JP2020143255A - Two-liquid type flame-retardant polyurea resin raw material for forming coating film and method for forming flame-retardant polyurea resin coating film - Google Patents

Abstract

To provide a two-liquid type flame-retardant polyurea resin raw material for forming a coating film that causes no clogging in a filter even when the filter is incorporated into an injection installation and can form a flame-retardant polyurea coating film having good quality and a uniform thickness.SOLUTION: The two-liquid type flame-retardant polyurea resin raw material for forming a coating film is composed of an A agent including isocyanate and a B agent including polyamine, ammonium polyphosphate in an amount of 26 pts.wt. to 50 pts.wt. and an organotin compound in an amount of 0.021 pt.wt to 10.5 pts.wt. in terms of tin, each based on 100 pts.wt. of the polyamine.SELECTED DRAWING: None

Description

The present invention relates to a two-component flame-retardant polyurea resin raw material for forming a coating film and a method for forming a flame-retardant polyurea resin coating film.

In recent years, a polyurea resin coating film having waterproof, abrasion resistance, chemical resistance and elasticity has been provided on the wall surface of facilities such as tunnels, tanks and manufacturing plants. Further, it is required to form a flame-retardant polyurea resin coating film according to the use of the facility. As a flame-retardant polyurea resin coating film, a polyurea resin coating film containing metal particles is known. In the polyurea resin coating film containing such metal particles, for example, an agent A containing isocyanate and an agent B containing metal particles and polyamine as raw materials are directed toward an object such as a wall surface of a facility by an injection facility. It can be formed by spraying and drying. Such an injection facility generally includes a filter for removing contamination in the raw material to form a high-quality coating film, and sprays each raw material after passing through the filter.

However, when the B agent containing metal particles is used as a raw material, the metal particles clog the eyes of the filter when forming the flame-retardant polyurea resin coating film, and the B agent cannot be sprayed, so that the flame-retardant polyurea cannot be sprayed. There is a risk that the resin coating film cannot be formed. If an injection facility from which the filter is removed is used in order to use the B agent containing metal particles, contamination in the raw material cannot be removed, and there is a possibility that a high-quality coating film cannot be formed.

The problem to be solved by the present invention is that even if a filter is incorporated in an injection facility, the filter does not cause clogging, and a high-quality, uniform-thickness flame-retardant polyurea resin coating film can be formed. It is to provide a liquid type flame-retardant polyurea resin raw material.

Further, the problem to be solved by the present invention is that even if a filter is incorporated in the injection equipment, the filter does not cause clogging, and a flame-retardant polyurea resin coating film having a high quality and a uniform thickness can be formed. The present invention provides a method for forming a polyurea resin coating film.

The two-component flame-retardant polyurea resin raw material for forming a coating film of the present invention is an agent A containing isocyanate; and polyamine and ammonium polyphosphate in an amount of 26 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the polyamine. It is composed of Agent B containing 0.021 parts by weight or more and 10.5 parts by weight or less of an organotin compound in terms of tin.

The method for forming the flame-retardant polyurea resin coating film of the present invention is as follows: (i) a first tank, a first introduction pipe having one end connected to the first tank, a second tank, and the first tank. A second introduction pipe having one end connected to the tank 2, a compressor having the other ends of the first and second introduction pipes connected to each other, and a first introduction pipe having one end connected to the compressor. A first outlet tube for deriving the compressed fluid of the fluid introduced from the compressor and a second outlet tube for deriving the compressed fluid of the fluid introduced from the second introduction pipe, one end of which is connected to the compressor. The outlet pipe, the first and second filters arranged in the part of the compressor to which the first and second outlet pipes are connected, and the other end of the first and second outlet pipes are attached. A step of preparing an injection facility provided with the injection nozzle; (ii) a step of accommodating the agent A containing isocyanate in the first tank; (iii) a polyamine in the second tank and 100 parts by weight of the above. A step of accommodating agent B containing 26 parts by weight or more and 50 parts by weight or less of ammonium polyphosphate and 0.021 parts by weight or more and 10.5 parts by weight or less of an organic tin compound in terms of tin with respect to the polyamine; (iv ) Drive the compressor and lead the agent A in the first tank to the injection nozzle through the first introduction pipe, the compressor, the first filter and the first outlet pipe, and at the same time, the first The agent B in the tank 2 is led out to the injection nozzle through the second introduction pipe, the compressor, the second filter and the second outlet pipe, and the agent A and the agent B are delivered from the injection nozzle. The step of spraying toward the coating film forming site and performing the curing reaction of the agent A and the agent B at the coating film forming site; and (v) the injection nozzle was predetermined during the step (iv). A method for forming a flame-retardant polyurea resin coating film, which comprises a step of sequentially moving to a coating film forming site.

According to the present invention, even if a filter is incorporated in an injection facility, a two-component flame retardant for coating film formation capable of forming a high-quality flame-retardant polyurea resin coating film without causing clogging in the filter during coating is possible. A raw material for a sex polyurea resin can be provided.

Further, according to the present invention, even if a filter is incorporated in the injection equipment, the flame-retardant polyurea resin coating can form a high-quality, uniform-thickness flame-retardant polyurea resin coating film without causing clogging in the filter. A method for forming a film can be provided.

FIG. 1 is a schematic view showing an example of an injection facility used for forming the flame-retardant polyurea resin coating film of the first and second embodiments. FIG. 2 is a flowchart showing an example of a method for forming a flame-retardant polyurea resin coating film according to the third embodiment.

Hereinafter, the two-component flame-retardant polyurea resin raw material for forming a coating film of the first and second embodiments and the method of forming the flame-retardant polyurea resin coating film of the third embodiment will be described in detail.

[Two-component flame-retardant polyurea resin raw material for coating film formation]
The two-component flame-retardant polyurea resin raw material for forming a coating film of the first embodiment is 26 parts by weight or more and 50 parts by weight or less with respect to the agent A containing isocyanate and the polyamine and 100 parts by weight of the polyamine. It is composed of Agent B containing ammonium polyphosphate and an organotin compound of 0.021 parts by weight or more and 10.5 parts by weight or less in terms of tin. The term "tin equivalent" as used herein means that, for example, when 351 g of 351 g / mol of dibutyltin diacetate was used as the organic tin compound, 119 g of tin was used.

Agent A contains isocyanate. The isocyanates are, for example, 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI). Aromatic isocyanates such as, aliphatic isocyanates such as isophorone diisocyanate (IPDI), or 1,3-propanediol, 2-ethyl-2- (hydroxymethyl)-, alpha-hydro, omega-hydroxypolyoxy (methyl-1). , 2-Ethandiyl) and 1,1-methylenebis4-isocyanatobenzene (CasNo. 9020-84-2), which is a polymer having an isocyanate group at the terminal.

Agent B is a polyamine, ammonium polyphosphate of 26 parts by weight or more and 50 parts by weight or less, and an organotin compound of 0.021 parts by weight or more and 10.5 parts by weight or less in terms of tin with respect to 100 parts by weight of the polyamine. And include.

The polyamine is, for example, a mixture of a polyamine compound having an average molecular weight of 1000 to 10000 and an aromatic diamine compound. The polyamine compound is, for example, poly (propylene glycol) diamine, poly (propylene glycol) triamine, or a mixture thereof. Aromatic diamine compounds include, for example, diethyltoluenediamine, 4,4'-methylenebis (N-sec-butylaniline), 2,4-diethyl-6-methyl-1,3-benzenediamine, 4,6-diethyl-. 2-Methyl-1,3-phenylenezendiamine, or a mixture thereof. The polyamine is, for example, a mixture containing 5 to 40 parts by weight of aromatic diamine with respect to 100 parts by weight of the polyamine compound. Such polyamines react with the above-mentioned isocyanates to form polyurea.

