WO2014027726A1

WO2014027726A1 - Thermosetting foam with improved thermal insulation and flame retardancy, and preparation method therefor

Info

Publication number: WO2014027726A1
Application number: PCT/KR2012/011229
Authority: WO
Inventors: 김지문; 이응기; 최철준; 김명희; 지승욱; 전병주
Original assignee: (주)엘지하우시스
Priority date: 2012-08-16
Filing date: 2012-12-21
Publication date: 2014-02-20
Also published as: KR20140023581A; CN104540885A; CN104540885B

Abstract

Provided is a thermosetting foam comprising: a polyisocyanurate foam formed by polymerizing a polyol-based compound and an isocyanate-based compound; a nucleating agent; and a flame retardant, wherein the thermal decomposition initiation temperature of the thermosetting foam measured by thermogravimetric analysis is 310 ℃ or higher. In addition, provided is a method for preparing a thermosetting foam having the thermal decomposition initiation temperature measured by thermogravimetric analysis of 310 ℃ or higher, comprising the steps of: mixing a polyol-based compound and a nucleating agent; adding a flame retardant to the mixture of the polyol-based compound and the nucleating agent; stirring an isocyanate-based compound with the mixture obtained by adding the flame retardant thereto to polymerize a polyisocyanurate.

Description

Thermosetting foam with improved insulation and flame retardancy, and method for manufacturing same

The present invention relates to a thermosetting foam and a method for manufacturing the same, and more particularly, to a thermosetting foam and a method for manufacturing the same having improved thermal insulation and flame retardancy.

Thermosetting foam can be mainly used as a heat insulating material of various buildings, warehouses, refrigerators. At this time, the heat insulating material is used to increase the heating and cooling efficiency by blocking or reducing the heat exchange between the building and the outside, it can be widely used in various fields such as building boards and panels, LNG ship insulation, home appliance packaging or automotive interior materials. In addition, the thermosetting foam used as the heat insulating material may be made of a foaming cell structure filled with a foaming gas to improve the thermal insulation performance.

The above-mentioned thermosetting foams are widely used because they have excellent thermal insulation performance, processability, and small physical property change according to temperature variation, compared to other synthetic resins. Research has been made to add and use.

In the method of manufacturing a thermoplastic resin-based flame retardant foam comprising the step of kneading the thermoplastic resin and the flame retardant in Korea Patent No. 10-0610392, thereafter continuously dissolution of the fluidized blowing agent in the thermoplastic resin to grow a foam cell Although described, the physical and thermal insulation performance of the thermosetting foam can be reduced, compared to the increase in flame retardancy by adding a flame retardant.

In one embodiment of the present invention, a polyisocyanurate foam is used while simultaneously introducing a nucleating agent and a flame retardant to provide a thermosetting foam having a small and uniform foam cell.

In another embodiment of the present invention, a method for preparing a thermosetting foam having improved thermal insulation and flame retardancy is provided.

One embodiment of the present invention includes a polyisocyanurate foam, a nucleating agent, and a flame retardant formed by polymerizing a polyol-based compound and an isocyanate-based compound, and provides a thermosetting foam having a pyrolysis start temperature of about 310 ° C. or higher. do.

The flame retardant may be in liquid form or in powder form.

The flame retardant may be at least one selected from the group consisting of a phosphorus flame retardant, a metal hydrate flame retardant, a halogen flame retardant, a flame retardant aid and a mixture thereof.

The phosphorus flame retardant may be at least one selected from the group consisting of triphenyl phosphate, cresyl diphenyl phosphate, isopropylphenyl diphenyl phosphate, and mixtures thereof.

The halogenated flame retardant may be decabromodiphenyl oxide or octabromodiphenyl oxide.

The flame retardant aid may be antimony trioxide.

The nucleating agent may include a silane compound or a siloxane compound.

An average diameter of the foam cells formed on the polyisocyanurate foam may be about 50 μm to about 200 μm.

