WO2023277564A1 - Self-extinguishing microcapsule composition and manufacturing method therefor - Google Patents

Abstract

The present invention relates to a self-extinguishing microcapsule composition and a manufacturing method therefor. In particular, the present invention relates to: a self-extinguishing microcapsule composition for fire suppression, in which a mixing ratio of two or more liquid extinguishing agents having different boiling points is adjusted such that a desired decapsulation temperature can be set, the manufacturing process thereof is simple, and the extinguishing performance thereof is excellent due to rapid decapsulation in the event of fire; and a manufacturing method therefor.

Description

Self-extinguishing microcapsule composition and method for its preparation

The present invention relates to a self-extinguishing microcapsule composition and a method for manufacturing the same, and more particularly, a desired decapsulation temperature can be set by adjusting the mixing ratio of two or more types of liquid fire extinguishing agents having different boiling points, the manufacturing process is simple, and the fire It relates to a self-extinguishing microcapsule composition for fire suppression with excellent fire extinguishing performance due to rapid decapsulation upon occurrence and a manufacturing method thereof.

In the case of liquid, gas, or aerosol fire extinguishing agents, not only are they difficult to transport and store, but also have disadvantages that they are difficult to apply to polymer materials, so the utilization of microcapsules containing liquid fire extinguishing agents is gradually increasing. In addition, solid state microcapsules are excellent in utilization in that they can be added to various polymer resins and commercialized for various purposes such as films, fabrics and pads.

Most fire extinguishing agents are low-boiling point, water-immiscible liquid, and lyophilic substances that evaporate at high temperatures, and these substances are manufactured into capsules by the coacervation method. . According to this method, the fire extinguishing agent is first emulsified using a surfactant, water-soluble polymer particles are formed, and then these particles are adsorbed on the surface of the fire extinguishing agent to finally form a solid shell. When a fire occurs in the microcapsules prepared in this way, decapsulation occurs in which the extinguishing agent is released from the outer shell in a narrow temperature range, and eventually the initial fire suppression efficiency can be increased.

Conventional microcapsules are composed of spherical particles with a diameter of 50 to 400 μm containing 75 to 95% by weight of a fire extinguishing agent. Since the thickness of the shell is relatively thin, the mechanical properties of the polymer constituting the shell are weak. Otherwise, if a porous shell is formed, there is a problem in that the fire extinguishing agent inside escapes over time and the self-extinguishing capsule does not function properly.

Recently, several technologies have been reported to increase the stability of microdigestive capsules. For example, a method of increasing the strength of the shell by injecting montmorllonite, a type of earth mineral, or a technique of suppressing the outflow of the internal fire extinguishing agent by creating a microcapsule with a double shell structure is known.

In addition, by using hydrophilic plasticizers such as glycerol and triethylene glycol to improve the flexibility of the shell or by filling the encapsulated fire extinguishing agent in the polymer matrix, the decapsulation speed and temperature can be increased and the thermal stability of the capsule can be improved. A possible method has also been reported.

On the other hand, digestive capsules can be commercialized for various purposes by being added to various polymer resins or products in liquid state, and play an important role in the initial stage of fire when a fire occurs. It is necessary to be able to control the decapsulation temperature of For example, in the case of a multi-tap, if overcurrent flows beyond the rated capacity, the temperature rises to 80℃ or more, increasing the risk of fire. In the case of an ESS (Energy Storage system), microcapsules having a sufficiently high decapsulation temperature of 100 ° C or more must be used in order for the equipment to be maintained without malfunction.

The ejection process of the fire extinguishing agent goes through a process in which the internal pressure of the microcapsule increases as the external temperature rises (internal pressure build-up), and when the internal pressure reaches a critical point enough to destroy the outer shell, it is ejected instantaneously. The decapsulation temperature at which the fire extinguishing agent is released from the shell is determined by a wide variety of factors. In other words, the decapsulation temperature varies depending on various factors such as the boiling point of the extinguishing agent, the content of the extinguishing agent, the type and thickness of the shell, and the particle size of the microcapsule. I mean it's not easy.

