Environmentally friendly fireproof paint and its manufacturing method

Abstract

The present invention relates mainly to the technical field of fire retardant paints, and in particular to an environmentally friendly fire retardant paint and its manufacturing method. Environmentally friendly fire-retardant paints are paint base materials that can withstand temperatures of 75°C or higher and / or open flame environments. When exposed to heat, it explodes and releases a fire-extinguishing material that vaporizes and cools and / or prevents and / or extinguishes the fire. The fire extinguishing agent microcapsules can be used to extinguish fires. Conventional fire prevention, fire extinguishing and flame retardant paints, It is difficult to simply prevent the expansion of the ignition area and to spontaneously extinguish the fire in a short time with high sensitivity. It is possible to break the current situation where it is difficult to cool down, prevent fires, and extinguish fires independently, and the response time is The fire extinguishing agent is stable in the paint and / or coating, and the coating can repeatedly extinguish the fire multiple times. The present invention provides a number of paints and / or coatings that can be triggered by a single action.

Description

[Technical field]

[0001] The present invention relates mainly to the technical field of fire retardant paints, and in particular to an environmentally friendly fire retardant paint and its manufacturing method. Regarding. [Background technology]

[0002] Fireproof paint is a paint that is applied to the surface of an object to prevent the outbreak of fire and to stop the spread of fire. It is also possible to prevent structural damage by isolating the fire source, extending the ignition time of the base material, and improving the insulation performance. It is a paint that can delay the time of destruction, and is used as a fireproof paint for steel structures, decorative fireproof paint, and These include fireproof paints for cables and fireproof paints for prestressed concrete decks. It is common to manufacture fireproofing materials by blending flame retardants and additives into the materials. It plays a role in fire protection through conductivity or heat absorption. Publication number is CN111073414 As shown in the Chinese invention patent A, the paint base material is ammonium polyphosphate, pentaerythritol, The addition of flame retardants, including fluoride and aluminum hydroxide, improves the flame retardancy of fireproof paints. It also achieves weather resistance. Thus, a low molecular weight carbon source, a carbon generating catalyst and a foaming agent are used to form an intumescent flame retardant, and a fireproof paint is produced. However, flame retardants only prevent the spread of ignition and the fire will go out spontaneously within a short period of time. On the other hand, fire extinguishing agents that have a fire-extinguishing effect usually exist stably in paint. Therefore, it is difficult to develop a fire-retardant coating that has a short fire-extinguishing response time and in which the extinguishing agent and the coating material coexist stably. The development of materials has important practical significance.

[0003] The background art described in the present invention belongs to the content of the present invention, and the knowledge of the above background art is included in the present invention. The purpose of the present invention is to aid in the understanding of the technical solutions, and it does not necessarily belong to the prior art of the present invention. If there is no convincing evidence that the above content was published on the filing date of the present invention, Therefore, knowledge of the aforementioned background art should not be used to evaluate the inventive step of the technical solution of the present application. Summary of the Invention [Problem to be solved by the invention]

[0004] Conventional fire prevention, fire extinguishing and flame retardant paints can only prevent the spread of ignition, but only for a short period of time. Breaking through the current situation where it is difficult to extinguish fires spontaneously with high sensitivity, we have developed a system that can automatically cool, prevent fires, and extinguish fires. It can be done spontaneously, has a short response time, and the extinguishing components are stable in the paint and / or coating. The coating can repeatedly trigger a fire extinguishing process, and the coating and / or paint are The aim is to provide several types. [Means for solving the problem]

[0005] According to a first aspect of the present invention, When exposed to paint base and temperatures above 75°C and / or direct flame, the material explodes and vaporizes. A fire extinguishing agent microcapsule that can be released to cool and / or prevent and / or extinguish a fire. A fire-retardant coating material is provided, comprising:

[0006] According to a second aspect of the present invention, a fire extinguishing agent microcapsule is provided, comprising: a film-forming substance; a solvent; and a fire extinguishing agent microcapsule. The extinguishing agent microcapsules have at least two layers of wall material, The cell wall material is rupturable at 75°C or higher, and the extinguishing agent microcapsules are capable of rupturing at the rupture of the wall material. A coating composition is provided which subsequently vaporizes and releases the core material.

[0007] According to a third aspect of the present invention, there is provided a fire extinguishing agent microcapsule comprising a film-forming component as a film-forming resin. The extinguishing agent microcapsules further include a microcapsule having at least two layers of wall material, The wall material of the fire extinguishing agent microcapsules is broken at 100°C or higher, preferably at 120°C to 150°C. The extinguishing agent microcapsules are broken into microcapsule cores containing extinguishing material after the destruction of the wall material. A powder coating is provided that vaporizes and releases.

[0008] The film-forming component as a coating film-forming resin forms a coating film by being cured with ultraviolet light.

[0009] The film forming components include a photocurable resin and a photoinitiator.

[0010] The photocurable resin may be an unsaturated polyacrylate, a methacrylate-modified polyester, an unsaturated Mixture of acrylate and polyester, acrylate grafted polyester, acrylate Polyacrylate, epoxy resin, epoxy acrylic resin, urethane acrylate and hyperbranched polyester acrylic resin. .

[0011] The paint powder is heated to a temperature lower than the extinguishing response temperature of the wall material of the fire extinguishing agent microcapsule and contains a film-forming component. The material is melted and leveled at a temperature equal to or higher than the melt leveling temperature of the material.

[0012] According to a fourth aspect of the present invention, a third method for producing a temperature-reducing and / or fire-resistant and / or fire-extinguishing coating is provided. Use of the powder coating according to the embodiment is provided.

[0013] According to the fifth aspect of the present invention, specifically, the surface of the base is coated or uncoated and dried. A coating that is a continuous and / or discontinuous thin film formed on the surface of a fire extinguishing material. A coating film is provided.

[0014] According to a sixth aspect of the present invention, A substrate; On the surface of the substrate A coating film formed from the environmentally friendly fireproof paint according to the first aspect, and / or A coating film formed from the coating composition according to the second aspect, and / or A coating film formed with the powder coating material according to the third aspect, and / or

[0015] and the coating film according to the fifth aspect.

[0016] In accordance with the common knowledge of those skilled in the art, the above preferred conditions may be combined with each other to produce a specific It is possible to obtain an embodiment.

[0017] The raw materials and reagents used in the present invention are all commercially available products and are not subject to any special description. Unless otherwise specified, all operations involved are conventional operations in the art. Effect of the Invention

[0018] According to the present invention, the paint base material and the fire extinguishing agent microcapsules coexist stably, and the coating is dried. Fire extinguishing agent microcapsules are evenly dispersed in the coating, and the wall material bursts under high temperatures or in an open flame environment, causing the encapsulated The extinguishing material vaporizes and is released, and the extinguishing material quickly absorbs heat, lowers its temperature, and spontaneously extinguishes the fire. It is possible to provide a highly practical, environmentally friendly fireproof paint that can be used in a wide range of applications.

[0019] According to the present invention, the fire extinguishing agent microcapsules are fire extinguishing agents that are easily volatile at room temperature and normal pressure and are difficult to store. Overcoming the shortcomings of the material, the presence of nano-silica and nano-metal oxides allows the microcapsules to be The adsorption of hydrolysis products after hydrolysis is facilitated, and the residual hydrofluoric acid is reduced, and the remaining The wall material of the microcapsules is protected from attack by hydrofluoric acid, and the The form of the fire extinguishing paint is maintained, and the storage stability and reusability of the fire extinguishing paint are improved.

[0020] According to the present invention, the compatibility of the fire extinguishing agent microcapsules with the film-forming substance and the solvent is good, and the fire extinguishing agent The core-wall ratio of the fire-extinguishing microcapsules is high, and the fire extinguishing sensitivity is high, so the temperature can be lowered, the fire can be prevented, and the fire can be extinguished spontaneously. A coating composition can be provided that can

[0021] According to the present invention, the material and manufacturing process of the wall of the fire extinguishing agent microcapsule are selected and limited. By this, for example, it is possible to select an appropriate polymer material, improve the degree of cross-linking of the polymer material, and improve the wall material. Increasing the number of layers etc. contributes to increasing the extinguishing response temperature of the fire extinguishing agent microcapsules, and the extinguishing response temperature is 100℃. As described above, it is preferable to obtain a fire extinguishing agent microcapsule whose wall material bursts at 120°C to 150°C. This can be applied to photocurable powder coatings to extinguish the fire in the wall of the fire extinguishing agent microcapsules. The powder coating is melted at a temperature below the response temperature and at a temperature at which melt leveling of the film-forming resin is possible. By forming a coating film through photocuring, it has excellent cooling and / or fire prevention and / or fire extinguishing properties. It is possible to provide a powder coating material capable of exhibiting excellent properties.

[0022] According to the present invention, when the temperature of the coating film rises to 75°C or higher or when it is exposed to an open flame environment, The fire-extinguishing material in the coating vaporizes and is released, and the fire-extinguishing material vaporizes and quickly absorbs the surrounding heat, It is possible to provide a coating film that can instantly lower the surrounding temperature and perform automatic temperature reduction and fire prevention. do.

[0023] According to the present invention, any substrate capable of forming a coating on its surface, preferably a substrate that is heated and and / or items that may be exposed to adverse environments, such as open flame environments, and When exposed to high temperature and / or direct flame environments, the coating applied to the surface of the product vaporizes due to the heat. Releases fire extinguishing material, quickly absorbs heat and reduces local temperature, resulting in spontaneous extinguishing of the fire. This can be done quickly and with minimal damage caused by erosion of the substrate by high temperatures or direct flames. It does not cause any other pollution to the materials, has a very high level of environmental protection, is safe, and has higher responsiveness. A coated article having utility value may be provided.

[0024] The present invention adopts the above technical solution to achieve the above object, and makes up for the shortcomings of the prior art. It is easy to use, has a rational design, and is simple to operate. [Brief description of the drawings]

[0025] To make the above and / or other objects, features, advantages, and examples of the present invention more clearly and comprehensibly. To that end, the drawings will be described as follows. [Figure 1] 1 is a microscope image of the extinguishing agent microcapsules obtained in Example 1 (highlighted is the liquid extinguishing material). [Diagram 2] 1 is a microscopic image of partial rupture of the fire extinguishing agent microcapsules obtained in Example 1 after drying. [Diagram 3] 1 is a micrograph of the fireproof coating obtained in Example 1 (highlighted is the liquid fire-extinguishing material). [Figure 4] FIG. 2 is a diagram showing the shape of the fireproof coating material obtained in Example 1 after application and drying. [Figure 6] FIG. 2 is a morphology diagram of the applied but not dried fireproof paint obtained in Example 1. [Figure 7] 1 is a micrograph of the fireproof coating obtained in Example 2 (highlighted is the liquid fire-extinguishing material). [Figure 8] FIG. 2 is a schematic diagram showing the weight loss of a paint sample not coated with a protective layer obtained in Example 1 in a room temperature environment. [Figure 9] 1 is a thermogravimetric analysis curve of the dried fire extinguishing paint obtained in Example 1. [Figure 10] FIG. 2 is a schematic diagram of a fire extinguishing verification device. [Figure 11] FIG. 2 is a schematic diagram showing an ignition state of the fire extinguishing verification device. [Figure 12] FIG. 2 is a schematic diagram showing a state of a simulated arrangement sample of a fire extinguishing verification device. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] Those skilled in the art will be able to appropriately substitute and / or change the process parameters based on the contents of this specification. The present invention may be realized in various ways, while still allowing all similar substitutions and / or modifications to be made by those skilled in the art. The above-mentioned products and and manufacturing methods described herein without departing from the content, spirit and scope of the present invention. The products and manufacturing methods may be modified or combined in suitable modifications to embody the technology of the present invention. It is clear that the principles can be applied and implemented.

