KR102679688B1 - Polyol composition for semi-non-combustible water-repellent polyurethane and method of manufacturing the same - Google Patents

Abstract

The present invention provides a method for producing a polyol composition for water-based polyurethane foam using pure water as a blowing agent.
The present invention relates to a method for producing a polyol composition for water-foamable polyurethane containing a polyol component, a flame retardant component, water, a catalyst that promotes the urethane reaction, and a retardant that delays the urethane reaction, wherein the flame retardant components are added. After making a flame retardant mixture and maintaining the flame retardant mixture in a stable state; During the urethane reaction, a first additive that delays the urethane reaction and a second additive that promotes the urethane reaction are sequentially added; Between the time of adding the first additive and the time of adding the second additive, pure water that acts as a foaming agent is added; Finally, the polyol component is added and mixed.

Description

Polyol composition for semi-non-combustible water-repellent polyurethane and method of manufacturing the same}

The present invention relates to a polyol composition for semi-incombustible water-foamable polyurethane, and to a polyol composition for semi-incombustible water-foamable polyurethane that uses pure water as a foaming agent without using a chemical blowing agent, and a method for producing the same.

Rigid polyurethane foam (foam) has excellent insulation performance, dimensional stability, and constructability, so it is widely used as an insulation material for refrigerators, freezers, and building materials. Rigid polyurethane foam takes advantage of its excellent insulation properties and is used as a material for housing and refrigeration ships. , LNG tanks, oil plants, etc., and it is expected that its use will continue to expand as an essential material for energy technology and low-temperature technology.

Conventionally, chlorofluorocarbons (CFC series) and hydrochlorofluorocarbons (HCFC series), which have low thermal conductivity and desirable boiling points, were used as blowing agents for rigid polyurethane foam. Chlorofluorocarbons (CFC series) contain chlorine atoms in their molecules and are stable molecules, so they reach the ozone layer through a diffusion effect and react with ozone to destroy the ozone layer, so their use is limited. In particular, since the Kyoto Protocol to the Climate Change Convention officially came into effect in 2005, CFCs and HCFCs, known as ozone-depleting substances, cannot be used in accordance with this convention. As an alternative to this, hydrochlorofluorocarbons (HCFC series), hydrofluorocarbons (HFC series), or cyclopentane (C-Pentane) are used as foaming agents for rigid polyurethane foam.

In particular, for applications requiring insulation performance, the use of HCFC-141b, which has low thermal conductivity among HCFCs, has become mainstream. However, since these substances are causing environmental damage problems such as global warming, this blowing agent has recently been replaced with pentane, etc. It is being used as a replacement.

However, blowing agents such as pentane have a risk of explosion, so explosion-proof equipment must be equipped when handling them. Explosion-proof equipment has the disadvantage of being expensive compared to general equipment, making it difficult for small and medium-sized manufacturers to invest in and install.

As an alternative technology, a method for producing water-blown rigid polyurethane foam using pure water as a blowing agent has been proposed. However, due to the sensitivity of the polyurethane reaction, it is difficult to obtain high-quality polyurethane foam, and in particular, it is difficult to obtain high-quality polyurethane foam and is especially environmentally friendly and has flame retardant performance. There is an urgent need for the emergence of improved manufacturing technology for water-based polyurethane foaming agents.

Republic of Korea Patent Publication No. 10-2008-77964 (publication date: August 26, 2008); Republic of Korea Patent Publication No. 10-2021-0006868 (Publication date: 2021. 01. 19)

The object of the present invention is to manufacture rigid polyurethane foam in an environmentally friendly manner by using only water as a foaming agent without using conventional chemical foaming agents such as ozone-depleting substances or similar foaming agents. To provide a method for producing a polyol composition for water foamed polyurethane.

In addition, another object of the present invention is to produce water-foamable polyurethane foam that can produce environmentally friendly semi-incombustible rigid polyurethane foam by using only water as a foaming agent without using conventional chemical foaming agents such as ozone-depleting substances or similar foaming agents. To provide a method for producing a polyol composition for urethane.

The present invention provides a method for producing a polyol composition for water-foamable polyurethane.

The method for producing the polyol composition for water-foamable polyurethane according to the present invention,

After adding flame retardant ingredients to create a flame retardant mixture and maintaining the flame retardant mixture in a stable state,

During the urethane reaction, a first additive that delays the urethane reaction and a second additive that promotes the urethane reaction are sequentially added,

Between the time of adding the first additive and the time of adding the second additive, pure water, which acts as a foaming agent, is added,

Finally, the polyol component is added and mixed.