Ammonium polyphosphate is contained in Agent B as a flame retardant and contributes to imparting flame retardancy to polyurea. Ammonium polyphosphate is contained in Agent B in the range of 26 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of polyamine. If the amount of ammonium polyphosphate is less than 26 parts by weight with respect to 100 parts by weight of polyamine, it becomes difficult to produce polyurea having high flame retardancy, which will be described later.
Further, when ammonium polyphosphate exceeds 50 parts by weight with respect to 100 parts by weight of polyamine, the viscosity of Agent B containing these components shows a high value exceeding 60 dPa · S. As a result, such a highly viscous agent B not only makes it difficult to adjust the mixing ratio with the agent A in the method for forming the flame-retardant polyurea resin coating film described later, but also the agent A injected from the injection nozzle and the agent A. The viscosity of the raw material made of Agent B also increases, making it difficult to form a high-quality, uniform-thickness flame-retardant polyurea resin coating film.
By adjusting the viscosity of ammonium polyphosphate to the range of 26 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of polyamine, the viscosity of Agent B is adjusted to the range of 30 dPa · S or more and 55 dPa · S or less. Can be done. The B agent having such a viscosity can easily adjust the mixing ratio with the A agent, and can be smoothly injected together with the A agent from the injection nozzle at the desired injection flow rate. In some embodiments, ammonium polyphosphate is preferably contained in Agent B in the range of 26 parts by weight or more and 45 parts by weight or less with respect to 100 parts by weight of polyamine. More preferably, ammonium polyphosphate is contained in Agent B in the range of 26 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of polyamine.

The organotin compound is contained in the agent B together with ammonium polyphosphate as a flame retardant aid. The organotin compound can exhibit a remarkable flame retardant effect on polyurea as compared with other organometallic compounds such as organotitanium compound, organozirconium compound, or organoaluminum compound. The organotin compound is contained in the agent B in the range of 0.021 parts by weight or more and 10.5 parts by weight or less in terms of tin with respect to 100 parts by weight of the polyamine.
By adding the organotin compound to the agent B, high flame retardancy can be imparted to polyurea, and since the addition of ammonium polyphosphate partially contributes to the flame retardancy, ammonium polyphosphate was used alone as the flame retardant. The amount of addition can be reduced as compared with the case. Therefore, the organotin compound reduces the viscosity of the agent B by reducing the amount of ammonium polyphosphate added, and contributes to the formation of a high-quality, uniform-thickness flame-retardant polyurea resin coating film.
If the amount of the organic tin compound is less than 0.021 parts by weight in terms of tin with respect to 100 parts by weight of polyamine, it becomes difficult to produce polyurea having high flame retardancy, which will be described later.
Further, when the amount of the organic tin compound exceeds 10.5 parts by weight in terms of tin with respect to 100 parts by weight of polyamine, the performance such as waterproofness, abrasion resistance, chemical resistance and elasticity peculiar to polyurea is deteriorated. There is a risk. In some embodiments, the organotin compound is preferably contained in the agent B in the range of 0.021 parts by weight or more and 8.0 parts by weight or less in terms of tin with respect to 100 parts by weight of the polyamine. More preferably, the organotin compound is contained in the agent B in the range of 0.021 parts by weight or more and 6.0 parts by weight or less in terms of tin with respect to 100 parts by weight of the polyamine.

The organic tin compound includes, for example, a dibutyltin compound.
Examples of the dibutyltin compound include dibutyltin dichloride, dibutyltinmalate, dibutyltin diacetate, dibutyltinbis (2-ethylhexyl mercaptoacetate), dibutyltinbis (isooctyl mercaptoacetate), dibutyltinbis (butylmalate), dibutyltinbis (ethylmalate), and the like. Dibutyltin bis (2-ethylhexyl malate), dibutyl tin bis (mercapto isooctyl acetate), dibutyl tin bis (butyl malate), dibutyl tin bis (oleyl malate), dibutyl bis (2,4-pentanedionato) tin, dibutyl tin-3-mercaptopropion Includes acids, bis (dibutyltin = benzyl = maleate) maleate, dibutyltin dibutoxide, dibutyl (methoxy) stannyl = methyl = maleate, dibutyltin diacetylacetonate, dibutyltin dioctate, dibutyltin dilaurate, or dibutyltin distearate.

Examples of the organotin compound include dioctyl tin oxide, bis (neodecanic acid) tin, and tin 2-ethylhexanoate (II) in addition to the above-mentioned dibutyltin compounds.

In addition, the agent B may contain a hindered amine compound or a melamine compound. The hindered amine compound is contained in the agent B as a light stabilizer. The hindered amine compound is contained in the agent B in the range of 0.1 part by weight or more and 1.0 part by weight or less with respect to 100 parts by weight of the polyamine, for example. In the polyurea resin formed by using the agent B containing the hindered amine compound, even if the polyurea resin is exposed to a flame or the like and heated, the hindered amine compound radically decomposes to suppress or prevent the generation of flammable gas and spread the fire. Can be prevented. The hindered amine compound is, for example, 4-hydroxy-2,2,6,6-tetramethylpiperidin1-oxyl free radical.

The melamine compound is contained in the agent B as a flame retardant like ammonium polyphosphate. The melamine compound is contained in the agent B in the range of 100 parts by weight or more and 300 parts by weight or less with respect to 100 parts by weight of the polyamine, for example. The melamine compound is, for example, melamine sulfate, melamine polyphosphate or melamine cyanurate.

In addition, the agent B may contain a higher fatty acid polyamide. The higher fatty acid polyamide is contained in the agent B as a sedimentation inhibitor. By adding the higher fatty acid polyamide to the agent B, the agent B in which ammonium polyphosphate is uniformly dispersed without precipitation can be prepared. The higher fatty acid polyamide is contained in the agent B in the range of 1.0 part by weight or more and 3.0 parts by weight or less with respect to 100 parts by weight of the polyamine, for example. The higher fatty acid polyamide is, for example, stearic acid amide.

Further, the agent B may contain a fluororesin or a silicon resin. Fluororesin or silicon resin is included in Agent B as a dispersant. By adding a fluororesin or a silicon resin to the agent B, an agent B in which ammonium polyphosphate is uniformly dispersed without precipitation can be prepared. Each of the fluororesin and the silicon resin is contained in the agent B in the range of 5.0 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the polyamine.

Further, the agent B may include a silane coupling agent. The silane coupling agent contributes to improving the adhesion of the polyurea resin coating film to the wall surface of the facility. The silane coupling agent is contained in the agent B in the range of 1.0 part by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the polyamine. The silane coupling agent is, for example, 3-glycidyloxypropyltrimethoxysilane.

Further, the agent B may contain a pigment. The pigment is contained in the agent B in the range of 1.0 part by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the polyamine. The pigment is, for example, dioxotitanium (IV), which is an inorganic metal compound.

Further, the agent B may include an antifoaming agent. The defoaming agent is contained in the agent B in the range of 1.0 part by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the polyamine. The defoaming agent is, for example, an amorphous silicon dioxide inorganic.

The two-component flame-retardant polyurea resin raw material for forming a coating film of the second embodiment is 21 parts by weight or more and 50 parts by weight or less with respect to agent A containing isocyanate and polyamine and 100 parts by weight of the polyamine. It is composed of Agent B containing ammonium polyphosphate and an organotin compound of 9.3 parts by weight or more and 10.5 parts by weight or less in terms of tin. In such a two-component flame-retardant polyurea resin raw material for forming a coating film, the isocyanate, polyamine, ammonium polyphosphate, and organotin compound have the same functions, actions, and the like as described in the first embodiment described above. Have. Further, the hindered amine compound, the melamine compound, the higher fatty acid polyamide, the fluororesin, the silicon resin, the silane coupling agent, the pigment, or the defoaming agent which can be contained in the agent B have also been described in the above-mentioned first embodiment. It has similar functions and actions.