When the decapsulation temperature is controlled while changing the structure of the shell, the reaction conditions and density of the shell vary depending on the type of shell, which complicates the manufacturing method and manufactures a polymer composite sheet using the microcapsules thus prepared. There is a disadvantage that causes difficulties in controlling the physical properties of the final product, such as completely changing the compatibility with the polymer matrix when processing.

In addition, if the extinguishing agent contained in the microcapsule contains only a specific extinguishing agent, it eventually becomes a state similar to the case of simply mixing two types of microcapsules with different decapsulation, and therefore has two decapsulation temperatures or There is a disadvantage of causing a problem in that the decapsulation temperature range is widened.

An object of the present invention is to provide a self-extinguishing microcapsule composition for fire suppression and a manufacturing method thereof, in which the decapsulation temperature can be controlled by adjusting the mixing ratio of two or more kinds of liquid fire extinguishing agents having different boiling points, and the manufacturing process is simple.

Another object of the present invention is to provide a self-extinguishing microcapsule composition that exhibits excellent fire extinguishing performance, is stable and reliable with little leakage of fire extinguishing agents, and can be manufactured with various fire extinguishing devices.

In order to solve the above technical problem, as an embodiment of the present invention, as a self-extinguishing microcapsule for fire suppression that has a core-shell structure and is decapsulated at high temperature, the core is selected from halogenated hydrocarbons and has a different boiling point. It includes a fire extinguishing agent and a second fire extinguishing agent, and the shell provides a self-extinguishing microcapsule composition made of a polymer formed on the outer surface of the core.

As an embodiment of the present invention, the first extinguishing agent and the second extinguishing agent provide a self-extinguishing microcapsule composition, characterized in that they satisfy the following [Formula 1] and [Formula 2]:

[Equation 1] … Δρ = ｜ρ ₁ - ρ ₂ ｜< 0.5

[Equation 2] … Δγ = ｜γ ₁ - γ ₂ ｜< 10

In [Formula 1] and [Formula 2], ρ ₁ and ρ ₂ are the specific gravity (g/cm ³ ) of the first extinguishing agent and the second extinguishing agent, respectively, and γ ₁ and γ ₂ are the first extinguishing agent, respectively. and the surface tension of the second extinguishing agent (dyne/cm). Here, the specific gravity of the first extinguishing agent and the second extinguishing agent is preferably less than 2 g / cm 3 .

In addition, as another embodiment of the present invention, the weight ratio of the first extinguishing agent and the second extinguishing agent may be in the range of 3:7 to 5:5, and accordingly, the decapsulation temperature may be controlled in the range of 105 to 155 ° C. can

In addition, as another embodiment of the present invention, the core may be made of an emulsion composition in which the first extinguishing agent, the second extinguishing agent and the surfactant are dispersed in water, and the average size of the microcapsules is 200 to 350 ㎛ range can

In addition, as another embodiment of the present invention, the first fire extinguishing agent and the second fire extinguishing agent may be hydrocarbons substituted with fluorine or bromine. Specific examples include 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone, ethyl nonafluorobutyl ether, 1,1, 1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)pentane, 2-(trifluoromethyl)-3-ethoxydodeca It may be selected from fluorohexane, but is not particularly limited thereto, and any compound satisfying the above [Formula 1] and [Formula 2] may be used.

In addition, the polymer may be one or more selected from urea-formaldehyde-resorcinol, gelatin, epoxy, polyurethane, and polyurea, but is not particularly limited thereto.

On the other hand, in another embodiment, the present invention is selected from fluorinated hydrocarbons or brominated hydrocarbons, and the first extinguishing agent and the second extinguishing agent having different boiling points are mixed in water with a surfactant to prepare an emulsion composition for core, the emulsion A core-shell structure comprising the steps of mixing the composition with an aqueous polymer solution forming a shell, adding an acid to adjust the pH, and raising the temperature of the pH-adjusted mixed solution and then cooling it to prepare a microcapsule. It provides a method for producing a self-extinguishing microcapsule composition for fire suppression having

The self-extinguishing microcapsule composition for fire suppression having a core-shell structure according to the present invention is characterized by including two or more types of liquid fire extinguishing agents having different boiling points in the core, and the decapsulation temperature by adjusting the mixing ratio of the two types of fire extinguishing agents. It has the advantage that it can be set to suit the purpose.