The method for producing the polyol composition for water-foamable polyurethane according to the present invention,

One). A first step of preparing a first flame retardant mixture by adding and mixing a flame retardant and then adding a defoaming agent and a dispersant to provide a stable and uniform dispersion state to the components of the flame retardant;

2). A second step of preparing a second flame retardant mixture by adding a reaction retardant and a foam stabilizer as first additives to the first flame retardant mixture and mixing them;

3). a third step of preparing a first flame retardant mixture for water foaming by adding pure distilled water as a foaming agent to the second flame retardant mixture;

4). a fourth step of preparing a second flame retardant mixture for water foaming by adding and mixing a catalyst that promotes a urethane reaction as a second additive to the first flame retardant mixture for water foaming;

5). A fifth step of preparing a polyol composition for rigid polyurethane by water foaming by adding polyol to the second water foaming flame retardant mixture; It is characterized by including.

In the present invention, it is preferable to add additional flame retardant components after the fifth step.

The present invention uses only pure water as a blowing agent. Because of this, there is an advantage in not using CFC-based or HCFC-based foaming agents, which are environmentally destructive substances, to improve the physical properties or heat conduction performance of rigid polyurethane foam. This shows that the present invention is an environmentally friendly technology.

Additionally, the present invention has the advantage of being able to manufacture semi-incombustible products while using only pure water. This means that the urethane foam according to the present invention is environmentally friendly and has the performance of a semi-non-flammable product beyond a flame retardant product.

Additionally, since the present invention uses pure water, there is no need to use a pentane-based blowing agent that has the risk of explosion. This has the advantage of ensuring the safety of manufacturing facilities and reducing investment costs for manufacturing facilities, including explosion-proof facilities, since explosion-proof facilities do not need to be installed when preparing the manufacturing facilities when the present invention is intended to be implemented. It means there is.

Hereinafter, the present invention will be described in more detail and detail. It is clear that the specific numerical values or specific examples provided in the present invention are preferred embodiments of the present invention, and are only intended to explain the technical idea of the present invention in more detail, and the present invention is not limited thereto.

In the specification of the present invention, various changes or modifications may be made to the various embodiments, and the scope of protection of the present invention is not limited or limited by these embodiments, and equivalents or equivalents thereof are included in the scope of protection. It is clear that it belongs.

In addition, in the specification of the present invention, detailed description of parts that are known in the technical field and can be easily used or easily created by those skilled in the art will be omitted.

Additionally, in the specification of the present invention, the terms "comprise", "contain", or "including" mean "including without limitation." Additionally, the singular form should be construed as including the plural form unless specifically limited by the context.

The present invention provides a method for producing a semi-incombustible polyol composition for water-foamable polyurethane.

The method of producing a polyol composition for semi-non-flammable water-foamable polyurethane according to the present invention includes adding flame retardant components, first adding a first additive that delays the urethane reaction during the urethane reaction, and pure water acting as a foaming agent during the urethane reaction. is added, and then, during the urethane reaction, a second additive that promotes the urethane reaction is sequentially added, and finally, the polyol component is added.

The present invention includes a first step of adding flame retardant ingredients and maintaining the flame retardant ingredients in a uniform and stable state.

In the first step, the flame retardant components are added to the container, and the flame retardant components are uniformly kneaded and maintained in a stable state. The flame retardant components are mainly composed of phosphorus-based flame retardants, and are used not only to improve flame retardancy, but also to improve dispersibility and reduce viscosity. It is preferable to typically use a phosphorus-based flame retardant as the flame retardant component. The phosphorus-based flame retardant produces phosphoric acid and polyphosphoric acid through thermal decomposition. The phosphoric acid and polyphosphoric acid produced at this time generate char through esterification and dehydration reactions, and this char is known to exert a flame retardant effect by blocking oxygen and heat. It is desirable to use TCPP (trichloropolyphosphate) as a representative phosphorus-based flame retardant. The flame retardant may be a halogen-based flame retardant in addition to the phosphorus-based flame retardant. However, the use of halogen-based flame retardants has the disadvantage of causing environmental problems.

