JPH08253710A - Intumescent fire resistant coating material - Google Patents

Abstract

PURPOSE: To obtain an intumescent coating material improved in resistances to water, fire, and weather by incorporating melamine-coated ammonium polyphosphate particles and/or insol. ammonium polyphosphate particles having cross-linked surfaces into the material. CONSTITUTION: Ammonium polyphosphate particles are heated at 300 deg.C or lower for 0.5-5hr to separate ammonia in an amt. of 5-10wt.% of the stoichiometric amt. Melamine is added to the heated particles at 250-300 deg.C to cause the addition reaction and/or adhesion of melamine to hydroxyl groups of acids formed on the surfaces of the particles by the separation of ammonia, giving melaminecoated ammonium polyphosphate particles (A). A compd. having functional groups reactive with active hydrogen atoms of amino groups of melamine molecules on the surfaces of particles A is added in an equivalent ratio to the amino groups of 0.5-6 to particles A and is heated at 80-200 deg.C for a necessary time to form cross-links with melamine on the surfaces, giving insol. ammonium polyphosphate particles (B). An intumescent fire resistant coating material is prepd. by compounding 100 pts.wt. synthetic binder resin with 50-400 pts.wt. particles A and/or B.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a foamed fire-resistant coating material containing melamine-coated ammonium polyphosphate and / or insoluble ammonium polyphosphate, which is excellent in fire resistance, water resistance and weather resistance.

[0002]

2. Description of the Related Art Conventionally, various paints are known for delaying the influence of a flame on many structures. These paints have the function of slowing the rate of temperature rise of the substrate to which they are applied and prolonging the time before the structure is damaged by the heat of the flame. Generally, there is a wet refractory coating material in which a paint in which an inorganic fibrous substance such as rock wool, asbestos, glass fiber or the like, a lightweight aggregate such as vermiculite or the like is mixed with an inorganic substance such as cement is thickened. However, these coating materials require a coating of about 1 to 3 cm, which is not preferable in terms of work process or aesthetics.

As a technique for solving such a problem, there has been proposed a foamed refractory paint which foams a coating film to impart fire resistance when the temperature rises due to a fire or the like. For example, JP-A-5-86
Japanese Unexamined Patent Publication No. 310 discloses a foaming fireproof paint comprising a one-pack modified epoxy resin containing ammonium polyphosphate as a foaming agent as a foamable fireproof paint and pentaerythritol, melamine and the like as a carbon-generating material. Also,
Japanese Unexamined Patent Publication (Kokai) No. 5-70540 discloses a thick coating foamable refractory composition containing expandable graphite, phosphorus or a phosphorus compound, a branched polyhydric alcohol, and a nitrogen-containing compound-based foaming agent. Further, Japanese Patent Application Laid-Open No. 6-16975 discloses a fire-preventive paint containing ammonium polyphosphate as a char-forming agent. However, the fire-resistant paint, the fire-resistant composition, or the fire-resistant paint described in the above publication is caused by the high water solubility of its component ammonium polyphosphate or a phosphorus compound. Alternatively, there is a problem that the water resistance of the coating film after drying applied to wood or the like is not satisfactory.

On the other hand, JP-A-5-65436 discloses a foam containing a high-molecular-weight ammonium polyphosphate microencapsulated with a melamine resin having high resistance to water extraction when mixed with an aqueous synthetic resin vehicle. Fire resistant coatings are disclosed. However, ammonium polyphosphate microencapsulated with a resin has high resistance to water extraction as disclosed in the above publication, but it does not yet have sufficient water resistance. Further, the ammonium polyphosphate causes an increase in particle size in the process of microencapsulation, resulting in a decrease in dispersibility in the synthetic resin binder, which causes a decrease in fire resistance. .

