KR20130007896A - Polyurethane foam composition of heating value controllable and manufacturing method thereof and foam therefrom - Google Patents

Abstract

PURPOSE: A polyurethane foam composition, a manufacturing method thereof and a foam body is provided to maintain excellent thermal insulation and adhesive properties. CONSTITUTION: A polyurethane foam(10) composition includes calorific material which includes one or more selected from 1-bromohexadeacne, n-docasane, n-octadecane or paraffin wax, polyether polyol, polyesterether polyol or one or more selected from bisphenol A polyether polyol and isocyanate. The calorific material is composed of a particle shape having a core inside a shell. The size of the particle is 50 nano meters - 2000 microns.

Description

Polyurethane foam composition controllable calorific value and method for manufacturing the same and foam thereof {POLYURETHANE FOAM COMPOSITION OF HEATING VALUE CONTROLLABLE AND MANUFACTURING METHOD THEREOF AND FOAM THEREFROM}

The present invention relates to a polyurethane foam composition capable of controlling calorific value, a method for manufacturing the same, and a foam thereof, and more particularly, by adding an optimal heat regulator, the foam can be stably foamed even under a high temperature condition of 50 to 120 ° C. Rather, the present invention relates to a calorific value controllable polyurethane foam composition capable of maintaining excellent thermal insulation and adhesion, a method for producing the same, and a foam thereof.

Polyurethane is widely used in automobile parts, synthetic wood, building materials, shoes, medicine and other household products because of its excellent molding and various physical properties. Rigid urethane foam consisting of a double independent bubble is generally used in low-temperature warehouses, double insulation tubes, refrigerated containers, refrigerators, building panels, etc. that require the highest thermal insulation as the most excellent insulation material among the various insulators used.

However, polyurethane is a thermosetting resin, has a weak disadvantage in heat, the ideal temperature for the reaction of the polyol mixture and the isocyanate to form a heat insulating material is 20 ~ 30 ℃, generally has a maximum use range of 10 ~ 40 ℃, If the temperature is lower than this temperature range, the heat of reaction is lost to the foaming object and the foaming is hardly obtained, so that the product of the desired density cannot be obtained. If the temperature is too high, the reaction rate is accelerated and over-foamed, so that the insulating material of the desired physical property cannot be obtained. , Scorch, cracks, etc. There was a problem that can not manufacture the desired product.

Therefore, inevitably, the temperature of the foaming object should be lowered, and if it is difficult to lower the temperature of the foaming object, there is a difficulty in applying foaming on top of the glass wool, rock wool, rubber insulation sheet, etc., on the foaming object.

The inventors of the present invention have already developed a polyurethane foam for high-temperature pipe insulation that can maintain the thermal insulation performance even after the foam is formed and maintained at a high temperature of 110 to 120 ° C. using a hydrochlorofluorocarbon blowing agent (HCFC-141b). Hydrogen fluorocarbon blowing agents used here are prohibited in developed countries due to the ozone depletion index, and Korea will also be banned with restrictions on usage. There is a need for development of polyurethane foams capable of stable reactions.

That is, even when the temperature of the foaming object is high, there is a demand for development of a foaming composition capable of stably foaming and controlling a foamable temperature.

The present invention is to solve the above problems, by adding the optimum heat control material, not only can be stably foamed even in a high temperature foaming object of about 120 ℃, the calorific value controllable poly that can maintain excellent heat insulation and adhesiveness It is an object to provide a urethane foam composition.

In addition, by using the heat control material of the core and shell structure, it is possible to foam even at high temperatures, even if the heat insulator damage occurs during use, it is possible to heat insulation by foaming directly to a high temperature tank, etc., not only improves usability, It is an object to provide a calorific value controllable polyurethane foam composition which is easy to work and which can significantly reduce the cost of operation.

In addition, by using a mixture of polyols mixed with heat regulators and optimum components, and catalysts with an optimal combination of an amine catalyst and a metal catalyst, the calorific value can be minimized and foamed by discontinuous injection. It is an object to provide a foamable calorific value controllable polyurethane foam composition while maintaining a stable reaction rate.

In addition, an object of the present invention is to provide a calorific value controllable polyurethane foam composition capable of maintaining excellent mechanical properties and thermal insulation performance without problems such as over-foaming and cracking by mixing each component at an optimum ratio.