[0027] Unless specifically indicated, the materials, methods, and examples described herein are illustrative. Methods and materials similar or equivalent to those described herein are not intended to be limiting. and materials may be used in the practice or testing of the invention, but the present disclosure includes suitable Methods and materials are described.

[0028] The amount, concentration, or other value or parameter is expressed as a range, a preferred range, or a set of preferred upper limits. and preferred lower limits, whether or not the ranges are disclosed. without regard to any higher range or preferred value and any lower range or preferred value. It is understood that all ranges formed by any pair of numerical values ​​are specifically disclosed. For example, when describing a range of "1 to 5 (1~5)," the range described should be The range is "1 to 4 (1~4)", "1 to 3 (1~3)", "1 to 2 (1~2)", " Ranges such as "1 to 2 (1-2) and 4 to 5 (4-5)", "1 to 3 (1-3) and 5", etc. Unless otherwise specified, when a numerical range is described herein, the range is , the range end value, and all integers and fractions within this range.

[0029] Unless otherwise specified, each clause of one or more features described in this application may refer to a corresponding feature described above. By "apply appropriately," it is meant that the limitations of the features described above are applicable and selective to the corresponding features described below. This means that the term "applies" to any part of this application unless otherwise specified. The disclosure of one or more features applies to corresponding features in other parts of this application and may be used interchangeably with other parts. It should be clear that the features of the invention are meant to be fully disclosed as well.

[0030] Unless otherwise specified, all percentages, parts, ratios, etc. are calculated by weight. "mol%" means mole percent, "vol%" means volume percent. Including, but not limited to, meaning product percentage.

[0031] Unless otherwise specified, the above "core material" and "fire extinguishing material" refer to the inside of the fire extinguishing agent microcapsule. The above "microcapsule rupture temperature" and "wall material rupture temperature" refer to the fire extinguishing active material enclosed in the microcapsule. ", "burst temperature" and "extinguishing response time" all have the same meaning. This refers to the temperature at which the wall material of a container bursts and releases its contents.

[0032] There are many studies on core-shell type fire extinguishing agent microcapsules, so we will briefly introduce them below.

[0033] As prior art, a Chinese invention patent with publication number CN105218714A discloses a core material and a core We have developed a flame-retardant microcapsule containing a coating layer that covers the outside of the material, as well as a manufacturing method and application thereof. The core material is liquid hexafluoropropane or liquid selenoflooropane. The coating layer is a polymethacrylate polymer polymerized by a suspension polymerization method. However, the boiling point of the core material, sevofluoropropane, is -16.4°C, while hexafluoropropane is Since the boiling point of propane is -1.4℃, the gaseous core material is liquefied by pressurizing it to 3-8MPa. It needs to be changed, the manufacturing process is complicated, and the manufacturing costs are high.

[0034] As a prior art, a Chinese invention patent with publication number CN1126571140A discloses a low melting point Microcapsule fire extinguishing agent including a flame retardant shell made of a copolymer and a temperature-reducing core containing a temperature-reducing material The present invention discloses an agent and a method for producing the same, and a low melting point copolymer is obtained by mixing a low melting point polymer monomer and a difficult-to- The low melting point copolymer is styrene-methyl methacrylate. It is a tri-methacrylic-2-bromo-3,3,3-trifluoropropene tetrapolymer. The heating material is one of fluorinated ketones, fluoropropanes, glycerin, and alcohols. However, the manufacturing process involves heating to 60-90°C and reducing the reaction pressure to 1.0- The relatively high pressure and temperature, up to 1.5Mpa, significantly increases the complexity of the technology. The requirements for industrial production are high.

[0035] As a prior art, the Chinese invention patent with publication number CN113476778A has high stability The present invention discloses a fire-extinguishing microcapsule and a method for producing the same, and the highly stable fire-extinguishing microcapsule The cell includes a core material containing a fire extinguishing agent, and a shell containing an inner layer, an outer layer, and an airtightness promoter. The inner layer is a mercury. produced by the reaction of amine, metaxylylenediamine, urea and formaldehyde solution It contains modified melamine-formaldehyde resin, and the outer layer is trimethylol dodecane-diisocyanate. The modified polyurethane resin produced by the reaction of an anate adduct with gelatin solution was used. As for organic fire extinguishing agents, pentaerythritol phosphate ester is used as an intumescent flame retardant. , perfluorohexanone, and decabromodiphenylethane are used. However, in this embodiment In step d) of the manufacturing process, the reaction temperature is high at 85°C, and The low boiling point of xanone makes it difficult to form microcapsules. The relatively high boiling point of ethane is unfavorable to the fire extinguishing response. In addition, the shell The burst temperature is high at 180-220℃, and it can lower the temperature and sound an alarm in the event of ignition. I can't come.

[0036] As prior art, a Chinese invention patent with publication number CN114558268A is Disclosed is a combustion suppressant medium of orohexanone microcapsules and its manufacturing method, product, and use. The combustion suppressing medium contains 140 parts by weight of a core material and 25 to 28 parts by weight of a shell material. The core material is perfluorohexanone, and the shell material is a polymeric capsule material and poly(ethylene glycol). A specific embodiment of the present invention is a mixture of vinyl alcohol and the like. The explosive crushing temperature of the obtained perfluorohexanone microcapsules was 97°C. and / or showed a failure to provide fire protection and a weak warning effect against ignition.

[0037] As a prior art, a Russian patent with application number RU2011125756 describes a 90-270°C Microcapsules that can explode within range to release their contents and put out a fire A fire extinguishing agent and its manufacturing method, a fire extinguishing composite material and a fire extinguishing coating are disclosed.

[0038] The prior art includes publication numbers CN109420281A and CN109453491A. A Chinese patent includes a main fire-extinguishing material, a microcapsule coating material and an auxiliary material. The material is covered with a coating material to form microcapsules, and the main extinguishing material is perfluoroacetone. , perfluorobutanone, perfluoropentanone, perfluorohexanone, perfluoro Perfluoropropane, perfluorobutane, perfluoropentane, perfluorohexane, perfluoroheptane, perfluorooctane, tetrafluorodibromoethane, trifluoro One or more of orthotrichloroethane, auxiliary materials are polymer resin, fiber, inorganic filler The inorganic filler is one or more of the following: calcium carbonate, silica, titania, alumina and a microencapsulated automatic fire extinguishing agent comprising one or more aluminum hydroxides. According to the manufacturing method, first, the covering material is a prepolymer, and the prepolymer is used as the main extinguishing agent. The material is reacted with water and a monomer emulsion at a temperature of 40 to 80°C to produce a micro After obtaining the capsule suspension, it is mixed with the auxiliary materials and molded. However, in the main fire extinguishing material , The boiling point of perfluorohexanone is 49°C, and that of perfluorohexane is 57.8°C. The boiling point of tetrafluorodibromoethane is 49.8°C, and that of trifluorotrichloroethane is The boiling point of the above materials is 47.57℃, which is significantly lower than the reaction temperature of 80℃. At the temperature of this technology, the main fire extinguishing material will escape in large quantities, resulting in a high yield of microcapsules. In addition, the microcapsule suspension is molded by adding an auxiliary material, and the auxiliary material The microcapsules are coated with calcium carbonate, silica, titania, and alumina. Even if inorganic fillers such as lumina and aluminum hydroxide are used, the microcapsules are not destroyed or preserved. There is no substantial protective effect.

[0039] The process of achieving the invention of this application will be described in detail below. [Environmentally friendly fireproof paint]

[0040] When exposed to paint base and temperatures above 75°C and / or direct flame, the material explodes and vaporizes. A fire extinguishing agent microcapsule that can be released to cool and / or prevent and / or extinguish a fire. A fire-retardant coating material is provided, comprising: [Fire extinguishing agent microcapsules]

[0041] In various embodiments, the extinguishing agent microcapsules comprise: A core material that vaporizes and absorbs heat when it receives heat and releases it, and at least and two layers of wall material, said wall material being burstable at 75°C or above.

[0042] In various embodiments, the wall material is heated to a temperature of 80°C or higher, 85°C or higher, 90°C or higher, 95°C or higher It can burst at temperatures above 100℃, 120℃, or 150℃.

[0043] In various embodiments, the extinguishing agent microcapsules are resistant to oxidative stresses at temperatures above 80° C., above 85° C., above 90° C., When exposed to environments with temperatures above 0℃, 95℃, 100℃, 120℃, or 150℃ It can explode, vaporize and release fire extinguishing material, lowering temperature and / or preventing and / or extinguishing the fire. Cut.

[0044] In various embodiments, the extinguishing agent microcapsules have a fire extinguishing response time of 25 seconds or less. do.

[0045] In various embodiments, the extinguishing agent microcapsules have a core-wall ratio of 1:1 to 9:1. .

[0046] In various embodiments, the extinguishing agent microcapsules have an embedment rate of 80% or more.

[0047] In various embodiments, the particle size of the extinguishing agent microcapsules is 20 to 400 μm. do.

[0048] In various embodiments, the extinguishing agent microcapsules crackle when exposed to heat. It makes a chi sound.

[0049] The purpose of the present invention is to provide an environmentally friendly fire-retardant paint containing a film-forming substance and a fire-extinguishing agent microcapsule. The fire extinguishing agent microcapsule material that gives the paint a fire-preventing and fire-extinguishing function is a type of film-forming material. There are no limitations to the above, and the paint can coexist stably with conventional paints. If the paint temperature rises to 75°C or higher, In the event of an open flame, the extinguishing agent microcapsules will burst and release the extinguishing agent inside. It absorbs heat from the environment and changes the temperature of the heat source, ignition point, and surrounding temperature to the flame point temperature. The environmentally friendly fireproof paint of this application achieves the following: Unlike ordinary fireproof paints, which simply prevent the spread of ignition points by applying flame retardants, It can cool and extinguish fires spontaneously, and in an ignition environment caused by a rise in temperature, its extinguishing effect is predictable. It has excellent visibility, significantly improves the convenience of fire prevention and extinguishing, and expands the range of applications, leading to higher utilization. It has value.