The content of the flame retardant may be about 1 part by weight to about 20 parts by weight based on 100 parts by weight of the polyol compound.

The content of the nucleating agent may be about 1 part by weight to about 10 parts by weight based on 100 parts by weight of the polyol-based compound.

The thermosetting foam may further include a polymerization catalyst, a surfactant, and a blowing agent.

The thermosetting foam may have a thermal conductivity of about 0.025 W / mk or less.

The thermosetting foam may have an independent bubble ratio of about 80% or more.

The thermosetting foam may have a density of about 10 kg / m ³ to about 150 kg / m ³ .

Another embodiment of the present invention comprises the steps of mixing the polyol-based compound and the nucleating agent; Adding a flame retardant to the mixture of the polyol compound and the nucleating agent; And polymerizing the polyisocyanurate by stirring the isocyanate compound in the mixture obtained by adding the flame retardant, and providing a thermosetting foam manufacturing method having a pyrolysis start temperature of about 310 ° C. or higher by thermogravimetric analysis.

The thermosetting foam which is one embodiment of the present invention has a low thermal conductivity, has improved mechanical properties such as compressive strength and flexural strength, and has excellent flame retardancy.

In addition, by using the thermosetting foam manufacturing method of another embodiment of the present invention, it is possible to obtain a small and uniform foaming cell through the addition of a nucleating agent while using an eco-friendly blowing agent that does not affect the ozone layer destruction.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

열경화성 발포체Thermosetting foam

In one embodiment of the present invention, a thermosetting foam comprising a polyisocyanurate foam, a nucleating agent, and a flame retardant formed by polymerization of a polyol-based compound and an isocyanate-based compound, and having a thermal decomposition starting temperature by thermogravimetric analysis of about 310 ° C. or more. to provide.

The foam is a plastic material containing a relatively high volume percentage of small pupils.The thermosetting foam causes a chemical reaction to harden by applying heat, and the thermosetting resin which does not soften and melt even when heated again after cooling to form a foam. Can be manufactured and used. The thermosetting foam can secure a certain level of thermal insulation, it can be used as a heat insulating material of various buildings, warehouses, refrigerators.

In general, when a flame retardant is added to improve the flame retardancy of a thermosetting foam having a certain level of thermal insulation, the size of the foam cell formed by increasing the surface tension when reacting with a polyisocyanurate foam or the like increases or causes it to burst. Can be. However, one embodiment of the present invention can compensate for the above negative effects resulting from the addition of flame retardants by controlling the surface tension through a nucleating agent with a limited average particle size.

Since the thermosetting foam includes a flame retardant, the thermal decomposition start temperature by thermogravimetric analysis may be about 310 ° C. or more. As described above, the thermosetting foam does not have a negative effect caused by the flame retardant by including a nucleating agent together with the flame retardant, and by including a flame retardant, it is possible to provide a thermosetting foam having excellent flame retardancy and heat resistance as well.

The thermogravimetric method refers to an analysis for measuring the change in weight occurring in a material during heating, which is usually measured to determine the heat stability of the material. Generally, it starts at room temperature and measures up to about 600 ℃, and measures by increasing the temperature by about 10 ℃ per minute. During the measurement, a section in which the mass decreases more than 5% occurs, which is called the pyrolysis start temperature or the mass reduction temperature. The pyrolysis start temperature by thermogravimetric analysis of the thermosetting foam by including the flame retardant is measured to be about 310 ° C. or more, and may include a nucleating agent and a flame retardant simultaneously to have a higher pyrolysis starting temperature than the conventional thermosetting foam.

The polyisocyanurate foam included in the thermosetting foam may be formed by polymerizing a polyol compound and an isocyanate compound. Polyisocyanate urate foam is a material including an isocyanurate group in the form of three isocyanate groups bonded in a ring structure to a polyurethane foam that has been widely used as a heat insulating material. Due to this ring structure, polyisocyanurate foam has excellent performance in terms of thermal stability and mechanical strength. The prior art has the effect of reducing the size of the foaming cell through the introduction of additives, such as clay or aerosil, to the polyol during the production of polyurethane foam, thereby improving the thermal insulation performance.

