KR102595797B1 - Self-extinguishing sheet comprising fire extinguishing microcapsules and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a self-extinguishing composite sheet containing fire extinguishing microcapsules and a method of manufacturing the same. More specifically, it relates to a self-extinguishing composite sheet containing fire extinguishing microcapsules surface-treated with a silane compound and a polymer composite composition containing a photocurable resin and a thermosetting resin. It relates to a self-extinguishing composite sheet manufactured through a two-step curing process and a method of manufacturing the same.

Description

Self-extinguishing composite sheet comprising fire extinguishing microcapsules and manufacturing method thereof {Self-extinguishing sheet comprising fire extinguishing microcapsules and manufacturing method thereof}

The present invention relates to surface-treated fire-extinguishing microcapsules, a self-extinguishing composite sheet containing the same, and a method for manufacturing the same. More specifically, it relates to the manufacture of fire-extinguishing microcapsules surface-treated with a silane compound, and a photocurable resin and thermosetting resin. It relates to a self-extinguishing composite sheet manufactured through a two-step curing process of a polymer composite composition mixed with a resin and a method of manufacturing the same.

Currently, the use of microcapsules containing liquid fire extinguishing agents is gradually increasing. This is because fire extinguishing agents in the form of liquid, gas, or aerosol not only have difficulty in transportation and storage, but also have the disadvantage of being difficult to apply to polymer materials. On the other hand, solid microcapsules have high utility because 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, lyophilic substances that evaporate at high temperatures, and these substances are produced by coacervation or interfacial polymerization. Capsules are manufactured. Fire extinguishing microcapsules can be manufactured by emulsifying the fire extinguishing agent using a surfactant, forming water-soluble polymer particles, adsorbing these particles to the surface of the fire extinguishing agent, and finally forming a solid shell. there is. Microcapsules manufactured by this method can increase initial fire suppression efficiency because decapsulation occurs in which the fire extinguishing agent is released from the shell in a narrow temperature range when a fire occurs.

In the case of microcapsules manufactured by the above method, they are spherical particles with a diameter of 50 to 400㎛ containing 75 to 95% by weight of fire extinguishing agent, but because the thickness of the shell is relatively thin, the mechanical properties of the polymer constituting the shell are poor. . Additionally, if a porous shell is formed, the fire extinguishing agent inside comes out over time, making the self-extinguishing capsule unable to function properly. For this reason, in order to increase the stability of the micro digestive capsule, the strength of the shell is increased by adding montmorllonite, a type of clay mineral, or the flexibility of the shell is improved by using hydrophilic plasticizers such as glycerol and dryethylene glycol, or encapsulated A method of improving the thermal stability of the capsule or manufacturing a fire extinguishing microcapsule with a double layer structure has been proposed by filling the polymer matrix with a fire extinguishing agent.

Meanwhile, in the case of extinguishing microcapsules, stability control issues due to the relatively thin polymer shell are important, but since the decapsulation temperature is around 100 to 160 degrees, it is difficult to apply them to general polymer injection and extrusion processes. Therefore, when it is necessary to mix extinguishing microcapsules with a polymer material capable of low-temperature heat curing and mold them into films, sheets, pads, etc., there are limitations in raising the curing temperature, so a relatively long curing time is required.

In addition, in order to sufficiently secure the fire extinguishing effect for fire suppression, the proportion of fire extinguishing agent input into the fire extinguishing sheet must be as high as 40% or more. Accordingly, the polymer composite fire extinguishing sheet has a composition containing a large amount of capsules with a size of hundreds of ㎛ or more. . At this time, when a polymer composite sheet is manufactured by simply mixing extinguishing microcapsules and a polymer resin, the mechanical properties of the polymer composite sheet deteriorate, such as becoming increasingly brittle over time. Moreover, since the specific gravity of commonly used fire extinguishing agents is very high at 1.5 g/cm ³ or more, there is a problem in that the non-uniformity of the polymer composite sheet increases, such as the capsule sinking to the bottom when cured at low temperature for a long time.