[0050] In various embodiments, the extinguishing agent microcapsules are produced by the following method: do. 1) Prepare a first wall material solution, add the first auxiliary agent and mix uniformly. Add 900% of the fire extinguishing material and emulsify by stirring to form a microcapsule emulsion. do. 2) A crosslinking agent is added to the microcapsule emulsion, crosslinked, filtered, washed, and separated. Thus, pre-cured fire extinguishing agent microcapsules are obtained. 3) A second wall material solution is prepared, and the pre-cured fire extinguishing agent microcapsules are dispersed in the second wall material solution. After hardening, the mixture is filtered, washed and dried to obtain fire extinguishing agent microcapsules.

[0051] In various embodiments, the first wall material and the second wall material are each independently a natural polymer, The polymer includes at least one of a semi-synthetic polymer and a synthetic polymer.

[0052] In various embodiments, the first coagent is selected from the group consisting of nanosilica, nanometal oxide, and UV protection. The composition contains at least one of the following inhibitors:

[0053] In various embodiments, in step 1), the concentration of the first wall material solution is 5 to 30% by weight. do.

[0054] In various embodiments, in step 1), the first auxiliary agent is a 1:2.5-5 weight ratio of sodium hydroxide. Nosilica and nanometal oxides.

[0055] In various embodiments, in step 1), the stirring and emulsification temperature is 0 to 40° C.; The stirring speed is 30 to 6000 r / min.

[0056] In various embodiments, in step 2), a second auxiliary agent is added to the second wall material solution to uniformly dissolve the second wall material. The second auxiliary agent is at least one of nanosilica, nanometal oxide, and ultraviolet ray inhibitor. Contains at least one species.

[0057] In various embodiments, in step 2), the crosslinking agent is potassium chromium sulfate, chloroacetate, At least one of the following crosslinking agents is added: The amount added is 0.1 to 10% based on the dry mass of the wall material.

[0058] In various embodiments, in step 2), the crosslinking time is at least 30 min.

[0059] In various embodiments, in step 3), if the second wall material solution cannot be formed into a membrane, the wall material height Conventional curing or crosslinking agents corresponding to the molecule are added in an amount of 0.1 to 10% of the dry mass of the polymer. will be added.

[0060] In various embodiments, in step 3), the curing or crosslinking agent is preferably chlorinated sulfate. potassium chromium, chromium acetate, formaldehyde or glutaraldehyde At most there is one species.

[0061] In various embodiments, in step 3), the curing time is at least 30 minutes.

[0062] In various embodiments, step 3) can be repeated to form a wall having two or more layers of wall material. Fire extinguishing agent microcapsules are obtained.

[0063] In the process of manufacturing the extinguishing agent microcapsules, a single wall material is used to encase the extinguishing agent material. However, it is not possible to form a stable core-shell structure by the sole method. Through research, it has been found that by encasing the extinguishing agent material in at least two layers of wall material, a stable and separate extinguishing agent can be produced. The microcapsules of the agent can be obtained, and the reaction temperature and stirring speed parameters during encapsulation are By this, the embedding rate is 80% or more, and the core-wall ratio can be adjusted within the range of 9:1 to 1:1, and the particle size It is possible to obtain fire extinguishing agent microcapsules having a particle size in the range of 20 to 400 μm, and The embedding rate can be adjusted by changing the mixing ratio, and the particle size can be adjusted by changing the stirring speed. By repeatedly covering the wall material on the black capsule, a fire extinguishing agent microcapsule with two or more layers of wall material is created. The presence of nano-silica and nano-metal oxides was found to be effective in obtaining microcapsules. It helps to keep the particles stable, and a small amount of moisture is absorbed into the microcapsules during the manufacturing process. When the extinguishing agent enters the cell, it undergoes partial hydrolysis, and the extinguishing material is also partially hydrolyzed during extinguishing and storage. The hydrolysis product, hydrofluoric acid, corrodes the components of the microcapsule wall material, This causes the contents to leak and slowly evaporate, reducing the fire-extinguishing effect of the microcapsules. On the other hand, when nano-silica and nano-metal oxide are added to the manufacturing process of the microcapsules, the fire extinguishing material The hydrolysis products of the feed are rapidly adsorbed, and the nano-oxide reacts with hydrofluoric acid to form ions. This reduces the amount of hydrofluoric acid remaining and reduces the amount of fluoride that is difficult to remove. The erosion of the microcapsule wall material is avoided, the inherent morphology of the unruptured microcapsules is maintained, and the microcapsules are The storage stability of the capsules is significantly improved. Core material

[0064] In various embodiments, the core material is perfluorohexanone, perfluorohexane , perfluoroheptane, perfluorooctane, tetrafluorodibromoethane, and At least one selected from trifluorotrichloroethane.

[0065] In various embodiments, the wicking material is perfluorohexanone.

[0066] Perfluorohexanone is a new environmentally friendly fire extinguishing agent that is liquid at room temperature and has a low heat of vaporization. It has only 4% of the water content and its vapor pressure is 2500% that of water, so it evaporates very easily and heats up. Perfluorohexanone is effective in reducing ozone loss. Since its loss factor is 0, its global warming potential is 1, and its atmospheric lifetime is 0.014 years (5 days), it is considered to be a fulong. Unfortunately, its boiling point is 4 Because the temperature is as low as 9°C, its use as a fire extinguishing agent is still limited to a certain extent. Application No. CN2019 In the utility model of 213773896, when a temperature-sensitive glass column is exposed to heat and bursts, the sealing The tank was dislodged from the exhaust port, and the perfluorohexanone in the tank was sprayed toward the source of the fire. A suspended perfluorohexanone fire extinguishing device is disclosed. The installation requires the tank to be filled with perfluorohexanone, and the obvious drawback is that the tank It takes up a relatively large volume, making it difficult to apply to precision instruments and solid materials, and difficult to move. Moreover, the fire cannot be extinguished without manual operation. The Chinese patents CN109420281A and CN109453491A are related to melamine and and / or a resin shell formed by reacting urea aldehyde and formaldehyde as the main extinguishing agent. The microcapsule automatic fire extinguishing agent was produced by coating the material with the microcapsule automatic fire extinguishing agent. However, the mass percentage of the main fire extinguishing material is 35-60%, the core-wall ratio is low, and the fire extinguishing effect is low. The effectiveness is low, and in the manufacturing process, the prepolymer, the main fire extinguishing material and water are emulsified. The monomer emulsion is obtained and heated to 40-80°C to completely react the coating material. A microcapsule suspension is obtained, but within this temperature range the main extinguishing material is vaporized and lost. Therefore, the final yield of microcapsules is extremely low and the trigger temperature is high at 96°C. Therefore, the core of the fire extinguishing material is made of a polymer material. A fire extinguishing agent microcapsule is provided, which is surrounded by at least two layers of a wall material containing the fire extinguishing agent. The microcapsules ensure structural stability and the extinguishing material does not volatilize under normal temperature and pressure. It overcomes the drawbacks of being easily damaged and difficult to store, and is a product that can be stored in an environment that does not have obvious high-temperature sources or open flames. In the environment, the properties and structural stability of the fire extinguishing agent microcapsules are maintained, and fire extinguishing properties are maintained even after long-term storage. The performance does not decrease. In addition, the fire extinguishing response temperature of the microcapsules is further increased to 80℃ or 75℃. When it reaches its extinguishing response temperature due to heat or encounters an open flame, the extinguishing agent The wall of the closable capsule bursts, releasing the fire extinguishing material, which vaporizes and quickly absorbs heat and releases it into the air. The present invention provides a barrier to reduce the temperature below the flame point, thereby achieving spontaneous extinguishing. Fire extinguishing microcapsules are useful as temperature-triggered cooling materials, fire prevention materials, and fire extinguishing materials. By combining with various materials and interfaces that do not corrode the microcapsule wall material, various temperature-lowering products can be produced. , fire prevention products, and fire extinguishing products. Wall material

[0067] In various embodiments, the polymeric material has a softening point of 30 to 100° C. before crosslinking; The softening point after crosslinking is 75 to 150°C.

[0068] In various embodiments, the softening point of the crosslinked polymeric material is between 100° C. and 150° C. .

[0069] In various embodiments, the softening point of the crosslinked polymeric material is between 120° C. and 150° C. .

[0070] In various embodiments, the polymeric material has a breathability of 700 mL / (cm 2 h ) or less 2 ·h).

[0071] In various embodiments, the polymeric material has a shrinkage of 5% or less after crosslinking.

[0072] In various embodiments, the polymeric material has a water absorption rate of 5% or less after crosslinking.

[0073] In various embodiments, the polymeric material has a tensile strength of 10 MPa or more after crosslinking.

[0074] The Chinese invention patent, with disclosure number CN112439154A, states that the capsule core is 98.2-9 8.8%, capsule shell 1.2-1.8%, and the core wall ratio is 55:1-82:1. The capsule size is 0.3 to 1.2 cm. 3 Perfluorohexanone fire extinguishing agent The company also discloses a capsule and its manufacturing method, and that perfluorohexanone is a liquid that easily vaporizes. Using this, we have developed a perfluorohexanone capsule with a large volume and an extremely high core-to-wall ratio. It is difficult to obtain a fire extinguishing agent microcapsule having a particle diameter of 20 to 400 μm. m, and various types of microcapsules can be produced by adjusting the stirring speed during production. It is possible to obtain microcapsules with particle sizes of 100 μm and the fine powder structure on the micron scale is suitable for use in paints, spray paints, etc. It is advantageous to add it to fire extinguishing agents such as rallies to manufacture fire extinguishing products, and the fire extinguishing agent microcapsules are It is uniformly distributed in the product and has a high core-wall ratio, and the outside temperature is higher than the extinguishing response temperature. After encountering an open flame environment, the wall material bursts, vaporizing and releasing the fire extinguishing material, lowering the temperature, preventing fire, and The polymer properties of the microcapsule wall material are the fire extinguishing agent microcapsules to achieve the purpose of fire extinguishing. The high strength of the crosslinked polymer material is necessary for the structural stability and excellent fire extinguishing performance of the micro It is advantageous for the molding and structural stability of the capsule, and the polymer material has low air permeability and low It has moisture permeability and low shrinkage, and its softening point before crosslinking is also advantageous for forming microcapsules. If the softening point before crosslinking is too high, it may result in loss of fire extinguishing material during the manufacturing process. If the value is too low, it may result in a decrease in the core-wall ratio and the embedding rate, which is disadvantageous for efficient fire extinguishing. The softening point of the polymer material after crosslinking is the only determinant of the bursting temperature of the microcapsules. Rather than being a constant factor, the rupture of microcapsules is a continuous and gradual process, The black capsules burst at 75°C and exert their functions of lowering temperature and / or preventing fire and / or extinguishing fire. That is, it bursts at 75°C and releases the contents of the extinguishing agent material. The softening point after crosslinking is directly related to the fire extinguishing response temperature of the microcapsules. If it is too low, it is not good for storage. Under normal circumstances, this may cause the extinguishing material to escape. If it is too high, The breathability of polymer materials depends on the density of the microcapsule wall material. However, if the air permeability is too high, the density of the wall material decreases, and the microcapsules This may lead to the vaporization and dissipation of the fire extinguishing material inside, which is unfavorable for long-term storage and reduces the fire extinguishing effect. The shrinkage rate of the polymer material is related to the dimensional stability of the microcapsules. If the particle size is too large or too small, it is detrimental to the structural stability of the microcapsules and may cause the microcapsules to burst. This may cause problems when compounding with other materials. The water absorption rate of polymer materials is This is related to the permeability of the capsule wall material. If the water absorption rate is too high, the humidity requirements for the storage environment will be high. Corrosion in a water environment can lead to leakage of the contents. They do not affect the properties of microcapsules individually, but rather act as complex elements, ultimately affecting the properties of the microcapsules. In general, it provides high stability, high sensitivity, and a low extinguishing response temperature under conventional environments. At least one change in the physical properties of the fire extinguishing agent microcapsules may result in difficulty in molding the microcapsules, poor storage stability, etc. As a non-limiting example, the selection of an appropriate polymeric material By improving the cross-linking degree of the polymer material and increasing the number of layers of the wall material, the fire extinguishing agent microcapsules One advantage is that it helps increase the fire extinguishing response temperature.