As a means for solving the above-mentioned problems, the inventors of the present invention are characterized in that, in JP-A-6-263416, melamine is added and / or attached to the surface of powdery ammonium polyphosphate particles. Invented melamine coated ammonium polyphosphate. Further, in Japanese Patent Application No. 6-93721, melamine-coated ammonium polyphosphate particles comprising melamine on the surface of the melamine-coated ammonium polyphosphate particles and a crosslinking agent having a functional group capable of reacting with active hydrogen of an amino group in the melamine molecule are disclosed. We have developed insoluble ammonium polyphosphate particles that are characterized by their cross-linked surfaces. These melamine-coated ammonium polyphosphates and / or insoluble ammonium polyphosphates have extremely high resistance to water without increasing the particle size of ammonium polyphosphate.

By the way, since the melamine-coated ammonium polyphosphate and / or the insoluble ammonium polyphosphate is not microencapsulated by the coating material, particles do not increase due to aggregation. The present invention has been completed by finding that the fireproof coating has improved dispersibility in a synthetic resin binder and not only water resistance but also fire resistance and weather resistance.

[0007]

The present invention has the following configuration. (1) A foamed fire-resistant paint containing a synthetic resin as a binder and containing melamine-coated ammonium polyphosphate and / or insoluble ammonium polyphosphate. (2) The content of the melamine-coated ammonium polyphosphate and / or the insoluble ammonium polyphosphate is 50 to 40 with respect to 100 parts by weight of the synthetic resin as the binder.
The foamed refractory paint, characterized in that it is 0 part by weight. (3) The foamed refractory paint, wherein the synthetic resin is a urethane resin, an epoxy resin, an acrylic resin, or an alkyd resin. (4) The foamed refractory paint, wherein the synthetic resin is a synthetic resin emulsion such as a vinyl acetate-based resin emulsion, an acrylate ester-based resin emulsion, a versatic vinyl acrylate-based resin emulsion, and an ethylene-based resin emulsion. (5) The foamed fire-resistant paint, wherein melamine-coated ammonium polyphosphate has melamine added and / or attached to the surface of powdery ammonium polyphosphate particles. (6) The surface of the insoluble ammonium polyphosphate is formed by the active hydrogen contained in the amino group in the melamine molecule present in the coating layer of the melamine-coated ammonium polyphosphate particles and the compound having a functional group capable of reacting with the active hydrogen. The foamed refractory paint, characterized in that the above is cross-linked.

The melamine-coated ammonium polyphosphate used in the present invention is obtained by adding and / or adhering melamine to the surface of ammonium polyphosphate particles. Such melamine-coated ammonium polyphosphate particles can be obtained by the following method. it can. That is, the ammonium polyphosphate particles are charged into a heating kneading device such as a heated kneader, the ammonium polyphosphate particles are not melted, and the temperature at which ammonia in the ammonium polyphosphate easily desorbs, that is, Heating is performed at 300 ° C. or lower, preferably 200 to 300 ° C. for 0.5 to 5 hours, and a part of the ammonia that is originally present in the stoichiometric amount in ammonium polyphosphate (5 to the stoichiometric amount of ammonia is 5 In a known production process of ammonium polyphosphate or ammonium polyphosphate in a state where ammonia is depleted (about 10% by weight), the amount of bound ammonium is less than the stoichiometric amount. , These are called ammonia-deficient ammonium polyphosphates) and then in the same equipment. Temperature at and melamine ammonia shortage ammonium polyphosphate particles do not melt Te is a temperature capable of sublimation 250
Melamine is added by heating to a temperature of 300 ° C., and the melamine is added and / or attached to the hydroxyl group which has become an acid due to the elimination of ammonia on the surface of the ammonium-deficient ammonium polyphosphate particles.

Here, the addition means a state in which melamine is ionically bound to a proton of an oxygen-proton bond derived from ammonium polyphosphate, and the added melamine is stable even when heated and cannot be desorbed again. Absent. Also,
Adhesion means a state in which melamine is physically or chemically adsorbed on the surface of ammonium polyphosphate particles, and melamine adsorbed on the surface of ammonium polyphosphate particles by continuous heating repeats sublimation and adsorption and oxygen-proton bond. Binds ionicly with the protons of.