Patent Publication No. 10-2023-0006194

The purpose of the present invention is to solve problems such as when producing a polymer composite material using digestive microcapsules, there is a limit to increasing the content of the digestive capsule, the curing time takes a long time, and the uniformity of the produced polymer composite material is low. The aim is to provide a method for synthesizing microcapsules for fire extinguishing that can solve the problem, a self-extinguishing composite sheet containing the same, and a method for manufacturing the same.

One aspect of the present invention is a fire extinguishing microcapsule having a core-shell structure, wherein the core contains a halogenated hydrocarbon fire extinguishing agent, the shell is formed of a high molecular weight polymer, and the outer surface of the shell is surface treated with a silane compound. Provided is an extinguishing microcapsule further comprising a formed coating layer.

According to embodiments, the halogenated hydrocarbon may be selected from one or more types of fluorine-based hydrocarbons or brominated hydrocarbons.

According to an example, the high molecular weight polymer forming the shell may be selected from one or more of urea formaldehyde resin or melamine formaldehyde resin having a hydroxyl group. Additionally, the polymer that forms the shell of the microcapsule may contain a hydroxyl group that can react with a silane compound.

The silane compound used for surface treatment may be a silane coupling agent having an epoxy reactive group. For example, 3-(glycidyloxypropyl)trimethoxysilane, 3-(glycidyloxypropyl)triethoxysilane, 2-(2,4-epoxycyclohexyl)ethyltrimethoxysilane, diethoxysilane, Toxy(3-glycidyloxypropyl)methylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, epoxypropoxy One or more may be selected from the group consisting of propyltrimethoxysilane.

According to examples, the silane compound used for surface treatment may range from 5 to 10% by weight based on the weight of the extinguishing microcapsules.

Another aspect of the present invention is a digestive microcapsule having a core-shell structure; Photocurable resin and photoinitiator; Thermosetting resins and thermosets; Provided is a self-extinguishing composite sheet composition comprising an acrylic monomer having an isocyanate reactive group, and the extinguishing microcapsules are surface treated with a silane compound.

Another aspect of the present invention includes treating the surface of the fire extinguishing microcapsules by reacting a fire extinguishing microcapsule with a core-shell structure with a silane compound; Preparing a polymer composite resin composition by mixing the surface-treated fire extinguishing microcapsules, a photocurable resin, a photoinitiator, a thermosetting resin, a thermosetting agent, and an acrylic monomer having an isocyanate reactive group; A first curing step of photocuring the polymer composite resin composition; and a second curing step of thermally curing the photocured polymer composite resin composition.

According to practice, the heat curing temperature in the second curing step is preferably in the range of 30°C to 60°C.

According to an example, the photocurable resin may be a resin containing an acrylate-based monomer or oligomer, and the thermosetting resin may be an epoxy resin. The epoxy resin preferably has a viscosity of 20,000 cps or less when measured at 25°C.

According to embodiments, the acrylic monomer having an isocyanate reactive group may be selected from 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, or mixtures thereof.

According to an embodiment, in the self-extinguishing composite sheet composition, the content of the extinguishing microcapsules surface-treated with the silane compound is in the range of 30 to 80% by weight, the content of the photocurable resin is in the range of 10 to 50% by weight, and The content of the thermosetting resin is in the range of 2 to 20% by weight, the content of the photoinitiator is in the range of 0.1 to 10% by weight, the content of the thermosetting agent is in the range of 0.1 to 20% by weight, and the content of the acrylic monomer having an isocyanate reactive group is 0.1% by weight. It may range from 5% by weight.

The surface-treated fire extinguishing microcapsule according to the present invention is mixed with a composite resin consisting of a photocurable resin, a photoinitiator, a thermosetting resin, a thermosetting agent, and an acrylic monomer having an isocyanate (-NCO) reactive group capable of chemically bonding with an epoxy reactive group. When producing a composite polymer sheet for fire extinguishing through primary photocuring and secondary thermal curing, the epoxy reactor present on the surface of the fire extinguishing microcapsule can chemically combine with the polymer resin, and this allows the fire extinguishing microcapsule to become a polymer. Not only can it be distributed uniformly within the resin, but problems such as agglomeration and precipitation do not occur over time.