[0075] In various embodiments, the polymeric material may be a natural polymer, a semi-synthetic polymer, or a synthetic polymer. At least one type is selected from the children.

[0076] In various embodiments, the natural polymer is gelatin, alginate, gum arabic, Chitosan, chitooligosaccharide, xanthan gum, β-cyclodextrin, polyglutamic acid and at least one selected from guar gum and carrageenan.

[0077] In various embodiments, the semi-synthetic polymer is sodium carboxymethylcellulose. , Hydroxypropyl methylcellulose, Carboxymethylcellulose, Carboxymethyl Sodium guar gum, octenyl succinate esterified starch, and low methoxyphenyl At least one selected from among cutins.

[0078] In various embodiments, the synthetic polymer is a polymethacrylate, an epoxy resin, a poly Urethane, polyester resin, amino resin, phenol resin, acrylic resin, furan resin , resorcinol-formaldehyde resin, xylene-formaldehyde resin, unsaturated polyethylene ester, melamine-formaldehyde prepolymer, polyimide, and urea-formaldehyde The resin is at least one selected from the group consisting of aldehyde resins.

[0079] The polymeric material in the wall material is at least one of the natural polymers listed above, and preferably Preferably, the natural polymer is gelatin, at least one of the semi-synthetic polymers listed above. Preferably, the semi-synthetic polymer is sodium carboxymethylcellulose. At least one of the synthetic polymers listed above, preferably the synthetic polymer is Resorcinol-formaldehyde resin, the above-listed polymeric materials or combinations thereof The combination has the above-mentioned moderate softening point after curing and crosslinking, low air permeability, shrinkage rate, water absorption, and excellent It has sufficient mechanical strength to be used to encase wall materials in fire-extinguishing materials, and Depending on the film-forming properties of the above polymeric materials, conventional hardeners or crosslinkers corresponding to the polymers of the wall materials are used. It can be applied selectively, and the application amount is 0.1 to 10% based on the dry weight of the corresponding wall material. %.

[0080] In various embodiments, the polymer material of the inner wall material in contact with the core material is Gelatin, alginate, gum arabic, chitosan, chitosan oligosaccharide, xanthan gum , guar gum, carrageenan, polyglutamic acid, carboxymethylcellulose, Sodium carboxymethyl guar gum, β-cyclodextrin, and octenyl succinate and carboxylate-esterified starch.

[0081] In various embodiments, the polymeric material of the second layer of the wall material that contacts the inner layer of the wall material is , polymethacrylate, epoxy resin, polyurethane, amino resin, phenolic resin, Kryl resin, furan resin, resorcinol-formaldehyde resin, xylene-formaldehyde Hydro resin, unsaturated polyester, melamine-formaldehyde prepolymer, polyimide and urea-formaldehyde resin.

[0082] In various embodiments, the inner wall material and / or the second layer may be selected from the group consisting of salicylates, vegetative, and the like. At least one ultraviolet inhibitor selected from the group consisting of benzophenones and benzotriazoles is included. Yes.

[0083] In various embodiments, the amount of the UV inhibitor added is based on the dry weight of the wall material layer. It is 0.05~0.2%.

[0084] In various embodiments, the salicylate esters include benzyl salicylate, salicylic acid ester, Hexyl salicylate, Ethylhexyl salicylate, Phenyl salicylate, Octyl salicylate, At least one selected from dimethylcyclohexyl lithylate and isocetyl salicylate It is a seed.

[0085] In various embodiments, the benzophenones are 2-hydroxy-4-methoxybenzophenones. Zofenone, 2-hydroxy-4-n-octyloxybenzophenone, and 2-hydroxy At least one selected from the group consisting of alkoxy-4-dodealkoxybenzophenone.

[0086] In various embodiments, the benzotriazoles are UV-326, UV-327, UV-328, UV-329, UV-330, UV-331, UV-332, UV-333, UV-334, UV-335, UV-336, UV-337, UV-338, UV-339 ... At least one selected from the group consisting of V328, UV329, UV-P, and UV5411. .

[0087] In various embodiments, the wall material comprises nano silicon oxide and / or nano metal oxide. do.

[0088] In various embodiments, the wall material is a mixture of nano silicon dioxide and nano SiO2 in a weight ratio of 1:2.5-5. Contains metal oxides.

[0089] In various embodiments, the inner wall material of the wall material is a nano-oxide ketone having a weight ratio of 1:2.5 to 5. Includes silicon and nano-metal oxides.

[0090] In various embodiments, the total loading of the nano silica and nano metal oxide is The ratio is 0.05 to 0.2% of the dry mass.

[0091] In various embodiments, the nano metal oxide is selected from the group consisting of nano zinc oxide, nano titanium oxide, nano Selected from calcium oxide, nano manganese dioxide, nano nickel oxide, and nano copper oxide At least one type.

[0092] In various embodiments, the particle size of the nano silicon oxide is 1 to 1000 nm, preferably It is 20 to 100 nm.

[0093] In various embodiments, the nano metal oxide has a particle size of 1 to 1000 nm, preferably It is 20 to 100 nm.

[0094] During the formation, extinguishing and storage of fire extinguishing agent microcapsules, they burst normally due to high temperature response. In addition, the wall material may be damaged by external factors such as temperature, humidity, oxidation, light exposure, and vibration, and the contents may be destroyed. Also, a small amount of moisture may be present during the manufacturing process of the microcapsules. This causes the perfluorohexanone to partially hydrolyze and become hydrolyzed. One of the decomposition products, hydrofluoric acid, corrodes the wall components of the microcapsules and destroys the complete The structure of the black capsule is destroyed, causing the wall material to become incomplete and the contents to leak out, resulting in the digestive tract becoming inoperable. The material slowly evaporates, reducing the fire-extinguishing effect of the microcapsules. Research has shown that adding nano-silicon oxide and nano-metal oxide to the wall material solution can effectively extinguish fires. It was discovered that the storage stability of the capsules could be significantly improved. It is well known to those skilled in the art that fire extinguishing materials are easily hydrolyzed, and Hydrofluoric acid will be formed, further corroding the wall material, further leaking the extinguishing material and shortening its service life. The nano-metal oxides adsorbed the hydrolysis products of the fire-extinguishing materials and reacted with hydrofluoric acid. It reacts with the fluoride to form fluorides that are difficult to ionize, reducing the amount of hydrofluoric acid remaining and Avoiding erosion of the microcapsule wall and maintaining the inherent morphology of unruptured microcapsules This significantly improves the storage stability of the microcapsules and significantly extends the service life of the finished product. This allows for more frequent extinguishing of fires. [Paint base material]

[0095] In various embodiments, the coating base forms a continuous film having consistent strength. This can be done.

[0096] In various embodiments, the paint base is an epoxy resin emulsion, an alkyd resin emulsion, or a combination thereof. emulsion, polyurethane emulsion, vinyl acetate-ethylene copolymer emulsion, Methacrylic resin emulsion, fluororesin emulsion, acrylic resin emulsion, and and styrene-acrylate emulsion.

[0097] In environmentally friendly fireproof paints, the paint base material is not limited to fire extinguishing agent microcapsules, so Any substrate can be selected that can form a continuous film having a certain strength, and the epoxy resin can be used. Grease emulsion, alkyd resin emulsion, polyurethane emulsion, vinyl acetate Ethylene copolymer emulsion, methacrylic resin emulsion, acrylic resin emulsion Conventional coating bases such as styrene-acrylate emulsions are preferably used. The selected paint base is designed to prevent adverse effects on the extinguishing agent microcapsules in conventional environments. It is clear that the fire extinguishing agent should not be used in a fire extinguishing agent. When microcapsules are mixed with a paint base material and applied, a continuous film with a certain strength is formed. The extinguishing agent microcapsules do not adversely affect the film formation of the paint base material, and The environmentally friendly fireproof paint has good, high sensitivity, and environmentally friendly properties for cooling and / or fire prevention and / or extinguishing. Perform the fire function at least once.

[0098] In various embodiments, the environmentally friendly fire retardant coating has a smoldering time after application and drying. The time required for fire spread is 0 seconds, and there is no molten dripping.

[0099] In various embodiments, the environmentally friendly fireproof paint is applied and dried by blowing air at 60° C. The weight loss rate after leaving it in a dryer for 8 hours is less than 5%.

[0100] In various embodiments, the environmentally friendly fire-retardant paint comprises a mass fraction of fire-extinguishing microcapsules. The rate is 40-70%.

[0101] In environmentally friendly fireproof paint, the paint base material and the fire extinguishing agent microcapsules coexist stably, After brush application and drying at low temperature, the fire extinguishing agent microcapsules are dispersed in the paint and applied at a constant temperature. Under low temperatures (up to 75°C) or open flame conditions, the microcapsule wall material bursts, releasing the contained fire extinguishing material. The fire extinguishing material quickly absorbs heat and vaporizes, causing the temperature to drop and the fire to be extinguished spontaneously. It can be realized without smoldering, flame spreading or melting dripping, and has good fire prevention and extinguishing functions. The paint can reliably protect the base material on which it is applied, and can completely prevent other Since the microcapsule structure is not affected, the fireproof paint of the present invention can be used under normal conditions. It has a validity period of more than two years and is highly practical.

[0102] In various embodiments, the environmentally friendly fire retardant coating further comprises an auxiliary agent.

[0103] In various embodiments, the environmentally friendly fireproof paint has a paint base content of 25 to 55 %, the content of the extinguishing agent microcapsules is 40-70% by weight, and the content of the auxiliary agent is The amount is 5 to 15% by weight.