In addition, the manufacturing method of the self-extinguishing microcapsule composition according to the present invention has a simple process and changes the type and mixing ratio of the fire extinguishing agent contained in the core while using the existing shell, so that whenever the structure of the shell changes, the polymer matrix and It can be freed from the inconvenience of having to conduct a new evaluation of compatibility and adhesiveness.

In addition, the fire extinguishing microcapsule composition according to the present invention rapidly decapsulates, in which the fire extinguishing agent destroys and releases the shell within a short time during the decapsulation process of the fire extinguishing agent, and extinguishes fire when the ambient temperature rises above a predetermined temperature in the event of a fire. The drug is released in a short time, so it can extinguish the fire at an early stage or prevent the fire from spreading. As described above, the fire extinguishing microcapsule composition according to the present invention exhibits excellent fire extinguishing performance for fire suppression, and has excellent long-term preservation and safety with little leakage of the fire extinguishing agent. In addition, the fire extinguishing microcapsule composition according to the present invention has high operational reliability and can be applied to various fire extinguishing devices.

1 is a graph showing the results of analyzing a self-extinguishing microcapsule composition according to an embodiment of the present invention using a thermogravimetric analyzer (TGA).

Figure 2 is an optical microscope photograph taken in an emulsion state (a) and a microcapsule state (b) of a self-extinguishing microcapsule composition according to an embodiment of the present invention.

The self-extinguishing microcapsule composition for fire suppression according to an embodiment of the present invention has a core-shell structure, is decapsulated at high temperature, the core is selected from halogenated hydrocarbons, and the first extinguishing agent and the second extinguishing agent having different boiling points are selected. A drug may be included, and the shell may be made of a high molecular weight polymer formed on the outer surface of the core.

In the self-extinguishing microcapsule composition according to an embodiment of the present invention, the first extinguishing agent and the second extinguishing agent preferably satisfy the following [Formula 1] and [Formula 2]:

[Equation 1] … Δρ = ｜ρ ₁ - ρ ₂ ｜< 0.5

[Equation 2] … Δγ = ｜γ ₁ - γ ₂ ｜< 10

In [Formula 1] and [Formula 2], ρ ₁ and ρ ₂ are the specific gravity (g/cm ³ ) of the first extinguishing agent and the second extinguishing agent, respectively, and γ ₁ and γ ₂ are the first extinguishing agent, respectively. and the surface tension of the second extinguishing agent (dyne/cm). Here, it is preferable that the specific gravity of the first extinguishing agent and the second extinguishing agent is less than 2g/cm 3 .

A method for producing a self-extinguishing microcapsule composition for fire suppression according to an embodiment of the present invention is a core emulsion composition by mixing a first extinguishing agent and a second extinguishing agent selected from halogenated hydrocarbons and having different boiling points in water with a surfactant Preparing a step, mixing the emulsion composition with an aqueous polymer solution for forming a shell, adjusting the pH by adding an acid, and raising the temperature of the pH-adjusted mixed solution and then cooling it to prepare microcapsules. can

The present invention will be described in more detail with reference to the following examples and drawings. However, since the present invention can have various changes and various forms, the present invention is not intended to be limited to specific embodiments, and all changes, equivalents or substitutes included in the spirit and technical scope of the present invention should be understood as including

In addition, terms used in this application are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In addition, in this application, terms such as "include" or "have" mean that other components may be further included without excluding other components unless otherwise stated.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in this application, it should not be interpreted in an ideal or excessively formal meaning. don't

The present invention relates to a self-extinguishing microcapsule composition for fire suppression, in particular, to provide self-extinguishing microcapsules having shells of the same chemical structure but having different decapsulation temperatures. It is evenly contained during use to provide a self-extinguishing microcapsule composition having only one decapsulation temperature.

More specifically, the self-extinguishing microcapsule composition for fire suppression according to an embodiment of the present invention has a core-shell structure, is decapsulated at high temperature, the core is selected from halogenated hydrocarbons, and a first extinguishing agent having a different boiling point and a second fire extinguishing agent, and the shell may be made of a polymer formed on the outer surface of the core.