In addition, not only can the curing time be significantly shortened through primary photocuring, but a polymer sheet with a more dense structure is formed through secondary thermal curing, significantly increasing the mechanical properties of the polymer composite sheet for fire extinguishing. This makes it possible to increase the input content of microcapsules for digestion by up to 80%. Meanwhile, in the case of an acrylic monomer with an isocyanate reactive group, it can participate in both photocuring and thermal curing reactions, effectively combining the acrylic polymer chain, the epoxy polymer chain, and the microcapsule with the epoxy reactive group for fire extinguishing.

1 is a cross-sectional view of a microcapsule surface treated with a silane compound according to an embodiment of the present invention.
Figure 2 is a cross-sectional view of a self-extinguishing composite sheet manufactured according to an embodiment of the present invention.
Figure 3 is a process flow chart showing a method of manufacturing a self-extinguishing composite sheet according to an embodiment of the present invention.

The present invention will be described in more detail below with reference to examples. However, the following examples are provided as examples to aid understanding of the present invention, and the scope of the present invention is not limited thereto. The present invention may be subject to various changes and may be implemented in various different forms, and should be understood to include all changes, equivalents, and substitutes included in the spirit and technical scope of the present invention.

Additionally, unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as generally understood by those skilled in the art to which the present invention pertains. Terms defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related technology, and should not be interpreted in an ideal or excessively formal sense unless explicitly defined in the present application. No.

The fire extinguishing microcapsule having a core-shell structure according to an embodiment includes a core containing a halogenated hydrocarbon fire extinguishing agent, a shell formed of a high molecular weight polymer, and a coating layer formed by surface treatment with a silane compound on the outside of the shell. It is characteristic.

Figure 1 shows a cross-sectional view of a fire extinguishing microcapsule having a core-shell structure surface treated with a silane compound and having a coating layer 12. The core 10 of the fire extinguishing microcapsule having a core-shell structure contains a fire extinguishing agent made of halogenated hydrocarbons such as fluorinated hydrocarbons or brominated hydrocarbons, and the shell 11 is made of a thin film made of a high molecular polymer material.

In the case of fire extinguishing microcapsules, they are manufactured through coacervation or interfacial polymerization, and are manufactured by forming a film made of high molecular weight polymer on the surface of a fluorine or brominated hydrocarbon fire extinguishing agent.

The halogenated hydrocarbon extinguishing agent may be a fluorinated hydrocarbon or a brominated hydrocarbon extinguishing agent, and 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 ) One or more may be selected from pentane and 2-(trifluoromethyl)-3-ethoxydodecafluorohexane, but are not particularly limited thereto.

Fire extinguishing microcapsules having a core-shell structure may contain a fire extinguishing agent in the range of about 90 to 95% by weight.

In the case of the polymer that makes up the shell, various polymer materials such as gelatin, urea formaldehyde resin, melamine formaldehyde resin, epoxy resin, and acrylic resin can be applied. In the present invention, it is preferable to use a polymer having a hydroxyl group (-OH) on the surface that can bind to a silane compound. For example, it is suitable to use urea formaldehyde resin having a hydroxyl group (urea-formaldehyde-resorcinol, etc.), melamine formaldehyde resin, etc., but is not limited thereto.

Meanwhile, such a shell may contain a precipitant or coagulant, and the appropriate thickness of the shell is about 50 to 2000 nm.

According to an example, the core-shell structured extinguishing microcapsule may be surface-treated with a silane compound having an epoxy reactive group. A compound called an epoxy silane coupling agent can be used. The hydroxy reactive group on the surface of the microcapsule and the silane compound are coated on the surface through Si-O chemical bonds (12), thereby attaching the epoxy reactive group to the surface of the microcapsule. It can be introduced.