The calorific value controllable polyurethane foam composition according to the present invention for achieving the above object is 1-bromohexadeacne, 1-bromohexadeacne, n-docasane, n-octadecane ( n-octadecane) or paraffin wax.

In addition, a mixed polyol made of at least one of polyether polyol, polyesterether polyol or bisphenol-a polyether polyol and isocyanate further comprises a first catalyst comprising potassium tertiary amine and potassium acetate (potassium acetate), And a second catalyst including at least one of potassium octoate or bismuth based gel catalyst.

In addition, the thermoregulator is formed in the form of particles having a core in the shell, the particle size is characterized in that 50nm to 2000㎛, the core is 1-bromohexadeacne (1-bromohexadeacne) In this case, the shell is made of aminoplastics, the core is n-docasane, the shell is polymethylmethacrylate, the core is n-octadecane ( n-octadecane), the shell is polymethylmethacrylate (polymethylmethacrylate), when the core is paraffin wax, the shell is characterized in that at least one of acacia rubber or gelatin.

In the mixed polyol, the hydroxyl value of the polyether polyol is 100 to 500 mgKOH / g, the hydroxyl value of the polyesterether polyol is 150 to 300 mgKOH / g, and the hydroxyl value of the bisphenol-A polyether polyol is 300 to 650 mgKOH / g. g, wherein the mixed polyol is 30 to 80% by weight of the polyether polyol, 10 to 40% by weight of the polyesterether polyol and 5 to 20% by weight of the bisphenol-A polyether polyol. .

In addition, with respect to 100 parts by weight of the mixed polyol, the heat control material is characterized in that it comprises 3 to 20 parts by weight, the isocyanate is a polymeric 4,4-diphenylmethane diisoyanate, the mixed polyol 100 It is characterized by including 130 to 220 parts by weight, based on parts by weight.

With respect to 100 parts by weight of the mixed polyol, the first catalyst is 0.01 to 2 parts by weight, the second catalyst is characterized in that it comprises 0.001 to 0.3 parts by weight, and further comprises at least one of a surfactant or blowing agent, The surfactant is a polysiloxane ether, and the surfactant comprises 1 to 10 parts by weight based on 100 parts by weight of the mixed polyol.

In addition, the blowing agent is made of a physical blowing agent consisting of at least one of hydrofluorocarbon (HFC) or hydrocarbon (HC) and a chemical blowing agent consisting of water (H ₂ O), with respect to 100 parts by weight of the mixed polyol, the physical blowing agent 5 to 30 parts by weight, the chemical blowing agent is characterized in that it comprises 0.5 to 2 parts by weight.

Next, the method for producing a calorific value controllable polyurethane foam composition according to the present invention is a mixed polyol in which a polyether polyol, a polyester ether polyol and a bisphenol a polyether polyol is mixed with 1-bromohexadecane (1- Reaction solution by mixing a first catalyst comprising a tertiary amine and a thermoregulator comprising at least one of bromohexadeacne, n-docasane, n-octadecane or paraffin wax Reaction solution manufacturing step of preparing a; An isocyanate preparation step of preparing an isocyanate including a polymeric 4,4-diphenylmethane diisocyanate; And a foaming step of injecting the reaction solution and the isocyanate into the foaming object and foaming the foamed object.

In the foaming step, the temperature of the reaction solution and the isocyanate is characterized in that the 20 ℃ to 40 ℃, in the foaming step, the temperature of the foaming object is 50 ℃ to 120 ℃, foaming pressure is 40 to 150kgf / It is characterized in that the cm2.

In addition, in the reaction solution preparation step, the reaction material, and a second catalyst comprising at least one of potassium acetate, potassium octoate or bismuth based gel catalyst; It is characterized in that it further comprises a blowing agent comprising a surfactant which is a polysiloxane ether and a chemical blowing agent consisting of water (H ₂ O) and a physical blowing agent consisting of at least one of hydrofluorocarbon (HFC) or hydrocarbon (HC).

In the reaction solution manufacturing step, with respect to 100 parts by weight of the mixed polyol, the heat control material is characterized in that it comprises 3 to 20 parts by weight, the first catalyst comprises 0.01 to 2 parts by weight, in the foaming step, Isocyanate is characterized by including 140 to 250 parts by weight based on 100 parts by weight of the reaction solution.