The two-component flame-retardant polyurea resin raw material for forming a coating film of the second embodiment is contained in the agent B as compared with the two-component flame-retardant polyurea resin raw material for forming a coating film of the first embodiment. While expanding the lower limit of ammonium polyphosphate from 26 parts by weight to 21 parts by weight, the lower limit of the organotin compound contained in Agent B is as high as 0.021 parts by weight to 9.3 parts by weight in terms of tin. Is shifting to. Therefore, the lack of flame retardancy of the polyurea resin coating film obtained by expanding the lower limit of ammonium polyphosphate from 26 parts by weight to 21 parts by weight was solved, and the blending amount of the organotin compound was 0.021. The polyurea resin coating film can be provided with flame retardancy by shifting from the weight part to a high value of 9.3 parts by weight to compensate, and as in the first embodiment.

Ammonium polyphosphate is contained in Agent B as a flame retardant and contributes to imparting flame retardancy to polyurea. Ammonium polyphosphate is contained in Agent B in the range of 21 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of polyamine. If the amount of ammonium polyphosphate is less than 21 parts by weight with respect to 100 parts by weight of polyamine, it becomes difficult to produce polyurea having high flame retardancy, which will be described later.
Further, when ammonium polyphosphate exceeds 50 parts by weight with respect to 100 parts by weight of polyamine, the viscosity of Agent B containing these components shows a high value exceeding 60 dPa · S. As a result, such a highly viscous agent B not only makes it difficult to adjust the mixing ratio with the agent A in the method for forming the flame-retardant polyurea resin coating film described later, but also the agent A injected from the injection nozzle and the agent A. The viscosity of the raw material made of Agent B also increases, making it difficult to form a high-quality, uniform-thickness flame-retardant polyurea resin coating film.
By adjusting ammonium polyphosphate to a range of 21 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of polyamine, the viscosity of Agent B is adjusted to a viscosity range of 25 dPa · S or more and 55 dPa · S or less. Can be done. The B agent having such a viscosity can easily adjust the mixing ratio with the A agent, and can be smoothly injected together with the A agent from the injection nozzle at the desired injection flow rate. In some embodiments, ammonium polyphosphate is preferably contained in Agent B in the range of 21 parts by weight or more and 45 parts by weight or less with respect to 100 parts by weight of polyamine. More preferably, ammonium polyphosphate is contained in Agent B in the range of 21 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of polyamine.

The organotin compound is contained in the agent B together with ammonium polyphosphate as a flame retardant aid. The organotin compound can exhibit a remarkable flame retardant effect on polyurea as compared with other organometallic compounds such as organotitanium compound, organozirconium compound, or organoaluminum compound. The organotin compound is contained in the agent B in the range of 9.3 parts by weight or more and 10.5 parts by weight or less in terms of tin with respect to 100 parts by weight of the polyamine. The "tin conversion" referred to here is as described above.
By adding the organotin compound to the agent B, high flame retardancy can be imparted to polyurea, and since the addition of ammonium polyphosphate partially contributes to the flame retardancy, ammonium polyphosphate was used alone as the flame retardant. The amount of addition can be reduced as compared with the case. Therefore, the organotin compound reduces the viscosity of the agent B by reducing the amount of ammonium polyphosphate added, and contributes to the formation of a high-quality, uniform-thickness flame-retardant polyurea resin coating film.
If the amount of the organic tin compound is less than 9.3 parts by weight in terms of tin with respect to 100 parts by weight of polyamine, it becomes difficult to produce polyurea having high flame retardancy, which will be described later.
Further, when the amount of the organotin compound exceeds 10.5 parts by weight in terms of tin with respect to 100 parts by weight of polyamine, the performance such as waterproofness, abrasion resistance, chemical resistance and elasticity peculiar to polyurea deteriorates. In addition, it may cause cracks or the like to occur in the flame-retardant polyurea resin coating film. In some embodiments, the organotin compound is preferably contained in the agent B in the range of 9.3 parts by weight or more and 10.0 parts by weight or less in terms of tin with respect to 100 parts by weight of the polyamine.

As described above, the raw material composed of the agent A containing isocyanate and the polyamine and the agent B containing a specific amount of ammonium polyphosphate and an organotin compound with respect to the polyamine is mixed and applied to a predetermined site to obtain an isocyanate. A flame-retardant polyurea resin coating film can be formed by reacting with polyamine.
The flame retardancy of such a flame-retardant polyurea resin coating film is measured, for example, by a method conforming to the flame resistance method A of JIS K 6911 1995 "General Test Method for Thermosetting Plastics", and the combustion distance is 25 mm or less. It can be expressed by either "nonflammability" indicating a case or "self-extinguishing property" indicating a case where the combustion distance is 25 mm or more and 100 mm or less. The polyurea resin formed by using the two-component flame-retardant polyurea resin raw material for forming a coating film of the first and second embodiments is "nonflammable" indicating a case where the combustion distance is 25 mm or less in the above-mentioned method. It is preferable to show.
Further, such a polyurea resin coating film has, for example, waterproofness, abrasion resistance, chemical resistance, elasticity and the like peculiar to polyurea. The polyurea resin coating film has, for example, an elongation rate of 400% or more, and can suppress or prevent peeling of the wall surface of the facility or the like.

Further, the two-component flame-retardant polyurea resin raw material for forming a coating film of the first and second embodiments is a B agent when the raw material composed of the A agent and the B agent is applied by using an injection facility equipped with a filter. Can be stably injected from the injection nozzle without clogging with the filter, and a high-quality, uniform-thickness flame-retardant polyurea resin coating film can be formed. The thickness of such a flame-retardant polyurea resin coating film is, for example, 0.10 mm or more and 2.0 mm or less.

[Method of forming flame-retardant polyurea resin coating film]
The method for forming the flame-retardant polyurea resin coating film of the third embodiment will be described below. The injection equipment used in this coating film forming method will be described with reference to FIG.

FIG. 1 is a schematic view showing an injection facility SP used in the method for forming a flame-retardant polyurea resin coating film of the third embodiment.
The injection facility SP includes a first tank T1 and a second tank T2. One end of the first introduction pipe IT1 is connected to the first tank T1 and the other end is connected to the compressor CP. One end of the second introduction pipe IT2 is connected to the second tank T2, and the other end is connected to the compressor CP. One end of the first lead-out pipe LT1 is connected to the compressor CP, and the compressed fluid of the fluid introduced from the first introduction pipe IT1 is led out. One end of the second lead-out pipe LT2 is connected to the compressor CP, and the compressed fluid of the fluid introduced from the second introduction pipe IT2 is led out. The first and second filters F1 and F2 are arranged in the part of the compressor CP to which the first and second outlet pipes LT1 and LT2 are connected, respectively. The other ends of the first and second lead-out pipes LT1 and LT2 are attached to the injection nozzle NZ, respectively.

The first tank T1 is made of, for example, synthetic resin or steel, has a volume of 5 liters or more and 200 liters or less, and is provided with a heater (not shown) inside or outside. Agent A containing isocyanate is contained in the first tank T1. The agent A may be heated to the curing reaction acceleration temperature of the agents A and B by the heater described above. The curing reaction acceleration temperature is, for example, 60 to 80 ° C, preferably 65 to 75 ° C. By heating the agents A and B to the curing reaction accelerating temperature, the viscosities of the agents A and B are lowered to facilitate spraying, and the curing reaction is also shortened.

The first introduction pipe IT1 may be provided with a heater H1 on the outer circumference. The first introduction pipe IT1 introduces the fluid of the agent A from the first tank T1 into the compressor CP. The first introduction pipe IT1 may heat the agent A to the curing reaction temperature of the agents A and B by the heater H1 before introducing the fluid of the agent A into the compressor CP.

The second tank T2 is made of, for example, synthetic resin or steel, has a volume of 5 liters or more and 200 liters or less, and is provided with a heater (not shown) inside or outside. In the second tank T2, the same polyamine as in the first embodiment described above, and ammonium polyphosphate of 26 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of polyamine, 0.021 in terms of tin. 21 parts by weight or more and 50 parts by weight or less with respect to agent B containing an organotin compound of 2 parts by weight or more and 10.5 parts by weight or less, or a polyamine similar to that of the second embodiment described above, and 100 parts by weight of polyamine. B agent containing ammonium polyphosphate and an organotin compound of 9.3 parts by weight or more and 10.5 parts by weight or less in terms of tin is contained. Agent B may be heated to the curing reaction acceleration temperature of Agent A and Agent B by the heater described above. As described above, the curing reaction acceleration temperature is 60 to 80 ° C, preferably 65 to 75 ° C.