[0104] In various embodiments, the coagents include curing agents, antioxidants, dispersants, plasticizers, thickeners, Antifoaming agent, anti-settling agent, leveling agent, anti-mold and anti-algae agent, UV absorber, film-forming agent, pH adjustment Agents, emulsifiers, corrosion inhibitors, drying accelerators, anti-skinning agents, pigments, fillers, antioxidants, lubricants Agents, antifreeze agents, color separation prevention agents, surfactants, tension prevention agents, moisture absorbents, deodorants, silane cuts The additive is at least one selected from the group consisting of anti-pull agents, anti-static agents, water repellents and oil repellents.

[0105] The environmentally friendly fireproof paint is a paint base material that contains the fire extinguishing agent microcapsules, and is 60r / This can be achieved by stirring uniformly at a speed of 0.1 min or less.

[0106] When using environmentally friendly fireproof paint, dry it at 45℃ or less for at least 2 hours after application. A film is formed. [Paint composition]

[0107] A film-forming material; A solvent; and a fire extinguishing agent microcapsule, The extinguishing agent microcapsules have at least two layers of wall material, The wall material of the fire extinguishing agent microcapsules is capable of bursting at 75°C or higher; The fire extinguishing agent microcapsules vaporize after the wall material is ruptured to release the core material. Provided. [Fire extinguishing agent microcapsules]

[0108] In various embodiments, the extinguishing agent microcapsules are The weight loss after storage for 6 months is 2% or less. Each of the above-mentioned fire extinguishing agent microcapsules is preferably applied.

[0109] In various embodiments, the wall material comprises an inner wall material in contact with the core material, and and a contacting second ply wall material.

[0110] In various embodiments, the wall material comprises 0.05 to 0.2% purple pigment based on the dry weight of the wall material. The wall material may be an inner wall material and / or an outer wall material. The radiation prevention agent has been used in the paint industry and has a negative effect on the fire extinguishing agent microcapsule components. It is possible to use an ultraviolet ray inhibitor component known per se that does not affect the ultraviolet ray inhibitor. The types of agents are appropriately selected from the items of the ultraviolet protection agents described above.

[0111] In various embodiments, the wall material comprises 0.05 to 0.2% NaCl based on the dry weight of the wall material. The wall material includes nano-silicon oxide and nano-metal oxide. The wall material is an inner wall material and / or an outer wall material. It is also possible.

[0112] In various embodiments, the weight ratio of the nano silicon oxide to the nano metal oxide is 1:2.5 to 5. The types of the nano metal oxides are appropriately selected from the items of the nano metal oxides.

[0113] In various embodiments, the mass content of the extinguishing agent microcapsules in the coating composition is 40-70%. [Film forming material]

[0114] In various embodiments, the mass content of the film-forming material in the coating composition is 10 to 55%. It is.

[0115] In various embodiments, the film-forming material is a matrix-based material that has been used in the field of conventional paints. and a curing agent required depending on the matrix resin. A resin component capable of forming a coating film can be used. The type of the film-forming material is, for example, , epoxy resin, alkyd resin, polyurethane, vinyl acetate-ethylene copolymer, methacrylate At least one of the following may be mentioned: styrene resin, acrylic resin, and styrene-acrylate. The state of the film-forming material includes a powder state or an emulsion state. [solvent]

[0116] In various embodiments, the solvent comprises an organic solvent and / or water.

[0117] In various embodiments, the solvent is a solvent that has been used in the conventional coating field. The solvent composition can be known per se and does not conflict with the remaining ingredients in the paint. The type of the solvent includes an organic solvent and / or water. Examples of suitable esters include esters, ketones, alcohols, aliphatic hydrocarbons, and aromatic hydrocarbons. Specifically, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, etc. esters; ketones such as methyl ethyl ketone and methyl isobutyl ketone; methanol, ethanol Alcohols such as ethanol, isopropanol, methoxypropanol, and ethoxypropanol n-Pentane, isopentane, n-Hexane, isohexane, cyclohexane, n - Aliphatic hydrocarbons such as heptane, isoheptane, 2,2,4-trimethylpentane; Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, and diaromatic hydrocarbons such as toluene. Organic solvents and water are preferred. [others]

[0118] In various embodiments, the coating composition further comprises a curing agent for curing the film-forming material. include.

[0119] In various embodiments, the film-forming material comprises an amino resin, a polyisocyanate compound, and and a curing agent selected from a blocked polyisocyanate compound. The types of agents include, for example, decanedicarboxylic acid, dodecanedicarboxylic acid, sebacic acid, etc. Acid hardening of aliphatic polycarboxylic acids, acid anhydrides of polycarboxylic acids, acid group-containing acrylic resins, etc. Agent: hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate Urea acid ester compounds of isocyanate compounds such as cyanate with ε-caprolactam, Blocked isocyanate hardeners blocked with blocking agents such as methyl ethyl ketone oxime curing agent, self-blocking type isocyanate curing agent with uretdione bond in the molecule; Aromatic polyamines, polyaminoamides, ketimines, alicyclic diamines, aromatic diamines, imidazolidins Amine hardeners such as azoles, dicyandiamides, polyamides, and β-hydroxyalkylamides hardeners; phenol resin hardeners, etc.

[0120] In various embodiments, the coating composition further comprises an auxiliary agent.

[0121] In various embodiments, the auxiliary agent is a coating agent that has been used in the conventional coating field, Auxiliary additives may be applied that are compatible with the remaining components of the coating used. The types of additives include, for example, antioxidants, dispersants, plasticizers, thickeners, defoamers, anti-settling agents, Leveling agent, anti-mold and anti-algae agent, UV absorber, film-forming agent, pH adjuster, emulsifier, corrosion prevention Agents, desiccants, anti-skinning agents, pigments, fillers, antioxidants, lubricants, antifreezing agents, color separation prevention agents Antistatic agents, surfactants, tension inhibitors, moisture absorbents, deodorants, silane coupling agents, antistatic agents, At least one of a water repellent and an oil repellent is included.

[0122] Antioxidants are used to improve the UV protection, yellowing resistance and oxidation properties of coatings. , for example, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, N-phenyl N-phenyl-α-aniline, N-phenyl-β-naphthylamine, N-phenyl-N'-isopropanol N-propyl-p-phenylenediamine, and N-N'-diphenyl-p-phenylenediamine The dispersant exerts a dispersing effect and disperses each component of the paint. It is used to thoroughly disperse, for example, polycarboxylic acid and polyacrylic acid. At least one selected from the group consisting of the above-mentioned plasticizers is used. The plasticizer reduces the hardness of the coating film and increases the ductility of the coating film. Used to improve the appearance of skin, for example, petrolatum, polybutene, silicone oil, epoxy Soybean oil, dioctyl sebacate, dioctyl adipate, hydroxy vinyl chloride At least one of vinyl acetate copolymers and chlorinated paraffins. Viscosity agents are used to prevent paint from dripping or scattering. For example, polyacrylic Acrylic acid thickener, polyurethane thickener, carboxymethylcellulose, hydroxypropyl Pyrmethylcellulose, Hydroxyethylcellulose, and Hydroxyethylmethylcellulose The antifoaming agent is at least one of the following: , to avoid the adverse effects on appearance and performance due to foaming, e.g., hexametha Sodium phosphate, sodium polyphosphate, potassium tripolyphosphate, and potassium pyrophosphate The anti-settling agent is at least one selected from the group consisting of thixotropic and anti-settling agents. It is used to impart properties and improve viscosity, for example, organic bentonite, amide modified Hydrogenated castor oil, attapulgite, polyamide wax powder, and fumed silica sachets The leveling agent is used to form a smooth and uniform coating film during film formation. For example, polyether modified silicone, polyester modified hydroxyl group-containing Silicone, isocyanate-modified silicone, polyacrylate, and polymethacrylic acid The antifungal and antialgal agent is a compound that inhibits the growth of microorganisms. For example, pentachlorophenol and its sodium salt, tetrachlorophenol, o-phenylphenol, 8-hydroxyquinoline, salicylic acid thiuram disulfide, tetramethylthiuram disulfide, and tetramethylthiuram disulfide. Absorbers absorb and block harmful radiation from high molecular weight polymers, thereby extending the life of the coating. For example, the salicylates, benzophenones, The film forming aid may be at least one of a low It is used to support good deposition of deposition materials under warm conditions, e.g., propylene glycol. , turpentine oil, polyethylene glycol, 2,2,4-trimethyl-1,3-pentane Diol monoisobutyrate, and dipropylene glycol butyl ether The pH adjuster is used to adjust the pH of the emulsion or liquid paint. For example, 2-amino-2-methyl-1-propanol, N-methylethanol ethanolamine, dimethylethanolamine, monoethanolamine, diethanolamine, Triethanolamine, butylethanolamine, sodium hydroxide, potassium hydroxide, and aqueous ammonia. The emulsifiers used are alkyl sulfonic acid, alkyl benzene sulfonic acid, alkyl lysine, Sodium salts, ammonium salts of carboxylic acids, polyoxyethylene phenyl ethers, polyoxyethylene Diethylene nonylphenyl ether, polyoxyethylene monolaurate, polyoxyethylene Polyoxyethylene monostearate, polyoxyethylene monooleate, sorbitol At least one of sorbitan monolaurate and sorbitan monostearate Corrosion inhibitors prevent or mitigate the rust phenomenon that occurs at the contact point between metal and paint. They are used to prepare, for example, molybdates, tungstates, phosphates, basic sulfides, etc. Sulfonates, zinc salts of organic nitrides, diphenylamine, dimethylethanolamine, and triphenylamine. The drying accelerator is at least one of the following: Used to shorten drying time and improve coating strength, e.g., cobalt naphthenate, Manganese naphthenate, zinc naphthenate, lead naphthenate, calcium naphthenate, naphthene Anti-skinning agents include at least one of cerium ricinoleate, zinc ricinoleate, and zinc ricinoleate. is used to inhibit the paint from oxidizing and gelling and forming a skin, e.g. Methyl ethyl ketone oxime, butyraldehyde oxime, and hexanone oxime The pigment may be at least one of the following: Used to distinguish between overcoats and overcoats, e.g. titania, barite, calcium carbonate CI Pigment Yellow 42, CI Pigment Blue 15, CI Pigment Blue -15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:4, CI Pigment CI Pigment Red 49:1, CI Pigment Red 57:1, Iron Red, Iron Yellow The filler may be at least one of the following: cellulose, cellulose acetate, and carbon black. It is used to reduce the wear and tear of coatings and to improve their abrasion resistance, scratch resistance and corrosion resistance. Lumina, zinc oxide, carbon black, graphite, calcium carbonate, kaolin, zinc oxide and At least one of the following may be used: talc; other antioxidants, lubricants, etc., without limitation. , antifreeze agent, color separation prevention agent, surfactant, tension prevention agent, moisture absorbent, deodorant, silane cup Ring agents, antistatic agents, water repellents, oil repellents, etc. are used. The purpose is to change at least one property of the paint, and the selective use of auxiliaries and The amount used should be in accordance with what is known in the art and should not adversely affect the fire extinguishing agent microcapsules. It shouldn't be given.