It is preferable to use 220 to 280 parts by weight of the flame retardant based on 100 parts by weight of the polyol component. When the flame retardant is used in an amount of 220 parts by weight or less, the viscosity of the polyol composition is lowered and the dispersibility is weakened, and the flame retardancy of the polyurethane foam obtained by urethane reaction is reduced. On the other hand, when the flame retardant is used in an amount of 280 parts by weight or more, the polyol As the viscosity of the composition increases, the dispersibility tends to deteriorate relatively, and the flame retardancy does not improve compared to the amount added, which is undesirable.

The flame retardant components are mixed and used, and it is desirable to use a defoamer to remove air bubbles during the kneading process and at the same time use a dispersant to improve dispersibility. The antifoaming agent and the dispersing agent may be products that are used in this technical field. The antifoaming agent is preferably used in an amount of 1 to 3 parts by weight based on 100 parts by weight of the polyol component. When the antifoaming agent is used in an amount of 1 part by weight or less, the bubble removal performance is weak, whereas when it is used in an amount of 3 parts by weight or more, the bubble removal performance is not improved compared to the amount added. Meanwhile, it is preferable to use 2 to 5 parts by weight of the dispersant based on 100 parts by weight of the polyol component. When the dispersant is used in an amount of 2 parts by weight or less, the dispersion performance is weak, while when it is used in an amount of 5 parts by weight or more, the dispersion performance is not improved compared to the amount added.

The present invention includes a second step of adding a first additive that delays the urethane reaction during urethane reaction to the flame retardant mixture obtained in the first step.

In the second step, a first additive that functions to delay the urethane reaction is added and the first additive is mixed with the flame retardant mixture obtained in the first step. The first additive contains a reaction retardant that delays the urethane reaction and a foaming agent that forms fine bubbles and uniformly disperses them during the kneading process of the liquid mixture.

In the second step, it is important to first add and knead the reaction retardant to the flame retardant mixture obtained in the previous step. It is preferable to use a weak acid as the reaction retardant. The most representative example of the weak acid is FA. The reaction retardant is used to control the reaction rate by delaying the urethane reaction when the polyol component and the isocyanate component undergo a urethane reaction. It is important to first add the reaction retardant to the flame retardant mixture obtained in the previous step and knead it. The reason is that when the reaction retardant is uniformly mixed with the flame retardant mixture, mixed again with water as an aqueous solution, and then a catalyst is added as a reaction accelerator, the most stable polyol composition is achieved. am. The reaction retardant is preferably used in the range of 8 to 13 parts by weight based on 100 parts by weight of the polyol component. If the reaction retardant is used in an amount of 8 parts by weight or less, the urethane reaction becomes too fast, whereas if it is used in an amount of 13 parts by weight or more, the urethane reaction becomes too slow, which is not preferable. This is because the reaction retardant, in its relationship with the catalyst components that will be explained below, has a significant opposing effect on the subsequent urethane reaction. In other words, when the reaction retardant is used in an amount of 8 parts by weight or less, it becomes difficult to control the reaction promotion performance by the catalyst, which will be explained below, whereas when it is used in an amount of 13 parts by weight or more, the reaction promotion performance by the catalyst components becomes difficult. This is because the urethane reaction is delayed by excessively controlling.

In the second step, the reaction retardant is preferably used together with the anti-foaming agent. The foam stabilizer helps to form bubbles that may be generated during the kneading process small but constant and uniform. The foam stabilizer is preferably used in the range of 8 to 15 parts by weight based on 100 parts by weight of the polyol component. When the antifoaming agent is used in an amount of 8 parts by weight or less, it is undesirable because the dispersibility of the liquid mixture is weakened, and when it is used in an amount of 15 parts by weight or more, the dispersibility of the liquid mixture is improved, but it tends to interfere with the function of the antifoaming agent. It is not desirable. As the foam stabilizer, silicone-based foam stabilizers and non-silicone foam stabilizers can be used, but it is preferable to use a silicone-based foam stabilizer. As the silicone-based foam stabilizer, it is preferable to use one selected from silicon, silicon glycol copolymer, and polysiloxane ether.

In the present invention, when the second step is performed, a second flame retardant mixture prepared by mixing the flame retardant mixture and the first additive is obtained.

The present invention includes a third step of adding pure water, which will act as a foaming agent during the urethane reaction, to the second flame retardant mixture obtained in the second step.