Epoxy silane coupling agents include, for example, 3-(glycidyloxypropyl)trimethoxysilane, 3-(glycidyloxypropyl)triethoxysilane, 2-(2,4-epoxycyclohexyl)ethyltri. Methoxysilane, diethoxy(3-glycidyloxypropyl)methylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxy One or more may be selected from the group consisting of silane and epoxypropoxypropyltrimethoxysilane, but are not limited thereto.

The silane compound is preferably contained in an amount of 5 to 10% by weight based on the weight of the extinguishing microcapsule. If the content of the silane compound is less than 5% by weight of the weight of the extinguishing microcapsules, the bonding property with the polymer resin is poor. On the other hand, if the content of the silane compound exceeds 10% by weight, there is a problem of aggregation between microcapsules during reaction.

According to an embodiment, a self-extinguishing composite sheet composition containing fire extinguishing microcapsules includes fire extinguishing microcapsules having a core-shell structure; Photocurable resin and photoinitiator; Thermosetting resins and thermosets; It contains an acrylic monomer having an isocyanate reactive group, and the extinguishing microcapsule is characterized by surface treatment with a silane compound.

In this way, when the fire extinguishing microcapsule is prepared by surface treatment with a silane compound and introducing a reactor, it can be mixed with a polymer resin and then reacted to produce sheets or films with various thicknesses and sizes.

As described above, the self-extinguishing composite sheet according to the present invention includes extinguishing microcapsules surface-treated with a silane compound. In addition, the polymer composite composition for producing a self-extinguishing composite sheet according to the present invention is characterized by containing both a photocurable resin and a thermosetting resin.

Referring to FIG. 3, the method of manufacturing a self-extinguishing composite sheet according to an embodiment first prepares extinguishing microcapsules having a core-shell structure (S101), comprising extinguishing microcapsules having the core-shell structure and silane. Treating the surface of the extinguishing microcapsule by reacting the compound (S102); Step S103) of preparing a polymer composite resin composition by mixing the surface-treated fire extinguishing microcapsules, a photocurable resin, a photoinitiator, a thermosetting resin, a thermosetting agent, and an acrylic monomer having an isocyanate reactive group; A first curing step (S104) of photocuring the polymer composite resin composition; And it may include a second curing step (S105) of thermally curing the photocured polymer composite resin composition, and through this process, a self-extinguishing composite sheet can be manufactured (S106).

It is preferable to use a photocurable resin containing an acrylate monomer or oligomer. For example, methyl acrylate, ethyl acrylate, butyl acrylate, hexanediol diacrylate, diethylene glycol diacrylate, Propylene glycol diacrylate, polyethylene glycol diacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexane Hexanediol dimethacrylate, diethyleneglycol dimethacrylate, dipropyleneglycol dimethacrylate, polyethylene glycol dimethacylate and urethane acrylate ( One or more types may be selected and used from the group consisting of urethane acrylate, but are not particularly limited thereto.

Additionally, the photoinitiator included in the polymer composite composition according to the present invention may be a commonly used radical photoinitiator, specifically, for example, phenylphosphineoxide, monoacrylphosphine, and alpha hydroxy ketone. (a-hydroxyketone), acetophenoe, benzyldimethylketal, methylidynetrisdimethyl aniline, sulfoniumphosphonate, benzoyl sulphide, benzophenone ), one or more types can be selected from the group consisting of aminobenzoate, but are not particularly limited thereto.

The polymer composite composition for producing a self-extinguishing composite sheet according to the present invention further includes a thermosetting resin and a thermosetting agent in addition to a photocurable resin and a photoinitiator.

Thermosetting resins include epoxy resins, and liquid epoxy resins with low viscosity are preferred. Specifically, it is appropriate to use an epoxy resin with a viscosity measured at 25°C of 20,000 cps or less. If the viscosity of the epoxy resin is high and exceeds the above range, the amount of extinguishing microcapsules that can be added is limited.