The self-extinguishing microcapsule composition according to the present invention is characterized by using two or more types of fire extinguishing agents having different boiling points, and the weight ratio of the first fire extinguishing agent and the second fire extinguishing agent may be mixed in the range of 3:7 to 5:5. there is. The decapsulation temperature can be set by adjusting the weight ratio of the two fire extinguishing agents, and the temperature range is about 105 to 155 °C.

In an embodiment of the present invention, the core of the microcapsule composition may be an emulsion composition in which a first extinguishing agent, a second extinguishing agent, and a surfactant are dispersed in water. At this time, the first extinguishing agent and the second extinguishing agent included in the core are halogenated hydrocarbons, and may be selected from hydrocarbons substituted with fluorine or bromine. As specific examples of fire extinguishing agents, 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone, ethyl nonafluorobutyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)pentane, 2-(trifluoromethyl)-3- Ethoxydodecafluorohexane etc. are mentioned. The first extinguishing agent and the second extinguishing agent may be selected from the above compounds, but are not particularly limited thereto, and any compound satisfying the following [Formula 1] and [Formula 2] may be used.

In addition, the polymer forming the outer shell of the self-extinguishing microcapsule composition according to an embodiment of the present invention may be at least one selected from, for example, urea-formaldehyde-resorcinol, gelatin, epoxy, polyurethane, and polyurea. , but is not particularly limited thereto.

The self-extinguishing microcapsule composition according to the present invention can be prepared by a coacervation mechanism. The first step of this manufacturing method is to emulsify the fire extinguishing agent in water using a surfactant. At this time, stirring or ultrasonic treatment is performed to form uniform droplets. In order to achieve a stable emulsion, the specific gravity and surface tension of the fire extinguishing agent play a very important role. Therefore, it is necessary to optimize manufacturing conditions such as selection of surfactant suitable for the extinguishing agent used, input content, mixing temperature and stirring speed. However, the situation is more complicated when two or more types of extinguishing agents with different boiling points, specific gravity and surface tension are used. Therefore, it is very difficult to form a stable emulsion, and as a result, it is difficult to prepare microcapsules with excellent properties.

In order to solve this problem, the present invention has found that when two or more types of fire extinguishing agents are used, when the emulsification reaction, which is the first step, is stabilized, microcapsules with excellent characteristics can be obtained, and a stable emulsion can be obtained. It was found that the fire extinguishing agents must have similar specific gravity and surface tension for this purpose.

Specifically, it is preferable that the first extinguishing agent and the second extinguishing agent included in the self-extinguishing microcapsule composition according to the present invention satisfy the following [Formula 1] and [Formula 2].

[Equation 1] … Δρ = ｜ρ ₁ - ρ ₂ ｜< 0.5

[Equation 2] … Δγ = ｜γ ₁ - γ ₂ ｜< 10

In [Formula 1] and [Formula 2], ρ ₁ and ρ ₂ are the specific gravity (g/cm ³ ) of the first extinguishing agent and the second extinguishing agent, respectively, and γ ₁ and γ ₂ are the first extinguishing agent, respectively. and the surface tension of the second extinguishing agent (dyne/cm). In addition, it is preferable that the specific gravity of the first extinguishing agent and the second extinguishing agent is less than 2g/cm 3 .

In the present invention, when halogen-substituted hydrocarbons are used as fire extinguishing agents, the type and structure are not particularly limited, but when the difference in specific gravity of the two types of fire extinguishing agents is greater than 0.5 or the difference in surface tension is greater than 10 The emulsification process does not proceed stably. For example, when the difference in specific gravity is large, it is difficult to completely uniformly mix the two types of fire extinguishing agents even if sufficiently stirred, and thus independent emulsion particles are formed. At this time, the specific gravity of each fire extinguishing agent is not particularly limited, but it is preferable that the specific gravity is less than 2 g / cm 3, because if the specific gravity is too large compared to water, some fire extinguishing agents may sink to the bottom of the reactor.

In addition, in the present invention, the difference in surface tension of the two types of fire extinguishing agents is also very important. Surface tension means the thermodynamic stability of emulsion particles, which has a close relationship with the type and content of surfactant. Therefore, even if the same surfactant is used, when two fire extinguishing agents having too large a difference in surface tension are used, it is difficult to completely uniformly mix the two fire extinguishing agents, and thus there is a problem in that independent emulsion particles are formed.