However, when the additive is introduced into the polyol, problems of dispersibility and storage stability may be caused. In one embodiment of the present invention, a nucleating agent is introduced to form a compact and uniform foam cell of the polyisocyanurate foam. You can. The smaller the foam cell formed in the insulation, the better the insulation effect and the higher the mechanical strength. Therefore, in addition to the foaming agent, materials that can help the initial nucleation are added to the polymer to reduce the foam cell size and increase the density of the foam cell. By increasing the physical properties of the heat insulating material can be improved.

The polyol compound is a substance including a plurality of hydroxyl groups in one molecule, and reacts with an isocyanate compound to generate a urethane bond and proceed with polymerization. The polyol-based compound may be a polyester polyol or a polyether polyol. Polyester polyol is phthalic anhydride

(phthalic anhydride) or adipic acid (adipic acid) may be prepared by reacting with ethylene oxide (propylene oxide), propylene oxide (propylene oxide) or a mixture thereof, the polyether polyol is ethylene glycol (ethylene glycol ), 1.2-propane glycol, butylene glycol, 1,6-hexanediol, 1,8-octanediol, 1,8-oxtanediol , Neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-1,3-propanediol, glycerol, trimethylolpropane, 1,2,3-hexane Triol (1,2,3-hexanetriol), 1,2,4-butanetriol (1,2,4-butanetriol), trimethylolmethane, pentaerythriol, diethyleneglycol ), Triethylene glycol, polyethyleneglycol, tripropylene glycol, polypropylen eglycol, dibutylene glycol, polybutyleneglycol, sorbitol, sucrose, hydroquinone, resorcinol, catechol and At least one selected from the group consisting of bisphenol may be prepared by reacting and polymerizing ethylene oxide, propylene oxide or a mixture thereof.

The isocyanate compound is a substance containing an isocyanate group in a molecule, and the isocyanate group reacts with a hydroxyl group of a polyol compound to generate a urethane bond, and also serves to form isocyanurate by reacting and triming three isocyanate groups. Do it. In order to form the isocyanurate, it is advantageous to use a material having a larger number of isocyanate groups than the isocyanate compound generally used for polymerization of polyurethane, and thus, a diisocyanate compound having an NCO index of about 250 can be used.

In one embodiment of the present invention, polymeric methylene diphenyl diisocyanate (polymeric MDI), monomeric methylene diphenyl diisocyanate (monomeric methylene diphenyl diisocyanate, monomeric MDI), polymeric toluene diisocyanate , polymeric TDI) and at least one selected from the group consisting of monomeric toluene diisocyanate (monomeric TDI) may be used as the isocyanate compound.

The flame retardant included in the thermosetting foam may be in liquid form or powder form. When the flame retardant is in liquid form, it has excellent dispersibility and has an advantageous effect in that it does not agglomerate with polyisocyanurate foam or nucleating agent or a mixture thereof.

In addition, the flame retardant may be in the form of a powder, and in particular, when using a flame retardant in the form of a powder, the flame retardant may secure dispersibility of the flame retardant by maintaining an average particle diameter of about 1 μm to about 100 μm, and It is possible to prevent foam cell breakage formed in the isocyanurate foam.

The flame retardant may be at least one selected from the group consisting of a phosphorus flame retardant, a metal hydrate flame retardant, a halogen flame retardant, a flame retardant aid and a mixture thereof. The flame retardant is an additive added to improve the flame retardant plasticity of plastics, and has a function of preventing combustion, and thus, the flame retardant may be used to increase its use as a thermosetting foam.