[0123] In various embodiments, the coating is prepared by dispersing the film-forming material in a solvent and then adding fire extinguishing agent microcapsules. Add the cell slowly and mix uniformly at a speed of 60 r / min or less to coat. The drying temperature of the coating is 45℃ or less.

[0124] A coating composition comprising a film-forming substance, a solvent, and a fire-extinguishing agent microcapsule, Kurocapsule has good compatibility with film-forming substances and solvents, and does not have any adverse effects after mixing. The fire extinguishing agent microcapsules are uniformly distributed, and the coating film formed after coating and drying is The extinguishing agent microcapsules have a high core-wall ratio and are excellent in fire prevention and / or extinguishing effects. When the outside temperature is higher than the fire extinguishing response temperature or when it encounters an open flame environment, the wall material The microcapsules burst and vaporize the extinguishing agent, which then quickly absorbs the heat and causes the fire to fall. A coating composition is provided that is capable of providing heat, fire protection, and fire extinguishing properties. [Powder paint]

[0125] The composition includes a film-forming component as a resin for forming a coating film, and further includes fire extinguishing agent microcapsules; The extinguishing agent microcapsules have at least two layers of wall material, The wall material of the extinguishing agent microcapsules is heated to 100° C. or higher, preferably 120° C. to 150° C. Rupture, The extinguishing agent microcapsules vaporize the extinguishing material in the microcapsule core after the wall material is ruptured. A powder coating is provided that releases the [Film forming components]

[0126] In various embodiments, the film-forming resin is a film-forming component that is cured by ultraviolet light. It forms a film.

[0127] In various embodiments, the film forming components include a photocurable resin and a photoinitiator.

[0128] In various embodiments, the photocurable resin is an unsaturated polyacrylate, methacrylate, modified polyester, mixture of unsaturated polyester and acrylate, acrylate graft Polyester, Acrylated Polyacrylate, Epoxy Resin, Epoxy Acrylic Resin, urethane acrylate, and hyperbranched polyester acrylic resin At least one of the following is possible:

[0129] In various embodiments, the photoinitiator may be selected from the group consisting of a photocurable resin, a photoinitiator ... A photoinitiator is selected that matches the

[0130] In various embodiments, the photoinitiator is Irgacure TM 184, 2959(C IBA), Irgacure TM 819, Irgacure TM 651, and Lucer in TPO3.

[0131] The types of photocurable resins include UVECOATR1000 and UVEC OATR1016, UVECOATR1043, UVECOATR2100, UVECOA TR2200, UVECOATR2200, UVECOATR2300, UVECOATR3 000, UVECOATR3001, UVECOATR3002, UVECOATR300 3. UVECOATR3005 is melted at 90℃ or higher and leveled. U is a material made by melting and leveling terephthalate and unsaturated polyester fumarate at 100°C or less. The combination of UracrossP3125 and UracrossP3307 is below 100℃. Melted and leveled with UracrossP3125 and UracrossP38 The combination of 98 and melting at 120℃ or less and leveling, Deco-Sai's VES TAGONREP-UV100, VESTAGONREP-UV300, VESTAGON REP-UV500 is melted at 115℃ or less and leveled.

[0132] In various embodiments, the film forming components include the photocurable resin, a photoinitiator and a compatible coagent. The auxiliary agent is selected from the above auxiliary agents. The criterion was that it did not affect the properties of the microcapsules.

[0133] In various embodiments, the paint powder is a coating material having a temperature that is greater than or equal to the extinguishing response temperature of the extinguishing agent microcapsule wall material. The film-forming component is melted and leveled at a temperature below the melting and leveling temperature of the film-forming component. [Fire extinguishing agent microcapsules]

[0134] In various embodiments, the extinguishing agent microcapsules are in the form of a powder, and / or Or it is present in a preserved state in a storage solvent.

[0135] In various embodiments, the extinguishing agent microcapsules are stored in a storage solvent. and has a weight loss of less than 2% over 6 months.

[0136] In various embodiments, the storage solvent is water and / or ethanol.

[0137] In addition, all of the above items of the fire extinguishing agent microcapsules and their manufacturing process are based on this powder coating. The selection and limitation of the materials and manufacturing process of the wall material of the fire extinguishing agent microcapsule, e.g. For example, by selecting appropriate polymer materials, improving the degree of cross-linking of polymer materials, and increasing the number of layers of wall materials, This contributes to increasing the fire extinguishing response temperature of the agent microcapsules. Preferably, it is possible to obtain a fire extinguishing agent microcapsule whose wall material bursts at 120°C to 150°C. Then, the film-forming resin and the fire extinguishing agent microcapsules are mixed, and then the fire extinguishing agent microcapsule wall material is The powder coating is melted at a temperature of a film-forming resin that can melt and flow at a temperature equal to or lower than the extinguishing response temperature of the powder coating. A coating film can be formed by UV curing, and the fire extinguishing agent microcapsules in the resulting coating film The structure of the fire extinguishing agent is completely maintained, there is no leakage of the fire extinguishing agent, and the coating is When exposed to temperatures above the cell's fire extinguishing response temperature or to direct flame, the microcapsule wall material ruptures. The fire extinguishing material in the contents is vaporized and released, thereby lowering the temperature and / or preventing and / or extinguishing the fire. In addition, each component of the film-forming ingredients in the powder coating must be compatible with each other. The photoresist must be compatible with the photoinitiator, and the photoresist or photoinitiator The temperature is not limited to the examples described in this application, and may be any temperature higher than the burst temperature of the fire extinguishing agent microcapsules. If the film-forming component can form a coating film at a temperature below the above, it can be applied to the powder coating material. Can be used.

[0138] The use of said powder coating in the manufacture of a temperature-reducing and / or fire-retardant and / or fire-extinguishing coating is provided. .

[0139] In various embodiments, the paint powder is a coating material having a temperature that is greater than or equal to the extinguishing response temperature of the extinguishing agent microcapsule wall material. The film is melted and leveled at a temperature equal to or higher than the melting temperature of the film-forming component, and then cured with ultraviolet light. Produce temperature-reducing and / or fire-retardant and / or fire-extinguishing coatings. [Paint film]

[0140] Specifically, the continuous and / or non-conductive layer is formed by drying on the surface of the base, whether or not it is applied thereto. A non-continuous thin coating is provided, the coating including a fire extinguishing material.

[0141] In various embodiments, the coating is formed of the environmentally friendly fire retardant paint; and / or , formed from the coating composition, and / or formed from the powder coating.

[0142] In various embodiments, the coating is exposed to temperatures of 75° C. or higher and / or a fire environment. The fire extinguishing material is vaporized and released to achieve the purpose of lowering temperature and / or preventing and / or extinguishing the fire. This can be done.

[0143] In various embodiments, the fire extinguishing material is perfluorohexanone, perfluorohexanone, San, perfluoroheptane, perfluorooctane, tetrafluorodibromoethane, and trifluorotrichloroethane.

[0144] In various embodiments, the fire extinguishing material is perfluorohexanone.

[0145] In various embodiments, the fire extinguishing material is encased in at least two layers of wall material and is stabilized in a coating. The wall material is destructive when exposed to temperatures above 75°C and / or direct flame. To split.

[0146] In various embodiments, the wall material comprises nano silicon oxide and / or nano metal oxide. do.

[0147] In various embodiments, the wall material is a mixture of nano silicon dioxide and nano SiO2 in a weight ratio of 1:2.5-5. Contains a metal oxide.

[0148] In various embodiments, the wall material comprises a polymeric material.

[0149] In various embodiments, the polymeric material may be a natural polymer, a semi-synthetic polymer, or a synthetic polymer. At least one of the natural polymers, semi-synthetic polymers and synthetic polymers is selected from the group consisting of For each term, the corresponding terms above will be used as appropriate.

[0150] In various embodiments, the wall material comprises salicylates, benzophenones, and The ultraviolet ray inhibitor contains at least one ultraviolet ray inhibitor selected from the group consisting of benzotriazoles. For each item of the ultraviolet protection agent, the items corresponding to the ultraviolet protection agent are used appropriately.

[0151] In addition, the fire extinguishing material is present in the coating film as the core material of the fire extinguishing agent microcapsules. The above-mentioned items of the fire extinguishing agent microcapsules and the items of the method for producing the same are preferably applied to the present coating film. Apparently, the coating has a low fire extinguishing response temperature of 75°C, and the coating temperature If the temperature rises above 75°C or if the product is exposed to an open flame, the fire extinguishing material in the coating will evaporate. It absorbs and releases heat from the environment, instantly lowers the surrounding temperature, and automatically cools down and prevents fires. By lowering the temperature of the heat point or ignition point below the flame point temperature, spontaneous fire extinguishing is achieved. The coating film has a simple structure and is more durable than the conventional flame-retardant coating film after curing. It does not prevent the spread of ignition points, but rather extinguishes the fire in an ignition environment caused by a rise in temperature. It has predictability, significantly improves the convenience of fire prevention and extinguishing, and expands the range of applications, resulting in higher profits. The difference is that they have utility value. [Painted items]

[0152] A substrate; On the surface of the substrate A coating film formed from the environmentally friendly fireproof paint, and / or A coating film formed from the coating composition, and / or A coating film formed from the powder coating material, and / or and the coating.

[0153] The coated object is provided with the environmentally friendly fireproof paint and / or paint composition, and / or powder paint and and / or the coating film, the corresponding items above apply as appropriate. [Base material]

[0154] In various embodiments, the substrate may optionally include: Wood-based substrates including wood boards, wood profiles, wood equipment, wood structural members, etc.; Iron products, stainless steel products, aluminum products, copper products, gold products, silver products, zinc products, tin products, etc. A metal-based substrate comprising: Cementitious substrates including cement, lime, gypsum, etc.; Carriers, wafer plates, wafer tanks, batteries, antennas, transistors, etc. Substrates for child devices; Natural rubber, isoprene rubber, butadiene rubber, chloroprene rubber, styrene butadiene rubber Rubber, hydrogenated butadiene rubber, butyl rubber, nitrile rubber, ternary ethylene propylene rubber, Rubber-based base materials including silicone rubber, fluororubber, silicon rubber, kneaded rubber, etc.; Natural fibers, synthetic fibers and woven or nonwoven fabrics containing them, glass, ceramics, paper, fiberboard, wallboard etc; Contains at least one of the following:

[0155] In various embodiments, the coating is formed directly on the surface of the substrate, either continuously or discontinuously. and / or a separation layer is formed on the surface of the substrate, either continuously or discontinuously. is formed.

[0156] In various embodiments, the separation layer is disposed continuously or discontinuously on the surface of the substrate. can be.

[0157] In various embodiments, the separating layer is made of natural polymers, semi-synthetic polymers, and synthetic polymers. The layer is formed of at least one of the above.