The second introduction pipe IT2 can be provided with a heater H2 on the outer circumference. The second introduction pipe IT2 introduces the fluid of agent B from the second tank T2 into the compressor CP. In the second introduction pipe IT2, the agent B may be heated to the curing reaction temperature of the agent A and the agent B by the heater H2 before introducing the fluid of the agent B into the compressor CP.

The compressor CP introduces the fluid of the agent A from the first tank T1 through the first introduction pipe IT1, then compresses the fluid of the agent A into a compressed fluid, and the compressed fluid is used as the first filter F1. , The fluid of the agent B is introduced from the second tank T2 through the second introduction pipe IT2 while being led out toward the first outlet pipe LT1, and then the fluid of the agent B is compressed into a compressed fluid. , The compressed fluid is led out toward the second filter F2 and the second lead-out pipe LT2.

The first filter F1 is made of, for example, stainless steel, has a plurality of holes having a diameter of 0.17 mm or more and 0.38 mm or less, and the compressed fluid of the agent A derived from the compressor CP is transferred to the first outlet pipe LT1. Remove contamination etc. while passing it toward. The second filter F2 is made of stainless steel, for example, has a plurality of holes having a diameter of 0.17 mm or more and 0.38 mm or less, and the compressed fluid of the agent B derived from the compressor CP is transferred to the second outlet pipe LT2. Remove contamination etc. while passing it toward.

The first and second lead-out pipes LT1 and LT2 have heaters H3 on the outer periphery of the first and second lead-out pipes LT1 and LT2, respectively. The first and second outlet pipes LT1 and LT2 may be heated to the curing reaction temperature of the agents A and B by the heater H3.
The first outlet pipe LT1 sends the compressed fluid of the agent A derived from the compressor CP through the first filter F1 to the injection nozzle NZ, and the second outlet pipe LT2 is the second filter from the compressor CP. The compressed fluid of the agent B derived through F2 is sent to the injection nozzle NZ.

The injection nozzle NZ includes, for example, a grip portion HL, a trigger portion TR, and an injection port JO. The injection nozzle NZ merges the compressed fluid of agent A led out through the first outlet pipe LT1 and the compressed fluid of agent B led out through the second outlet pipe LT2 immediately before injection, and then joins the agent A. The agent B is sprayed from the injection port JO toward the coating film forming site. In such an injection nozzle NZ, the user has a grip portion HL, directs the injection port JO to the coating film forming portion, and pulls the trigger portion TR to inject a mixed fluid of the agent A and the agent B.

FIG. 2 is a flowchart showing a method of forming the flame-retardant polyurea resin coating film of the third embodiment. The method for forming the flame-retardant polyurea resin coating film of the third embodiment includes steps (S1) to (S5).

In the step (S1), the injection equipment SP as shown in FIG. 1 is prepared.
Next, in the step (S2), the agent A containing isocyanate is contained in the first tank T1, and in the step (S3), the polyamine is contained in the second tank T2, and the weight is 26 with respect to 100 parts by weight of the polyamine. With respect to agent B or polyamine containing ammonium polyphosphate of parts of parts or more and 50 parts by weight or less and an organotin compound of 0.021 parts by weight or more and 10.5 parts by weight or less in terms of tin, and 100 parts by weight of polyamine. The agent B containing 21 parts by weight or more and 50 parts by weight or less of ammonium polyphosphate and 9.3 parts by weight or more and 10.5 parts by weight or less of an organotin compound in terms of tin is contained.

Next, in the step (S4), the compressor CP is driven, and the heated agent A in the first tank T1 is introduced into the first introduction pipe IT1, the compressor CP, the first filter F1 and the first outlet pipe LT1. At the same time, the heated B agent in the second tank T2 is led out to the injection nozzle NZ through the second introduction pipe IT2, the compressor CP, the second filter F2 and the second outlet pipe LT2. To do.
Next, the user holds the grip portion HL, directs the injection port JO toward the coating film forming portion, and pulls the trigger portion TR to simultaneously inject the A agent and the B agent, and the A agent and the B agent are injected at the coating film forming portion. Perform a curing reaction.
Here, the coating film forming site is, for example, a tunnel, tanks (water tank, waterway, etc.), a manufacturing plant, a roof of a building, an inner surface of a duct, a wall surface of a facility such as a hot water pit, a floor, a roof, etc. It is not limited to.

Next, in the step (S5), the injection nozzle NZ is sequentially moved to a predetermined coating film forming portion during the step (S4).
As described above, neither the A agent nor the B agent in the raw material contains a powder solid such as a metal powder, and in the step (S4), the A and B agents pass through the filters (first and second). Since the filters F1 and F2) of the above do not cause clogging, a high-quality flame-retardant polyurea resin coating film containing no reaction by-products can be smoothly formed.

Further, in the method for forming the flame-retardant polyurea resin coating film of the third embodiment, the flame-retardant polyurea resin coating film can be continuously formed at the coating film forming site in a short time. Therefore, a seamless, that is, seamless, flame-retardant polyurea coating film can be formed in a short time, so that the construction period such as construction can be shortened.

A top coat may be applied to the surface of the flame-retardant polyurea resin coating film to form the coating film.
Further, before the step (S4), degreasing of the coating film forming portion, removal of keren, fragile portion and the like, cracks, repair, removal of rust and the like may be performed. If the base is concrete, the non-landing may be adjusted with a putty material or the like. Subsequently, a primer may be applied to the coating film forming site to form the coating film. The method for forming the flame-retardant polyurea resin coating film of the third embodiment is preferably used for a portion where flame retardancy is required.

<Example>
Hereinafter, in order to confirm the effect of the present invention, a two-component flame-retardant polyurea resin raw material for forming a coating film is prepared, and polyurea resin samples of Examples 1-1 to 1-4 are produced and comparative experiments are performed. It was.

<Example 1-1>
As a raw material for Agent A, it has 110 parts by weight (110 g) of 1,3-propanediol, 2-ethyl-2- (hydroxymethyl)-, alpha-hydro, and omega-hydroxy (methyl-1,2-ethandyl). A polymer of a polymer and 1,1-methylenebis 4-isocyanatobenzene was prepared and used as Agent A.
As a raw material for the B agent, 100 parts by weight (100 g) of the B agent composition, 100 parts by weight (100 g) of ammonium polyphosphate, and 2 parts by weight (2 g) of stearic acid amide are prepared and stirred. , Mixed to prepare Agent B.
The above-mentioned B agent composition is 65% by weight of poly (propylene glycol) diamine, 10% by weight of poly (propylene glycol) triamine, and 15% by weight of 2,4-diethyl-6-methyl-1,3-benzenediamine. , 7% by weight 4,6-diethyl-2-methyl-1,3-phenylenezendiamine, 1% by weight 3-glycidyloxypropyltrimethoxysilane, 1% by weight dioxotitanium (IV), and 1% by weight. Contains silicon dioxide (amorphous). Therefore, the raw material of the agent B in Example 1-1 contains 97 parts by weight of polyamine.
That is, the agent B in Example 1-1 contains 103 parts by weight of ammonium polyphosphate when the polyamine is 100 parts by weight.
Next, the prepared agents A and B were mixed, and the mixture was dried to prepare a rectangular parallelepiped example 1-1 polyurea resin sample having a length of 127 mm and a width and thickness of 13 mm, respectively.