Specifically, the phosphorus flame retardant includes at least one selected from the group consisting of triphenyl phosphate, cresyl diphenyl phosphate, isopropylphenyl diphenyl phosphate and mixtures thereof. In addition, the halogenated flame retardant may be decabromodiphenyl oxide or octabromodi phenyl oxide, the flame retardant aid may include antimony trioxide.

The nucleating agent may include a silane compound or a siloxane compound. By including the nucleating agent, thermal conductivity inevitably rises due to the addition of the flame retardant can be suppressed to some extent, and the surface tension can be controlled.

The kind of the nucleating agent is not particularly limited, and a silane-based nucleating agent, a siloxane-based nucleating agent, or a perfluoroalkane-based nucleating agent may be used. Specifically, silane-based compounds and siloxane-based compounds having low surface tension and excellent compatibility with methylene diphenyl diisocyanate or polyol may be used, and one or more of them may be mixed and used. As the silane compound, compounds such as hexamethyldisilase and dimethoxydimethylsilane may be used, and as the siloxane compound, hexamethyldisiloxane may be used.

The average diameter of the foam cells formed on the polyisocyanurate foam may be about 50㎛ to about 200㎛. The average diameter refers to the average diameter or representative diameter of the formed foam cell. If the average diameter of the foam cell is less than about 50 μm, the thermal conductivity may increase rather than the contribution due to conduction in the thermal conductivity, about 200 If the size exceeds the size of the formed foam cell is too large, there is a problem that the foam cell is not produced uniformly. Therefore, there is an advantage in that uniform and small foam cells can be produced by keeping the content of the foam cell in the above range.

The content of the flame retardant may be about 1 part by weight to about 20 parts by weight based on 100 parts by weight of the polyol compound. When the flame retardant is included in less than about 1 part by weight, the flame retardancy may be poor. When the flame retardant is included in an amount exceeding about 20 parts by weight, the workability may be poor. Therefore, there is an advantage in that the content of the flame retardant can express all effects of maintaining workability and improving flame retardancy by maintaining the above range.

The content of the nucleating agent may be about 1 part by weight to about 20 parts by weight based on 100 parts by weight of the polyol-based compound. When the nucleating agent is included in less than about 1 part by weight, the nucleating agent added in a small amount is insignificant as the nucleating agent, and when it exceeds about 10 parts by weight, a non-uniform foaming cell may be formed due to the plasticizing effect. Therefore, there is an advantage in that the content of the nucleating agent can produce a small and uniform foaming cell even though the flame retardant is added by maintaining the above range.

The thermosetting foam may further include a polymerization catalyst, a surfactant, and a blowing agent. Specifically, the polymerization catalyst promotes trimerization of isocyanates and improves the reaction rate to serve to form isocyanurate groups. The polymerization catalyst is acetic acid, octanoic acid, 2,4,6-tris dimethylaminomethylphenol (2,4,6-tris [(dimethylamino) methyl] phenol), 1,3,5 -Tris 3-dimethylamine-propyl hexahydrotrizine (1,3,5-tris 3-dimethylamine-propyl hexahydrotrizine) and potassium hexanoate (potassium hexanoate) at least one selected from the group consisting of.

The blowing agent serves to form a foam cell in the heat insulating material by generating a gas in the polymerization process. Since the blowing agent is present in the cell after forming the polyisocyanurate foam, it is advantageous to use a material having low thermal conductivity and high stability. The blowing agent is composed of cyclopentane, chlorofluorocarbon, isopentane, isopentane, n-pentane, hydrochlorofluorocarbon, hydrofluorocarbon and water. Cyclopentane, water or mixtures thereof, which may be at least one selected from the group, in particular a blowing agent that does not contain chlorine, is environmentally advantageous.

The surfactant controls the surface tension at the time of formation of the foaming cell to suppress the size of the foaming cell from becoming too large, and serves to stabilize the formation of the foaming cell. As the type of the surfactant, it is possible to use various kinds known in the art.