A method for producing a self-extinguishing microcapsule composition for fire suppression according to an embodiment of the present invention is a core emulsion composition by mixing a first extinguishing agent and a second extinguishing agent selected from halogenated hydrocarbons and having different boiling points in water with a surfactant Preparing; adjusting the pH by adding an acid after mixing the emulsion composition with an aqueous solution of a polymer to form a shell; and preparing microcapsules by raising the temperature of the pH-adjusted mixed solution and then cooling it. Here, the heating temperature is in the range of 45 to 60 ° C, and the pH is preferably in the range of 2 to 4.

In the method for producing the self-extinguishing microcapsule composition of the present invention, it is preferable that the first fire extinguishing agent and the second fire extinguishing agent satisfy the above [Formula 1] and [Formula 2], and the two kinds of mixed fire extinguishing agents are mixed with a surfactant. After emulsification, water-soluble polymer particles are formed, the particles are adsorbed on the surface of the mixed fire extinguishing agent, and finally a solid shell is formed to complete the self-extinguishing microcapsule.

Surfactants used in the preparation of the core emulsion composition may include polyvinyl alcohol (PVA), ethylene maleic anhydride (EMA), sodium dodecyl benzene sulfonate (SDBS), etc., but are not particularly limited thereto.

The average size of the self-extinguishing microcapsules prepared according to the manufacturing method of the present invention is preferably in the range of 200 to 350 μm, but is not limited to this range, and the size can be adjusted in the capsule manufacturing process to suit the field to which the microcapsules are applied. can be adjusted

Hereinafter, examples and comparative examples will be described in detail to aid understanding of the present invention. However, the following Examples and Comparative Examples are merely illustrative of the content of the present invention and should not be construed as limiting the scope of the present invention to the following Examples and Comparative Examples.

Example

The fire extinguishing agents used in the examples of the present invention were purchased from TCI, and basic information on each compound is shown in [Table 1]. The fire extinguishing agent was mixed in the ratio shown in Table 1, stirred at 200 rpm for 30 minutes at room temperature, and then left for 30 minutes.

digestion drugs	chemical name	CAS No.	boiling point ℃
A-1	1,1,1,2,2,4,5,5,5-Nonafluoro-4-(trifluoro methyl)-3-pentanone	756-13-8	49
A-2	Ethyl nonafluorobutyl ether	163702-05-4	76
A-3	(1,1,1,2,2,3,4,5,5,5-Decafluoro-3-methoxy -4-(trifluoromethyl)-pentane	132182-92-4	100
B-1	Di-bromomethane	74-95-3	97
B-2	1,2-Di-bromo-tetrafluoroethane	124-73-2	47.2
B-3	1,1,2-Tri-bromo ethane	78-74-0	189

[Example 1]

First, 50 g of 1,1,1,2,2,4,5,5,5-Nonafluoro-4-(trifluoromethyl) -3-pentanone (A-1) as the first extinguishing agent and 1,1 as the second extinguishing agent A mixed fire extinguishing agent was prepared using 50 g of 1,2,2,3,4,5,5,5-Decafluoro-3-methoxy-4-(trifluoromethyl)pentane (A-3). After putting 88g of PVA (Polyvinyl alcohol) aqueous solution having a solid content of 30%, the mixed fire extinguishing agent prepared above, and 63g of distilled water into the reactor, it was stirred at 32 ° C. for 2 hours. In another reactor, 0.6 g of Urea and 3 g of Resorcinol were mixed with 70 g of distilled water and stirred at 32 ° C for 30 minutes. At this time, the pH was maintained at 6-7 using NaOH aqueous solution. After adding 11 g of 37% Formaldehyde solution and stirring for 5 minutes, the prepared Urea-Resorcinol-Formaldehyde solution was added to the previously prepared PVA-extinguishing agent solution. After adjusting the pH to 2 with a 10% sulfuric acid solution, the mixture was stirred at 32° C. for 30 minutes. The temperature was raised to 45 ° C. and reacted for 50 minutes, then naturally cooled to 32 ° C. and maintained at this temperature for 20 hours. After cooling the reactant to room temperature, it was washed with distilled water to prepare self-extinguishing microcapsules containing an extinguishing agent.