In addition, the insoluble ammonium polyphosphate particles used in the present invention are obtained by reacting active hydrogen having an amino group in a melamine molecule existing in the melamine-coated layer of melamine-coated ammonium polyphosphate with an isocyanate group, a glycidyl group or an aldehyde group. It is ammonium polyphosphate in which a crosslinked structure is formed between melamine molecules on the same particle by reacting a compound having a functional group capable of reacting with active hydrogen, and such insoluble ammonium polyphosphate can be obtained by the following method. it can. That is, a melamine-coated ammonium polyphosphate particle and a compound having a functional group capable of reacting with active hydrogen belonging to an amino group in a melamine molecule, for example, an aqueous formaldehyde solution are charged and mixed in a reactor equipped with a heating stirring or kneading mechanism. . Temperature 80 at which a crosslinked structure between active hydrogens is easily formed
To 200 ° C., preferably 100 to 150 ° C., and insoluble ammonium polyphosphate particles having a crosslinked structure formed in the coating layer of the melamine-coated ammonium polyphosphate particles by reacting for a sufficient time to complete the crosslinking reaction. Can be obtained. This crosslinking reaction may be either a non-solvent system or a solvent system, and the solvent system may be water, an organic solvent or a mixed solvent composed of two or more kinds of these solvents. The functional group contained in the cross-linking agent is 0.5 to 6 times equivalent, preferably 1 to 3 times equivalent to the amino group in the melamine molecule of the melamine-coated ammonium polyphosphate. If it is less than 0.5 times equivalent, crosslinking between melamines is not sufficiently performed. On the other hand, when the amount is more than 6 times equivalent, unreacted substances remain, which is not preferable.

The functional group which reacts with the active hydrogen belonging to the amino group in the melamine molecule is an isocyanate group, a glycidyl group, a carboxyl group, a methylol group or an aldehyde group, and the number of the functional groups is 1 or 2 or more. . Examples of the compound having the functional group include hexamethylene diisocyanate, tolylene diisocyanate,
3,3'-dimethyldiphenyl-4,4'-diisocyanate, 1,5-diisocyanonaphthalate, monomethylol urea, dimethylol urea, monomethylol melamine, dimethylol melamine, trimethylol melamine,
Tetramethylolmelamine, pentamethylolmelamine, hexamethylolmelamine, methylolmelamine initial condensate, trimethylolethane, trimethylolpropane, formaldehyde, malonaldehyde, glyoxal, ethylene glycol diglycidyl ether, glycerol polyglycidyl ether, bisphenol A
Examples of the epoxy resin include various epoxy resins represented by epoxy resin, phenol novolac epoxy resin, cycloaliphatic epoxy resin, and the like, and all of them can be commercially available products.

As the synthetic resin binder used in the present invention, a resin usually known by those skilled in the art can be used. For example, urethane resin, epoxy resin, acrylic resin, alkyd resin, or the like, or synthetic resin emulsion such as vinyl acetate-based resin emulsion, acrylic ester-based resin emulsion, or ethylene-based resin emulsion.

As the urethane resin, a polyol component and a polyisocyanate component which are usually used as a room temperature curable two-component polyurethane resin can be arbitrarily selected. Examples of the polyols include polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol. Furthermore, ethylene glycol, 1,2-propylene glycol, 2,3-butylene glycol, 1,4-
Butylene glycol, 2,2'-dimethyl-1,3-propanediol, diethylene glycol and the like, glycol alone or a mixture thereof and succinic acid, adipic acid,
Examples thereof include dibasic acids such as glutaric acid, pimelic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid, and their acid esters and polyester polyols obtained by polycondensation with acid halides.

Examples of polyisocyanates include:
Hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, xylene diisocyanate, cyclohexane diisocyanate, toluidine diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, p-phenylene diisocyanate, m- Phenylene diisocyanate, 1,
Examples include 5-naphthylene diisocyanate and the like and mixtures thereof.