The thermosetting foam may have a thermal conductivity of about 0.025 W / mk or less. Thermal conductivity refers to a physical property indicating the magnitude of thermal conductivity. It can be inferred that the lower the thermal conductivity, the better the thermal insulation performance. The thermosetting foam includes a polyisocyanurate foam, a nucleating agent, and a flame retardant together, thereby showing not only flame retardancy but also excellent heat insulating property, thereby ensuring low thermal conductivity and maintaining the thermal conductivity of about 0.025 W / mk or less. It can increase the utilization of building, home appliances, automobiles, etc.

The thermosetting foam may have an independent bubble ratio of about 80% or more. The thermosetting foam consists of a small honeycomb-shaped cell, the percentage of the closed cells of the cells is referred to as the independent bubble ratio. The higher the independent bubble ratio, the better the thermal insulation. If the independent bubble ratio is less than about 80%, a certain level of thermal insulation may not be obtained. The upper limit of the independent bubble ratio is not limited, but when the independent bubble ratio is excessively high, physical properties such as poor air permeability, low elasticity, and poor durability may be exhibited.

The thermosetting foam may have a density of about 10 kg / m ³ to about 150 kg / m ³ , specifically about 20 kg / m ³ to about 100 kg / m ³ . By maintaining the density of the thermosetting foam in the above range it can be provided a relatively light thermosetting foam.

열경화성 발포체 제조방법Thermosetting Foam Manufacturing Method

In another embodiment of the invention, the step of mixing the polyol-based compound and nucleating agent; Adding a flame retardant to the mixture of the polyol compound and the nucleating agent; And a step of polymerizing the polyisocyanurate by stirring the isocyanate compound in the mixture obtained by adding the flame retardant, and providing a thermosetting foam production method having a pyrolysis start temperature of 310 ° C. or higher by thermogravimetric analysis. The pyrolysis start temperature may be about 310 ° C. or more, as described above.

The mixing rate of the polyol compound and the nucleating agent in the step of mixing the polyol compound and the nucleating agent may be about 500rpm to about 5,000rpm. In order to uniformly disperse the polyol-based compound and the nucleating agent, the mixture may be mixed at a low speed of about 500 rpm at about 30 seconds to about 60 seconds at an initial stage, and the speed may be gradually increased to increase the mixing speed up to about 5,000 rpm at a later stage of mixing. . On the other hand, if the mixing is too slow at the time of initial mixing, the viscosity of the polyol-based compound is high and the viscosity of the nucleating agent is low may cause a problem that the nucleating agent is not sufficiently dispersed.

In addition, the step of mixing the polyol-based compound and the nucleating agent may be carried out at a temperature of about 0 ℃ to about 30 ℃. If the advancing temperature is less than about 0 ° C., the dispersion between the polyol-based compound and the nucleating agent may not sufficiently occur. On the contrary, when the advancing temperature is higher than about 30 ° C., the nucleating agent may be evaporated because the volatile point of the nucleating agent is low.

The stirring speed of adding the flame retardant to the mixture of the polyol-based compound and the nucleating agent may be about 500 rpm to about 5,000 rpm. This is a rate set so that the flame retardant may be uniformly mixed, and if it is out of this range, each material may be unevenly distributed, thereby deteriorating the physical properties of the polyisocyanurate foam.

In addition, the step of adding a flame retardant to the mixture of the polyol-based compound and the nucleating agent may be carried out at a temperature of about 0 ℃ to about 40 ℃. Exceeding this temperature range can change the properties of the flame retardant. Specifically, when the flame retardant is added after the addition of the surfactant, the flame retardant may be more effectively mixed with the mixture of the polyol-based compound having a low surface tension and the nucleating agent.