[Example 2]

First, 50 g of 1,1,1,2,2,4,5,5,5-Nonafluoro-4-(trifluoromethyl)-3-pentanone (A-1) as the first extinguishing agent and 1,1 as the second extinguishing agent A mixed fire extinguishing agent was prepared using 50 g of 1,2,2,3,4,5,5,5-Decafluoro-3-methoxy-4-(trifluoromethyl)pentane (A-3). 9 g of gelatin was added to 143 g of distilled water and heated to 50 ° C. for 30 minutes, and then mixed with 100 g of the mixed fire extinguishing agent prepared above at room temperature. 21 g of sodium polyphosphate (sodium polyphosphate) with a solid content of 5 wt% was added to the mixed solution, and the pH was adjusted to 4 with a 10 wt% sulfuric acid solution. After slowly lowering the temperature to 10℃, 9g of an aqueous solution of Glutaraldehyde (glutaric acid aldehyde) with a solid content of 25wt% was added to the reaction mixture to cure the formed shell, maintained at room temperature for 5-6 hours, washed, and microcircuit containing a fire extinguishing agent. Capsules were prepared.

[Example 3]

In Example 1, when preparing the mixed fire extinguishing agent, it is the same as in Example 1 except that 70 g of the fire extinguishing agent A1 and 30 g of the fire extinguishing agent A3 were used.

[Example 4]

In Example 1, when preparing the mixed fire extinguishing agent, it is the same as in Example 1 except that 30 g of the fire extinguishing agent A1 and 70 g of the fire extinguishing agent A3 were used.

[Comparative Example 1]

In Example 1, when preparing the mixed fire extinguishing agent, it is the same as in Example 1 except that 50 g of the fire extinguishing agent A1 and 50 g of the fire extinguishing agent B1 were used.

[Comparative Example 2]

In Example 1, when preparing the mixed fire extinguishing agent, it is the same as in Example 1 except that 50 g of the fire extinguishing agent A1 and 50 g of the fire extinguishing agent B3 were used.

[Comparative Example 3]

In Example 1, when preparing the mixed fire extinguishing agent, it is the same as in Example 1 except that 50 g of the fire extinguishing agent A1 and 50 g of the fire extinguishing agent B2 were used.

[Comparative Example 4]

In Example 1, when preparing the mixed fire extinguishing agent, it is the same as in Example 1 except that 50 g of the fire extinguishing agent B1 and 50 g of the fire extinguishing agent B3 were used.

[Evaluation example]

The characteristics of the microcapsules prepared in Examples and Comparative Examples according to the present invention were evaluated through the following experiments, and the results are shown in Table 2. First, the specific gravity of the fire extinguishing agent was calculated and measured using the relative gravity method for distilled water using a pycnometer, and the surface tension was measured using a surface tension meter (Tensiometer, KRUSS Model K100). The yield of the prepared microcapsules was calculated through the theoretical yield versus the yield of microcapsules obtained after washing and drying. , TA instrument's Q500) was measured.

	Microcapsule composition				Characteristics of Mixed Fire Extinguishing Agent
	fire extinguishing agent			shell	density (ρ, g/cm3)			surface tension (γ, dyne/cm)
	No. 1	2nd	content ratio	URF	No. 1	2nd	△ρ	my	2nd	△γ
Example 1	A1	A3	5:5	Gelatin	1.62	1.69	0.07	11.1	15.2	4.1
Example 2	A1	A3	5:5	URF	1.62	1.69	0.07	11.1	15.2	4.1
Example 3	A1	A3	7:3	URF	1.62	1.69	0.07	11.1	15.2	4.1
Example 4	A1	A3	3:7	URF	1.62	1.69	0.07	11.1	15.2	4.1
Comparative Example 1	A1	B1	5:5	URF	1.62	2.48	0.86	11.1	38.5	27.4
Comparative Example 2	A1	B3	5:5	URF	1.62	2.63	1.01	11.1	44.2	33.1
Comparative Example 3	A1	B2	5:5	URF	1.62	2.19	0.57	11.1	18.0	6.9
Comparative Example 4	B1	B3	5:5	URF	2.48	2.63	0.15	38.5	44.2	5.7