[0158] In various embodiments, the natural polymer is gelatin, alginate, gum arabic, Chitosan, chitooligosaccharide, xanthan gum, β-cyclodextrin, polyglutamic acid , guar gum, and carrageenan.

[0159] In various embodiments, the semi-synthetic polymer is sodium carboxymethylcellulose. , Hydroxypropyl methylcellulose, Carboxymethylcellulose, Carboxymethyl Sodium guar gum, octenyl succinate esterified starch, and low methoxyphenyl At least one selected from among cutins.

[0160] In various embodiments, the synthetic polymer is a polymethacrylate, an epoxy resin, a poly Urethane, polyester resin, amino resin, phenol resin, acrylic resin, furan resin , resorcinol-formaldehyde resin, xylene-formaldehyde resin, unsaturated polyethylene ester, melamine-formaldehyde prepolymer, polyimide, and urea-formaldehyde The resin is at least one selected from the group consisting of aldehyde resins.

[0161] A substrate for providing a coated article, comprising the environmentally friendly fireproof paint and coating composition described herein. Any substrate for applying a powder coating or coating film may be used. and powder coatings or paint films, particularly preferably in hostile environments such as high temperature and / or open flame environments. It may be applied appropriately to articles that may be exposed to the environment, and the coated article may be exposed to high temperatures and / or open flames. When exposed to the environment, the coating on the coated article heats up and vaporizes, releasing the fire-extinguishing material, which It quickly absorbs heat and lowers the local temperature, which allows the body to cool down and digest food spontaneously. The purpose is to minimize damage caused by high temperatures or open flames on the substrate. It does not cause any other pollution, has a very high level of environmental protection, is safe, and has high responsiveness. It has utility value.

[0162] In various embodiments, a coating is formed on the surface of a substrate, and then a polymeric material is sprayed onto the surface of the coating. After the paint is applied, a specific polymer is applied to the surface of the paint to form a protective film. By spraying the substance to form a protective film, it acts as a barrier against air and moisture, prevents aging, and has an acid alkali. It has mist prevention, UV protection, and maintains moderate humidity while providing self-repairing properties under certain conditions. By changing the composition of the polymer solution and the thickness of the protective film, the degree of adhesion varies. The fire extinguishing response temperature of the coating can be increased, so that the coating can meet the requirements of various use environments. Can be applied to cooling and / or fire protection and / or fire extinguishing trigger conditions, providing high flexibility of application It can be done.

[0163] The polymeric material is generally hydrophobic and film-forming, and has an appropriate softening point and glass temperature. Polyester, polyurethane, phenolic resin, urea-formaldehyde resin, Polyurea resin, polymeric silicon, naturally derived polymer, acrylic resin, epoxy resin, etc. The thickness of the protective film is 10 to 500 μm, preferably 50 to 200 μm. m. The present invention will be described in detail below. Example 1

[0164] The environmentally friendly fire retardant paint has a manufacturing method including the following steps: 100 g of 10% gelatin solution was prepared as a wall material solution, and 0.002 g of nanosilica powder was added. 0.01 g of nano titania powder was added and stirred at 60°C to mix and disperse uniformly. Add 80 g of fluorohexanone and stir at 25°C and 450 rpm for 40 min. Then, 3 mL of 10% by weight glutaraldehyde solution was slowly added and the mixture was stirred for 30 minutes. After filtering, washing and isolating, about 80 g of pre-hardened microcapsules were obtained. 80g of pre-cured microcapsules were added to 60g of melamine-formaldehyde pre-polymerized solution. After stirring for 1 hour, the mixture was filtered, washed, and dried at low temperature to obtain the fire extinguishing agent microcapsule powder. The microscope image is shown in Figure 1, and the microscope image after the explosion at high temperature is shown in Figure 2. Add 70g of fire extinguishing agent microcapsule powder slowly to 20g of polyurethane solution, and then mix for 30 minutes. Stir at 300rpm to disperse evenly, add 100g of water-based latex paint, and mix for 30r. The mixture was stirred uniformly at 1000 ml / min to obtain a fireproof paint. The micrographs of the paint are shown in Figure 3. The micrographs of the paint are shown in Figures 4 and 5. The above fireproof paint was applied and dried as shown in the figure. Also, the fire-extinguishing paint was applied to the surface of the substrate and dried. Then, as shown in Figure 6, a 50 μm polyurea protective layer was applied to the surface of the fire extinguishing coating. Then dried. Example 2

[0165] A fire-retardant paint, the manufacturing method of which includes the following steps: 100 g of gelatin solution with a mass percentage of 15% was prepared as a wall material solution, and nanosilica powder was added. Add 0.004g and 0.016g of nano calcium dioxide powder, and stir at 20°C to homogenize. 75 g of perfluorohexanone was added and the mixture was stirred at 15°C and 900 rpm. The mixture was emulsified by stirring at a speed of n for 1 h to form a microcapsule emulsion, and the mass percentage was Slowly add 2 mL of 10% glutaraldehyde solution and stir for 45 min to crosslink. After filtering, washing and isolating, about 82 g of pre-hardened microcapsules were obtained. 80 g of pre-cured microcapsules were immersed in 50 g of melamine-formaldehyde pre-polymerized solution. Add the mixture, stir for 1 hour, filter, wash, and dry at low temperature to obtain the fire extinguishing agent microcapsule powder. I got the end. 70g of fire extinguishing agent microcapsule powder was added to 20g of polyurethane solution and rotated at 30r / min. Stir to disperse evenly, add 100g of water-based latex paint, and mix at 30 rpm. The mixture was stirred uniformly to obtain a fireproof paint. The micrograph of the paint is shown in Figure 7. After coating and drying, a 50 μm polyurea protective layer was further coated on the surface of the coating and dried. . Verification example 1

[0166] The dried coating sample obtained in Example 1 without the polyurea protective layer was heated at room temperature (temperature 25 The weight loss of the fireproof paint was examined by leaving it at room temperature at ℃±2℃ and relative humidity of 60%±5%, and the results are shown in Figure 8. As shown in Figure 8, the mass change in the previous period was due to the evaporation of the small amount of residual moisture in the paint and the micro This is due to capsule rupture, and due to loss of moisture, weight loss occurs in the later stages, especially after 20 days. The loss of the fire extinguishing agent was slow, indicating that the extinguishing agent microcapsules were stable in the paint. After being left in the room temperature for 2 months, the remaining dry weight was approximately 95%, indicating good storage stability. It was shown that the extinguishing agent microcapsules do not continuously burst even when left standing for an extended period of time. , which has been shown to be advantageous for the retention of fire-extinguishing materials in the microcapsules and the retention of fire-extinguishing performance. Verification example 2

[0167] The fire extinguishing paint (dry) obtained in Example 1 of the present invention was subjected to thermogravimetric analysis, and the results are shown in FIG. A thermogravimetric analysis curve was obtained, in which the extinguishing response temperature was about 75°C, but exceeded 80°C. At 40-75°C, the release of fire extinguishing material becomes more noticeable. At 40-75°C, a small amount of the microcapsules absorbs heat. When it reaches 80℃, the microcapsule walls burst and the contents are significantly When the fire extinguishing material leaks, it quickly vaporizes and is released, so the release of the fire extinguishing material in the paint is rapid. From Figure 9, the dry weight of the fire extinguishing paint at temperatures between about 99°C and about 163°C The loss was also found to be 28.85%, which means that all the extinguishing agent microcapsules were lost during one heating process. It was shown that none of the specimens exploded, suggesting that the fire-extinguishing performance of the fire-extinguishing paint is reproducible. In addition, the thermogravimetric analysis was performed by program heating, and the entire microcapsule did not burst. Therefore, the mass lost is not equal to the mass of perfluorohexanone actually contained. Verification example 3

[0168] The flame is about 800℃, the temperature is measured with an infrared thermometer, and the time when the fire is extinguished is recorded with a stopwatch. The distance was measured, the sheet was fixed to the surface of a pressed steel plate, and the sheet was placed 1.5 cm away from the outer flame of the flame. The sheet is placed facing down on the floor, and the time it takes to extinguish the fire and the temperature difference before and after the fire is extinguished are measured. and fire protection and / or extinguishing sheets, which characterize the fire protection and / or extinguishing effect by temperature difference, e.g. For example, a method for verifying the fire-preventing and / or fire-extinguishing properties of a fire-extinguishing coating is provided. Based on the above method, the fire extinguishing time of the coating films obtained in Examples 1 and 2 was verified. To facilitate ignition testing, double-sided adhesive tape was attached to the back of the coating film, and the coating film was placed in the outer flame of a flame. The test equipment was placed about 1.5 cm from the ground, and the flame size was as shown in Figures 10 to 12. The temperature was kept constant at 200°C, the coating film was attached to a pressed steel plate, and the flame temperature was set to about 800°C. Three points were selected to test the fire extinguishing response time, and the results are shown in Table 1. Table 1 Extinguishing time TIFF0007644319000001.tif65136Note: " / " means extinguishing was not completed within 7 seconds. As can be seen from Table 1, the paints produced in Examples 1 and 2 of the present application had a viscosity of 3s or more. The fire can be extinguished within 4 to 5 times at the same test point without melting or dripping on the coating film. It is possible to extinguish the fire, and if it encounters an open flame, the surface layer of the microcapsules in the paint component will soften and The fire extinguishing function is automatically triggered and the extinguishing agent is released. The addition of nano-oxide in microcapsules rapidly adsorbs the hydrolysis products of fire-extinguishing materials, This contributes to reducing the residual hydrolysis products and the addition of water to the unruptured microcapsule walls. It avoids the erosion of decomposition products, maintains the inherent morphology of the microcapsules, and enhances the reusability of the coating material. This has significantly expanded the range of applications for fire extinguishing microcapsules. Example 3

[0169] The environmentally friendly fire retardant paint has a manufacturing method including the following steps: Gelatin 12.5g, Hexyl Salicylate 0.01g, Nano Silica Powder 0.015g, Na Prepare 100 g of a wall material solution containing 0.005 g of zinc oxide powder, and stir at 60°C to homogenize. 90 g of perfluorohexanone was added and the mixture was stirred at 35°C and 2000 rpm. The mixture was stirred at a speed of 1000 x 1000 mm for 60 min, and gelatin was added to the wall and perfluorohexanone was added to the embedded matrix. A microcapsule emulsion was formed. 3 ml of glutaraldehyde with a mass percentage of 20% After the reaction was completed, the microcapsules were filtered and deionized. The mixture was washed twice with deionized water to obtain 90 g of a microcapsule pre-product. 90g of the microcapsule preliminary product was dissolved in resorcinol-formaldehyde resin prepolymer. Add to 100g of the liquid, stir for 2 hours, then filter, wash, and dry at low temperature to obtain a fire extinguishing agent micro-cathode. The fire extinguishing agent microcapsule powder was obtained in an amount of about 85 g. Fire extinguishing agent microcapsule powder 85g melamine-formaldehyde resin emulsion 90 g, stirred at 30 rpm for 10 min, poured into a mold, dried and molded at 40°C, and The surface is blade-coated with approximately 50 μm of polyurea, dried at 40°C, and a coating film approximately 1 mm thick is formed. obtained. Verification example 4

