JP2013014669A - Covering material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a covering material capable of forming a carbonized heat-insulating layer having a sufficient expansion coefficient, strength and the like, and having excellent heat protection.SOLUTION: The covering material includes a binding material, flame retardant, foaming agent, carbonizing agent and filler, wherein the filler contains TiOand an inorganic powder having a phase transition temperature of ≥1,000°C.

Description

  The present invention relates to a novel coating material.

As a material that protects a base material such as steel, concrete, wood, and synthetic resin from a fire, a thermally expandable coating material that forms a thermally expandable layer by a temperature rise during a fire is known.
Such a covering material contains, in its components, a component that decomposes due to an increase in temperature and generates a nonflammable gas, and a component that carbonizes to form a porous carbonized heat insulation layer. The fire extinguishing effect is exhibited by the occurrence of fire, and the heat insulating effect is exhibited by the formation of a porous carbonized heat insulating layer by the carbonized component. Advantages include that the film can be made thin and that the feeling of pressure is small and the finish is refreshed.

  With respect to such a covering material, various proposals have been made for the purpose of improving various physical properties such as heat resistance. For example, JP-A-10-17796 (Patent Document 1) describes that in addition to a polyhydric alcohol, a nitrogen-containing foaming agent, a flame retardant dehydrating agent, and a synthetic resin, further expandable graphite is blended. Yes. Japanese Patent Laid-Open No. 2001-40290 (Patent Document 2) describes that in addition to polyhydric alcohol, a nitrogen-containing foaming agent, a flame retardant foaming agent, and a synthetic resin, titanium dioxide is further blended. Japanese Patent Laid-Open No. 2001-323216 (Patent Document 3) describes that the average particle size of solids such as inorganic fillers and phosphorus flame retardants is adjusted to 10 to 50 μm.

JP-A-10-17796 Japanese Patent Laid-Open No. 2001-40290 JP 2001-323216 A

  However, with the above-mentioned coating material, there are cases where sufficient heat protection performance cannot be obtained even if various ideas are applied to the formulation. In particular, depending on the type of filler to be blended, the expansion coefficient and strength of the carbonized heat insulating layer may be insufficient, and there is room for improvement in practice.

  The present invention has been made in view of such problems, and an object of the present invention is to provide a coating material that can form a carbonized heat insulating layer having a sufficient expansion coefficient, strength, and the like and has excellent heat-resistant protective properties. Is.

As a result of intensive studies, the present inventor has confirmed that the above-described object can be achieved by using TiO ₂ and inorganic powder having a phase transition temperature of 1000 ° C. or higher as a filler among the components constituting the coating material. The headline and the present invention were completed.

That is, the coating material of the present invention has the following characteristics.
1. A covering material containing a binder, a flame retardant, a foaming agent, a carbonizing agent and a filler,
A coating material comprising TiO ₂ and an inorganic powder having a phase transition temperature of 1000 ° C. or higher as the filler.
2. The inorganic powder contains SiO ₂ or Al ₂ O ₃ . The coating material described.
3. The synthetic resin includes a vinyl acetate resin. Or 2. The coating | covering material as described in.

  According to the covering material of the present invention, it is possible to form a dense carbonized heat insulating layer excellent in foamability at the time of a fire, and to effectively suppress the temperature rise of a base material such as a steel material.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

The coating material of the present invention contains a binder, a flame retardant, a foaming agent, a carbonizing agent, and a filler, and the filler includes TiO ₂ and an inorganic powder having a phase transition temperature of 1000 ° C. or higher. .

  Examples of the binder of the present invention include water-dispersed, water-soluble, NAD, solvent-soluble, and solvent-free types. One-component type, two-component type, etc. are not particularly limited and can be used. . Specifically, vinyl acetate resin, vinyl acetate / versaic acid vinyl ester copolymer resin, vinyl acetate / ethylene copolymer resin, vinyl acetate / versaic acid vinyl ester / acrylic copolymer resin, vinyl acetate / acrylic copolymer resin, acrylic Examples thereof include organic synthetic resins such as resins, acrylic / styrene resin copolymer resins, epoxy resins, urethane resins, polyester resins, polybutadiene resins, alkyd resins, and vinyl chloride resins. These may be used alone or in combination of two or more. In the present invention, in particular, it is preferable to contain a vinyl acetate resin, whereby an excellent effect in terms of foamability can be obtained.