According to the calorific value controllable polyurethane foam composition of the present invention and a method for manufacturing the same, the foam can be stably foamed even at a high temperature foaming object of about 120 ° C. by adding an optimal heat control material, and has excellent thermal insulation and adhesion. There is an advantage in maintaining the castle.

In addition, by using the heat control material of the core and shell structure, it is possible to foam even at high temperatures, even if the heat insulator damage occurs during use, it is possible to heat insulation by foaming directly to a high temperature tank, etc., not only improves usability, There is an advantage that the work is easy, and the work cost can be significantly reduced.

In addition, by using a mixture of polyols mixed with heat regulators and optimum components, and catalysts with an optimal combination of an amine catalyst and a metal catalyst, the calorific value can be minimized and foamed by discontinuous injection. It has the advantage of foaming while maintaining a stable reaction rate.

In addition, by mixing each component in an optimum ratio, there is an advantage that can maintain excellent mechanical properties and thermal insulation performance without problems such as over-foaming, cracks.

1 is a flow chart sequentially showing a method for producing a calorific value controllable polyurethane foam composition of the present invention
Figure 2 is a first application of the method for producing a calorific value controllable polyurethane foam composition of the present invention
Figure 3 is a second application of the method for producing a calorific value controllable polyurethane foam composition of the present invention
Figure 4 is a photograph of the foaming results of Comparative Example 1 out of the calorific value controllable polyurethane foam composition range of the present invention
Figure 5 is a photograph of the foaming result of Example 1 which is a calorific value controllable polyurethane foam composition of the present invention

Hereinafter, one embodiment of the present invention will be described in detail with reference to the accompanying drawings for a calorific value controllable polyurethane foam composition, a method for producing the same, and a foam thereof according to the present invention. The present invention may be better understood by the following examples, which are for the purpose of illustrating the present invention and are not intended to limit the scope of protection defined by the appended claims.

First, the calorific value controllable polyurethane foam composition of the present invention is characterized in that it comprises a heat regulating material. This can minimize the calorific value of the foam, and serves to enable foaming stably even at high temperatures.

The thermoregulator, preferably comprises at least one of 1-bromohexadeacne, n-docasane, n-octadecane or paraffin wax. More preferably, it is effective to include 1-bromohexadeacne and n-docasane. This is through several experiments to measure the exothermic properties of the foam composition of the present invention when foaming, to find the optimum heat regulation material, to minimize the amount of heat generated during the reaction, depending on the reaction temperature, By adjusting the content, the calorific value can be controlled.

In addition, the heat regulation material is preferably made of a particle form having a core (core) in the shell (Shell). That is, the shell is laminated on the core to form a wrap. This can prevent the core material from inhibiting the reaction during the reaction, and serves to control the exothermic reaction so that the core suppresses the exotherm while the shell melts at a point where heat is generated to some extent.

The average particle size of the thermoregulator is preferably from 50 nm to 2000 μm, more preferably from 10 μm to 200 μm. If the thickness is less than 50 nm, not only the formation of shell-core particles is difficult, but also the content of the core is less than that of the shell, and it is difficult to sufficiently control the calorific value. The content can be increased, it is difficult to minimize the calorific value, there is a problem that inhibits the foaming reaction.

The core preferably includes at least one of 1-bromohexadeacne, n-docasane, n-octadecane or paraffin wax. The shell is preferably at least one of aminoplastics, polymethylmethacrylate, polymethylmethacrylate, acacia rubber or gelatin.

More preferably, since the core and the shell interact with each other, in order to realize the optimum heat control effect in the present invention, when the core is 1-bromohexadeacne, the shell is aminoplastics. (aminoplastics), the core is n-docasane, the shell is polymethylmethacrylate, the core is n-octadecane, When the shell is polymethylmethacrylate, and the core is paraffin wax, it is effective to use the shell in combination of at least one of acacia rubber or gelatin.

In addition, the content of the heat regulating material, it is preferable to include 3 to 20 parts by weight, more preferably 8 to 15 parts by weight, most preferably 12 parts by weight based on 100 parts by weight of the mixed polyol below. It is effective. If it is less than 3 parts by weight, it is difficult to sufficiently control the calorific value, and if it exceeds 20 parts by weight, the foaming reaction is inhibited and the physical properties and the thermal insulation performance of the foam are significantly reduced.