The third step is characterized by adding pure water to the second flame retardant mixture obtained in the second step. In the process of manufacturing a polyol composition, the water acts as a kind of aqueous solution component and helps disperse the added components. Among these, it especially contributes to uniformly and homogeneously dispersing the reaction retardant in the polyol composition. This is because, if the water does not uniformly and homogeneously disperse the reaction retardant in the polyol composition, it is difficult to control the reaction promotion performance by the catalyst components in the second additive, which will be described later, during the urethane reaction. Meanwhile, the water functions as a foaming agent during urethane reaction. Water reacts with an isocyanate group according to the NCO/H ₂ O reaction, releasing carbon dioxide, and functions as a blowing agent in the process of creating a urethane chain through the reaction between the polyol component and the isocyanate component. The technical feature of the present invention is that pure water is used as a foaming agent and no other chemical components are separately added. It is preferable to use 7 to 15 parts by weight of water based on 100 parts by weight of the polyol. If used in less than 7 parts by weight, it cannot function as a sufficient foaming agent and the hardness of the urethane foam becomes very high. On the other hand, if used in less than 15 parts by weight, it is difficult to obtain a stable cell structure due to excessive foaming performance, so it is not desirable. You won't be able to do it.

In the present invention, when the third step is performed, pure distilled water is added as a foaming agent to the second flame retardant mixture to prepare a first flame retardant mixture for water foaming.

The present invention includes a fourth step of adding a second additive that promotes the urethane reaction during the urethane reaction to the first water-foaming flame retardant mixture obtained in the third step.

The fourth step is characterized by adding a second additive that promotes the urethane reaction during the urethane reaction to the first water-foaming flame retardant mixture obtained in the third step. The second additive is preferably a catalyst that promotes the urethane reaction when the polyol component and the isocyanate component undergo a urethane reaction. As the catalyst, it is preferable to use a gelation catalyst that promotes the gelation reaction during the urethane reaction and a trimerization catalyst that reacts three isocyanate groups during the urethane reaction.

The second additive performs contradictory functions in at least two aspects in relation to the reaction retardant added in the second step. First, the reaction retardant and the second additive are introduced at different times in relation to the introduction of water, which is a pure water-soluble liquid. This is done by adding the water after adding the reaction retardant and mixing them evenly, so that the reaction retardant is uniformly mixed in the aqueous solution components, and then adding the second additive. This is because the reaction retardant is acidic, while the second additive is alkaline, so that even when they are mixed in an aqueous solution, they do not directly or indirectly react with each other, or even if they do react with each other, as described later. This is to minimize the effect on the urethane reaction. In this regard, the reaction retardant is added in the second step before the water added in the third step, while the second additive is added in the fourth step after the water added in the third step is added. It is invested from. Next, the reaction retardant and the second additive perform opposite functions of delaying the urethane reaction or promoting the urethane reaction when focusing on the urethane reaction. This is because the reaction retardant delays the urethane reaction, while the second additive promotes the urethane reaction.

As the second additive, the gelation catalyst is preferably used in an amount of 3 to 8 parts by weight based on 100 parts by weight of the polyol component. When the gelation catalyst is used in an amount of 3 parts by weight or less, the gelation reaction becomes slow, whereas when it is used in an amount of 8 parts by weight or more, the gelation reaction becomes too fast, which is not desirable. It is preferable to use an amine-based catalyst as the gelation catalyst. Meanwhile, it is preferable to use 10 to 20 parts by weight of the trimerization catalyst based on 100 parts by weight of the polyol component. When the trimerization catalyst is used in an amount of 10 parts by weight or less, the trimerization reaction does not occur properly and the hardness of the final urethane foam becomes weak. On the other hand, if the trimerization catalyst is used in an amount of 20 parts by weight or more, isocyanurate is formed due to excessive trimerization reaction. It is produced excessively. It is preferable to use a metallic potassium catalyst and a tertiary amine catalyst as the trimerization catalyst. These catalysts may be catalysts already known in the art.

In the present invention, when the fourth step is performed, a second additive is added to the first flame retardant mixture for water foaming to prepare a second flame retardant mixture for water foaming.

The present invention includes a fifth step of preparing a semi-incombustible polyol composition for water-foamable polyurethane by finally adding a polyol component to the second water-foamable flame retardant mixture obtained in the fourth step.

In the fifth step, the polyol component is finally added to the second water-foaming flame retardant mixture obtained in the fourth step to prepare a polyol composition that will undergo a reaction with the isocyanate component and urethane. As the polyol component, polyether polyol and polyester polyol used in this technical field can be used.