<Example 1-2>
The same raw materials as in Example 1-1 were prepared except that 50 parts by weight (50 g) of ammonium polyphosphate was prepared as the raw material for the agent B, the agent A and the agent B were mixed, and the mixture was dried to lengthen. A rectangular parallelepiped example 1-2 polyurea resin sample having a width of 127 mm and a width and thickness of 13 mm was prepared.
Here, the agent B in Example 1-2 contains 52 parts by weight of ammonium polyphosphate when the polyamine is 100 parts by weight.

<Example 1-3>
The same raw materials as in Example 1-1 were prepared except that 45 parts by weight (45 g) of ammonium polyphosphate was prepared as the raw material for the agent B, the agent A and the agent B were mixed, and the mixture was dried to lengthen. A rectangular parallelepiped example 1-3 polyurea resin sample having a width of 127 mm and a width and thickness of 13 mm was prepared.
Here, the agent B in Example 1-3 contains 46 parts by weight of ammonium polyphosphate when the polyamine is 100 parts by weight.

<Example 1-4>
The same raw materials as in Example 1-1 were prepared except that 40 parts by weight (40 g) of ammonium polyphosphate was prepared as the raw material for the agent B, the agent A and the agent B were mixed, and the mixture was dried to lengthen. A rectangular parallelepiped example 1-4 polyurea resin sample having a width of 127 mm and a width and thickness of 13 mm was prepared.
Here, the agent B in Examples 1-4 contains 41 parts by weight of ammonium polyphosphate when the polyamine is 100 parts by weight.

Next, the flame retardancy of the polyurea resin samples of Examples 1-1 to 1-4 was evaluated based on the flame resistance method A of JIS K 6911 1995 "General test method for thermosetting plastics" shown below. This evaluation was carried out under the conditions of a temperature of 21 ° C. and a relative humidity of 46%.
First, an experimental stand equipped with two grips, a Bunsen burner with a diameter of 8.5 to 11.5 mm fueled by city gas or liquefied petroleum gas, and a combustion tester equipped with a support stand (Toyo Seiki Co., Ltd.) A UL combustion tester HVUL-C manufactured by Mfg. Co., Ltd., a sieve (corresponding to 850 μm of JIS Z 8801 and a length and width of about 100 mm each), and a stop watch with a 0.2 second scale were prepared.

Next, after setting the height of the flame of the Bunsen burner to about 25 mm, the Bunsen burner was tilted 30 degrees with respect to the vertical line and fixed to the support base.

Next, marking lines were added at 25 mm and 100 mm from one end (free end) of the polyurea resin sample of Example 1-1. The polyurea resin samples of Examples 1-2 to 1-4 were similarly marked.

Next, the polyurea resin sample of Example 1-1 is arranged so that the length direction is horizontal, the width direction (thickness direction) is an angle of 45 ° with respect to the horizontal, and the lower end of the height is the tip height of the flame. In addition, one end was held on the stand. Sieves were placed at intervals under the fixed Polyurea resin sample of Example 1-1.
Next, the lower end of the non-fixed free end of the polyurea resin sample of Example 1-1 was brought into contact with the lower end of the blue flame at an angle of 30 ° for 30 seconds, and then the flame of the gas burner was applied to the polyurea resin sample. It was separated from the above by 450 mm or more. The stopwatch was started at the same time as the flame of the gas burner was removed.
Next, when the flame of the polyurea resin sample was extinguished, the stopwatch was stopped, the time was read in seconds, and this was taken as the burning time. If the burning time was 180 seconds or more, it was blown out and flammable. ..

After extinguishing the fire, the burning length of the test piece was measured from the lower end, and the burning distance was measured in millimeters (mm). The evaluation is "A" indicating "nonflammability" when the combustion distance is 25 mm or less, "B" indicating "self-extinguishing property" when the combustion distance is 25 mm or more and 100 mm or less, and the combustion distance is 100 mm. When the amount exceeded or the flame did not extinguish for 180 seconds or more, it was rated as "C" indicating "flammability".

Subsequently, using the polyurea resin samples of Examples 1-2 to 1-4, the evaluation based on the above-mentioned JIS K 6911 1995 flame resistance method A was carried out. These results are shown in Table 1.

From the results in Table 1, it can be seen that a flame-retardant polyurea resin coating film can be formed by using Agent B containing 52 parts by weight or more of ammonium polyphosphate with respect to 100 parts by weight of polyamine.
Here, the viscosity of Agent B containing 52 parts by weight of ammonium polyphosphate with respect to 100 parts by weight of polyamine was measured using a Viscotester (manufactured by Rion Co., Ltd., model number: VT-04F) and found to be 63 dPa · S. It was. Such a highly viscous agent B not only makes it difficult to adjust the mixing ratio with the agent A in the above-mentioned method for forming the flame-retardant polyurea resin coating film, but also from the agents A and B injected from the injection nozzle. The viscosity of the raw material is also increased, and it becomes difficult to form a high-quality, uniform-thickness flame-retardant polyurea resin coating film.

Subsequently, the polyurea resin samples of Examples 2-1 to 2-5 were produced and evaluated based on the above-mentioned JIS K 6911 1995 flame resistance method A.

<Example 2-1>
As a raw material for Agent A, it has 110 parts by weight (110 g) of 1,3-propanediol, 2-ethyl-2- (hydroxymethyl)-, alpha-hydro, and omega-hydroxy (methyl-1,2-ethandyl). A polymer of a polymer and 1,1-methylenebis 4-isocyanatobenzene was prepared and used as Agent A.
As a raw material for the B agent, 100 parts by weight (100 g) of the B agent composition, 30 parts by weight (30 g) of ammonium polyphosphate, and 2 parts by weight (2 g) of stearic acid amide are prepared and stirred. , Mixed to prepare Agent B.
The above-mentioned B agent composition is as described in Example 1-1. Therefore, the raw material of the agent B in Example 2-1 contains 97 parts by weight of polyamine.
That is, the agent B in Example 2-1 contains 31 parts by weight of ammonium polyphosphate when the polyamine is 100 parts by weight.
Next, the prepared agents A and B were mixed and the mixture was dried to prepare a rectangular parallelepiped example 2-1 polyurea resin sample having a length of 127 mm and a width and thickness of 13 mm, respectively.

<Example 2-2>
The same raw materials as in Example 2-1 were prepared, except that 30 g of dibutyltin diacetate (10.2 parts by weight (10.2 g) in terms of tin) was additionally prepared as a raw material for Agent B, and Agent A and B were prepared. The agent was mixed and the mixture was dried to prepare a rectangular parallelepiped example 2-2 polyurea resin sample having a length of 127 mm and a width and thickness of 13 mm each.
Here, the agent B in Example 2-2 contains 10.5 parts by weight of dibutyltin acetate in terms of tin, when the polyamine is 100 parts by weight.

<Example 2-3>
The same raw materials as in Example 2-1 were prepared except that 72 g of titanium tetrabutoxide (10.2 parts by weight (10.2 g) in terms of titanium) was additionally prepared as a raw material for Agent B, and Agent A and B were prepared. The agent was mixed and the mixture was dried to prepare a rectangular parallelepiped example 2-3 polyurea resin sample having a length of 127 mm and a width and thickness of 13 mm each. The term "titanium equivalent" as used herein means that, for example, when 340 g of titanium tetrabutoxide of 340 g / mol was used as the organic titanium compound, 48 g of titanium was used.
Here, the agent B in Example 2-3 contains 10.5 parts by weight of titanium tetrabutoxide in terms of titanium when the polyamine is 100 parts by weight.

<Example 2-4>
As the raw material of Agent B, the same raw material as in Example 2-1 was prepared except that 43 g of zirconium tetranormalbutoxide (10.2 parts by weight (10.2 g) in terms of zirconium) was additionally prepared. The agent B was mixed and the mixture was dried to prepare a rectangular parallelepiped example 2-4 polyurea resin sample having a length of 127 mm and a width and a thickness of 13 mm, respectively. In addition, "zirconium conversion" here means that when 384 g of zirconium tetranormalbutoxide of 384 g / mol was used as the organic zirconium compound, 91 g of zirconium was used.
Here, the agent B in Example 2-4 contains 10.5 parts by weight of zirconium tetranormalbutoxide in terms of zirconium, where 100 parts by weight of the polyamine is taken.