In addition, the calorific value controllable polyurethane foam composition of the present invention preferably further comprises a mixed polyol, isocyanate and catalyst. This is the core configuration of the foam and reaction.

The mixed polyol is preferably made of at least one of polyether polyol, polyesterether polyol or bisphenol-A polyether polyol, more preferably, 30 to 80% by weight of the polyether polyol, 10 to 40% by weight of the polyesterether polyol % And 5 to 20% by weight of the bisphenol-A polyether polyol is effective. When the three polyols are mixed at the above ratios, the physical properties and the thermal insulation performance of the foam can be maximized, and the amount of heat generated can be controlled by effectively reacting with the heat regulating material of the present invention.

In the mixed polyol, the hydroxyl value of the polyether polyol is 100 to 500 mgKOH / g, the hydroxyl value of the polyesterether polyol is 150 to 300 mgKOH / g, and the hydroxyl value of the bisphenol A polyether polyol is 300 to It is preferred that it is 650 mgKOH / g. When it has a value of the hydroxyl value in this range, the foaming reaction occurs effectively, and the foam has excellent physical properties and thermal insulation.

Moreover, it is preferable that the said isocyanate consists of polymeric 4, 4- diphenylmethane diisoyanate. The content is preferably 130 to 220 parts by weight, more preferably 160 to 190 parts by weight based on 100 parts by weight of the mixed polyol. If it is less than 130 parts by weight, there is a problem that the foaming reaction is difficult to proceed, if it exceeds 220 parts by weight, not only inhibits the foaming reaction, but also there is a problem that the economical efficiency is also lowered because there are many isocyanates that do not react.

In addition, the catalyst preferably further includes at least one of the first catalyst and the second catalyst, and more preferably, it is effective to mix the first catalyst and the second catalyst.

The first catalyst serves as a main catalyst, it is preferable to use an amine catalyst, more preferably it is effective to include a tertiary amine. The second catalyst serves as a cocatalyst, and preferably includes at least one of potassium acetate, potassium octoate, or bismuth based gel catalyst.

Using these catalysts is not only able to maximize the reaction yield, but also improve the reactivity with the heat regulating material is effective.

The content of the catalyst is preferably based on 100 parts by weight of the mixed polyol, the first catalyst is 0.01 to 2 parts by weight, and the second catalyst is preferably included in 0.001 to 0.3 parts by weight, more preferably, the first It is effective that the catalyst comprises 0.1 to 0.5 parts by weight, and the second catalyst comprises 0.01 to 0.09 parts by weight. When the content ratio of the catalyst is maintained in the above range, the reaction yield can be maximized.

Next, the calorific value controllable polyurethane foam composition of the present invention preferably further comprises at least one of a surfactant or a blowing agent. This is a configuration for improving the foaming efficiency and the performance of the foam.

The surfactant may be any surfactant, but in the present invention, it is most preferable to use a polysiloxane ether, and the content thereof is preferably 1 to 10 parts by weight, more preferably 100 parts by weight of the mixed polyol. Preferably 3 to 8 parts by weight, most preferably 5 parts by weight. If it is less than 1 part by weight, the diffusion of gas by foaming cannot be prevented. If it is more than 10 parts by weight, the surface tension of the reactants is lowered, so that the effect of the surfactant is prevented from collapsing the closed cell structure. Almost disappeared.

In addition, the blowing agent is preferably made of a physical blowing agent consisting of at least one of hydrofluorocarbon (HFC) or hydrocarbon (HC) and a chemical blowing agent consisting of water (H ₂ O), more preferably a physical blowing agent consisting of hydrocarbon It is effective to mix and use chemical blowing agents consisting of purple and water. Unlike the prior art, even without using hydrochlorofluorocarbon (HCFC), by the other composition of the present invention, there is an advantage that can be effectively foamed.