As the epoxy resin, those which are usually used as aliphatic, aromatic, cyclic, acyclic, alicyclic or heterocyclic can be arbitrarily selected. For example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4
-Butylene glycol, 1,5-pentanediol,
Mention may be made of polyglycidyl ethers derived from polyhydric alcohols such as 1,2,6-hexanetriol, glycerol, trimethylolpropane, bisphenol-A and bisphenol-F. Furthermore, oxalic acid, succinic acid, glutaric acid, teleephthalic acid, 2,6-
Mention may be made of polyglycidyl ethers of carboxylic acids which are the reaction products of aliphatic or aromatic polycarboxylic acids such as naphthalene dicarboxylic acids and divalent linoleic acids with epichlorohydrin.

As the acrylic resin, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate,
From methacrylates such as alkyl methacrylate, tridecyl methacrylate, stearyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, etc. 1 or 2 chosen
Combinations of more than one species can be mentioned.

Examples of the alkyd resin include saturated polybasic acids such as phthalic anhydride, terephthalic acid, succinic acid, adipic acid and sebacic acid, or unsaturated polybasic acids such as maleic acid, maleic anhydride and fumaric acid, and ethylene glycol, Examples thereof include reaction products with a polyol arbitrarily selected from diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, glycerin, trimethylolpropane, diglycerol, triglycerol, pentaerythritol and the like.

Examples of the synthetic resin emulsion include acrylic acid ester type resin emulsions synthesized from monomers such as methyl acrylate, ethyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylic acid and styrene. Other examples include polyvinyl acetate emulsions, vinyl acetate-ethylene copolymer emulsions, vinyl acetate-vinyl propionate copolymer emulsions, vinyl acetate-acrylate copolymer emulsions.

The amount of melamine-coated ammonium polyphosphate and / or insoluble ammonium polyphosphate added to the above resin is 50 to 400 parts by weight, preferably 100 to 300 parts by weight, based on 100 parts by weight of the synthetic resin binder. When the amount added is less than 50 parts by weight, the fire resistance is extremely insufficient, and when the amount added is more than 400 parts by weight, the effect of the fire resistance is hardly improved.

In addition to the melamine-coated ammonium polyphosphate and / or the insoluble ammonium polyphosphate, a foaming agent and a carbon-forming agent can be simultaneously added to the foamed refractory paint of the present invention. As a foaming agent, melamine, melamine-formaldehyde resin, melamine derivatives such as C4-9 methylol melamine, and melamine cyanurate,
(Thio) urea, (thio) urea-formaldehyde resin,
Urea derivatives such as methylol (thio) urea having 2 to 5 carbon atoms, guanamines such as benzoguanamine, phenylguanamine, acetoguanamine and succinylguanamine, and reaction products of the guanamines and formaldehyde,
Mention may be made of nitrogen-containing compounds such as dicyandiamide, guanidine and guanidine sulfamate.

Examples of the carbon-forming agent include monopentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, tris (2-hydroxyethyl) isocyanate, triethylene glycol, sorbitol, resorcinol, glycerin, trimethylolmethane, trimethylolmethane, and trimethylolmethane. Mention may be made of polyhydric alcohols such as methylol propane, diethylene glycol, propylene glycol, hexamethylene glycol, inositol and carbohydrates such as starch, glucose, sucrose and starch.

The foamed fire-resistant coating material of the present invention contains inorganic metal hydrates such as aluminum hydroxide and magnesium hydroxide as flame retardant aids, smoke suppressants or fillers, fumed silica, precipitated silica, silicic acid anhydride, Zinc borate, carbon black, carbon fiber, calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, mica, titanium oxide, bentonite, kaolin, montmorillonite, wollastonite, rockwool, glass fiber, asbestos, hydrotal Any amount of site, zinc oxide, zirconium oxide, inorganic compounds such as alumina, silica alumina, magnesia, zeolite and the like, and heat resistant organic fibers such as polyester fiber, polyamide fiber, polyimide fiber and the like can be blended. In addition, silane coupling agents such as vinyltrimethoxysilane and aminotrimethoxysilane, epoxy resins, phenol resins, rosins, C5-based petroleum resins, C9-based petroleum resins, cyclopentadiene-based petroleum resins, etc. are also compounded as adhesion-imparting agents. can do.