In the present invention, when attempting to manufacture a semi-incombustible product from polyurethane foam after performing the fifth step, it is preferable to add second flame retardant components. As the second flame retardant component, it is preferable to use an inorganic flame retardant in the form of red phosphorus powder, which forms tar when burned, and calcium borate in the form of a metal powder, which improves flame retardancy and suppresses the generation of combustion gases during combustion. The second flame retardant components are inorganic flame retardants and are in powder form, which is in contrast to the fact that the flame retardant components added in the first step are in liquid form. It is preferable to add 40 to 55 parts by weight of the red phosphorus powder inorganic flame retardant per 100 parts by weight of polyol, and 40 to 55 parts by weight of calcium borate in the metal powder form is preferably added to 100 parts by weight of polyol. When the red phosphorus powdered inorganic flame retardant is added in an amount of 40 parts by weight or less, it is difficult to be recognized as a semi-non-flammable product. On the other hand, when it is added in an amount of 55 parts by weight or more, the semi-non-flammable performance does not improve according to the dosage ratio of the inorganic flame retardant. In addition, when the calcium borate in the metal powder is used in an amount of 40 parts by weight or less, a relatively large amount of combustion gas is generated, making it difficult to be recognized as a semi-incombustible product. On the other hand, when the calcium borate in the metal powder is used in an amount of 55 parts by weight or more, the injection ratio of the inorganic flame retardant The semi-incombustibility performance is not improved according to.

Hereinafter, the present invention will be described in more detail through examples.

It is obvious that the components and their usage amounts presented in the examples of the present invention are for illustrative purposes only, and the scope of the present invention is not limited thereto.

Example 1

Prepare a mixing container (2 L), weigh and add 480 g of phosphorus-based flame retardant (TCPP) into the mixing container, knead for 3 minutes, and then weigh 4 g of defoamer (K-348SL) and 8 g of dispersant (PON 98). It was placed in the mixing container and kneaded for 5 minutes to obtain a first flame retardant mixture. To the first flame retardant mixture, 17 g of reaction retardant (FA) and 23 g of silicone foam stabilizer (B-8462) were each weighed and added, and kneaded uniformly for 5 minutes to obtain the first flame retardant mixture.

After that, 23 g of distilled water was weighed and added to the mixing container containing the first flame retardant mixture, and the distilled water and the first flame retardant mixture were mixed uniformly and homogeneously to obtain a first flame retardant mixture for water foaming.

After that, 15 g of amine catalyst (PC-8), which is a gelling catalyst, and 30 g of trimerization catalyst (PC-46) were weighed, added to the mixing container, and kneaded to obtain a second flame retardant mixture for water foaming. Next, 200 g of polyester polyol (SL-460) was weighed, placed in the mixing container, and kneaded with the second water-foaming flame retardant mixture in the mixing container, to finally obtain 800 g of polyol composition.

800 g of the polyol composition was mixed with 1300 g of polyisocyanate (M-200) and urethane reaction was performed while rotating at high speed.

Example 2 and Example 3

It was carried out in the same manner as Example 1, except that each example was carried out by varying the amount of each ingredient added. The amounts added to each example are shown in Table 1 below. As a result, 800g of each polyol composition was finally obtained.

800 g of the polyol composition was mixed with 1300 g of polyisocyanate and urethane reaction was performed while rotating at high speed.

Comparative Example 1 and Comparative Example 2

It was carried out in the same manner as Example 1, but each comparative example was conducted by varying the amount of each ingredient added. The amounts added to each comparative example are shown in Table 1 below. As a result, 800g of each polyol composition was finally obtained.

800 g of the polyol composition was mixed with 1300 g of polyisocyanate and urethane reaction was performed while rotating at high speed.

Raw material mixing of polyol composition for water-foaming polyurethane
Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 phosphorus flame retardant 480 480 480 480 480 defoamer 4 4 4 4 4 dispersant 8 8 8 8 8 reaction retardant 17 20 23 27 30 antiseptic 23 23 24 24 24 Foaming agent (distilled water) 23 23 23 24 23 gelling catalyst 15 12 10 8 6 trimerization catalyst 30 30 28 25 25 polyol 200 200 200 200 200 Isocyanate 350 350 350 350 350

In the present invention, the components presented in the above examples were kneaded uniformly to obtain a polyol composition for water-foamable polyurethane according to the present invention, and this was mixed with polyisocyanate to proceed with the urethane reaction.

While proceeding with the urethane reaction for each example, data on the progress of the reaction were measured, and the measured data is shown in Table 2 below. Each measurement data was repeated 5 times based on the same mixing ingredients and mixing ratio, and then averaged the measurement values.