[0170] Based on the method described in Verification Example 3, the extinguishing time and temperature before and after extinguishing of the coating film obtained in Example 3 Double-sided adhesive tape was attached to the back of the coating to verify the change and to facilitate ignition testing. The back surface temperature of the coating before and after extinguishing was measured using a Bosch GIS 500 infrared thermometer. The coating was placed approximately 1.5 cm from the outer flame of the flame and the sample was placed at a distance of 0 cm. The flame was attached to a press steel plate and the flame temperature was set to about 800°C. The equipment was 500 It can only measure within ℃ and requires a certain distance from the sample, so it is difficult to measure the temperature of the sample or It can only test the temperature 10cm away from the flame, and the hotter areas will show lower readings. A comparison was also made using the Russian PYCINTEX fire extinguishing sticker. Ten sites were selected for testing on the samples of this patent, and the results are shown in Table 2. Table 2. Firefighting time and temperature change TIFF0007644319000002.tif104149 As can be seen from Table 2, all of the coating samples of the present application were able to extinguish the fire within 3 seconds. During the fire extinguishing process, the temperature rises slightly, never exceeding 40°C, and the coating can quickly extinguish the fire. The temperature of the extinguishing part rises slightly, and the coating film is excellent in spontaneous extinguishing performance. The comparative analysis shows that the Russian PYCINT The EX fire extinguishing sticker was not able to spontaneously extinguish the fire, and the sample ignited after 7 seconds. The temperature rose to 130°C, and the fire prevention and extinguishing measures were unable to function. Example 4

[0171] A powder coating is provided that contains fire-extinguishing agent microcapsules and a film-forming component. Fire extinguishing agent microcapsules Gelatin 15g, Sodium Carboxymethylcellulose 5g, Nanosilica Powder 0.01 100 g of wall material aqueous solution containing 0.5 g of cellulose acetate and 0.005 g of nano calcium dioxide powder was prepared. The mixture was stirred at 30°C to uniformly mix and disperse. 90 g of perfluorohexanone was added. The mixture was stirred at 15°C and 2400 rpm for 1 hour to obtain a microcapsule emulsion. Then, 3 mL of 15% formaldehyde solution was slowly added and the mixture was cooled to 60°C. Stir for 0 min to crosslink, filter, wash, and separate the pre-hardened microcapsules. 100 g of the pre-cured microcapsules were dissolved in resorcinol-formaldehyde resin. Slowly add 40 g of 10% formaldehyde solution, and then add 15% formaldehyde solution. Add 5 mL of the liquid, stir for 1 h, filter, wash, and dry at low temperature to obtain microcapsule powder. 80 g of the microcapsule powder was dissolved in 60 ml of 1% sodium carboxymethylcellulose solution. Slowly add to 100g of granules, stir for 1 hour, filter, wash, and dry at low temperature to obtain a particle size of approximately 50 to 80μ. A microcapsule powder of m was obtained. Film forming components 70%UracrossP3125, 20%UracrossP3307, 5%Luce rin TPO3(Ciba Geigy), 3.5%Irgacure TM 651, 1.5% Resiflow P67 (Estron) was melt extruded at 83℃ and cooled in air. It was crushed, 0.2% alumina C6 was added, crushed and sieved through a 150 mesh sieve. The fire-extinguishing agent microcapsules and the film-forming component were mixed in a ratio of 1:5 to obtain a powder coating material. The powder coating was sprayed onto the preheated surface of the substrate using a corona discharge lance and then heated in a convection oven for 10 Melt at 0℃, melt at 95℃ for 5 minutes, level, and then use a 600WV lamp (40 The film was cured by irradiating it with radiation (0-420 nm) at a speed of 1 cm / s for 20 s, and the thickness was approximately A coating thickness of 0.6 mm was obtained. Verification example 5

[0172] The fire extinguishing time and temperature change before and after extinguishing of the coating film obtained in Example 4 were measured using the method of Verification Example 3. We conducted a verification test on 10 selected areas of the sample of this patent, and the results are shown below. Shown in 3. Table 3. Extinguishing time and temperature change TIFF0007644319000003.tif102137As can be seen from Table 3, perfluorohexanone was coated with three layers of wall material to create a fire extinguishing agent micro. After capsules are formed, film-forming ingredients are mixed to make powder coatings, and the coating film after hardening is The extinguishing time is less than 5 seconds, and the temperature rises slightly to less than 60°C during the extinguishing process. The photocurable coating film can quickly extinguish an open flame, has excellent spontaneous extinguishing properties, and has good heat transfer properties. It has low efficiency, which is advantageous for protecting the object on which the coating is applied. Russia's PYCINTEX fire extinguishing The stickers were unable to extinguish the fire spontaneously and therefore failed to fulfill their role of fire prevention and extinguishing. Example 5

[0173] No nano silica powder was added during the pre-curing of the microcapsules, and nano calcium dioxide powder was used. The same procedure as in Example 2 was followed except that 0.02 g of the glycerol was added. The fire retardant paint coating was prepared according to the following parameters and steps. Example 6

[0174] No nano-calcium dioxide powder was added during the pre-hardening of the microcapsules, and nano-silica The same procedure as in Example 2 was followed, except that 0.02 g of the base powder was added. The fire retardant paint coating was produced with the same other parameters and steps. Example 7

[0175] Nano calcium dioxide powder and nano silicon dioxide powder are added during the pre-hardening of the microcapsules. Except for not adding, the same method as in Example 2 was followed, and other parameters were the same as in Example 2. The fireproof paint coating was produced in the following steps: Example 8

[0176] The weight ratio of nano silica powder and nano calcium dioxide powder during the pre-hardening of the microcapsules Except for the mixing ratio being different from that of Example 2, the fireproof paint coating was prepared in substantially the same manner as in Example 2. A series of coatings were obtained based on the weight ratio of nano silica powder to nano calcium dioxide powder, The weight ratios are 2:1, 1:1, 1:2, 5:1, 7:1, and 9:1, respectively. Verification example 6

[0177] The coating films obtained in Examples 5 to 8 (Table 5: Sample 5, Sample 6, Sample 7, Sample Group 8) The extinguishing time of the above is verified by the method of verification example 3, and 1 to 3 points are selected for each sample and the test is repeated. The results are shown in Table 4. Table 4 Extinguishing time TIFF0007644319000004.tif107120 Note: " / " means that the fire was not extinguished within 7 seconds, and " / / " means that the previous result was " / " means that no testing was conducted this time. In Table 4, many parts of Sample 5 and Sample 6 were unable to extinguish the flames on the fourth try. On the other hand, the extinguishing effect of the third time in sample 7 was significantly reduced, and 2, there was a different degree of decrease in its fire-extinguishing effect. Similarly, the sample groups In the eighth and eighth varieties of samples, there were some that could not be extinguished on the fourth or third try, and the nanosilica If moss and nano metal oxide are not added at the same time, the reproducibility of the fire extinguishing action and the long-term effect will be poor. It has been shown to be disadvantageous, and the data of various samples in sample group 8 and examples 1 and 2 As a result of repeatedly testing the weight ratio of nano metal oxide and nano silica When the weight ratio of the nano metal oxide to the nano metal oxide is 1:2.5-5, and further 1:2-5, excellent properties are obtained. It can repeatedly exert a fire-extinguishing effect, and is also beneficial for storage stability under normal use conditions. .

[0178] The prior art in the above embodiment is well known to those skilled in the art, and therefore will not be described in detail here. Not clear.

[0179] The specific examples described herein are merely illustrative of the spirit of the invention. If so, various modifications, supplements, or equivalent substitutions may be made to the specific embodiments described. However, it is possible to deviate from the spirit of the present invention or exceed the scope defined in the claims. There is nothing to do. All that is not detailed in this invention is known technology.

Claims

1. A fireproof paint comprising: A paint base material; When exposed to temperatures above 75°C and / or an open flame environment, it explodes and vaporizes and releases the fire extinguishing material; and a fire extinguishing agent microcapsule for cooling and / or fire prevention and / or fire extinguishing, The extinguishing agent microcapsules are A core material that absorbs heat by vaporizing when it is released from heat, at least two layers of wall material containing a polymeric material; The wall material is burstable at 75° C. or higher; The inner wall material of the wall material contains nano silicon oxide and nano metal oxide in a weight ratio of 1:2.5-5. fruit, The total amount of the nano silicon oxide and the nano metal oxide added is based on the dry mass of the inner wall material. 0.05 to 0.2%. The nano metal oxides include nano zinc oxide, nano titanium oxide, nano calcium oxide, nano diacid At least one selected from the group consisting of manganese oxide, nano nickel oxide, and nano copper oxide; A fireproof paint characterized by:

2. A coating composition comprising: A film-forming material; A solvent; and a fire extinguishing agent microcapsule, The extinguishing agent microcapsules have at least two layers of wall material, The wall material of the fire extinguishing agent microcapsules is rupturable at 75° C. or higher; The extinguishing agent microcapsules vaporize and release the core material after the wall material ruptures, The inner wall material of the wall material contains nano silicon oxide and nano metal oxide in a weight ratio of 1:2.5-5. fruit, The total amount of the nano silicon oxide and nano metal oxide added is based on the dry mass of the inner wall material. 0.05 to 0.2%, The nano metal oxides include nano zinc oxide, nano titanium oxide, nano calcium oxide, nano diacid At least one selected from the group consisting of manganese oxide, nano nickel oxide, and nano copper oxide; A coating composition comprising:

3. A powder coating material comprising: The composition includes a film-forming component as a resin for forming a coating film, and further includes fire extinguishing agent microcapsules; The extinguishing agent microcapsules have at least two layers of wall material, The wall material of the fire extinguishing agent microcapsules ruptures at 100° C. or higher, The extinguishing agent microcapsules vaporize and release the microcapsule core material after the wall material is ruptured. 、 The inner wall material of the wall material contains nano silicon oxide and nano metal oxide in a weight ratio of 1:2.5-5. fruit, The total amount of the nano silicon oxide and nano metal oxide added is based on the dry mass of the inner wall material. 0.05 to 0.2%, The nano metal oxides include nano zinc oxide, nano titanium oxide, nano calcium oxide, nano diacid At least one selected from the group consisting of manganese oxide, nano nickel oxide, and nano copper oxide; Powder paint.

4. Use of the powder coating according to claim 3 in the production of temperature-reducing and / or fire-resistant and / or fire-extinguishing coatings. 。

5. A coated article, comprising: A substrate; On the surface of the substrate A coating film formed from the fireproof paint according to claim 1, and / or A coating film formed from the coating composition according to claim 2, and / or A coated article comprising a coating film formed from the powder coating material according to claim 3.

Images