Additionally, the self-extinguishing composite sheet composition includes a heat curing agent, that is, an epoxy curing agent, necessary to cure the epoxy resin. Thermosetting agents include, for example, cyclic aliphatic amines, polycarboxylic acids and their acid anhydrides, polyphenol compounds, and mixtures thereof, but are not particularly limited thereto.

According to examples, the epoxy resin and the epoxy curing agent may be mixed at a weight ratio of 1.5 to 2.5:1, but are not limited thereto.

The self-extinguishing composite sheet composition containing fire extinguishing microcapsules according to the present invention is characterized by containing both a photocurable resin and a thermosetting resin. Specifically, in the self-extinguishing composite sheet composition, the content of the extinguishing microcapsules surface-treated with a silane compound is in the range of 30 to 80% by weight, the content of the photocurable resin is in the range of 10 to 50% by weight, and the content of the thermosetting resin is in the range of 30 to 80% by weight. The content is in the range of 2 to 20% by weight, the content of the photoinitiator is in the range of 0.1 to 10% by weight, the content of the thermosetting agent is in the range of 0.1 to 20% by weight, and the content of the acrylic monomer having an isocyanate reactive group is in the range of 0.1 to 5% by weight. It may be in the % range.

The reason why the content of fire-extinguishing microcapsules surface-treated with a silane compound is in the range of 30 to 80 weight is because it can exhibit excellent fire-extinguishing effects in the event of a fire and does not impair the physical properties of the self-extinguishing composite sheet that is ultimately manufactured. If the content of fire extinguishing microcapsules is less than 30% by weight, the fire suppression effect is low, and if the content exceeds 80% by weight, the mechanical properties of the fire extinguishing sheet deteriorate, resulting in low stability.

In the present invention, the ratio between the photocurable resin and the thermosetting resin is important, and it is appropriate that the content of the photocurable resin is 50% or more compared to the total polymer content. If the content of photocurable resin is less than 50%, there is no significant effect in shortening the manufacturing process through photocuring. Also, if the amount of photocurable resin with relatively low viscosity decreases, there is a limit to the amount of microcapsules that can be added. . On the other hand, the content of the thermosetting resin is preferably 2 to 20% by weight relative to the total polymer content. If it is less than 2% by weight, it is less effective in improving the physical properties of the sheet by epoxy reaction, and if it is more than 20%, the viscosity is too high and the curing time is long. A problem arises.

It is appropriate to include the photoinitiator and the thermosetting agent only in the amounts necessary for the curing reaction with the photocurable resin and the thermosetting resin. It is uneconomical and unnecessary to include them in excess of the above range.

Meanwhile, according to one embodiment of the present invention, an acrylic monomer having an isocyanate (-NCO) reactive group capable of chemically bonding with an epoxy reactive group is used, for example, 2-isocyanatoethyl methacrylate. ), 2-isocyanatoethyl acrylate, or mixtures thereof. Since the above monomers can participate in both photocuring and thermal curing reactions, they effectively combine the acrylic polymer chain, the epoxy polymer chain, and the fire extinguishing microcapsule.

It is appropriate to use the acrylic monomer having an isocyanate reactive group in the range of 0.1 to 5% by weight. If it is less than 0.1%, it reacts with the epoxy group on the capsule surface and has no effect of introducing an acrylic reactive group into the capsule. On the other hand, if it is more than 5%, excessive network formation occurs. The disadvantage is that not only does the sheet become too hard due to the formation of the structure, but the manufacturing cost also increases.

In an embodiment, the photocuring process, which is the first curing step (S104), may be performed by placing the polymer composite resin composition into a molding of a desired product and then irradiating light using a mercury lamp. In addition, after performing the first curing step (S104), which is a photocuring process, the second curing step (S105), which is a thermal curing process, can be performed by heating to a certain temperature in an oven. The heat curing process is preferably performed at a temperature of 30 to 60°C. If the heat curing process is performed at a temperature higher than this range, there is a problem that some capsules may be destroyed and the fire extinguishing liquid inside may leak out.

According to another embodiment of the present invention, the self-extinguishing composite sheet may further have an adhesive layer 22 formed on the polymer resin layer containing extinguishing microcapsules, and may further include a release film 23 if necessary. can do.