The stirring rate of the step of polymerizing the polyisocyanurate by stirring the isocyanate compound in the mixture obtained by adding the flame retardant may be about 3,000 rpm to about 5,000 rpm. This is a rate set so that the reaction of the polyol compound and the isocyanate compound and the trimerization reaction of the isocyanates can be made within a sufficiently fast time. Stirring at a rate lower than about 3,000 rpm causes a problem that the polyol compound and the isocyanate compound do not mix sufficiently to smoothly react. On the contrary, if it exceeds 5,000 rpm, the contact time between the polyol compound and the isocyanate compound is short. The reaction may be incomplete.

In addition, the step of polymerizing the polyisocyanurate by stirring the isocyanate compound in the mixture obtained by adding the flame retardant may be carried out in a temperature range of about 0 ℃ to about 20 ℃. If the operating temperature is less than 0 ℃ condensation reaction between the polyol compound and the isocyanate compound and the trimerization reaction of the isocyanate groups is less likely to occur, on the contrary, if the operating temperature exceeds 20 ℃, too fast reaction is induced to Problems arise when stabilization is hindered or reactants evaporate.

The following presents specific embodiments of the present invention. However, the embodiments described below are merely for illustrating or explaining the present invention in detail, and thus the present invention is not limited thereto.

Example 1

3.0 g of tetramethyl silane (TMS), which is a nucleating agent, and 1.0 g of isopropyl phenyl diphenyl phosphate (IPPP) were added to a polyol having a weight of 100 g. As the polyol, a mixture of a polyester polyol and a polyester polyol in a middle ratio of 4: 6 was used. Since the viscosity of the polyol used is relatively high compared to the tetramethylsilane, which is a nucleating agent, a mechanical stirrer is used at a low speed of 500 rpm at the beginning of the reaction so that the tetramethylsilane can be intercalated between the polyol compounds. The mixture was stirred for 1 second (1 step agitation), and then each was stirred at 1,000 rpm, 2,000 rpm, 3,000 rpm, 4,000 rpm, and 5,000 rpm for 30 seconds (two stage stirring) to prepare a mixed solution.

A polyisocyanurate foam was prepared by stirring 1.0 g of flame retardant isopropyl phenyl diphenyl phosphate (IPPP) at 20 ° C. at 3000 rpm for 10 seconds. In addition, the reaction mixture of the polyol compound and diisocyanate was stirred at 5,000 rpm for 20 seconds using a mechanical stirring device, and then a thermosetting foam was prepared in the mold.

Example 2

A thermosetting foam was prepared in the same manner as in Example 1 except that the amount of the flame retardant isopropyl phenyl diphenyl phosphate (IsoPropylPhenyl Diphenyl Phosphate, IPPP) was increased to 3.0 g.

Example 3

A thermosetting foam was prepared in the same manner as in Example 1 except that the amount of the flame retardant isopropyl phenyl diphenyl phosphate (IPPP) was increased to 5.0 g.

Example 4

Cresyl Diphenyl Phosphate (CDP) was used instead of IsoPropylPhenyl Diphenyl Phosphate (IPPP) as a flame retardant, except that the amount added was 1.0 g. Cured foams were prepared.

Example 5

A thermosetting foam was prepared in the same manner as in Example 4, except that the amount of the flame retardant, Cresyl Diphenyl Phosphate (CDP), was increased to 3.0 g.

Example 6

A thermosetting foam was prepared in the same manner as in Example 4, except that the crotch of the flame retardant Cresyl Diphenyl Phosphate (CDP) was increased to 5.0 g.

Comparative Example 1

In order to remove moisture contained in the organic clay (30B clay, Southern Clay Co.) containing a hydroxyl group it was dried for 24 hours in a vacuum oven. Next, to 100 g of the polyol used in Example 1, 160 g of polymer 4,4-diphenyldetane diisocyanate (M50, BASF) and 3.0 g of the 30B clay were added, and an oil thermostat was maintained at 60 ° C. The reaction was carried out in a water bath. In order to uniformly mix the M50 and 30B clay and to proceed with a smooth reaction, a mixed solution was prepared by stirring at a speed of 3,000 rpm for 2 hours using a mechanical stirrer.

