyl group, and a surfactant.}

In general, a heat insulating material including a foam and a face material may be attached to the wall of a building to provide heat insulation. However, when moisture is absorbed by the heat insulating material, there is a problem that the heat insulating property is significantly deteriorated due to high thermal conductivity of water.

Accordingly, a cotton material having high moisture resistance may be used, or a material having high moisture resistance may be applied to the surface of the foam to prevent deterioration in heat insulation. However, as the heat insulating material is used for a long time, the face material falls off, and the surface of the foam is worn, so that the heat insulating effect cannot be expected. In addition, as time passes, cracks occur in the insulation material, and moisture absorbed through the cracked gap undergoes a freeze-thawing process according to a sudden change in external temperature, thereby significantly reducing the durability and insulation properties of the insulation material.

Thus, in one embodiment, the foam itself, while maintaining the thermal conductivity at a certain level, including a thermosetting product of a foamable composition comprising a thermosetting resin, a foaming agent, _{a siloxane-based compound having a C 2} to C _{15 alkyl group, and a surfactant.} It can improve the moisture resistance of, and can implement excellent long-term weather resistance.

The foamable composition includes a thermosetting resin. The thermosetting resin may include one selected from the group consisting of an epoxy resin, a polyurethane resin, a polyisocyanate resin, a polyisocyanurate resin, a polyester resin, a polyamide resin, a phenol resin, and combinations thereof. I can. For example, the foamable composition may include a phenolic resin obtained by reacting phenol and formaldehyde as a thermosetting resin, for example, a resol-based phenolic resin.

The foamable composition may contain the thermosetting resin in an amount of about 30% to about 90% by weight.

By including the thermosetting resin in an amount within the above range, a foam cell can be stably formed and excellent thermal insulation properties can be implemented. Specifically, when the thermosetting resin is included in less than the above range, it is difficult to form a foaming cell and thermal insulation is deteriorated, and if it exceeds the above range, the ratio of other additives is relatively low, and the shape or foaming of the foaming cell Defects may occur in the process.

The thermosetting resin, for example, the phenolic resin may have a viscosity of about 1,000 cps to about 40,000 cps under a temperature condition of about 25 °C, specifically, may have a viscosity of about 15,000 cps to about 25,000 cps. . The viscosity can be measured using a Brookfield viscometer.

The foamable composition may include a thermosetting resin having a viscosity in the above range, and may properly adjust the foaming force, thereby forming a foam cell well, and improving the closed cell ratio, thereby imparting excellent heat insulation. Specifically, when the viscosity of the thermosetting resin is less than the above range, the foaming gas may be lost at the initial stage of foaming, and accordingly, the thermal conductivity may increase and the heat insulation may decrease. And, when the viscosity exceeds the above range, the pressure load of the raw material stirring mixer increases, so that the mixing is not uniform, the foaming ratio is lowered, and the foaming pressure decreases, so there may be a problem in that it is not possible to produce a normal foam. .

In addition, the thermosetting resin may have a moisture content of about 5% by weight or more, and specifically, about 10% by weight to about 20% by weight. The moisture content can be measured by the Karl Fischer Titration method. The thermosetting resin may implement excellent workability and excellent heat insulation by having a moisture content within the above range. Specifically, when the moisture content is out of the above range and the moisture content is too low, it is difficult to control the process due to a rapid curing reaction, and when the moisture content is too high, the curing reaction becomes too slow, resulting in a decrease in thermal insulation properties and poor adhesion of the thermosetting foam. , It may be difficult to firmly attach other configurations, for example, a surface material, etc. by a lamination method.

In addition, the phenolic resin may not contain a urea bond. Accordingly, moisture generated by the urea-formaldehyde reaction may not be generated in the polymerization process of the phenol resin, so that the viscosity and moisture of the foamable composition can be easily adjusted.