[0023]

EXAMPLES In order to specifically explain the present invention, examples and comparative examples are shown below, but the present invention is not limited thereto. The evaluations in Examples and Comparative Examples were carried out by the following methods. 1) Preparation of coating film Steel plate (JIS.G3141 SPCC-SD Dimension 0.
8 mm thick × 70 mm × 150 mm), a fire-resistant paint having the following formulation was applied at a rate of about 300 g / m ^{2 in} terms of solid content, and dried at room temperature for 7 days. 2) Fire resistance A coated steel plate is erected vertically and 1000 ± 5 on the surface of this coated plate.
A 0 ° C. oxygen-mixed propane gas flame was applied with a Bunsen burner for 10 minutes, and the back surface temperature of the coated steel sheet was measured with a thermocouple. 3) Water resistance A coated steel sheet was immersed in hot water at 50 ° C for 7 days and then dried at 50 ° C for 3 days, and the fire resistance after immersion in hot water and the fire resistance before immersion were compared by measuring the backside temperature of the steel sheet. . 4) Weather resistance Accelerated weather resistance is evaluated according to JIS. K5400 Based on the sunshine carbon arc lamp system. The coated steel sheet is exposed to a weather meter (black panel thermometer 60 ° C, rainfall cycle; 120-minute cycle-18-minute rain) for 600 hours,
The fire resistance after exposure and the fire resistance before exposure were compared by measuring the backside temperature of the steel sheet.

Example 1 As a synthetic resin binder, 100 parts by weight of a beckozole ES-5504-50 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.), an always dry alkyd resin, was used as an insoluble ammonium polyphosphate TERRAJU C60 (trade name, 250 parts by weight, manufactured by Chisso Corporation, 50 parts by weight of melamine as a foaming agent, and 100 of dipentaerythritol as a carbon former.
Parts by weight, 60 parts by weight of titanium dioxide, and 200 parts by weight of toluene as a diluent were mixed in advance and then sufficiently kneaded with a three-roll mill, which was applied as a paint to a steel sheet. The coated steel sheet was evaluated for fire resistance, water resistance and weather resistance, and the results are shown in Table 1.

Example 2 Acrylic resin Acrydic 52-204 (trade name, Dainippon Ink and Chemicals, Inc.) as a synthetic resin binder
100 parts by weight of insoluble ammonium polyphosphate T
ERRAJU C60 (trade name, manufactured by Chisso Corporation) 30
0 parts by weight, 50 parts by weight of dicyandiamide as a foaming agent,
80 parts by weight of tris (2-hydroxyethyl) isocyanurate as a carbon former, 50 parts by weight of titanium dioxide, and 180 parts by weight of toluene as a diluent were mixed in advance and then sufficiently kneaded with a three-roll mill to obtain a paint. Was applied to the steel sheet as. The coated steel sheet was evaluated according to Example 1, and the results are shown in Table 1.

Example 3 49 parts by weight of polyester polyol Vernock D-220 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) as a synthetic resin binder and polyisocyanate Vernock DN-980S (trade name, Dainippon Ink and Chemicals, Inc.) )) 51 parts by weight, TERRAJU C60 (trade name, manufactured by Chisso Corporation) as insoluble ammonium polyphosphate, and 60 parts by weight of melamine as a foaming agent.
Parts by weight, dipentaerythritol 1 as carbon former
00 parts by weight, 50 parts by weight of alumina, and 150 parts by weight of xylene as a diluent were mixed in advance and then sufficiently kneaded with a three-roll mill, and applied as a paint to a steel sheet. The coated steel sheet was evaluated according to Example 1, and the results are shown in Table 1.