  The flame retardant of the present invention generally exhibits at least one effect such as a dehydration cooling effect, an incombustible gas generation effect, and a binder carbonization promoting effect during a fire, and has an action of suppressing the combustion of the binder. The flame retardant used in the present invention is not particularly limited as long as it has such an action, and a known flame retardant can be used. For example, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, tri (β-chloroethyl) phosphate, tributyl phosphate, tri (dichloropropyl) phosphate, triphenyl phosphate, tri (dibromopropyl) phosphate Organophosphorus compounds such as phosphate, chlorophosphonate, bromophosphonate, diethyl-N, N-bis (2-hydroxyethyl) aminomethyl phosphate, di (polyoxyethylene) hydroxymethyl phosphonate; chlorination Chlorine compounds such as polyphenyl, chlorinated polyethylene, diphenyl chloride, triphenyl chloride, pentachloride fatty acid ester, perchloropentacyclodecane, chlorinated naphthalene, tetrachlorophthalic anhydride; trioxide Nchimon, antimony compounds such as antimony pentachloride; phosphorus trichloride, phosphorus pentachloride, ammonium phosphate, phosphorus compounds such as ammonium polyphosphate; other zinc borate, boron compounds such as boric acid sodium and the like. A flame retardant can be used individually or in combination of 2 or more types. Moreover, although an uncoated product can be used, a coated product etc. can also be used.

  In the present invention, it is particularly preferable to use ammonium polyphosphate as the flame retardant. In the case of using ammonium polyphosphate, the dehydration cooling effect and the incombustible gas generation effect can be more effectively exhibited.

The mixing ratio of the flame retardant is preferably 50 to 1000 parts by weight, more preferably 100 to 800 parts by weight, and more preferably 200 to 600 parts by weight with respect to 100 parts by weight (solid content) of the binder. In this invention, a flame retardant is contained in a comparatively high ratio in this way, and favorable performance can be obtained in heat-resistant protection.

  The foaming agent of the present invention generally has an action of generating a non-combustible gas in the event of a fire, foaming a carbonizing binder and a carbonizing agent, and forming a carbonized heat insulating layer having pores. The foaming agent is not particularly limited as long as it has such an action, and a known foaming agent can be used. Examples thereof include melamine and derivatives thereof, dicyandiamide and derivatives thereof, azodicarbonamide, urea, thiourea and the like. These can be used alone or in combination of two or more. Among these, melamine, dicyandiamide, azodicarbonamide and the like are preferable because they are excellent in generating efficiency of nonflammable gas. In particular, melamine is more preferable. The mixing ratio of the foaming agent is preferably 5 to 500 parts by weight, more preferably 30 to 200 parts by weight with respect to 100 parts by weight (solid content) of the binder. By being in such a range, excellent foaming properties can be exhibited, and good performance in heat protection can be obtained.

  The carbonizing agent of the present invention generally has a function of forming a thick carbonized heat insulating layer having excellent heat insulating properties by dehydrating and carbonizing itself together with carbonization of the binder due to fire. The carbonizing agent used in the present invention is not particularly limited as long as it has such an action, and a known carbonizing agent can be used. For example, polyhydric alcohols such as pentaerythritol, dipentaerythritol and trimethylolpropane; starch, casein and the like can be mentioned. A carbonizing agent can be used individually or in combination of 2 or more types. In the present invention, pentaerythritol and dipentaerythritol are particularly preferable because they are excellent in dehydration cooling effect and carbonized heat insulation layer forming action. The mixing ratio of the carbonizing agent is preferably 5 to 600 parts by weight, more preferably 10 to 400 parts by weight with respect to 100 parts by weight (solid content) of the binder. By being in such a range, the dehydration cooling effect and the carbonized heat insulation layer forming action can be exhibited, and good performance in heat resistance protection can be obtained.