The foamable composition includes a blowing agent, and the blowing agent may include one blowing agent selected from the group consisting of a hydrofluoroolefin (HFO) compound, a hydrocarbon compound, a hydrochlorofluorocarbon, and a combination thereof. . The hydrofluoroolefin-based compound may include, for example, a chlorinated hydrofluoroolefin-based compound, a non-chlorinated hydrofluoroolefin-based compound, or both. The hydrofluoroolefin-based compound may be of any kind known in the art, for example, CF3CH=CClH(1233zd), CHF2CF=CClH(1233yd), CHF2CH=CClF(1233zb), CHF2CCl=CHF( 1233xe), CH2FCCl=CF2(1233xc), CHFClCF=CFH(1233ye), CH2ClCF=CF2(1233yc), and CF2ClCF=CH2(1233xf) monochlorotrifluoropropenes; Trifluoropropenes such as CHF ₂ CF=CH ₂ , CH ₃ CF=CF ₂ , CH ₂ FCF=CF ₂ , CH ₂ FCH=CF ₂ , and CHF ₂ CH=CHF; Pentafluoropropene; It may include at least one selected from the group consisting of hexafluorobutene and combinations thereof.

In addition, the hydrocarbon-based compound may include a hydrocarbon having 1 to 5 carbon atoms, and may include, for example, a chlorinated hydrocarbon compound, a non-chlorinated hydrocarbon compound, or both. The hydrogen-based compound is dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride, n-butane, isobutane, n-pentane, isopentane, cyclopentane, and combinations thereof. It may include at least one selected from the group consisting of, but is not limited thereto.

In addition, the hydrochlorofluorocarbon is in the group consisting of chlorodifluoromethane (HCFC-22), 1,1-dichloro-1-fluoroethane (HCFC-141b), chlorononafluorobutane, and combinations thereof It may include at least one selected, but is not limited thereto.

The foamable composition may include about 5 parts by weight to about 15 parts by weight of the foaming agent relative to about 100 parts by weight of the thermosetting resin. By including the foaming agent in an amount within the above range, the foaming force can be adjusted, thereby imparting durability such as excellent strength to the thermosetting foam, stably forming a foaming cell, and imparting a high closed cell rate.

The foamable composition may _{include a siloxane-based compound having a C 2} to C ₁₅ alkyl group, and water resistance to the foamable composition may be remarkably improved. And, the siloxane-based compound may lower the surface tension of the thermosetting resin. Accordingly, by appropriately mixing the thermosetting resin having a certain viscosity and reactivity with the siloxane-based compound, the foam cells of the foam may be more uniformly formed, and excellent mechanical strength and thermal conductivity may be imparted to the foam. At this time, the siloxane-based compound having an alkyl group of C ₂ ~ C ₁₅ means a compound having an alkyl group of C ₂ ~ C ₁₅ represents a hydrophobic siloxane-based compound in the main chain as side chains.

On the other hand, _{when the siloxane-based compound having a C 1} alkyl group is included, it is difficult to obtain large moisture resistance because it exhibits low hydrophobicity. A siloxane-based compound having a C _{1 alkyl group may include silicone oil.}

The _{siloxane-based compound having an alkyl group of C 2} to C ₁₅ imparts high hydrophobicity to the thermosetting foam and remarkably improves moisture resistance, thereby significantly reducing the rate of change in weight due to moisture absorption, that is, the moisture absorption rate.

Specifically, the siloxane-based compound having an alkyl group of _{C 2} to C _{15 may not contain an ether group.} Specifically, polyether groups including ethyl ether and propyl ether may not be included in the side chain. When the foamable composition contains a siloxane-based compound containing an ether group in the side chain rather than a siloxane-based compound having an alkyl group of _{C 2} to C _{15, for example, polydimethylsiloxane, a silicone-based surfactant, does not exhibit sufficient hydrophobicity.} And, the moisture resistance is lowered, and the moisture absorption rate may be remarkably increased.

More specifically, the _{siloxane-based compound having an alkyl group of C 2} to C ₁₅ may have a structure represented by Formula 1 below.