The amount of the blowing agent is preferably based on 100 parts by weight of the mixed polyol, the physical blowing agent is 5 to 30 parts by weight, the chemical blowing agent comprises 0.5 to 2 parts by weight, more preferably the physical blowing agent is 10 to 20 parts by weight, the chemical blowing agent is effective to comprise 1 to 1.5 parts by weight. Outside the content range, not only the desired density does not come out, there is a problem that the insulation of the polyurethane foam is inferior and the foam is broken, the adhesive strength with the face material is weakened.

Next, the method of producing a calorific value controllable polyurethane foam composition of the present invention, as shown in Figure 1, comprises a reaction solution preparation step (S10), isocyanate preparation step (S20) and foaming step (S30). Portions not described below are as described in the calorific value controllable polyurethane foam composition of the present invention.

First, the reaction solution preparation step (S10) is a mixed polyol in which a polyether polyol, a polyesterether polyol, and a bisphenol-A polyether polyol is mixed, 1-bromohexadeacne, n-docasein (n -docasane), n-octadecane (n-octadecane) or a paraffin wax is a step of preparing a reaction solution by mixing a first catalyst comprising a tertiary amine and a heat regulator including at least one. This is a process for preparing the core composition for the reaction.

In the reaction solution preparation step (S10), a second catalyst comprising at least one of potassium acetate, potassium octoate or bismuth based gel catalyst in the reactant And a blowing agent including a surfactant which is a polysiloxane ether and a chemical blowing agent made of water (H ₂ O) and a physical blowing agent made of at least one of hydrofluorocarbon (HFC) or hydrocarbon (HC) and water (H ₂ O).

In addition, in the reaction solution manufacturing step (S10), with respect to 100 parts by weight of the mixed polyol, the heat regulation material is preferably 3 to 20 parts by weight, the first catalyst preferably comprises 0.01 to 2 parts by weight.

Next, the isocyanate preparation step (S20) is a step of preparing an isocyanate including the polymeric 4,4-diphenylmethane diisocyanate. This is a process for preparing isocyanate for reaction with the reaction solution.

Finally, the foaming step (S30) is a step of injecting the reaction solution and the isocyanate into the foaming object, and foaming. This is a process of causing a foaming reaction by mixing a reaction solution and an isocyanate. This process produces a polyurethane foam.

In the foaming step (S30), the temperature of the reaction solution and the isocyanate is preferably 20 ° C to 40 ° C, more preferably 25 ° C to 30 ° C. When the temperature is less than 20 ° C., a sufficient foaming reaction is unlikely to occur due to a large temperature difference with the foaming target. When the temperature exceeds 40 ° C., a sufficient foaming reaction is difficult to occur due to a small temperature difference with the foaming target.

In addition, in the foaming step (S30), the temperature of the foaming object is preferably 50 ℃ to 120 ℃, more preferably 80 to 100 ℃ it is effective. If the temperature is less than 50 ℃, not only the effect of suppressing the calorific value of the heat regulating material is reduced, but there is a problem that cannot be applied to reinforcement due to the damage of the insulator in use. There is.

In addition, in the foaming step (S30), the foaming pressure is preferably 40 to 150kgf / ㎠, more preferably, 50 to 80kgf / ㎠ is effective. If it is less than 40kgf / cm 2 It is difficult to foam the foam composition of the present invention sufficiently, and if it exceeds 150kgf / cm 2 There is a problem that the mechanical properties are significantly reduced due to cracks in the foam.

In addition, in the foaming step (S30), the isocyanate, it is preferable to include 140 to 250 parts by weight, more preferably 180 to 220 parts by weight based on 100 parts by weight of the reaction solution. If it is less than 140 parts by weight it is difficult to foam sufficiently in the foaming reaction of the present invention, if it exceeds 250 parts by weight maintains the calorific value and the foaming reaction does not occur stably, there are a lot of unreacted isocyanate has a problem of low economic efficiency have.

Hereinafter, the experimental results for the superiority of the foam prepared using the calorific value controllable polyurethane foam composition of the present invention.

First, high-temperature reactivity evaluation experiments were performed according to the composition of the mixed polyol, the content of the catalyst and the heat regulating material, and the composition as described in Table 1 below was reacted at 120 ° C. 315 mm HDPE was produced in the form of a thermal insulation pipe.