The adhesive layer can use adhesive materials that are generally applied to film sheets, for example, acrylic, silicone, urethane, epoxy, natural or synthetic rubber components.

Additionally, the self-extinguishing composite sheet may further include a release film to protect the polymer composite layer or adhesive layer containing the extinguishing microcapsules. For example, polyethyl phthalate (PET), polypropylene (PP), stretched polypropylene (OPP), polybutylene terephthalate (PBT), polybutylene naphthalate (PBN), polyimide (PI) and mixtures thereof. You can hear...

Hereinafter, the present invention will be described in more detail through examples. These examples are intended to illustrate the present invention in more detail, and the scope of the present invention is not limited to these examples.

[Synthesis Example 1] Synthesis of microcapsules for digestion

100g of fire extinguishing agent 1,1,1,2,2,4,5,5,5-Nonafluoro-4-(trifluoromethyl)-3-pentanone, 88g of PVA (Polyvinyl alcohol) aqueous solution with 30% solid content, and 63g of distilled water. After being added to 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 to 7 using an aqueous NaOH solution. 11 g of 37% Formaldehyde solution was added here and stirred for 5 minutes, and then the prepared Urea-Resorcinol-Formaldehyde solution was added to the previously prepared PVA-fire extinguishing agent solution. The pH was adjusted to 2 with a 10% sulfuric acid solution and 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. The reactant was cooled to room temperature and washed with distilled water to prepare microcapsules containing a fire extinguishing agent.

[Synthesis Example 2] Synthesis of digestive microcapsule S-1 (5% by weight)

50 g of the microcapsule prepared through Synthesis Example 1 and 2.5 g of (3-Glycidyloxypropyl) trimethoxy silane, a silane coupling compound, were mixed with 100 g of distilled water, and then stirred at 60-60 g while maintaining pH = 3-4 at a stirring speed of rpm = 250. The temperature was raised to 70 degrees. After lowering the temperature to 50 degrees, the mixture was stirred for 24 hours, and the final compound was washed with water and dried to obtain microcapsules coated with a silane compound.

[Synthesis Example 3] Synthesis of microcapsule S-2 (10% by weight)

It is the same as Synthesis Example 2 except that 5g of (3-Glycidyloxypropyl) trimethoxy silane, a silane coupling compound, was added.

[Example 1] Manufacturing of self-extinguishing composite sheet

Silane-coated microcapsule S-1 50g, Diethyleneglycol diacrylate 17g, Hexandiol diacrylate 7g, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide as photoinitiator (Phenylbis(2,4,6-trimethylbenzoyl)phosphineoxide) 0.5g, epoxy resin (YD-115) 17g, epoxy resin hardener (KH-819) 7.5g, and 2-isocyanatoethyl acrylate 1g are mixed together to contain fire extinguishing agent. A polymer composite resin solution was prepared. This was poured into a transparent silicone mold with a thickness of 3 mm and irradiated for 5 minutes using a mercury lamp. At this time, the irradiation amount was adjusted to 800mJ/cm ² . The sheet manufactured through the first photocuring was heat-cured in an oven at 40 degrees for 12 hours to finally produce a self-extinguishing polymer composite sheet.

[Example 2] Increase in microcapsule content

Silane-coated microcapsule S-1 70g, Diethyleneglycol diacrylate 10.2g, Hexandiol diacrylate 4.2g, phenylbis(2,4,6-trimethylbenzoyl)phos as photoinitiator A self-extinguishing polymer composite sheet was manufactured by adding 0.3g of phenylbis(2,4,6-trimethylbenzoyl)phosphineoxide, 10.2g of epoxy resin (YD-115), and 4.5g of epoxy resin hardener (KH-819). Same as Example 1 except.