[Formula 1]

In Formula 1, R ₁ , R ₃ , R ₅ , R ₇ and R ₈ are each independently a C ₁ to C ₃ alkyl group, and R ₂ and R ₆ are each independently a C ₂ to C ₁₅ alkyl group or a hydroxy group And R ₄ means a C ₂ to C ₁₅ alkyl group.

In the siloxane-based compound has the general formula (1) having an alkyl group of said C ₂ ~ C _15, in particular, R ₄ is a compound having an alkyl group of C ₂ ~ C ₁₅ in position, high water contact angle and a significantly lower excellent moisture resistance to water absorption Can represent. Specifically, the foamable composition may include a siloxane-based compound having a _{C 4} to C _{10 alkyl group, for example, a siloxane-based compound having a C 6} -C ₈ alkyl group, thereby providing a further improved effect.

The _{siloxane-based compound having an alkyl group of C 2} to C ₁₅ may have a weight average molecular weight of about 1,000 to about 10,000. Specifically, it is more preferable to have a weight average molecular weight of about 2,000 to about 4,000. The weight average molecular weight can be measured by gel permeation chromatography (GPC, alliance 2695, Waters). _{The foamable composition may include a siloxane-based compound having a C 2} to C ₁₅ alkyl group having a weight average molecular weight in the above range, and may exhibit more improved moisture resistance.

The foamable composition may include about 0.1 parts by weight to about 2.0 parts by weight of the siloxane-based compound having an alkyl group of _{C 2} to C ₁₅ relative to 100 parts by weight of the thermosetting resin. If the _{content of the siloxane-based compound having an alkyl group of C 2} to C ₁₅ is less than the above range, there may be a problem that the moisture resistance effect is not exhibited, and if it exceeds the above range, the surface tension of the resin is too low. There may be a problem of lowering thermal conductivity and mechanical strength because a closed cell cannot be formed.

The foamable composition includes a surfactant, and improves the dispersibility of the thermosetting resin, the foaming agent, and the _{siloxane-based compound having an alkyl group of C 2} to C ₁₅ , and makes the interface stable and uniform in the process of growing the foam cell. Formed, and can implement a high closed cell rate, excellent strength and excellent thermal conductivity.

_{As described above, the siloxane-based compound having an alkyl group of C 2} to C ₁₅ contained in the foamable composition has high hydrophobicity and can impart excellent moisture resistance, but is uniformly dispersed in the thermosetting resin due to high hydrophobicity. There is a problem that the thermal insulation is deteriorated due to the failure. Accordingly, there may be a problem in that the foamed cell bursts or does not grow uniformly, the closed cell rate decreases, and the thermal conductivity significantly decreases. In addition, moisture resistance may not be evenly dispersed in the thermosetting foam. In particular, moisture resistance inside the center of the thermosetting foam may be significantly lowered.

The surfactant has excellent compatibility with the siloxane compound having an alkyl group of _{C 2} to C _{15 , and the siloxane compound having an alkyl group of C 2} to C ₁₅ is uniformly dispersed between the thermosetting resin and the foaming agent. Mixing and stabilizing the interface in the process of growing the foam cells can form a stable and uniform foam cells. Accordingly, the thermosetting foam, which is a cured product thereof, can consistently maintain excellent durability and high thermal conductivity along with improved moisture resistance.

The surfactant is at least one selected from the group consisting of castor oil ethylene oxide, polyoxyalkenylenesorbitan alkyl ester, polyoxyalkylene alkyl ester, polydimethylsiloxane-polyoxyalkylene copolymer as a silicone surfactant, and combinations thereof. It may include, and preferably may include castor oil ethylene oxide.

The foamable composition may contain the surfactant in an amount of about 1.0 to about 10.0 parts by weight based on 100 parts by weight of the thermosetting resin. Specifically, by including the surfactant in an amount within the above range, it is possible to easily disperse the components in the foamable composition, while sufficiently and stably forming the foam structure of the thermosetting foam, excellent thermal conductivity, excellent physical strength, and excellent moisture May show resistance.