The filler of the present invention generally has an action of maintaining the strength of the carbonized heat insulating layer. In the present invention, a filler containing TiO ₂ and an inorganic powder having a phase transition temperature of 1000 ° C. or higher is used. In the present invention, “phase transition” includes, for example, the following.
・ Dehydration reaction of inorganic powder (desorption of crystal water and hydrated water)
・ Change in crystal structure of inorganic powder (polymorphic transition)
・ Melting or decomposition reaction of inorganic powder

By using an inorganic powder having a phase transition temperature of 1000 ° C. or higher, a carbonized heat insulating layer having a high expansion ratio and excellent strength can be obtained without impairing the effects of the flame retardant and the foaming agent. . Moreover, the carbonization heat insulation layer which has a uniform bubble can be obtained. Furthermore, when the foaming property is set to the same level as that of the conventional product, the amount of the flame retardant, the foaming agent, and the carbonizing agent can be reduced as compared with the conventional product.

The above mechanism of action is not clear, but is generally estimated as follows.
When an inorganic powder undergoes phase transition, it is accompanied by a change in volume or shape. At this time, phase transition heat is generated. In general, since the strength of the inorganic powder is high, the strength of the carbonized heat insulating layer is expected to increase when the inorganic powder is present in the structural skeleton of the carbonized heat insulating layer having fine voids formed during combustion.
However, when the inorganic powder that causes volume or shape change is present in the structural skeleton of the carbonized thermal insulation layer, the adhesive strength decreases at the interface between the carbide and the inorganic powder in the structure, resulting in the entire carbonized thermal insulation layer. It causes a decrease in strength. In addition, the thermal decomposition of the foaming agent and flame retardant is hindered by the phase transition heat, and the gas component generated by the thermal decomposition becomes difficult to act on the carbonization mechanism, so the foaming property of the carbonized thermal insulation layer is reduced, and the original purpose It is presumed that the heat insulating property is low.

  On the other hand, in the case of an inorganic powder having a phase transition temperature of 1000 ° C. or higher, the phase transition does not occur due to the temperature rise at the time of fire, and thus does not hinder the thermal decomposition of the foaming agent and the flame retardant. Further, it is considered that the formed carbonized heat insulation layer maintains a dense structure, exhibits excellent heat insulation properties due to high foaming, and can form a high strength carbonized heat insulation layer.

Such an inorganic powder is not particularly limited as long as the phase transition temperature is 1000 ° C. or higher, and a known inorganic powder other than TiO ₂ can be used. Examples include α-alumina, calcined kaolin, calcined clay, calcined diatomaceous earth, calcined silica, calcined hiruishi, shirasu, shirasu balloon, fly ash, portland cement, calcined diatomaceous earth, flux calcined diatomaceous earth, warrasnite and the like. In addition to the above, an inorganic powder obtained by treating a known mineral or inorganic compound in advance so that the phase transition temperature is 1000 ° C. or higher can also be used. In the present invention, as the inorganic powder having a phase transition temperature of 1000 ° C. or higher, an inorganic powder that has been fired at a temperature of 1000 ° C. or higher in advance is particularly suitable. Inorganic powder can be used individually or in combination of 2 or more types.
Among these, in order to improve the strength of the carbonized heat insulating layer, those containing at least SiO ₂ or Al ₂ O ₃ are preferred, and those containing SiO ₂ and Al ₂ O ₃ are more preferred. As such inorganic powder, calcined kaolin, calcined clay and the like are suitable.

  In addition, the shape of the inorganic powder is not particularly limited, and examples thereof include a spherical shape, a granular shape, a plate shape, a rod shape, a flake shape, a needle shape, and a fibrous shape, and these are used alone or in combination of two or more. You can also In the present invention, a plate shape, a flake shape, a needle shape, and a fiber shape are particularly preferable.

In the present invention, as TiO ₂ , anatase type, rutile type and the like can be used, and rutile type is particularly preferable.
The weight ratio of TiO ₂ to the inorganic powder in the filler is preferably 95: 5 to 50:50, more preferably 85:15 to 60:40.

In the present invention, the particle size of the filler is preferably 800 μm or less, more preferably 0.01 μm or more and 500 μm or less. In addition, when the shape of a filler is fibrous, fiber length should just be in the said range.
Moreover, the compounding ratio of the filler is preferably 10 to 300 parts by weight, more preferably 20 to 250 parts by weight with respect to 100 parts by weight (solid content) of the binder. By being in such a range, the strength of the carbonized heat insulating layer can be maintained, and good performance in heat protection can be obtained.