Comparative Example 1 Comparative Example 2 Example 1 Example 2 Polyether polyol 85 55 70 55 Polyester polyol 10 40 25 40 Bisphenol A
Polyether polyol 5 5 5 5 Heat regulator - - 12 4 Surfactants 2 2 2 2 Amine catalyst 0.7 0.5 0.6 0.5 Potassium acetate
catalyst - 0.001 0.2 0.1 water 0.8 0.8 0.8 0.8 Hydrofluorocarbons
blowing agent 15 15 15 15 Isocyanate 184 204 201 201

* In case of polyol, the weight unit is 100% of the total polyol

* In the remainder, parts by weight relative to 100 parts by weight of the mixed polyol

The foam compositions of Comparative Examples 1 and 2 and Examples 1 and 2 of Table 1 were prepared according to the foam production method of the present invention, and their physical properties were measured. Physical properties were also measured, and the measurement method and measurement results are as follows.

First, accelerated aging tests were conducted in accordance with EN 253. EN 253 was adopted as a standard in Europe to predict the service life of thermal insulation pipes using rigid urethane foams. It is known as the only way to apply the same standard in Korea. That is, this method makes it possible to predict the service life of polyurethane insulation used as a high temperature insulating material not higher than normal temperature.

The service life is achieved through accelerated aging test, and the heat medium oil is flowed into the pipe for more than 1000 hours at 170 ℃, and after 1450 hours, the physical strength and thermal conductivity of the heat insulating material are measured. This will determine the degree of aging of the insulation and predict the remaining life.

At this time, the size of the specimen was 315mm, the inner tube 200A, the thickness of the insulation was produced to 43.8mm. Specimen preparation was carried out using a foamer, the composition temperature of the polyol mixture and 4,4-diphenylmethane diisocyanate at 20 ~ 40 ℃, the foaming pressure is 130 ~ 150kgf / ㎠, the temperature of the foam object 120 ℃, The demolding time was made into 24 hours.

As shown in the physical property results of the polyurethane foam before accelerated aging of Table 2, Comparative Example 1, Comparative Example 2 carbonization, over-exposure, cracks are generated, the processing and physical properties of the specimen is impossible, Example 1 , Example 2 was carried out before and after the accelerated aging physical properties test.

Physical property analysis and reactivity measurement

The polyurethane foam prepared by the above method was tested before and after accelerated aging, and the results are shown as values before and after accelerated aging in Tables 2 and 3 below. Measurements were made horizontally and vertically using a universal test machine (UTM).

Compressive Strength

The compressive strength of the polyurethane foam was measured using a universal test machine (UTM) by the KS M 3809-2006 test method.

<Bending Strength>

Flexural strength of the polyurethane foam was measured using a universal test machine (UTM) by the KS M 3809-2006 test method.

<Absorption rate>

The water absorption of the polyurethane foam was measured by the EN-253 test method.

<Thermal conductivity>

The thermal conductivity of the polyurethane foam was measured by the KS L 9016-2005 test method.

Shear Strength

The shear strength of the polyurethane foam was measured using a universal test machine (UTM) by the ISO 022-2006 test method.

<Independent Bubble Rate>

Independent foam ratio of the polyurethane foam was measured by the ISO 4590-2002 test method.

<Reactivity>

It is the result measured by foaming by hand, It is the result measured by foaming on condition of stirring speed 3000rpm, stirring time 10sec, liquid temperature (A / B) 20/20 degreeC.

Acceleration Aging Test

The accelerated aging test was performed under conditions of a test temperature of 170 ° C. and an aging time of 1450 hours in a room (temperature 205 ° C.) using an aging tester according to standard EN253 with an external HDPE diameter of 315 mm in a 200 A pipe.

The experimental results before accelerated aging are shown in <Table 2> below, and the experimental results after accelerated aging are shown in <Table 3> below.