Specifically, the _{weight ratio of the siloxane-based compound having an alkyl group of C 2} to C ₁₅ to the surfactant may be about 1: 3 to about 1: 20, and specifically, about 1: 4 to about 1: 15 And, more specifically, it may be about 1:4 to about 1:10. When the _{weight ratio of the siloxane-based compound having an alkyl group of C 2} to C ₁₅ is less than the above range, sufficient moisture resistance may not be exhibited, and accordingly, a water contact angle may be lowered and water absorption may be increased. And, when the weight ratio of the siloxane-based compound having an alkyl group of _{C 2} to C _{15 exceeds the above range.} That is, when the content of the surfactant is less, the _{siloxane compound having the C 2} to C ₁₅ alkyl group is not evenly dispersed in the thermosetting resin showing hydrophilicity, and the hydrophobic foaming agent also has dispersibility in the thermosetting resin. This decreases, thereby interfering with the formation of cells of the thermosetting foam, which is a thermosetting product of the foamable composition containing the same, thereby lowering the closed cell ratio, lowering the strength of the foam, and lowering the thermal conductivity.

_{The foamable composition may include the siloxane-based compound having an alkyl group of C 2} to C ₁₅ and the surfactant in a mass ratio of the above range, and provide excellent thermal conductivity even under severe conditions. Therefore, the foam, which is a thermosetting product of the foamable composition, may exhibit excellent long-term weather resistance. For example, the foam is about 0.0200 W/m· even after going through severe conditions such as a high temperature of 70°C and a relative humidity of 15%, a humid condition of 50°C, a relative humidity of 50%, and a low temperature of -20°C. It may represent a thermal conductivity of K to about 0.0223 W/m·K, and specifically, a thermal conductivity of about 0.0200 W/m·K to about 0.0210 W/m·K.

The foamable composition may further include at least one selected from the group consisting of a flame retardant, a plasticizer, a neutralizing agent, and a combination thereof as a curing agent, a solvent, and other additives.

The curing agent may include, for example, at least one selected from the group including an acid anhydride compound, an inorganic or organic acid compound, an isocyanate compound, and a combination thereof, but is not limited thereto.

The curing agent may be included in an amount of about 5 parts by weight to about 30 parts by weight based on about 100 parts by weight of the phenolic resin.

The foamable composition may be foamed and cured to obtain the thermosetting foam.

The thermosetting foam may have a moisture absorption rate of about 0.5% to about 4.0%, measured according to KS M ISO 2896, according to Equation 1 below, and may be, for example, about 0.5% to about 3.0%.

[Equation 1]

Specifically, the moisture absorption rate can be measured using an apparatus as shown in FIG. 1. In Equation 1, WAv is the moisture absorption rate (%) of the foam, m1 is the initial weight of the foam 20 itself before immersion in water, m2 is the weight of the net 10 itself for containing the foam, m3 is The combined weight of the foam and the mesh in water after immersion in water for 4 days, V ₀ is the volume of the foam before immersion in water, V ₁ is the volume of the foam after immersion in water for 4 days , Vc is the volume of the bubble observed from the outside by being located on each side of the foam, and ρ is the density of water in which the foam is immersed.

The thermosetting foam may implement excellent thermal insulation and durability for a long time by having a moisture absorption rate within the above range. Specifically, when the moisture absorption rate of the thermosetting foam exceeds the above range, problems such as decrease in thermal conductivity and durability due to moisture absorption of the insulation product, condensation, and mold may occur in the long term.

The water contact angle of the thermosetting foam may be about 60° to about 120°. The thermosetting foam may exhibit high resistance to moisture by having a water contact angle within the above range, and thus, deformation, dropping and condensation of the foam may be prevented, and excellent thermal insulation and durability for a long period of time may be realized.

The thickness of the thermosetting foam may be about 30mm to about 200mm. Specifically, when the thickness of the thermosetting foam exceeds the above range, heat generated during the curing process accumulates in the center of the foam, thereby reducing thermal insulation properties and hindering cell structure formation.