[Example 3] Increase in photocurable resin content

22g of Diethyleneglycol diacrylate, 10g of Hexandiol diacrylate, phenylbis(2,4,6-trimethylbenzoyl) phosphine oxide as photoinitiator )phosphineoxide) 0.7g, 11g of epoxy resin (YD-115), and 5.3g of epoxy resin hardener (KH-819) were added to prepare a self-extinguishing polymer composite sheet.

[Example 4] Use of photocurable resin alone

Without adding epoxy resin or epoxy hardener, 34g of Diethyleneglycol diacrylate, 14g of Hexandiol diacrylate, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide ( It is the same as Example 1 except that 1 g of phenylbis (2,4,6-trimethylbenzoyl)phosphineoxide) was added to produce a self-extinguishing polymer composite sheet.

[Example 5]

It is the same as Example 1 except that 50 g of S-2 was used instead of silane-coated microcapsule S-1.

[Comparative Example 1]

It is the same as Example 1 except that microcapsules without silane coating were used.

[Comparative Example 2]

It is the same as Example 1, except that microcapsules without silane coating were used and a composite sheet was manufactured using only 35 g of epoxy resin and 15 g of epoxy curing agent without adding photocurable resin, photocuring agent, or additives. At this time, only the thermal curing process was performed without the photo curing process, but the thermal curing time was not enough, so it was cured in an oven at 40 degrees for 24 hours.

[Evaluation example]

The properties of the microcapsule and polymer composite sheets prepared in Synthesis Examples and Examples according to the present invention were evaluated through the following experiments, and the results are shown in Tables 1 and 2. First, the size and decapsulation temperature of the prepared microcapsules were measured using an optical microscope (Eclipse E 200 from Nikon) and a thermogravimetric analyzer (TGA, Q500 from TA instruments). The solvent resistance of microcapsules was calculated by mixing 10 g of capsules with 50 g of isopropyl alcohol, drying the capsules after 125 hours, and calculating the weight loss rate. For heat resistance, 10 g of microcapsules were stored in an oven at 50 degrees for 30 days, then taken out and the weight loss rate was calculated.

As can be seen from the results in Table 1, the solvent resistance and heat resistance of the microcapsules are improved after silane treatment, but there is no significant effect on particle size or decapsulation temperature.

The fire extinguishing power of the self-extinguishing polymer composite sheet manufactured by the present invention was achieved by using a metal fire extinguishing box with a volume of 40 liters, and the box had holes on both sides to prevent natural fire extinguishing. Normal heptane (n-Haptahne) was used as the fire source, and the time it took for complete combustion after ignition and touching the door was measured. The tensile strength of the self-extinguishing polymer composite sheet was measured using a universal tensile tester after cutting the manufactured sheet into a KS M 6518 standard specimen (dumbbell type 3), and the uniformity of the molded product was measured by molding a 100x200 mm sheet and then After cutting into 1x1 mm, each weight was measured and the weight deviation was calculated. If the weight deviation is less than 0.5, it is denoted as O, if it is 0.5 to 2.0, it is denoted as △, and if it is more than 2.0, it is denoted as X.

Microcapsule-S1: silane treated (5wt% compared to capsule)

Microcapsule-S2: silane treated (3wt% compared to capsule)

Microcapsule: not treated with silane

Photocuring Resin-1: Diethyleneglycol diacrylate

Photocurable Resin-2: Hexandiol diacrylate

Photoinitiator: phenylbis(2,4,6-trimethylbenzoyl)phosphineoxide

Epoxy Resin: YD-115

Epoxy Hardener: KH-819

Additive: KarenzAOI (2-isocyanatoethyl acrylate)

As can be seen in Table 2, when silane-treated microcapsules are mixed with a photocurable resin and a thermosetting resin and then subjected to primary photocuring and secondary thermal curing to produce a polymer composite sheet (Examples 1 to 5) It can be seen that fire extinguishing power, tensile strength, and sheet uniformity are excellent. On the other hand, when a composite sheet is manufactured by photocuring and heat curing using microcapsules that have not been treated with silane (Comparative Example 1), it can be seen that the uniformity of the sheet is reduced, and when the microcapsules that are not treated with silane are heated, If a sheet is manufactured by mixing only the cured resin, not only does the sheet uniformity become very poor, but it also takes a long time for curing and the mechanical properties of the sheet deteriorate.