Clay-polyisocyanurate nanocomposite was prepared by adding a catalyst and a surfactant to the mixture and reacting at room temperature. The polymeric 4,4′-diphenylmethane diisocyanate containing the organic clay was stirred at 5,000 rpm for 10 seconds using a mechanical stirring device to produce a thermosetting foam in a mold.

Comparative Example 2

A thermosetting foam was prepared in the same manner as in Example 1, except that 5.0 g of IsoPropylPhenyl Diphenyl Phosphate (IPPP) was added as a flame retardant without adding a nucleating agent such as tetramethylsilane.

Comparative Example 3

A thermosetting foam was prepared in the same manner as in Example 1, except that a nucleating agent such as tetramethylsilane and a flame retardant such as isopropyl phenyl diphenyl phosphate (IPPP) were not added.

Table 1

	Nuclear agent	Flame retardant	Flame Retardant Form
Example 1	Tetramethylsilane 3.0g	Isopropylphenyl diphenyl phosphate 1.0 g	Liquid
Example 2	Tetramethylsilane 3.0g	3.0 g of isopropylphenyl diphenyl phosphate	Liquid
Example 3	Tetramethylsilane 3.0g	5.0 g of isopropylphenyl diphenyl phosphate	Liquid
Example 4	Tetramethylsilane 3.0g	1.0 g of cresyl diphenyl phosphate	Liquid
Example 5	Tetramethylsilane 3.0g	3.0 g of cresyl diphenyl phosphate	Liquid
Example 6	Tetramethylsilane 3.0g	5.0 g of cresyl diphenyl phosphate	Liquid
Comparative Example 1	3.0g organic clay	-	-
Comparative Example 2	-	Isopropylphenyl diphenyl phosphate 1.0 g	Liquid
Comparative Example 3	-	-	-

<실험예> - 열경화성 발포체의 물리적 특성Experimental Example Physical Properties of Thermosetting Foams

The thermal conductivity, compressive strength, bending strength and thermal decomposition start temperature of the Examples and Comparative Examples were measured. First, in order to compare the thermal insulation performance of the thermosetting foams prepared according to the Examples and Comparative Examples, the thermal conductivity was based on ASTM C518. The degree was measured and then the compressive strength was measured according to ASTM D 1621.

In addition, the flexural strength was measured according to ASTM D790, and the pyrolysis start temperature when the weight change of the thermosetting foam occurred by thermogravimetric analysis.

TABLE 2

	Thermal Conductivity (W / mK)	Compressive strength (kg / cm ² )	Flexural Strength (kg / cm ² )	Pyrolysis start temperature (℃)	Foam cell average particle diameter (㎛)
Example 1	0.021	1.56	7.23	315	172
Example 2	0.022	1.47	6.98	321	165
Example 3	0.022	1.39	6.81	329	148
Example 4	0.021	1.59	7.10	316	170
Example 5	0.022	1.53	6.92	327	150
Example 6	0.023	1.41	6.87	341	130
Comparative Example 1	0.026	0.98	3.62	302	320
Comparative Example 2	0.029	1.04	4.87	309	280
Comparative Example 3	0.027	1.28	5.45	300	250

From the above experimental example, it was confirmed that the thermosetting foams according to Examples 1 to 6 were lower in thermal conductivity than the thermosetting foams of Comparative Examples 1 to 3. This is a property related to the thermal insulation performance, which is the most important property when the thermosetting foam is used as the heat insulating material, it can be seen that the heat insulating performance of the heat insulating material is improved when the silane-based compound is used as the nucleating agent. In the case of Comparative Example 1, the organic clay was mixed with the nucleating agent, but the storage stability was lowered, and as a result, the heat insulating performance was also disadvantageous.

As a result of the measurement of compressive strength and flexural strength, the embodiment was measured as a more favorable result than the comparative example, and the compressive strength and flexural strength were accompanied by thermosetting foams, and both of the examples showed sufficient physical properties to be used as insulation. Showed.