The thermosetting foam may have a thermal conductivity of about 0.017 W/m·K to about 0.021 W/m·K at an average temperature of 20° C. according to the measurement conditions of KS L 9016. Specifically, the thermal conductivity of the thermosetting foam was measured in the thickness direction under the conditions of 10°C for the top plate, 30°C for the bottom plate, and 20°C for the average temperature without the severe conditions as described above, and from about 0.017 W/m·K to about 0.021 It can be W/m·K.

In the case of using a conventional water repellent for the foamable composition, the moisture absorption rate can be lowered, but it is not easy to control the surface tension of the thermosetting resin, and the water repellent interferes with the formation of the foaming cell, resulting in a decrease in the closed cell ratio and increase in thermal conductivity. There may be. On the other hand, the thermosetting foam can maintain a constant thermal conductivity within the above range even without a face material such as aluminum and at the same time improve water contact angle and water absorption.

In addition, the thermosetting foam may have a density of about 20 kg/m3 to about 50 kg/m3. By having a density within the above range, the thermosetting foam can implement excellent strength and excellent heat insulation.

In addition, the closed cell ratio of the thermosetting foam may be about 85% to about 95%. Specifically, when the closed cell ratio is less than the above range, there is a problem that the thermal conductivity is increased and the moisture absorption rate is increased.

Another embodiment of the present invention is a step of preparing a foamable composition comprising a _{thermosetting resin, a foaming agent, a siloxane-based compound having a C 2} to C _{15 alkyl group, and a surfactant;} And foaming and curing by applying heat to the foamable composition. The thermosetting foam described above can be manufactured by the above manufacturing method.

In the above production method, a foamable composition including a thermosetting resin, a foaming agent, _{a siloxane-based compound having a C 2} to C ₁₅ alkyl group, and a surfactant is prepared, and details of the foamable composition are as described above.

In addition, the manufacturing method includes the step of foaming and curing by applying heat to the prepared foamable composition. The foamable composition may simultaneously foam and cure, and at this time, either foaming or curing may be initiated first, or they may be simultaneously initiated.

The foaming and curing may be performed under a temperature condition of, for example, about 50 to about 90. In addition, the foaming and curing may be performed for a time of about 2 minutes to about 20 minutes, but is not limited thereto, and may be appropriately changed according to the purpose and use of the invention.

The foamable composition may be foamed and cured, for example, in a predetermined mold, or foamed and cured while being injected or discharged between both surface materials, for example, but is not limited thereto.

Through this, it is possible to manufacture the above-described thermosetting foam. The thermosetting foam may simultaneously satisfy a thermal conductivity of about 0.017 W/m·K to about 0.021 W/m·K, a moisture absorption rate of about 0.5% to about 4.0%, and a water contact angle of about 60° to about 120°. In addition, the thermosetting foam has a thermal conductivity of about 0.017 W/m·K to about 0.020 W/m·K, a moisture absorption rate of about 0.5% to about 3.0%, and an excellent water contact angle of about 75° to about 120°, as well as, Even under severe conditions, excellent thermal conductivity of about 0.017 W/m·K to about 0.0210 W/m·K can be simultaneously satisfied, and the best performance specifications can be exhibited.

Another embodiment of the present invention provides an insulating material comprising the thermosetting foam.

The thermosetting foam can be applied, for example, as an insulating material for construction, and accordingly, it can simultaneously satisfy the high-thickness standard and excellent insulating properties required as an insulating material for construction, while preventing the occurrence of mold etc. with excellent moisture resistance. Last name can be implemented.

The building insulation material may further include a surface material on one or both sides of the thermosetting foam, and the surface material may be of a type known in the art, for example, a fabric derived from an organic material or an inorganic material. , Non-woven fabric, cloth, metal foil, such as aluminum, may be a material including paper, but is not limited thereto.