Example 4 Epoxy resin Adeka Resin E as a synthetic resin binder
P-4520 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.) 60 parts by weight and modified aliphatic polyamine Adeka Hadner EH-22
0 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.) to 40 parts by weight of melamine-coated ammonium polyphosphate TERRAJUM
30 (trade name, manufactured by Chisso Corporation) 250 parts by weight, melamine as a foaming agent 50 parts by weight, tris (2-hydroxyethyl) isocyanurate as a carbon former 100 parts by weight, titanium dioxide 60 parts by weight, diluted After previously mixing 200 parts by weight of xylene as an agent, the mixture sufficiently kneaded with a three-roll mill was applied as a paint to a steel sheet. The coated steel sheet was evaluated according to Example 1, and the results are shown in Table 1.

Example 5 Acrylic copolymer emulsion as synthetic resin binder Iodozole AD51 (trade name, manufactured by Kanebo NSC Co., Ltd., solid content 43%) 232 parts by weight, ammonium insoluble polyphosphate TERRAJU C60 (trade name, After mixing 150 parts by weight of Chisso Corporation, 100 parts by weight of melamine as a foaming agent, 100 parts by weight of pentaerythritol as a carbon forming agent, 60 parts by weight of titanium dioxide, and 50 parts by weight of water as a diluent. A material sufficiently kneaded with a three-roll mill was applied to a steel sheet as a paint. The coated steel sheet was evaluated according to Example 1, and the results are shown in Table 1.

Comparative Example 1 Sumisafe PM was used instead of insoluble ammonium polyphosphate.
(Trade name, manufactured by Sumitomo Chemical Co., Ltd.) was used according to Example 1, and the obtained coated steel sheet was also evaluated according to Example 1. Table 1 shows the results. Comparative Example 2 The procedure of Example 4 was repeated except that Exolit462 (trade name, manufactured by Hoechst) was used instead of the insoluble ammonium polyphosphate, and the obtained coated steel sheet was also evaluated according to Example 4. . Table 1 shows the results.

The foamed fire-resistant coating material of the present invention containing the melamine-coated ammonium polyphosphate and / or the insoluble ammonium polyphosphate is, as is clear from Table 1, after the hot water immersion test and further after the weather resistance test. It is clear that the backside temperature is maintained in the evaluation of fire resistance. However, for the comparative example, after the hot water immersion test,
Alternatively, it is considered that in the fire resistance evaluation after the accelerated weather resistance test, the back surface temperature increased and the fire resistance performance decreased.

[0031]

[Table 1]

[0032]

As described above, it is clear that the fire-resistant coating material of the present invention is excellent in water resistance, fire resistance and weather resistance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takashi Takebayashi No. 2-301 Otsumen-cho, Kanazawa-ku, Yokohama-shi, Kanagawa

Claims (6)

[Claims] 1. A foamed fire-resistant coating material comprising a synthetic resin as a binder and melamine-coated ammonium polyphosphate and / or insoluble ammonium polyphosphate. 2. The content of melamine-coated ammonium polyphosphate and / or insoluble ammonium polyphosphate is 50 to 400 parts by weight with respect to 100 parts by weight of the synthetic resin as a binder. Foamed fire-resistant paint as described in the item. 3. The synthetic resin is urethane resin, epoxy resin,
The foamed refractory paint according to claim 1 or 2, which is an acrylic resin or an alkyd resin. 4. The synthetic resin emulsion according to claim 1, wherein the synthetic resin is a vinyl acetate resin emulsion, an acrylate ester resin emulsion, a versatic vinyl acrylate resin emulsion, an ethylene resin emulsion, or the like. The foamed refractory paint according to item 2. 5. The foamed fire-resistant paint according to claim 1 or 2, wherein the melamine-coated ammonium polyphosphate has melamine added and / or attached to the surface of the powdery ammonium polyphosphate particles. 6. The insoluble ammonium polyphosphate is formed by the active hydrogen contained in the amino group in the melamine molecule present in the coating layer of the melamine-coated ammonium polyphosphate particles and the compound having a functional group capable of reacting with the active hydrogen. The foamed refractory paint according to claim 1 or 2, wherein the particle surfaces are crosslinked.