Measured values during urethane reaction Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Cream Time(s) 15 17 25
No foam formation
No foam formation
Gelling Time(s) 32 38 48 Tacfree Time(s) 46 58 75

As confirmed by Table 2 above, the present invention can confirm that, in the case of Examples 1 to 3, a normal urethane reaction is proceeding even though only pure distilled water is used as a blowing agent.

On the other hand, in the case of Comparative Example 1 and Comparative Example 2, the polyol composition was outside the scope of the present invention, showing that the urethane reaction could not be performed normally.

Example 4

In order to manufacture the water-blown polyurethane foam according to the present invention into a semi-incombustible product, it was decided to add a second flame retardant component.

For the polyol composition for water foaming according to Example 1, 90 g of red phosphorus flame retardant (RP-15) was weighed and 90 g of calcium borate (Ca B) in the form of metal powder was weighed, and these were sequentially added and kneaded uniformly. As a result, 960 g of polyol composition was finally obtained. A urethane reaction was performed by mixing 960 g of the polyol composition with 350 g of polyisocyanate. At this time, Cream Time was 16 seconds, Gelling Time was 33 seconds, and Tacfree Time was 46 seconds.

These results were understood to reveal that the urethane reaction can proceed in a normal manner even when the polyol composition for water-polyurethane foam is produced by the production method of the present invention.

Semi-non-flammable performance test

Using the water-blown polyurethane foam prepared in Example 4, the quasi-incombustibility performance of the product was measured. For this purpose, the water-based polyurethane foam completed according to Example 4 was sent to FITI Testing and Research Institute, an external specialized organization (Location: 21 Yangcheong 3-gil, Ochang-eup, Cheongwon-gu, Cheongju-si, Chungcheongbuk-do), and was approved for use in Ministry of Land, Infrastructure and Transport Notice No. 2023-24, “Building Materials.” It was carried out in a manner based on quality recognition and management standards.

One). Preparation of specimens for testing:

First, in order to conduct a heat release test, three specimens were made. The conditions of the specimen were as shown in Table 3 below.

Specimen conditions for heat release rate testing Psalm 1 Psalm 2 Psalm 3 Width (mm) 100.1 100.5 100.1 Height (mm) 99.9 100.1 100.3 Thickness (mm) 50.4 50.8 51.0 Mass (g) 22.0 21.6 21.7 Density (kg/m ³ ) 43.7 42.3 42.4 Pretreatment Temperature (23±2) ℃, Humidity (50±5) % R.H

2). Test conditions for heat release:

A test piece like this was made, one side of the test piece was heated, and the heat release amount was measured for 10 minutes. The test conditions were as shown in Table 4 below.

Test conditions for heat release rate testing heated noodles Front side of polyurethane test piece (same as back side) test environment Temperature (21.0 ~ 25.0) ℃,
Humidity (48.0~52.0) % RH Test time (min) 10 Orifice constant C (m ^1/2 g ^1/2 K ^1/2 ) 0.038405 Radiant heat (kW/m ² ) 50±1 Discharge device flow rate (m ³ /s) 0.024 ± 0.002

3). Heat release test progress and measurement results:

Each test piece shown in Table 3 was subjected to a heat release test under the test conditions shown in Table 4. The results of the heat release test were measured for each test piece, and the measured values were shown in Table 5 below.

Measured values of heat release rate test progress
Test Items
unit Test result
Criteria 1 time Episode 2 3rd time total emissions MJ/ ^m2 5.2 2.5 4.5 8 or less Time during which the heat release rate continuously exceeds 200 kW/m ²
s
0
0
0
less than 10 Harmful factors from arson burns in specimens
Occurrence or not
-
doesn't exist
doesn't exist
doesn't exist
Probably not

4). Confirmation of quasi-non-flammable performance by specimen:

As such, the water-based polyurethane foam completed by the manufacturing method according to the present invention has a total emission amount in the range of 2.5 to 5.2 MJ/m ² , which is much lower than the judgment standard of 8 MJ/m ² It can be seen that there is almost no point in time when the heat release rate continuously exceeds 200 kW/m ² , and no harmful factors are generated due to arson of the test specimen.

As a result, the water-based polyurethane foam completed by the manufacturing method according to the present invention complies with Article 24 (Performance Standards for Semi-Noncombustible Materials) No. 1 of the Quality Recognition and Management Standards for Building Materials, etc., Notification No. 2023-24 of the Ministry of Land, Infrastructure and Transport. It can be seen that it was found to be suitable for the heat release rate (cone calorimetry) test results.