	Microbead Characteristics
	transference number	size	decapsulation temperature
	%	micron	℃
Example 1	92	200-350	125
Example 2	93	200-350	123
Example 3	91	200-350	110
Example 4	90	200-350	135
Comparative Example 1	NG	NG	NG
Comparative Example 2	NG	NG	NG
Comparative Example 3	48	50-400	115
Comparative Example 4	75	200-350	150

As shown in the results of Tables 2 and 3 and FIG. 1, when two types of fire extinguishing agents having a difference in specific gravity of 0.5 or less and a difference in surface tension of 10 or less are mixed, microcapsules with uniform particle distribution can be obtained by 90% or more. It is produced in high yield, and it can be seen that the decapsulation temperature can be controlled by adjusting the blending ratio of the two types of fire extinguishing agents. In addition, it was confirmed that microcapsules having a desired decapsulation temperature were prepared even when the polymer material constituting the shell was changed (Example 2).

On the other hand, when two types of fire extinguishing agents with a difference in specific gravity of 0.5 or more or a difference in surface tension of 10 or more were mixed, the stability of the emulsion rapidly decreased, and perfect microcapsules were not produced (Comparative Examples 1 and 2). In addition, when two types of fire extinguishing agents having a difference in specific gravity slightly greater than 0.5 and a difference in surface tension of about 7 are mixed (Comparative Example 3), microcapsules could be obtained, but the yield dropped sharply and the particle size distribution significantly increased. It can be seen that productivity decreases rapidly.

On the other hand, when mixing two types of bromine-based fire extinguishing agents with a difference in specific gravity of 0.5 or less and a difference in surface tension of 10 or less, encapsulation proceeds normally, but the yield is greatly reduced due to the specific gravity of the fire extinguishing agent being greater than 2, resulting in a problem in economic efficiency. It was confirmed that there was (Comparative Example 4).

As such, the present invention prepares a self-extinguishing microcapsule composition that equally contains two or more types of liquid fire extinguishing agents having the same chemical structure and different boiling points, thereby adjusting the mixing ratio of the fire extinguishing agents to decapsulate the temperature. can be adjusted to the desired temperature. In addition, the manufacturing method of the self-extinguishing microcapsule composition according to the present invention has a simple manufacturing process and high work efficiency. It eliminates the inconvenience of having to conduct a new evaluation of compatibility and adhesiveness with the polymer matrix whenever the structure of the shell is changed, and provides a self-extinguishing microcapsule composition with improved operational reliability by securing long-term preservation and safety. can do. In addition, in the present invention, in the process of decapsulating the fire extinguishing agent, decapsulation in which the fire extinguishing agent destroys and releases the shell occurs quickly, and when the ambient temperature rises above a predetermined temperature in the event of a fire, the fire extinguishing agent is released at the beginning of the fire. Excellent fire extinguishing function, such as suppressing fire or preventing the spread of fire, exhibits excellent fire extinguishing performance such as enabling fire suppression in a short time, and stable and reliable with little leakage of fire extinguishing agent It can be manufactured with a variety of high fire extinguishing devices.

Claims (20)

1. A self-extinguishing microcapsule composition that has a core-shell structure and is decapsulated at high temperature,

   The core is selected from halogenated hydrocarbons and includes a first extinguishing agent and a second extinguishing agent having different boiling points,

   The shell is made of a high-molecular polymer formed on the outer surface of the core,

   A self-extinguishing microcapsule composition for fire suppression.
2. According to claim 1,

   The first extinguishing agent and the second extinguishing agent satisfy the following [Formula 1] and [Formula 2], the self-extinguishing microcapsule composition.