<Example 2-5>
The same raw material as in Example 2-1 was prepared except that 104 g of aluminum ethylacetate acetate diisopropylate (10.2 parts by weight (10.2 g) in terms of aluminum) was additionally prepared as a raw material for Agent B. Agents A and B were mixed and the mixture was dried to prepare a rectangular parallelepiped example 2-5 polyurea resin sample having a length of 127 mm and a width and thickness of 13 mm each. The term "aluminum equivalent" as used herein means that, for example, when 274 g of aluminum ethylacetate acetate diisopropylate of 274 g / mol was used as the organoaluminum compound, 27 g of aluminum was used.
Here, the agent B in Example 2-5 contains 10.5 parts by weight of aluminum ethylacetacetate diisopropyrate in terms of aluminum when the polyamine is 100 parts by weight.

Subsequently, the above-mentioned combustion test was carried out using the polyurea resin samples of Examples 2-1 to 2-5. These results are shown in Table 2.

From the results in Table 2, it is difficult to use Agent B containing 10.5 parts by weight of an organotin compound (dibutyltin diacetate) in terms of tin with respect to 100 parts by weight of polyamine and 31 parts by weight of ammonium polyphosphate. It can be seen that a flammable polyurea resin coating can be formed.
In other words, it can be seen that the organotin compound can exhibit a remarkable flame retardant effect on polyurea as compared with other organometallic compounds such as organotitanium compounds, organozirconium compounds, or organoaluminum compounds.

Subsequently, the polyurea resin samples of Examples 3-1 to 3-8 were produced and evaluated based on the above-mentioned JIS K 6911 1995 flame resistance method A.

<Example 3-1>
As a raw material for Agent A, it has 110 parts by weight (110 g) of 1,3-propanediol, 2-ethyl-2- (hydroxymethyl)-, alpha-hydro, and omega-hydroxy (methyl-1,2-ethandyl). A polymer of a polymer and 1,1-methylenebis 4-isocyanatobenzene was prepared and used as Agent A.
As raw materials for the B agent, 100 parts by weight (100 g) of the B agent composition, 45 parts by weight (45 g) of ammonium polyphosphate, and 26.6 g of dibutyltin diacetate (9.0 parts by weight (9. 0 g)) and 2 parts by weight (2 g) of stearic acid amide were prepared, and these were stirred and mixed to prepare Agent B.
The above-mentioned B agent composition is as described in Example 1-1. Therefore, the raw material of the agent B in Example 3-1 contains 97 parts by weight of polyamine.
That is, the agent B in Example 3-1 contains 46 parts by weight of ammonium polyphosphate and 9.3 parts by weight of dibutyltin acetate in terms of tin, when the polyamine is 100 parts by weight.
Next, the prepared agents A and B were mixed, and the mixture was dried to prepare a rectangular parallelepiped example 3-1 polyurea resin sample having a length of 127 mm and a width and thickness of 13 mm, respectively.

<Example 3-2>
The same raw materials as in Example 3-1 were prepared except that 40 parts by weight (40 g) of ammonium polyphosphate was prepared as the raw material for the B agent, the A agent and the B agent were mixed, and the mixture was dried to lengthen. A rectangular parallelepiped example 3-2 polyurea resin sample having a length of 127 mm and a width and thickness of 13 mm was prepared.
Here, the agent B in Example 3-2 contains 41 parts by weight of ammonium polyphosphate when the polyamine is 100 parts by weight.

<Example 3-3>
The same raw materials as in Example 3-1 were prepared except that 35 parts by weight (35 g) of ammonium polyphosphate was prepared as the raw material for the agent B, the agent A and the agent B were mixed, and the mixture was dried to lengthen. A rectangular parallelepiped example 3-3 polyurea resin sample having a length of 127 mm and a width and thickness of 13 mm was prepared.
Here, the agent B in Example 3-3 contains 36 parts by weight of ammonium polyphosphate when the polyamine is 100 parts by weight.

<Example 3-4>
The same raw materials as in Example 3-1 were prepared except that 30 parts by weight (30 g) of ammonium polyphosphate was prepared as the raw material for the agent B, the agent A and the agent B were mixed, and the mixture was dried to lengthen. A rectangular parallelepiped example 3-4 polyurea resin sample having a width of 127 mm and a width and thickness of 13 mm was prepared.
Here, the agent B in Example 3-4 contains 31 parts by weight of ammonium polyphosphate when the polyamine is 100 parts by weight.

<Example 3-5>
The same raw materials as in Example 3-1 were prepared except that 25 parts by weight (25 g) of ammonium polyphosphate was prepared as the raw material for the B agent, the A agent and the B agent were mixed, and the mixture was dried for length. A rectangular parallelepiped example 3-5 polyurea resin sample having a width of 127 mm and a width and thickness of 13 mm was prepared.
Here, the agent B in Example 3-5 contains 26 parts by weight of ammonium polyphosphate when the polyamine is 100 parts by weight.

<Example 3-6>
The same raw materials as in Example 3-1 were prepared except that 20 parts by weight (20 g) of ammonium polyphosphate was prepared as the raw material for the B agent, the A agent and the B agent were mixed, and the mixture was dried to lengthen. A rectangular parallelepiped example 3-6 polyurea resin sample having a width of 127 mm and a width and thickness of 13 mm was prepared.
Here, the agent B in Example 3-6 contains 21 parts by weight of ammonium polyphosphate when the polyamine is 100 parts by weight.

<Example 3-7>
The same raw materials as in Example 3-1 were prepared except that 10 parts by weight (10 g) of ammonium polyphosphate was prepared as the raw material for the agent B, the agent A and the agent B were mixed, and the mixture was dried to lengthen. A rectangular parallelepiped example 3-7 polyurea resin sample having a width of 127 mm and a width and thickness of 13 mm was prepared.
Here, the agent B in Example 3-7 contains 10 parts by weight of ammonium polyphosphate when the polyamine is 100 parts by weight.

<Example 3-8>
As the raw material of the agent B, the same raw material as in Example 3-1 was prepared except that it did not contain ammonium polyphosphate, the agent A and the agent B were mixed, and the mixture was dried to obtain 127 mm in length, width and width. Polyurea resin samples of Example 3-8 of a rectangular parallelepiped having a thickness of 13 mm were prepared.

Subsequently, the above-mentioned combustion test was carried out using the polyurea resin samples of Examples 3-1 to 3-8. The results are shown in Table 3. The values (parts by weight) of ammonium polyphosphate and dibutyltin acetate in Table 3 show the values when 100 parts by weight of polyamine is taken.

From the results in Table 3, by using agent B containing 9.3 parts by weight of dibutyltin diacetate and 21 parts by weight or more and 46 parts by weight or less of ammonium polyphosphate with respect to 100 parts by weight of polyamine. It can be seen that a flame-retardant polyurea resin coating can be formed.

Subsequently, the polyurea resin samples of Examples 4-1 to 4-6 were produced and evaluated based on the above-mentioned JIS K 6911 1995 flame resistance method A.

<Example 4-1>
As a raw material for Agent A, it has 110 parts by weight (110 g) of 1,3-propanediol, 2-ethyl-2- (hydroxymethyl)-, alpha-hydro, and omega-hydroxy (methyl-1,2-ethandyl). A polymer of a polymer and 1,1-methylenebis 4-isocyanatobenzene was prepared and used as Agent A.
As raw materials for the B agent, 100 parts by weight (100 g) of the B agent composition, 45 parts by weight (45 g) of ammonium polyphosphate, and 14.8 parts by weight (5.0 parts by weight (5.0 g) in terms of tin). ) Dibutyltin diacetate (organic tin compound) and 2 parts by weight (2 g) of stearic acid amide were prepared, and these were stirred and mixed to prepare Agent B.
The above-mentioned B agent composition is as described in Example 1-1. Therefore, the raw material of the agent B in Example 4-1 contains 97 parts by weight of polyamine.
That is, the agent B in Example 4-1 contains 46 parts by weight of ammonium polyphosphate and 5.2 parts by weight of dibutyltin acetate in terms of tin, when the polyamine is 100 parts by weight.
Next, the prepared agents A and B were mixed and the mixture was dried to prepare a rectangular parallelepiped example 4-1 polyurea resin sample having a length of 127 mm and a width and thickness of 13 mm, respectively.

<Example 4-2>
The same raw materials as in Example 4-1 were prepared except that 40 parts by weight (40 g) of ammonium polyphosphate was prepared as the raw material for the agent B, the agent A and the agent B were mixed, and the mixture was dried to lengthen. A rectangular parallelepiped example 4-2 polyurea resin sample having a length of 127 mm and a width and thickness of 13 mm was prepared.
Here, the agent B in Example 4-2 contains 41 parts by weight of ammonium polyphosphate when the polyamine is 100 parts by weight.

<Example 4-3>
The same raw materials as in Example 4-1 were prepared except that 35 parts by weight (35 g) of ammonium polyphosphate was prepared as the raw material of the agent B, the agent A and the agent B were mixed, and the mixture was dried to lengthen. A rectangular parallelepiped example 4-3 polyurea resin sample having a length of 127 mm and a width and thickness of 13 mm was prepared.
Here, the agent B in Example 4-3 contains 36 parts by weight of ammonium polyphosphate when the polyamine is 100 parts by weight.

<Example 4-4>
The same raw materials as in Example 4-1 were prepared except that 30 parts by weight (30 g) of ammonium polyphosphate was prepared as the raw material for the B agent, the A agent and the B agent were mixed, the mixture was dried, and the length was changed. A rectangular parallelepiped example 4-4 polyurea resin sample having a length of 127 mm and a width and thickness of 13 mm was prepared.
Here, the agent B in Example 4-4 contains 31 parts by weight of ammonium polyphosphate when the polyamine is 100 parts by weight.

<Example 4-5>
The same raw materials as in Example 4-1 were prepared except that 25 parts by weight (25 g) of ammonium polyphosphate was prepared as the raw material for the agent B, the agent A and the agent B were mixed, and the mixture was dried to lengthen. A rectangular parallelepiped example 4-5 polyurea resin sample having a width of 127 mm and a width and thickness of 13 mm was prepared.
Here, the agent B in Example 4-5 contains 26 parts by weight of ammonium polyphosphate when the polyamine is 100 parts by weight.

<Example 4-6>
The same raw materials as in Example 4-1 were prepared except that 20 parts by weight (20 g) of ammonium polyphosphate was prepared as the raw material for the B agent, the A agent and the B agent were mixed, the mixture was dried, and the length was changed. A rectangular parallelepiped example 4-6 polyurea resin sample having a width of 127 mm and a width and thickness of 13 mm was prepared.
Here, the agent B in Example 4-6 contains 21 parts by weight of ammonium polyphosphate when the polyamine is 100 parts by weight.

Subsequently, the above-mentioned combustion test was carried out using the polyurea resin samples of Examples 4-1 to 4-6. The results are shown in Table 4. The values (parts by weight) of ammonium polyphosphate and dibutyltin acetate in Table 4 show the values when 100 parts by weight of polyamine is taken.

From the results in Table 4, by using the B agent containing 5.2 parts by weight of dibutyltin diacetate and 26 parts by weight or more and 46 parts by weight or less of ammonium polyphosphate with respect to 100 parts by weight of polyamine. It can be seen that a flame-retardant polyurea resin coating can be formed.

Subsequently, the polyurea resin samples of Examples 5-1 to 5-6 were produced and evaluated based on the above-mentioned JIS K 6911 1995 flame resistance method A.

<Example 5-1>
As a raw material for Agent A, it has 110 parts by weight (110 g) of 1,3-propanediol, 2-ethyl-2- (hydroxymethyl)-, alpha-hydro, and omega-hydroxy (methyl-1,2-ethandyl). A polymer of a polymer and 1,1-methylenebis 4-isocyanatobenzene was prepared and used as Agent A.
As raw materials for the B agent, 100 parts by weight (100 g) of the B agent composition, 25 parts by weight (25 g) of ammonium polyphosphate, and 0.26 g of dibutyltin diacetate (0.088 parts by weight (0. 088 g)) and 2 parts by weight (2 g) of stearic acid amide were prepared, and these were stirred and mixed to prepare Agent B.
The above-mentioned B agent composition is as described in Example 1-1. Therefore, the raw material of the agent B in Example 5-1 contains 97 parts by weight of polyamine.
That is, the agent B in Example 5-1 contains 26 parts by weight of ammonium polyphosphate and 0.091 parts by weight of dibutyltin acetate in terms of tin, when the polyamine is 100 parts by weight.
Next, the prepared agents A and B were mixed, and the mixture was dried to prepare a rectangular parallelepiped example 5-1 polyurea resin sample having a length of 127 mm and a width and thickness of 13 mm, respectively.

<Example 5-2>
The same raw materials as in Example 5-1 were prepared, except that 0.20 g of dibutyltin diacetate (0.068 parts by weight (0.068 g) in terms of tin) was prepared as the raw material for Agent B, and Agent A and Agent B were prepared. And dried the mixture to prepare a rectangular parallelepiped example 5-2 polyurea resin sample having a length of 127 mm and a width and thickness of 13 mm each.
Here, the agent B in Example 5-2 contains 0.070 parts by weight of dibutyltin acetate in terms of tin, when the polyamine is 100 parts by weight.

<Example 5-3>
The same raw materials as in Example 5-1 were prepared, except that 0.14 g of dibutyltin diacetate (0.047 parts by weight (0.047 g) in terms of tin) was prepared as the raw material for Agent B, and Agent A and Agent B were prepared. And the mixture was dried to prepare a rectangular parallelepiped example 5-3 polyurea resin sample having a length of 127 mm and a width and thickness of 13 mm, respectively.
Here, the agent B in Example 5-3 contains 0.048 parts by weight of dibutyltin acetate in terms of tin, when the polyamine is 100 parts by weight.

<Example 5-4>
As the raw material for Agent B, the same raw materials as in Example 5-1 were prepared except that 0.10 g of dibutyltin diacetate (0.034 parts by weight (0.034 g) in terms of tin) was prepared, and Agent A and Agent B were prepared. And dried the mixture to prepare a rectangular parallelepiped example 5-4 polyurea resin sample having a length of 127 mm and a width and thickness of 13 mm each.
Here, the agent B in Example 5-4 contains 0.035 parts by weight of dibutyltin acetate in terms of tin, when the polyamine is 100 parts by weight.

<Example 5-5>
The same raw materials as in Example 5-1 were prepared except that 0.060 g of dibutyltin diacetate (0.020 parts by weight (0.020 g) in terms of tin) was prepared as the raw material for Agent B, and Agent A and Agent B were prepared. And the mixture was dried to prepare a rectangular parallelepiped example 5-5 polyurea resin sample having a length of 127 mm and a width and thickness of 13 mm, respectively.
Here, the agent B in Example 5-5 contains 0.021 parts by weight of dibutyltin acetate in terms of tin, when the polyamine is 100 parts by weight.

<Example 5-6>
The same raw materials as in Example 5-1 were prepared, except that 0.026 g of dibutyltin diacetate (0.0088 parts by weight (0.0088 g) in terms of tin) was prepared as the raw material for Agent B, and Agent A and Agent B were prepared. And dried the mixture to prepare a rectangular parallelepiped example 5-6 polyurea resin sample having a length of 127 mm and a width and thickness of 13 mm each.
Here, the agent B in Example 5-6 contains 0.0091 parts by weight of dibutyltin acetate in terms of tin, when the polyamine is 100 parts by weight.

Subsequently, the above-mentioned combustion test was carried out using the polyurea resin samples of Examples 5-1 to 5-6. The results are shown in Table 5. The values (parts by weight) of ammonium polyphosphate and dibutyltin acetate in Table 5 show the values when 100 parts by weight of polyamine is taken.

From the results in Table 5, flame retardancy was achieved by using Agent B containing 0.021 parts by weight or more of dibutyltin diacetate and 26 parts by weight of ammonium polyphosphate with respect to 100 parts by weight of polyamine. It can be seen that a polyurea resin coating can be formed.

Subsequently, the polyurea resin samples of Examples 6-1 and 6-2 were produced and evaluated based on the above-mentioned JIS K 6911 1995 flame resistance method A.

<Example 6-1>
As a raw material for Agent A, it has 110 parts by weight (110 g) of 1,3-propanediol, 2-ethyl-2- (hydroxymethyl)-, alpha-hydro, and omega-hydroxy (methyl-1,2-ethandyl). A polymer of a polymer and 1,1-methylenebis 4-isocyanatobenzene was prepared and used as Agent A.
As raw materials for the B agent, 100 parts by weight (100 g) of the B agent composition, 20 parts by weight (20 g) of ammonium polyphosphate, and 39.4 g of dibutyltin bis (ethylmalate) (9.0 parts by weight (tin equivalent)). 9.0 g)) and 2 parts by weight (2 g) of stearic acid amide were prepared, and these were stirred and mixed to prepare Agent B.
The above-mentioned B agent composition is as described in Example 1-1. Therefore, the raw material of the agent B in Example 6-1 contains 97 parts by weight of polyamine.
That is, the agent B in Example 6-1 contains 21 parts by weight of ammonium polyphosphate and 9.3 parts by weight of dibutyltin bis (ethylmalate) in terms of tin, when the polyamine is 100 parts by weight.
Next, the prepared agents A and B were mixed and the mixture was dried to prepare a rectangular parallelepiped example 6-1 polyurea resin sample having a length of 127 mm and a width and thickness of 13 mm, respectively.

<Example 6-2>
Example 6 except that 30 parts by weight (30 g) of ammonium polyphosphate and 0.026 g of dibutyltin bis (ethylmalate) (5.0 parts by weight (5.0 g) in terms of tin) were prepared as raw materials for Agent B. Prepare the same raw material as -1, mix agents A and B, and dry the mixture to obtain the polyurea resin sample of Example 6-2 of a rectangular parallelepiped having a length of 127 mm and a width and thickness of 13 mm each. Made.
Here, the agent B in Example 6-2 contains 31 parts by weight of ammonium polyphosphate and 5.2 parts by weight of dibutyltin bis (ethylmalate) in terms of tin, when the polyamine is 100 parts by weight.

Subsequently, the above-mentioned combustion test was carried out using the polyurea resin samples of Examples 6-1 and 6-2. The results are shown in Table 6. The numerical values (parts by weight) of ammonium polyphosphate and dibutyltin bis (ethylmalate) in Table 6 are the values when 100 parts by weight of polyamine is taken.

From the results in Table 6, even if dibutyltin bis (ethylmalate) was used as the organic tin compound instead of dibutyltin diacetate, the same results as those in Example 3-6 in Table 3 and Example 4-4 in Table 4 were obtained. You can see that it was done.

Although some embodiments of the present invention have been described, these embodiments are presented as examples and are not intended to limit the scope of the invention. These novel embodiments can be implemented in various other embodiments, and various omissions, replacements, and changes can be made without departing from the gist of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are also included in the scope of the invention described in the claims and the equivalent scope thereof.

SP ... Injection equipment T1 ... 1st tank T2 ... 2nd tank IT1 ... 1st introduction pipe IT2 ... 2nd introduction pipe CP ... Compressor LT1 ... 1st outlet pipe LT2 ... 2nd outlet pipe F1 ... Second 1 filter F2 ... 2nd filter NZ ... Injection nozzle

Claims (6)

Agent A containing isocyanate; and polyamine, and ammonium polyphosphate of 26 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the polyamine, and 0.021 parts by weight or more and 10.5 parts by weight or less in terms of tin. Agent B containing an organotin compound;
A two-component flame-retardant polyurea resin raw material for forming a coating film. Agent A containing isocyanate; and polyamine, 21 parts by weight or more and 50 parts by weight or less of ammonium polyphosphate, and 9.3 parts by weight or more and 10.5 parts by weight or less in terms of tin with respect to 100 parts by weight of the polyamine. Agent B containing an organotin compound;
A two-component flame-retardant polyurea resin raw material for forming a coating film. The two-component flame-retardant polyurea resin raw material for forming a coating film according to claim 1 or 2, wherein the organotin compound is a dibutyltin compound. The two-component flame-retardant polyurea resin raw material for forming a coating film according to any one of claims 1 to 3, wherein the agent B further contains a hindered amine compound or a melamine compound. (I) A first tank, a first introduction pipe having one end connected to the first tank, a second tank, and a second introduction pipe having one end connected to the second tank. A compressor in which the other ends of the first and second introduction pipes are connected to each other, and a first for deriving a compressed fluid of a fluid introduced from the first introduction pipe by connecting one end to the compressor. The first and second lead-out pipes are connected to the lead-out pipe of the above, a second lead-out pipe for leading out the compressed fluid of the fluid introduced from the second introduction pipe, and one end connected to the compressor. A step of preparing an injection facility including first and second filters arranged in the portion of the compressor and an injection nozzle attached to the other end of the first and second outlet pipes;
(Ii) A step of accommodating the agent A containing isocyanate in the first tank;
(Iii) Polyamine in the second tank, ammonium polyphosphate in an amount of 26 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the polyamine, and 0.021 parts by weight or more and 10.5 parts by weight in terms of tin. Step of accommodating agent B containing the following organotin compounds;
(Iv) The compressor is driven, and the agent A in the first tank is led out to the injection nozzle through the first introduction pipe, the compressor, the first filter and the first outlet pipe, and at the same time. The agent B in the second tank is led out to the injection nozzle through the second introduction pipe, the compressor, the second filter and the second outlet pipe, and the agent A and the B are taken out from the injection nozzle. The step of injecting the agent toward the coating film forming site and performing the curing reaction of the agent A and the agent B at the coating film forming site; and (v) the injection nozzle is predetermined during the step (iv). Step of sequentially moving to the formed coating film formation site;
A method for forming a flame-retardant polyurea resin coating film containing. (I) A first tank, a first introduction pipe having one end connected to the first tank, a second tank, and a second introduction pipe having one end connected to the second tank. A compressor in which the other ends of the first and second introduction pipes are connected to each other, and a first for deriving a compressed fluid of a fluid introduced from the first introduction pipe by connecting one end to the compressor. The first and second lead-out pipes are connected to the lead-out pipe of the above, a second lead-out pipe for leading out the compressed fluid of the fluid introduced from the second introduction pipe, and one end connected to the compressor. A step of preparing an injection facility including first and second filters arranged in the portion of the compressor and an injection nozzle attached to the other end of the first and second outlet pipes;
(Ii) A step of accommodating the agent A containing isocyanate in the first tank;
(Iii) Polyamine in the second tank, ammonium polyphosphate of 21 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the polyamine, and 9.3 parts by weight or more and 10.5 parts by weight in terms of tin. Step of accommodating agent B containing the following organotin compounds;
(Iv) The compressor is driven, and the agent A in the first tank is led out to the injection nozzle through the first introduction pipe, the compressor, the first filter and the first outlet pipe, and at the same time. The agent B in the second tank is led out to the injection nozzle through the second introduction pipe, the compressor, the second filter and the second outlet pipe, and the agent A and the B are taken out from the injection nozzle. The step of injecting the agent toward the coating film forming site and performing the curing reaction of the agent A and the agent B at the coating film forming site; and (v) the injection nozzle is predetermined during the step (iv). Step of sequentially moving to the formed coating film formation site;
A method for forming a flame-retardant polyurea resin coating film containing.

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