Gas toxicity test

Using the water-blown polyurethane foam prepared in Example 4, the gas hazard performance of the product was measured. For this purpose, the water-blown polyurethane foam completed according to Example 4 was sent to the FITI Testing Research Institute, an external specialized organization (Location: 21 Yangcheong 3-gil, Ochang-eup, Cheongwon-gu, Cheongju-si, Chungcheongbuk-do), and was used as a test method for construction purposes according to Ministry of Land, Infrastructure and Transport Notice No. 2023-24. It was carried out in a “method based on quality recognition and management standards for materials, etc.”

One). Preparation of specimens for testing:

First, in order to conduct a gas toxicity test, two test specimens were created. The conditions of the test specimen were as shown in Table 6 below.

Conditions of test specimens for gas toxicity testing Test specimen 1 Test body 2 Width (mm) 219.8 219.7 Height (mm) 219.8 219.5 Thickness (mm) 50.3 50.7 Mass (g) 102.1 100.6 Density (kg/m ³ ) 42.0 41.1 Pretreatment Temperature (23±2) ℃, Humidity (50±5) % R.H

2). Test conditions for gas toxicity:

A test specimen like this was made, and measurements were made on white rats for 15 minutes by heating a secondary heat source and a main heat source on one side of the test specimen for 3 minutes. The test conditions were as shown in Table 7 below.

Test conditions for measuring gas toxicity performance heating conditions After heating for 3 minutes with a secondary heat source (LPG),
Heat again with main heat source (electric heat) for 3 minutes. heated cotton Front (same as back) test environment Temperature (21.0 ~ 25.0) ℃,
Humidity (48.0 ~ 52.0) % RH Test time (min) 15 white rat for testing ICR female; Age: 5 weeks; Weight: 18 to 22 g

3). Progress of gas toxicity test:

A gas toxicity test was conducted using each of the test specimens shown in Table 6 above and the rats shown in Table 7 above. Temperatures measured by time according to the above gas toxicity test are presented in Table 8 below for each test.

Measurement results of gas toxicity test Elapsed time (s) of test body 1
Measurement temperature (℃) of test body 2
Measurement temperature (℃) 0 29.2 29.6 60 177.3 146.1 120 195.8 173.9 180 206.0 182.5 240 245.8 255.7 300 281.2 306.2 360 308.9 310.9

4). Measurement results of gas toxicity test:

In addition, the results of measuring the activity and stopping time of white rats for each test specimen according to the above gas toxicity test are presented in Table 9 below.

Measurement results of gas toxicity test test body 1 test body 2 M 1 15 min 00 s M 1 14 min 56 s M 2 15 min 00 s M 2 15 min 00 s M 3 15 min 00 s M 3 13 min 46 s M 4 14 min 59 s M 4 14 min 49 s M 5 15 min 00 s M 5 09 min 57 s M 6 14 min 59 s M 6 12 min 22 s M 7 15 min 00 s M 7 14 min 51 s M 8 14 min 59 s M 8 14 min 34 s medium 15 min 00 s medium 13 min 47 s Standard Deviation 00 min 01 s Standard Deviation 01 min 40 s Average stoppage time 14 min 59 s Average stoppage time 12 min 07 s

5). Confirmation of gas toxicity performance by test specimen:

As such, the survival time of the water-blown polyurethane foam completed by the production method according to the present invention for white rats was an average of 14 minutes 59 seconds for test body 1, and an average of 12 minutes 07 seconds for test body 2. These measurement results show that, considering that the judgment standard is 9 minutes, the survival time of white rats is extended by 3 to 5 minutes.

As a result, the water-based polyurethane foam completed by the manufacturing method according to the present invention complies with Article 24 (Performance Standards for Semi-Noncombustible Materials) No. 2 of the Quality Recognition and Management Standards for Building Materials, etc., Notification No. 2023-24 of the Ministry of Land, Infrastructure and Transport. This means that it was found to be suitable for the gas toxicity test results.

In the above, the method for producing the polyol composition for semi-incombustible water-foamable polyurethane according to the present invention and the polyurethane foam according to the production method have been specifically presented, but this is only specified in the process of explaining the embodiment of the present invention. All features of the present invention should not be construed as limited to applying only to the items mentioned above.