   [Equation 1] … Δρ = ｜ρ ₁ - ρ ₂ ｜< 0.5

   [Equation 2] … Δγ = ｜γ ₁ - γ ₂ ｜< 10

   In [Formula 1] and [Formula 2], ρ ₁ and ρ ₂ are the specific gravity (g/cm ³ ) of the first extinguishing agent and the second extinguishing agent, respectively, and γ ₁ and γ ₂ are the first extinguishing agent, respectively. and the surface tension of the second extinguishing agent (dyne/cm).
3. According to claim 1,

   The self-extinguishing microcapsule composition, wherein the specific gravity of the first extinguishing agent and the second extinguishing agent is less than 2 g / cm 3 .
4. According to claim 1,

   The weight ratio of the first extinguishing agent and the second extinguishing agent is in the range of 3:7 to 5:5, self-extinguishing microcapsule composition.
5. According to claim 1,

   The average size of the microcapsules is in the range of 200 to 350 μm, self-extinguishing microcapsule composition.
6. According to claim 1,

   The self-extinguishing microcapsule composition of claim 1, wherein the decapsulation temperature ranges from 105 to 155 °C.
7. According to claim 1,

   The core is an emulsion composition in which a first extinguishing agent, a second extinguishing agent and a surfactant are dispersed in water, a self-extinguishing microcapsule composition.
8. According to claim 1,

   The halogenated hydrocarbon is selected from hydrocarbons substituted with fluorine or bromine, the self-extinguishing microcapsule composition.
9. According to claim 1,

   The first and second extinguishing agents are 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone, ethyl nonafluoro Robutyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)pentane, 2-(trifluoromethyl ) -3-ethoxydodecafluorohexane, each selected from, self-extinguishing microcapsule composition.
10. According to claim 1,

    The polymer is one or more selected from urea-formaldehyde-resorcinol, gelatin, epoxy, polyurethane, and polyurea, the self-extinguishing microcapsule composition.
11. According to claim 7,

    The surfactant is at least one selected from polyvinyl alcohol (PVA), ethylene maleic anhydride (EMA), and sodium dodecyl benzene sulfonate (SDBS), self-extinguishing microcapsule composition.
12. Preparing a core emulsion composition by mixing a first extinguishing agent and a second extinguishing agent selected from halogenated hydrocarbons and having different boiling points in water with a surfactant;

    adjusting the pH by adding an acid after mixing the emulsion composition with an aqueous polymer solution forming a shell; and

    A method for producing a self-extinguishing microcapsule composition for fire suppression having a core-shell structure, comprising the step of raising the temperature of the pH-adjusted mixed solution and then cooling it to prepare microcapsules.
13. According to claim 12,

    The method of producing a self-extinguishing microcapsule composition, wherein the pH ranges from 2 to 4.
14. According to claim 12,

    The elevated temperature is in the range of 45 to 60 ° C., a method for producing a self-extinguishing microcapsule composition.
15. According to claim 12,

    The method for producing a self-extinguishing microcapsule composition, wherein the first extinguishing agent and the second extinguishing agent satisfy the following [Formula 1] and [Formula 2].

    [Equation 1] … Δρ = ｜ρ ₁ - ρ ₂ ｜< 0.5

    [Equation 2] … Δγ = ｜γ ₁ - γ ₂ ｜< 10

    In [Formula 1] and [Formula 2], ρ ₁ and ρ ₂ are the specific gravity (g/cm ³ ) of the first extinguishing agent and the second extinguishing agent, respectively, and γ ₁ and γ ₂ are the first extinguishing agent, respectively. and the surface tension of the second extinguishing agent (dyne/cm).
16. According to claim 12,

    The specific gravity of the first extinguishing agent and the second extinguishing agent is less than 2 g / cm 3, a method for producing a self-extinguishing microcapsule composition.
17. According to claim 12,

    The weight ratio of the first extinguishing agent and the second extinguishing agent is in the range of 3:7 to 5:5.
18. According to claim 12,

    The method of producing a self-extinguishing microcapsule composition, wherein the halogenated hydrocarbon is selected from hydrocarbons substituted with fluorine or bromine.
19. According to claim 12,

    The first and second extinguishing agents are 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone, ethyl nonafluoro Robutyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)pentane, 2-(trifluoromethyl )-3-ethoxydodecafluorohexane, each selected from, a method for producing a self-extinguishing microcapsule composition.
20. According to claim 12,

    The method of producing a self-extinguishing microcapsule composition, wherein the polymer is at least one selected from urea-formaldehyde-resorcinol, gelatin, epoxy, polyurethane, and polyurea.

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