10: Core (extinguishing agent)
11: Shell (polymer membrane)
12: Silane coating layer with epoxy termination
20: Surface-treated digestive microcapsules
21: polymer resin
22: Adhesive layer
23: Release film

Claims (15)

A digestive microcapsule with a core-shell structure,
The core contains a halogenated hydrocarbon extinguishing agent,
The shell is formed of a high molecular weight polymer,
A fire extinguishing microcapsule further comprising a coating layer formed on the outer surface of the shell by surface treatment with a silane compound. According to paragraph 1,
The halogenated hydrocarbon is a fluorine-based hydrocarbon or a brominated hydrocarbon, and the polymer forming the shell is selected from one or more of urea formaldehyde resin or melamine formaldehyde resin having a hydroxyl group. A microcapsule for fire extinguishing. According to paragraph 1,
The silane compound is a microcapsule for fire extinguishing that is a silane coupling agent having an epoxy reactive group. According to paragraph 3,
The silane coupling agent having the epoxy reactive group is 3-(glycidyloxypropyl)trimethoxysilane, 3-(glycidyloxypropyl)triethoxysilane, and 2-(2,4-epoxycyclohexyl)ethyltri. Methoxysilane, diethoxy(3-glycidyloxypropyl)methylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxy A fire extinguishing microcapsule containing at least one selected from the group consisting of silane and epoxypropoxypropyltrimethoxysilane. According to paragraph 1,
The silane compound is a fire extinguishing microcapsule of 5 to 10% by weight based on the weight of the fire extinguishing microcapsule. Digestive microcapsules having a core-shell structure;
Photocurable resin and photoinitiator;
Thermosetting resins and thermosets;
Contains an acrylic monomer having an isocyanate reactive group,
A self-extinguishing composite sheet composition, wherein the extinguishing microcapsules are surface treated with a silane compound. According to clause 6,
A self-extinguishing composite sheet composition wherein the silane compound is a silane coupling agent having an epoxy reactive group. According to clause 6,
The photocurable resin is a resin containing an acrylate-based monomer or oligomer, and the thermosetting resin is an epoxy resin. According to clause 6,
The epoxy resin is a self-extinguishing composite sheet composition having a viscosity of 20,000 cps or less measured at 25°C. According to clause 6,
The acrylic monomer having the isocyanate reactive group is selected from 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, or mixtures thereof. In paragraph 6.
The content of the extinguishing microcapsules surface-treated with the silane compound ranges from 30 to 80% by weight, the content of the photocurable resin ranges from 10 to 50% by weight, and the content of the thermosetting resin ranges from 2 to 20% by weight. , the content of the photoinitiator is in the range of 0.1 to 10% by weight, the content of the thermosetting agent is in the range of 0.1 to 20% by weight, and the content of the acrylic monomer having an isocyanate reactive group is in the range of 0.1 to 5% by weight. Self-extinguishing composite sheet composition. Treating the surface of the fire extinguishing microcapsules by reacting a fire extinguishing microcapsule with a core-shell structure with a silane compound;
Preparing a polymer composite resin composition by mixing the surface-treated fire extinguishing microcapsules, a photocurable resin, a photoinitiator, a thermosetting resin, a thermosetting agent, and an acrylic monomer having an isocyanate reactive group;
A first curing step of photocuring the polymer composite resin composition; and
A method of manufacturing a self-extinguishing composite sheet comprising a second curing step of thermally curing the photocured polymer composite resin composition. According to clause 12,
A method of producing a self-extinguishing composite sheet wherein the heat curing temperature is in the range of 30°C to 60°C. According to clause 12,
The photocurable resin is a resin containing an acrylate-based monomer or oligomer, and the thermosetting resin is an epoxy resin. According to clause 12,
The method of producing a self-extinguishing composite sheet wherein the silane compound is a silane coupling agent having an epoxy reactive group.

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