Hereinafter, specific embodiments of the present invention are presented. However, the examples described below are merely for illustrating or explaining the present invention in detail, and the present invention is not limited thereto.

< Example And Comparative example >

Example One

A resol-based phenolic resin having a viscosity of 15,000 cps and a moisture content of 10% by weight was prepared under a temperature condition of 25°C at a temperature of 20°C. With respect to the resol-based phenol resin, a colorless foaming agent in which cyclopentane and isopentane, which are hydrocarbon compounds, are mixed in a weight ratio of 8:2, and castor oil as a siloxane compound having a _{C 2} to C _{15 alkyl group in the side chain and a surfactant.} A foamable composition was prepared by mixing a composition containing ethylene oxide. At this time, the siloxane-based compound is a _{C 6} alkyl group in the _{R 4} position, R1, R3, R5, R7 and R8 are C ₁ alkyl group, and R ₂ and R ₆ have a C ₂ alkyl group in Formula 1 , Has a weight average molecular weight of 2,000. In addition, 8 parts by weight of the foaming agent was included with respect to 100 parts by weight of the resol-based phenol resin, and 4.0 parts by weight of the surfactant was included. In addition, a foamable composition was prepared such that the weight ratio of the siloxane-based compound to the surfactant was 1:3.

Then, the foamable composition was flowed under the caterpillar to finally prepare a thermosetting foam.

At this time, the caterpillar, which is a mold, was set so that the thickness of the thermosetting foam was 70 mm at a line speed of 8 m/min and a temperature of 70°C.

Example 2

A thermosetting foam was prepared in the same manner as in Example 1, except that the weight ratio of the siloxane-based compound having an alkyl group of _{C 2} to C _{15 to the surfactant was 1:4.}

Example 3

A thermosetting foam was prepared in the same manner as in Example 1, except that the weight ratio of the siloxane-based compound having an alkyl group of _{C 2} to C _{15 to the surfactant was 1:10.}

Example 4

A thermosetting foam was prepared in the same manner as in Example 1, except that the weight ratio of the siloxane compound having an alkyl group of _{C 2} to C _{15 to the surfactant was 1:15.}

Example 5

A siloxane-based compound having an alkyl group of C ₂ to C _{15. In Formula 1, a C 10} alkyl group at the _{R 4} position, R 1, R 3, R 5, R 7 and R 8 are a C ₁ alkyl group, and R ₂ and R ₆ A thermosetting foam was prepared in the same manner as in Example 2, except that a compound having a C2 alkyl group was used.

Comparative example One

A thermosetting foam was prepared in the same manner as in Example 1, except that the siloxane-based compound having an alkyl group of _{C 2} to C _{15 was not included.}

Comparative example 2

A thermosetting foam was prepared in the same manner as in Example 1, except that silicone oil was included instead of the siloxane-based compound having an alkyl group of _{C 2} to C _15.

Comparative example 3

Polydimethylsiloxane (product of Evonik's TEGOSTAB B 8462) which does not contain the siloxane-based compound having an alkyl group of C ₂ to C ₁₅ and is a siloxane-based surfactant containing an ether group in the side chain instead of castor oil ethylene oxide as the surfactant. A thermosetting foam was prepared in the same manner as in Example 1, except that it was included.

<Evaluation>

Experimental example 1: heat Conductivity (W/m·K)

The thermosetting foams of Examples and Comparative Examples were cut to a size of 300 mm×300 mm and a thickness of 50 mm from the top to prepare each specimen, and dried at 70° C. for 12 hours to pretreat the sample. Then, for each of the specimens, thermal conductivity was measured using a HC-074-300 (EKO company) thermal conductivity device at an average temperature of 20° C. according to the measurement conditions of KS L 9016 (plate heat flux measurement method). And, the results are shown in Table 1 below.

Experimental example 2: long-term weather resistance

The thermosetting foam is included in the insulation and adhered to the exterior wall of a building, and is likely to cause cracks due to moisture penetration due to external climate. Accordingly, long-term weatherability of the thermosetting foam under various climatic conditions was measured using the following method.