In addition, anyone skilled in the art will be able to make various modifications and imitations based on the contents of the specification of the present invention, but it will be clear that these are not beyond the scope of the present invention.

Claims (11)

A method for producing a polyol composition for water-foamable polyurethane comprising a polyol component, a flame retardant component, water, a catalyst that promotes the urethane reaction, and a retardant that delays the urethane reaction,
After adding flame retardant ingredients to create a flame retardant mixture and maintaining the flame retardant mixture in a stable state,
During the urethane reaction, a first additive that delays the urethane reaction and a second additive that promotes the urethane reaction are sequentially added,
Between the time of adding the first additive and the time of adding the second additive, pure water, which acts as a foaming agent, is added,
Finally, the polyol component is added and mixed,
Manufacturing method for producing a polyol composition for water-foaming polyurethane.
A first step of adding flame retardant components, adding a defoaming agent that removes air bubbles during the kneading process of the flame retardant components, and a dispersing agent that uniformly disperses the kneaded liquid mixture, and kneading to obtain a flame retardant mixture;
To the flame retardant mixture obtained in the first step, a reaction retardant that delays the urethane reaction during the urethane reaction and a foam stabilizer that forms fine bubbles and uniformly disperses them during the kneading process of the liquid mixture are added and kneaded, a second step of obtaining a second flame retardant mixture;
A third step of preparing a first flame retardant mixture for water foaming by adding pure water, which will act as a foaming agent during the urethane reaction, to the second flame retardant mixture obtained in the second step;
a fourth step of preparing a second flame retardant mixture for water foaming by adding a second additive that promotes the urethane reaction during urethane reaction to the first flame retardant mixture for water foaming obtained in the third step;
A fifth step of preparing a polyol composition for a flame-retardant water-foamable polyurethane by adding a polyol component to the second water-foaming flame retardant mixture obtained in the fourth step; cast
A method for producing a polyol composition for water-foamable polyurethane, characterized in that it contains.
According to claim 2,
The flame retardant is 220 to 280 parts by weight based on 100 parts by weight of the polyol component,
The antifoaming agent is 1 to 3 parts by weight based on 100 parts by weight of the polyol component, and
A method for producing a polyol composition for water-foamable polyurethane, characterized in that the dispersant is used in an amount of 2 to 5 parts by weight based on 100 parts by weight of the polyol component.
According to claim 2,
A method for producing a polyol composition for water-foamable polyurethane, wherein the reaction retardant is used in the range of 8 to 13 parts by weight based on 100 parts by weight of the polyol component.
According to claim 4,
The reaction retardant is a weak acid, and is used to control the reaction rate by delaying the urethane reaction when the polyol component and the isocyanate component undergo a urethane reaction. Preparation of a polyol composition for water-foamable polyurethane. method.
According to claim 2,
A method for producing a polyol composition for water-foamable polyurethane, characterized in that the foam stabilizer is used in the range of 8 to 15 parts by weight based on 100 parts by weight of the polyol component.
According to claim 2,
The second additive uses a catalyst that promotes the urethane reaction,
The catalyst includes a gelation catalyst that promotes the gelation reaction during the urethane reaction, and a trimerization catalyst that reacts three isocyanate groups during the urethane reaction,
A method for producing a polyol composition for water-foamable polyurethane, characterized by:
According to claim 7,
A method for producing a polyol composition for water-foamable polyurethane, characterized in that the gelation catalyst is used in an amount of 3 to 8 parts by weight based on 100 parts by weight of the polyol component.
According to claim 7,
A method for producing a polyol composition for water-foamable polyurethane, characterized in that the trimerization catalyst is used in an amount of 10 to 20 parts by weight based on 100 parts by weight of the polyol component.
According to claim 2,
After performing the fifth step, red phosphorus powder inorganic flame retardant is added,
The inorganic flame retardant in the form of red phosphorus powder is used in an amount of 40 to 55 parts by weight based on 100 parts by weight of the polyol component, and thus,
Giving semi-non-flammable performance to water-blown polyurethane foam
A method for producing a polyol composition for water-foamable polyurethane, characterized by:
According to claim 2,
After performing the fifth step, calcium borate in the form of metal powder is added,
The inorganic flame retardant of calcium borate in the form of metal powder is used in an amount of 40 to 55 parts by weight based on 100 parts by weight of the polyol component, thereby,
Giving semi-non-flammable performance to water-blown polyurethane foam
A method for producing a polyol composition for water-foamable polyurethane, characterized by: