CN110628258A - Water-based phosphorus-containing ultrathin fireproof coating material and preparation method thereof - Google Patents
Water-based phosphorus-containing ultrathin fireproof coating material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
- C09D5/185—Intumescent paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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Abstract
The invention provides a water-based phosphorus-containing ultrathin fireproof coating material and a preparation method thereof, belongs to the technical field of fireproof coatings, and can overcome the defects that the existing fireproof coating for a steel structure is poor in heat resistance and releases harmful gases when being heated. The water-based phosphorus-containing ultrathin fireproof coating material comprises the following raw material components in parts by weight: 20-30% of phosphoric acid modified epoxy/acrylate emulsion, 20-25% of ammonium polyphosphate, 5-10% of pentaerythritol, 5-10% of melamine, 2-5% of expanded graphite, 5-10% of titanium dioxide and 0-5% of an auxiliary agent. The water-based phosphorus-containing ultrathin fireproof coating material provided by the invention has the advantages of good temperature resistance, excellent fireproof, heat-insulating and smoke-inhibiting performances, tight combination with a steel structure, simple preparation process, lower cost and good economic value.
Description
Technical Field
The invention relates to the technical field of fireproof coatings, in particular to a water-based phosphorus-containing ultrathin fireproof coating material for a steel structure and a preparation method thereof.
Background
The steel structure building has high strength, good shock resistance, flexible design and convenient construction, thereby having wide application. However, some steel structural materials used at present generally have the defect of poor fire resistance. Especially when the temperature of the fire scene is higher than 600 ℃, the strength and hardness of the steel structure are all lost (refer to Zhai Quercus, fire Forum, 2018,4, 108-. Because of the heat resistance problem of the steel structure, serious potential safety hazards are brought to the production and life of people, the steel structure needs to be processed before being used, so that the temperature resistance of the steel structure is improved or the tolerance of the steel structure in case of fire and other sudden situations is improved.
According to the difference of coating thickness, the fire-retardant coating can be divided into thick (>7mm), thin (3-7mm) and ultra-thin (<3mm) fire-retardant coating. According to the difference of fire-proof mechanism, the fire-proof coating can be divided into non-expansion type and expansion type, the non-expansion type fire-proof coating is mainly composed of incombustible base material, inorganic filler and fire retardant, etc. and can absorb heat by means of a series of physicochemical reactions under the condition of high temperature, so that the heating rate of coating and base material can be reduced, in addition, after the material is molten, an inorganic glaze-like protective layer is formed on the surface of the material, and the air and base material can be separated, so that the protective action can be obtained, and generally a thicker coating is required (see Lebo et al, novel chemical material, 2018, 46: 227). The intumescent fire-retardant coating plays a role in heat insulation and mass insulation through a honeycomb-shaped carbon structure formed by the decomposition of a fire-retardant gas and the occurrence of a carbonization reaction when the temperature rises, thereby achieving a fire-retardant effect (see the Poplar, the contemporary chemical industry, 2017, 46: 1923). Compared with the prior art, the intumescent fire-retardant coating can be made into thin and ultrathin fire-retardant coatings, is convenient to construct, has better bonding performance with a base material, and is more widely applied. Intumescent fire-retardant coatings are generally composed of organic resin binders, intumescent agents, fillers and other auxiliary agents, the intumescent agents being phosphorus (ammonium polyphosphate) -carbon (pentaerythritol) -nitrogen (melamine) components that vaporize and carbonize when heated (see zhao panyu et al, "coatings and protections", 2018, 39: 44). Organic resin binders, which serve to bind the various components together and form an integral part of the substrate, are also critical in fire-retardant coatings. The low temperature resistance of organic resin binders and the thermal effects of burning when heated typically impair the fire-retardant effect of the coating, and the burning process often produces toxic fumes. Therefore, it is an important direction to improve the fire-proof effect of the fire-proof coating by using an organic resin binder with excellent heat resistance or by modifying the resin to improve the heat-resistant and fire-resistant properties.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the water-based phosphorus-containing ultrathin fireproof coating material for the steel structure and the preparation method thereof2Less gas discharge, high carbon conversion rate and good fireproof, flame-retardant and heat-insulating effects.
The invention provides a water-based phosphorus-containing ultrathin fireproof coating material and a preparation method thereof, which are characterized by comprising the following components in parts by weight:
phosphoric acid modified epoxy/acrylate emulsion: 20 to 30 percent
Ammonium polyphosphate: 20 to 25 percent;
pentaerythritol: 5 to 10 percent;
melamine: 5 to 10 percent;
expanded graphite: 2 to 5 percent;
titanium dioxide: 5 to 10 percent;
auxiliary agent: 0 to 5 percent;
preferably, the phosphoric acid modified epoxy/acrylate emulsion is synthesized by a seed emulsion semi-continuous method from the following components.
Epoxy resin: 5 to 15 percent;
acrylate ester monomer: 30-40%;
phosphorus-containing acrylate monomer: 1 to 10 percent;
initiator: 0.001-0.01%;
emulsifier: 1 to 5 percent;
deionized water: 30 to 50 percent of
(step 1) Pre-emulsification: weighing a certain amount of emulsifier, stirring and dissolving in deionized water to obtain an emulsion. Adding half of the emulsion into a three-neck flask equipped with a constant-pressure dropping device, a mechanical stirring device and a ventilating device, dropwise adding the mixed epoxy resin, acrylate monomer and phosphorus-containing acrylate monomer into the three-neck flask, stirring at a high speed, and pre-emulsifying to obtain pre-emulsion;
(step 2) semi-continuous seed-initiated polymerization: adding a certain amount of pre-emulsion and the rest of emulsion into a three-necked bottle equipped with a constant pressure dropping device, a mechanical stirring device and a ventilation device, dropwise adding a part of initiator solution (aqueous solution containing the initiator), reacting for a period of time at a certain temperature, dropwise adding the rest of pre-emulsion and the initiator solution, continuing to react for a period of time, and cooling to obtain the phosphoric acid modified epoxy/acrylate emulsion.
Optionally, the epoxy resin is one of E44 and E51.
Preferably, the acrylate monomer is a mixture of methyl methacrylate, butyl acrylate and acrylic acid.
Preferably, the phosphorus-containing acrylic monomer is obtained by reacting phosphoric acid and glycidyl methacrylate under heating.
Optionally, the initiator is at least one of potassium persulfate and ammonium persulfate.
Preferably, the emulsifier is a compound emulsifier composed of octyl phenol polyoxyethylene ether and sodium dodecyl sulfate according to a certain proportion.
Preferably, the expanded graphite has a size of 50-500 μm.
A water-based phosphorus-containing ultrathin fireproof coating material and a preparation method thereof comprise the following steps: the components are added into a high-speed stirrer in sequence according to the water, the auxiliary agent, the expanded graphite, the titanium dioxide, the melamine, the ammonium polyphosphate, the pentaerythritol and the phosphoric acid modified epoxy/acrylate emulsion, and the rotating speed is adjusted according to the requirement to uniformly disperse the materials, so that the water-based phosphorus-containing ultrathin fireproof coating material can be prepared.
The water-based phosphorus-containing ultrathin fireproof coating material prepared by the method and the preparation method.
The invention provides a water-based phosphorus-containing ultrathin fireproof coating material and a preparation method thereof, and the water-based phosphorus-containing ultrathin fireproof coating material has the following beneficial effects:
(1) phosphorus is introduced into the resin matrix, and the heat release process is interrupted by capturing free radicals during combustion, so that the combustion is inhibited, the flame resistance of the resin adhesive is improved, and the fireproof effect of the fireproof coating is greatly improved.
(2) The introduction of phosphorus in the resin matrix participates in the thermal degradation process of the resin matrix, the carbon forming rate is improved, the emission of CO and CO2 gas is reduced, and the smoke suppression effect is achieved on the whole.
(3) The epoxy/acrylate resin is modified by phosphoric acid, so that the adhesion and durability of the coating and the steel structure substrate are further improved, and the adaptability is stronger.
(4) The expanded graphite is introduced as an auxiliary expansion agent and a heat-resistant framework material, is beneficial to supplement of a phosphorus (ammonium polyphosphate) -carbon (pentaerythritol) -nitrogen (melamine) expansion agent, and can optimize an expansion structure of the fireproof coating when being heated, so that the fireproof coating has more excellent fireproof, heat-resistant and smoke-suppression effects.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a water-based silicon-based ultrathin fireproof coating material and a preparation method thereof, wherein the water-based silicon-based ultrathin fireproof coating material comprises the following components in percentage by weight: 20-30% of phosphoric acid modified epoxy/acrylate emulsion, 20-25% of ammonium polyphosphate, 5-10% of pentaerythritol, 5-10% of melamine, 2-5% of expanded graphite, 5-10% of titanium dioxide and 0-5% of an auxiliary agent. The epoxy/acrylate emulsion modified by phosphoric acid is used as an adhesive, so that the heat resistance, the flame resistance and the smoke suppression of the resin can be effectively improved, the conversion rate of solid carbon when heated is improved, and more excellent temperature resistance, flame retardance and smoke suppression effects are provided.
In one embodiment of the invention, the phosphoric acid modified epoxy/acrylate emulsion is synthesized by 5-15% of epoxy resin, 30-40% of acrylate monomer, 1-10% of phosphorus-containing acrylate monomer, 0.001-0.01% of initiator, 1-5% of emulsifier and 30-50% of deionized water through a seed emulsion semi-continuous method. The introduction of the epoxy resin can improve the cohesiveness among the components and the binding force with a steel structure base material when the epoxy resin is used as an adhesive, and improve the comprehensive rationalization performance of the fireproof coating.
(S1) pre-emulsification: weighing a certain amount of emulsifier, stirring and dissolving in deionized water to obtain an emulsion. Adding half of the emulsion into a three-neck flask equipped with a constant pressure dropping device, a mechanical stirring device and a ventilating device, dropwise adding the mixed epoxy resin, acrylate monomer and phosphorus-containing acrylate monomer into the three-neck flask, stirring at high speed, and pre-emulsifying to obtain pre-emulsion.
In the step, the epoxy resin and the acrylic ester monomer emulsion which are uniformly dispersed in the aqueous medium are obtained in a pre-emulsification mode, so that preparation is provided for the next emulsion polymerization reaction.
(S2) semi-continuous seed initiated polymerization: adding a certain amount of pre-emulsion and the rest of emulsion into a three-necked bottle equipped with a constant pressure dropping device, a mechanical stirring device and a ventilation device, dropwise adding a part of initiator solution (aqueous solution containing the initiator), reacting for a period of time at a certain temperature, dropwise adding the rest of pre-emulsion and the initiator solution, continuing to react for a period of time, and cooling to obtain the phosphoric acid modified epoxy/acrylate emulsion.
In the step, acrylate monomers are polymerized into polymers through semi-continuous seed initiation polymerization reaction, and the polymers and epoxy resin form an interpenetrating network structure, so that a high-performance adhesive is provided for the fireproof coating material. It should be noted that, in this step, many factors are involved, such as stirring rate, relative concentrations of monomers and initiator in the reaction system, reaction temperature, reaction time, etc., and different processes may result in phosphoric acid modified epoxy/acrylate emulsion with large difference in performance.
In an embodiment of the present invention, the epoxy resin is one of E44 and E51. Different designations represent different epoxy values in the resin and also represent different physical and chemical properties. In contrast, the higher viscosity of the epoxy resin is lower than that of E44, and the viscosity of E51 is lower than that of E44, but the cured product is brittle, so that the researchers can select the epoxy resin according to the application place and the whole material formula system.
In an embodiment of the present invention, the acrylate monomer is a mixture of methyl methacrylate, butyl acrylate and acrylic acid. Different acrylate monomers have different reactivity and the physical properties of the resulting polymers are different, for example, methacrylate and acrylate, methyl acrylate and butyl acrylate, although the structure is only the difference of one or more alkyl groups, the change of the coating performance is brought, for example, the toughness, elasticity, water resistance and the like of the coating, and the better effect can be obtained by compounding different acrylate monomers.
In one embodiment of the present invention, the phosphorus-containing acrylate monomer is obtained by reacting phosphoric acid and glycidyl methacrylate under heating. The phosphorus-containing acrylate monomer is the key for introducing phosphorus into the organic resin adhesive, and in the embodiment, the phosphorus-containing acrylate monomer is prepared through the condensation reaction of phosphoric acid and glycidyl methacrylate, the reaction needs heating, and the phosphoric acid is a reactant and also plays a role of a catalyst, so that the condensation reaction has an autocatalytic property.
In one embodiment of the present invention, the initiator is at least one of potassium persulfate and ammonium persulfate. Ammonium sulfate or potassium sulfate is redox initiator, which decomposes to generate free radicals under heating, can initiate polymerization at a lower temperature, has a higher polymerization speed, is a common initiator for aqueous phase polymerization, and can initiate polymerization by adopting a concentration of about 1 per thousand.
In an embodiment of the present invention, the emulsifier is a compound emulsifier composed of octylphenol polyoxyethylene ether and sodium dodecyl sulfate in a certain proportion. The proper emulsifier can show better emulsifying effect at lower concentration, and our research finds that when a certain proportion of octylphenol polyoxyethylene ether and sodium dodecyl sulfate are used as the emulsifier, the effect is obviously better than that of a single emulsifier or the effect of compounding with other emulsifiers.
In one embodiment of the invention, the expanded graphite has a size of between 50 and 500 μm. The graphite has a lamellar structure, and when the graphite is heated, the lamellar moves along the c axis, so that the volume of the graphite can be expanded to more than 50 times of the original volume, a hollow network structure is provided for the fireproof coating, the heat conductivity of the coating is reduced, and the transmission of flame and temperature is prevented. Researches find that the fireproof effect is better when the graphite and the binding resin have synergistic effect. Therefore, the proper proportion and the interaction between the graphite and the silicon-based resin promote the synergistic effect between the graphite and the silicon-based resin, and when the size of the expanded graphite is between 50 and 500 mu m, a better fireproof effect can be achieved.
The invention also provides a water-based phosphorus-containing ultrathin fireproof coating material and a preparation method thereof, wherein the preparation method comprises the following steps: the components are added into a high-speed stirrer in sequence according to the water, the auxiliary agent, the expanded graphite, the titanium dioxide, the melamine, the ammonium polyphosphate, the pentaerythritol and the phosphoric acid modified epoxy/acrylate emulsion, and the rotating speed is adjusted according to the requirement to uniformly disperse the materials, so that the water-based phosphorus-containing ultrathin fireproof coating material can be prepared.
The invention also provides the aqueous phosphorus-containing ultrathin fireproof coating material prepared by the preparation method of the aqueous phosphorus-containing ultrathin fireproof coating material. When the prepared water-based phosphorus-containing ultrathin fireproof coating material is used as a steel structure protective coating, the water-based phosphorus-containing ultrathin fireproof coating material has good flame retardant, heat resistant and smoke suppression effects.
In order to make the technical solution of the present invention better understood by those skilled in the art, the following will explain the product of the present invention in detail with reference to specific embodiments.
Example one
Dispersing 2g of expanded graphite, 5g of titanium dioxide and 2g of auxiliary agent in deionized water, stirring at a high speed to uniformly mix the materials, then adding 5g of melamine, 5g of pentaerythritol and 20g of ammonium polyphosphate, stirring at a high speed to uniformly mix the materials, finally adding 20g of phosphoric acid modified epoxy/acrylate emulsion, and uniformly mixing the materials to obtain the aqueous phosphorus-containing ultrathin fireproof coating material 1.
Example two
Dispersing 5g of expanded graphite, 10g of titanium dioxide and 5g of auxiliary agent in deionized water, stirring at a high speed to uniformly mix the materials, then adding 10g of melamine, 10g of pentaerythritol and 25g of ammonium polyphosphate, stirring at a high speed to uniformly mix the materials, finally adding 30g of phosphoric acid modified epoxy/acrylate emulsion, and uniformly mixing the materials to obtain the aqueous phosphorus-containing ultrathin fireproof coating material 2.
EXAMPLE III
Dispersing 3g of expanded graphite, 8g of titanium dioxide and 3g of auxiliary agent in deionized water, stirring at a high speed to uniformly mix the materials, then adding 8g of melamine, 8g of pentaerythritol and 22g of ammonium polyphosphate, stirring at a high speed to uniformly mix the materials, finally adding 25g of phosphoric acid modified epoxy/acrylate emulsion, and uniformly mixing the materials to obtain the aqueous phosphorus-containing ultrathin fireproof coating material 3.
The use effect of the invention is as follows:
in conclusion, the invention provides the water-based phosphorus-containing ultrathin fireproof coating material and the preparation method thereof, and the method has the advantages of simple process and low cost. The water-based phosphorus-containing ultrathin fireproof coating material prepared by the method has good adhesive property and excellent fireproof, flame-retardant and heat-insulating effects, and the fire endurance can reach more than 100 minutes.
Claims (10)
1. The water-based phosphorus-containing ultrathin fireproof coating material is characterized by comprising the following components in parts by weight:
phosphoric acid modified epoxy/acrylate emulsion: 20 to 30 percent
Ammonium polyphosphate: 20 to 25 percent;
pentaerythritol: 5 to 10 percent;
melamine: 5 to 10 percent;
expanded graphite: 2 to 5 percent;
titanium dioxide: 5 to 10 percent;
auxiliary agent: 0 to 5 percent.
2. The aqueous phosphorus-containing ultrathin fireproof coating material and the preparation method thereof as claimed in claim 1, characterized in that phosphoric acid modified epoxy/acrylate emulsion is synthesized by seed emulsion semi-continuous method from the following components.
Epoxy resin: 5 to 15 percent;
acrylate ester monomer: 30-40%;
phosphorus-containing acrylate monomer: 1 to 10 percent;
initiator: 0.001-0.01%;
emulsifier: 1 to 5 percent;
deionized water: 30 to 50 percent of
(1) Pre-emulsification: weighing a certain amount of emulsifier, stirring and dissolving in deionized water to obtain an emulsion. Adding half of the emulsion into a three-neck flask equipped with a constant-pressure dropping device, a mechanical stirring device and a ventilating device, dropwise adding the mixed epoxy resin, acrylate monomer and phosphorus-containing acrylate monomer into the three-neck flask, stirring at a high speed, and pre-emulsifying to obtain pre-emulsion;
(2) semi-continuous seed initiated polymerization: adding a certain amount of pre-emulsion and the rest of emulsion into a three-necked bottle equipped with a constant pressure dropping device, a mechanical stirring device and a ventilation device, dropwise adding a part of initiator solution (aqueous solution containing the initiator), reacting for a period of time at a certain temperature, dropwise adding the rest of pre-emulsion and the initiator solution, continuing to react for a period of time, and cooling to obtain the phosphoric acid modified epoxy/acrylate emulsion.
3. The aqueous phosphorus-containing ultrathin fireproof coating material and the preparation method thereof as claimed in claims 1 and 2, wherein the epoxy resin is one of E44 and E51.
4. The aqueous phosphorus-containing ultrathin fireproof coating material and the preparation method thereof as claimed in claims 1 and 2, characterized in that the acrylate monomer is a mixture of methyl methacrylate, butyl acrylate and acrylic acid.
5. The water-based phosphorus-containing ultrathin fireproof coating material and the preparation method thereof as claimed in claims 1 and 2, characterized in that the phosphorus-containing acrylic acid monomer is obtained by reacting phosphoric acid and glycidyl methacrylate under heating.
6. The aqueous phosphorus-containing ultrathin fireproof coating material and the preparation method thereof as claimed in claims 1 and 2, characterized in that the initiator is at least one of potassium persulfate and ammonium persulfate.
7. The aqueous phosphorus-containing ultrathin fireproof coating material and the preparation method thereof as claimed in claims 1 and 2, characterized in that the emulsifier is a compound emulsifier composed of octylphenol polyoxyethylene ether and sodium dodecyl sulfate in a certain proportion.
8. The aqueous phosphorus-containing ultrathin fireproof coating material and the preparation method thereof of claim 1, wherein the size of the expanded graphite is 50-500 μm.
9. The aqueous phosphorus-containing ultrathin fireproof coating material and the preparation method thereof according to claims 1 to 8, characterized by comprising the following steps: the components are added into a high-speed stirrer in sequence according to the water, the auxiliary agent, the expanded graphite, the titanium dioxide, the melamine, the ammonium polyphosphate, the pentaerythritol and the phosphoric acid modified epoxy/acrylate emulsion, and the rotating speed is adjusted according to the requirement to uniformly disperse the materials, so that the water-based phosphorus-containing ultrathin fireproof coating material can be prepared.
10. The aqueous phosphorus-containing ultrathin fireproof coating material and the preparation method of the aqueous phosphorus-containing ultrathin fireproof coating material according to claims 1 to 9.
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Application publication date: 20191231 |
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