Test Items unit SPEC Comparative Example 1 Comparative Example 2 Example 1 Example 2 Test Methods Responsive
(CT / GT) sec - 35/230 45/240 73/350 75/355 density Kg / ㎥ ≥60 Carbonization cracks occur
So

Property
Psalter
Processing
And
Measure
Impossible Carbonization cracks occur
So

Property
Psalter
Processing
And
Measure
Impossible 90 85 KS M 3809: 2006 Flexural strength N / cm 2 ≥30 65 62 KS M 3809: 2006 Compressive strength N / cm 2 ≥30 45 38 KS M 3809: 2006 Shear strength N / cm 2 ≥20 31 30 ISO 1922: 2001 Absorption rate % ≤10 5 5 EN 253 Thermal conductivity
20 ± 5 ℃ kcal / mh ℃ ≤0.022 0.020 0.021 KS L 9016: 2005
(Plate heat flow method) Independent Bubble Rate % ≥88 89 90 ISO 4590: 2002

* CT (Cream time): Time taken from when the mixed polyol A and isocyanate are mixed until the stock solution starts to swell

* GT (gel time): the time taken from the time when the mixed polyol A and the isocyanate is mixed to have a strength of the gel that can withstand the light impact and have a somewhat stable spatial shape.)

As shown in Table 2, Comparative Examples 1 and 2, which are out of the content of the mixed polyol and the catalyst of the present invention and do not add the heat regulating material of the present invention, not only remarkably deteriorate, but also carbonize the foam. Cracks occurred, which caused a problem that foams could not be formed to such an extent that physical properties such as density could not be measured. A photograph taken of this is shown in FIG. 4.

On the other hand, Examples 1 and 2, which fall within the scope of the present invention, have significantly slowed down the reaction due to the heat regulating material of the present invention, thereby forming a foam of good shape without cracking or carbonization. A photograph taken of this is shown in FIG. 5.

In addition, the excellent physical properties of Example 1 and Example 2 of the present invention satisfied the EN253 standard.

Test Items unit SPEC Example 1 Example 2 Test Methods Aging test
(170 ° C, 1450H) - - - - EN 253: 2009 Thermal conductivity
[Average temperature
(20 ± 5) ℃] kcal / mh ℃ ≤0.028 0.022 0.022 KS M 3809: 2006
(Plate heat mooring method) Compressive strength N / cm 2 ≥15 32 36 KS M 3809: 2006 Shear strength N / cm 2 ≥10 28 19 KS M 3809: 2006 Flexural strength N / cm 2 ≥15 68 65 KS M 3809: 2006

In addition, as shown in Table 3, in the case of Example 1 and Example 2 of the present invention, excellent physical properties were maintained even after the aging test, which satisfies the EN253 standard.

As shown in the above experimental results, the heat control material of the present invention has a direct influence on the foam formation at high temperature, and its superiority has been clearly demonstrated, and the composition ratio of the catalyst and mixed polyol of the foam composition of the present invention is also physical property. It could be confirmed that it had a positive effect on.

2 and 3 are examples of the application of the method for producing a calorific value controllable polyurethane foam composition of the present invention.

In the above, the configuration of the present invention was described in detail with reference to one embodiment. However, the scope of the present invention is not limited to the above embodiment, and may be embodied in various forms of embodiments within the appended claims. Without departing from the gist of the invention as claimed in the claims, it is intended that such modifications can be made by anyone of ordinary skill in the art to be within the scope of the claims.

1: hot mold
2: mixing head
3: polyurethane foam
10: polyurethane foam
20: mixing head
30: reserve tank
40: jacket (steel, sus, etc.)
50: hot water, steam or oil

Claims (19)

Characterized in that it comprises a heat regulation material comprising at least one of 1-bromohexadeacne, n-docasane, n-octadecane or paraffin wax Calorific value controllable polyurethane foam composition
The method of claim 1,
A calorific value controllable polyurethane foam composition further comprising an isocyanate and a mixed polyol consisting of at least one of a polyether polyol, a polyesterether polyol or a bisphenol a polyether polyol
3. The method according to claim 1 or 2,
Further comprising a first catalyst comprising a tertiary amine and a second catalyst comprising at least one of potassium acetate, potassium octoate or bismuth based gel catalyst A calorific value controllable polyurethane foam composition