The thermosetting foams of the Examples and Comparative Examples were cut to a size of 300 mm×300 mm and a thickness of 50 mm from the top to prepare a specimen. And, the harsh conditions were measured by modifying the Hygrothermal Behavior method of European ETAG004. Specifically, as a first step, the specimen is completely immersed in water for 5 hours and then naturally dried at room temperature for 3 hours. Thereafter, the specimen is placed in a constant temperature and humidity chamber and dried for 16 hours at 70° C. and 15% relative humidity. The first step was repeated three times. In the second step, the specimen is dried for 8 hours at 50°C and 50% relative humidity for 8 hours, and dried at -20°C for 16 hours. The second step was repeated twice. After that, it was finally dried at 70° C. for 12 hours to pretreat the specimen. In addition, for each of the specimens, the thermal conductivity was measured using a HC-074-300 (EKO company) thermal conductivity device at an average temperature of 20° C. according to the measurement conditions of KS L 9016 (plate heat flux measurement method). The value thus obtained is a thermal conductivity measured under severe conditions, and should be distinguished from the thermal conductivity measured in Experimental Example 1.

Experimental example 3: water absorption rate ( % )

The thermosetting foams of Examples and Comparative Examples were dried for at least 12 hours in an environment at a temperature of 25±5°C and a humidity of 50±10%. In addition, the thermosetting foam was cut with a band saw to prepare a specimen having a width of 15 cm, a length of 15 cm, and a height of 4 cm. At this time, the specimen was prepared by cutting so as to be obtained at the central position of the thermosetting foam.

The rate of change in weight according to the moisture absorption of the specimen, that is, the moisture absorption rate, was measured according to the KS M ISO 2896 standard, was calculated according to Equation 1 below, and the results are shown in Table 1 below.

[Equation 1]

Specifically, the moisture absorption rate was measured using an apparatus as shown in FIG. 1. In Equation 1, WAv is the water absorption rate (%) of the foam, m1 is the initial weight of the foam 20 itself before immersion in water, and m2 is the weight of the net 10 itself to contain the foam. . The net (10) on which the foam (20) is placed is hung on the net (40), and the net (10) is immersed in the water tank (50) using a weight (30). m3 is the weight of the foam 20 and the mesh 10 in the water after being immersed in the water in the water tank 50 for 4 days using the measuring scale 60, and V0 is the water The volume of the foam 20 before being immersed in, V1 is the volume of the foam 20 after being immersed in water for 4 days, Vc is the volume of air bubbles that are located on each side of the foam 20 and observed from the outside , ρ means the density of water into which the foam is immersed.

Experimental example 4: water Contact angle (°)

A drop of distilled water was dropped on the thermosetting foams of Examples and Comparative Examples using a syringe, and the shape of the drop was enlarged with a microscope provided in a contact angle measuring device (German KRUSS, DSA100), and the specimen at the critical points at the left and right ends The angle formed with the surface of the was measured.

In the above measurement method, each contact angle was measured at three arbitrary points per thermosetting foam, and the respective measured values were averaged to evaluate each water contact angle, and the results are shown in Table 1.

Thermal conductivity Long-term weatherability Moisture absorption rate Water contact angle Example 1 0.0210 0.0222 2.2 100 Example 2 0.0197 0.0203 2.3 92 Example 3 0.0194 0.0205 2.6 78 Example 4 0.0193 0.0218 3.8 61 Example 5 0.0204 0.0209 2.5 81 Comparative Example 1 0.0195 0.0238 4.8 42 Comparative Example 2 0.0210 0.0251 4.6 49 Comparative Example 3 0.0205 0.0244 5.6 32

As shown in Table 1, the embodiment maintains the thermal conductivity of 0.017 W/m·K to 0.021 W/m·K, while maintaining the moisture absorption rate at 0.5% to 4.0%, and the water contact angle at 60° to 120 Can be maintained at °. In addition, the embodiment can maintain the thermal conductivity of 0.0222 W/m·K or less even in long-term weather resistance. Therefore, the embodiment can exhibit excellent moisture resistance and long-term weather resistance while maintaining the thermal conductivity at a certain level for a long period of time.