In addition, in Examples 1 to 6, since the flame retardant is included together with the nucleating agent, it is excellent in the flame retardant performance together with the thermal insulation performance, and pyrolysis was started at a temperature of about 310 ° C. or higher, whereas the comparative example 1 included the flame retardant. Pyrolysis began at temperatures below about 310 ° C. In Comparative Example 2, although the flame retardant was included, the pyrolysis start temperature was relatively high because it did not contain the nucleating agent, but the thermal conductivity was measured to be 0.029 W / mK. Comparative Example 3 did not include both the nucleating agent and the flame retardant, it was found that both the thermal insulation performance and the flame retardant performance is significantly reduced.

Furthermore, in contrast to the average particle diameter of the foam cells formed on the polyisocyanurate foam measured in the range of about 50 μm to about 200 μm in the Examples, the average particle diameters of the foam cells of the Comparative Example were all measured to be about 200 μm or more. Bar, when not including the flame retardant and nucleating agent at the same time, it was confirmed that there is a difficulty in forming a foam cell of uniform and small size.

As a result, the thermosetting foam according to one embodiment of the present invention is flame retardant by including a flame retardant in the polyisocyanurate foam, and at the same time to control the surface tension of the thermosetting foam by containing a nucleating agent to the polyisocyanurate foam It can be seen that it can maintain a constant size of the formed foam cell and also secure the thermal conductivity.

Claims

A polyisocyanurate foam formed by polymerizing a polyol compound and an isocyanate compound, a nucleating agent and a flame retardant,

Starting temperature of pyrolysis by thermogravimetric analysis

Thermosetting foam.
The method of claim 1,

The flame retardant is in liquid form or powder form

Thermosetting foam.
The method of claim 1,

The flame retardant is at least one selected from the group consisting of phosphorus flame retardant, metal hydrate flame retardant, halogen flame retardant, flame retardant aid and mixtures thereof.

Thermosetting foam.
The method of claim 3, wherein

The phosphorus flame retardant is at least one selected from the group consisting of triphenyl phosphate, cresyl diphenyl phosphate, isopropylphenyl diphenyl phosphate and mixtures thereof

Thermosetting foam.
The method of claim 3, wherein

The halogenated flame retardant is decabromodiphenyl oxide or octabromodiphenyl oxide

Thermosetting foam.
The method of claim 3, wherein

The flame retardant aid is antimony trioxide

Thermosetting foam.
The method of claim 1,

The nucleating agent comprises a silane compound or a siloxane compound

Thermosetting foam.
The method of claim 1,

The average diameter of the foam cells formed on the polyisocyanurate foam is 50㎛ to 200㎛

Thermosetting foam.
The method of claim 1,

The content of the flame retardant is 1 part by weight to 20 parts by weight based on 100 parts by weight of the polyol compound.

Thermosetting foam.
The method of claim 1,

The content of the nucleating agent is 1 part by weight to 10 parts by weight based on 100 parts by weight of the polyol-based compound.

Thermosetting foam.
The method of claim 1,

Further comprising a polymerization catalyst, a surfactant and a blowing agent in the thermosetting foam

Thermosetting foam.
The method of claim 1,

The thermosetting foam has a thermal conductivity of 0.025 W / mk or less

Thermosetting foam.
The method of claim 1,

The thermosetting foam has an independent foam ratio of 80% or more

Thermosetting foam.
The method of claim 1,

The thermosetting foam has a density of 10 kg / m 3 to 150 kg / m 3

Thermosetting foam.
Mixing the polyol compound and the nucleating agent;

Adding a flame retardant to the mixture of the polyol compound and the nucleating agent; And

Stirring the isocyanate compound to the mixture obtained by adding the flame retardant to polymerize the polyisocyanurate,

A thermosetting foam manufacturing method of the pyrolysis start temperature by the thermogravimetric analysis is 310 ℃ or more.