3. The method according to claim 1 or 2,
The heat regulating material is in the form of particles having a core in the shell, the size of the particles are calorific value controllable polyurethane foam composition, characterized in that 50nm to 2000㎛
5. The method of claim 4,
When the core is 1-bromohexadeacne, the shell is made of aminoplastics, and when the core is n-docasane, the shell is polymethyl Methacrylate (polymethylmethacrylate), the core is n-octadecane (n-octadecane), the shell is polymethylmethacrylate (polymethylmethacrylate), if the core is paraffin wax, the shell is acacia rubber or gelatin Calorific value controllable polyurethane foam composition, characterized in that at least one of
The method of claim 2,
In the mixed polyol, the hydroxyl value of the polyether polyol is 100 to 500 mgKOH / g, the hydroxyl value of the polyesterether polyol is 150 to 300 mgKOH / g, and the hydroxyl value of the bisphenol-A polyether polyol is 300 to 650 mgKOH / g. calorific value controllable polyurethane foam composition, characterized in that g
The method of claim 2,
The mixed polyol is 30 to 80% by weight of the polyether polyol, 10 to 40% by weight of the polyesterether polyol and 5 to 20% by weight of the bisphenol-A polyether polyol, calorific value controllable polyurethane foam composition
The method of claim 2,
Based on 100 parts by weight of the mixed polyol, the heat regulating material is 3 to 20 parts by weight of calorific value controllable polyurethane foam composition
The method of claim 2,
The isocyanate is a polymeric 4,4-diphenylmethane diisoyanate, and the calorific value controllable polyurethane foam composition comprising 130 to 220 parts by weight based on 100 parts by weight of the mixed polyol. The method of claim 3,
The calorific value controllable polyurethane foam composition according to 100 parts by weight of the mixed polyol, wherein the first catalyst comprises 0.01 to 2 parts by weight and the second catalyst comprises 0.001 to 0.3 parts by weight.
The method of claim 2,
And at least one of a surfactant or a blowing agent, wherein the surfactant is a polysiloxane ether, and the surfactant includes 1 to 10 parts by weight based on 100 parts by weight of the mixed polyol. Foam composition
The method of claim 10,
The blowing agent is composed of a physical blowing agent consisting of at least one of hydrofluorocarbon (HFC) or hydrocarbon (HC) and a chemical blowing agent consisting of water (H ₂ O), with respect to 100 parts by weight of the mixed polyol, the physical blowing agent is 5 To 30 parts by weight, wherein the chemical blowing agent comprises 0.5 to 2 parts by weight of the calorific value controllable polyurethane foam composition
1-bromohexadeacne, 1-bromohexadeacne, n-docasane, n-octadecane (polyether polyol, polyester ether polyol, and bisphenol a polyether polyol mixed) n-octadecane) or a reaction solution preparing step of preparing a reaction solution by mixing a first catalyst comprising a tertiary amine and a heat control material comprising at least one of paraffin wax;
An isocyanate preparation step of preparing an isocyanate including a polymeric 4,4-diphenylmethane diisocyanate; And
Method of producing a calorific value controllable polyurethane foam composition comprising a; foaming step of injecting the reaction solution and the isocyanate in the foaming object, and foaming
The method of claim 13,
In the foaming step, the temperature of the reaction solution and the isocyanate is a method for producing a calorific value control polyurethane foam composition, characterized in that 20 ℃ to 40 ℃.
The method according to claim 13 or 14,
In the foaming step, the temperature of the foaming object is 50 ℃ to 120 ℃, the foaming pressure is a method for producing a calorific value controllable polyurethane foam composition, characterized in that 40 to 150kgf / ㎠.
The method according to claim 13 or 14,
In the reaction solution preparation step, the second catalyst and polysiloxane ether comprising at least one of potassium acetate, potassium octoate or bismuth based gel catalyst in the reactant. A calorific value controllable polyurethane characterized in that it further adds a blowing agent comprising a physical blowing agent consisting of at least one of phosphorus surfactant and hydrofluorocarbon (HFC) or hydrocarbon (HC) and a chemical blowing agent consisting of water (H ₂ O). Method of Making Foam Composition
The method according to claim 13 or 14,
In the step of preparing the reaction solution, the calorific value controllable polyurethane foam composition, characterized in that the heat regulation material comprises 3 to 20 parts by weight, and the first catalyst comprises 0.01 to 2 parts by weight based on 100 parts by weight of the mixed polyol. Manufacturing Method
The method according to claim 13 or 14,
In the foaming step, the isocyanate is a method for producing a calorific value controllable polyurethane foam composition, characterized in that it comprises 140 to 250 parts by weight based on 100 parts by weight of the reaction solution.
A calorific value controllable polyurethane foam produced by any of claims 13-18.

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