10: mesh
20: foam
30: weight
40: net hanging place
50: water tank
60: measuring mirror

Claims (12)

It is a thermosetting product of a foamable composition containing a thermosetting resin, a foaming agent, _{a siloxane compound having a C 2} to C ₁₅ alkyl group, and a surfactant,
The siloxane-based compound having an alkyl group of _{C 2} to C _{15 has the structure of Formula 1 below.}
Thermosetting foam:

[Formula 1]

In Formula 1,
R ₁ , R ₃ , R ₅ , R ₇ and R ₈ are each independently a C ₁ to C ₃ alkyl group, R ₂ and R ₆ are each independently a C ₂ to C ₁₅ alkyl group or a hydroxy group, and R ₄ is C is an alkyl group of C ₂ ~ _15.
The method of claim 1,
The thermosetting resin includes one selected from the group consisting of epoxy resins, polyurethane resins, polyisocyanate resins, polyisocyanurate resins, polyester resins, polyamide resins, phenol resins, and combinations thereof.
Thermosetting foam.
The method of claim 1,
The weight average molecular weight of the siloxane-based compound having an alkyl group of _{C 2} to C _{15 is 1,000 to 10,000}
Thermosetting foam.
The method of claim 1,
The siloxane-based compound having an alkyl group of _{C 2} to C _{15 does not contain an ether group.}
Thermosetting foam.
delete The method of claim 1,
The surfactant is one selected from the group consisting of castor oil ethylene oxide, polyoxyalkenylene sorbitan alkyl ester, polyoxyalkylene alkyl ester, polydimethylsiloxane-polyoxyalkylene copolymer as a silicone surfactant, and combinations thereof. Included
Thermosetting foam.
The method of claim 1,
The weight ratio of the siloxane-based compound having an alkyl group of _{C 2} to C _{15 to the surfactant is 1: 3 to 1: 20}
Thermosetting foam.
The method of claim 1,
Measured according to KS M ISO 2896, the water absorption rate of the foam according to the following formula 1 is 0.5% to 4.0%
Thermosetting foam:

[Equation 1]

In Equation 1, WAv is the water absorption rate of the foam, m1 is the initial weight of the foam before immersion in water, m2 is the weight of the net for containing the foam, and m3 is water after immersion in water for 4 days. The combined weight of the foam and the net in the _{inside, V 0} is the volume of the foam before immersion in water, V1 is the volume of the foam after immersion in water for 4 days, Vc is located on each side of the foam Thus, the volume of air bubbles observed from the outside, ρ, means the density of water in which the foam is immersed.
The method of claim 1,
The thermosetting foam has a water contact angle of 60° to 120°.
Thermosetting foam.
The method of claim 1,
The thermal conductivity measured at an average temperature of 20℃ according to the measurement conditions of KS L 9016 is 0.017 W/m·K to 0.021 W/m·K.
Thermosetting foam.
Preparing a foamable composition comprising a thermosetting resin, a foaming agent, _{a siloxane compound having a C 2} to C ₁₅ alkyl group, and a surfactant; And
Including; foaming and curing by applying heat to the foamable composition,
The siloxane-based compound having an alkyl group of _{C 2} to C _{15 has the structure of Formula 1 below.}
Method for producing thermosetting foam:

[Formula 1]

In Formula 1,
R ₁ , R ₃ , R ₅ , R ₇ and R ₈ are each independently a C ₁ to C ₃ alkyl group, R ₂ and R ₆ are each independently a C ₂ to C ₁₅ alkyl group or a hydroxy group, and R ₄ is C is an alkyl group of C ₂ ~ _15.
Insulation material comprising the thermosetting foam according to any one of claims 1 to 4 and 6 to 10.

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