  Various additives etc. can also be mix | blended with the coating | covering material of this invention as components other than the above. Examples of such components include pigments, fibers, thickeners, film-forming aids, leveling agents, wetting agents, plasticizers, antifreezing agents, pH adjusters, antiseptics, antifungal agents, antialgae agents, and antibacterial agents. Agents, dispersants, antifoaming agents, adsorbents, crosslinking agents, ultraviolet absorbers, antioxidants, catalysts and the like. Moreover, expansive substances, such as expansive graphite and unexpanded vermiculite, can also be mix | blended.

  The coating material of this invention can be manufactured by mixing the above components uniformly by a conventional method. Examples of the form of the coating material of the present invention include a coating material containing the above-described constituents, or a material obtained by previously molding the coating material into a sheet shape.

  The coating material of this invention can exhibit the effect by applying or sticking to the to-be-coated object which should give fire resistance. Examples of the object to be coated include a wall, a pillar, a floor, a beam, a roof, and a staircase. Such an object to be coated is formed of a base material such as concrete or steel, and may be subjected to rust prevention treatment or the like. The coating material of the present invention can be applied not only to concrete and steel materials but also to base materials for wooden members, resin-based members and the like.

  When a coating material (coating material) is applied to an object to be coated, it may be applied once or several times using a coating device such as a spray, a roller, a brush, a trowel, or a spatula. At the time of application, the paint can be diluted with water or a solvent as required.

Moreover, what is necessary is just to shape | mold the mixture obtained by mixing each above-mentioned component uniformly by a well-known method, when shape | molding a coating | covering material in a sheet form previously. When mixing each component, it is also possible to mix a solvent or to heat as necessary. When a binding material such as a bead or pellet is used, each component may be mixed while heating with a heating device up to the softening temperature of the binding material and kneading with a kneader or the like. The obtained sheet-like coating material can be attached using an adhesive, a nail, a heel or the like.

The thickness of the coating material of the present invention may be appropriately set according to the application site and the like, but is preferably about 0.2 to 10 mm, more preferably about 0.5 to 6 mm. By laminating such a covering material, excellent heat resistance can be exhibited when exposed to high temperatures such as in a fire.

  In this invention, in order to protect the surface of a coating | covering material, an overcoat layer can also be laminated | stacked as needed. Such an overcoat layer can be formed by applying a known water-based or solvent-type paint. As the overcoat layer, for example, an acrylic resin-based, urethane resin-based, acrylic silicon resin-based, or fluororesin-based paint can be used. These coatings may be performed by a known coating method, and a coating tool such as a spray, a roller, or a brush can be used.

Examples and Comparative Examples are shown below to clarify the features of the present invention. However, the scope of the present invention is not limited to these examples.

(Coating materials 1-10)
According to the formulation shown in Table 1, coating materials 1 to 10 were produced by mixing and stirring each raw material by a conventional method. In addition, the following were used as a raw material.
・ Binder A: Acrylic / styrene copolymer resin emulsion ・ Binder B: Vinyl acetate / vinyl versatate copolymer emulsion ・ Foaming agent: Melamine ・ Carbide: Dipentaerythritol ・ Flame retardant: Ammonium polyphosphate ・ Filler A: Titanium oxide (TiO ₂ , rutile type, average particle size 0.3 μm)
Filler B: calcined clay (Al ₂ O ₃ .2SiO ₂ , average particle size 1.4 μm, calcining temperature: 1000 ° C. or higher)
Filler C: heavy calcium carbonate (CaCO ₃ , average particle size 50 μm, decomposition temperature 825 ° C.)
Filler D: Kaolin clay (Al ₂ O ₃ · 2SiO ₂ · 2H ₂ O, average particle size 1.4 μm, dehydration temperature 400 to 600 ° C.)

(Test Example 1)
The coating material 1 was coated on a hot-rolled steel plate (300 × 300 × 9 mm) with a brush so that the dry film thickness was about 2 mm, and dried for 1 week at a temperature of 20 ° C. and a relative humidity of 65%. This was designated as Specimen 1. The test body 1 was evaluated as follows. The results are shown in Table 2.

-Evaluation After heating the test body 1 for a fixed time (1 hour) according to the standard heating curve of ISO834, and cooling the test body to room temperature, the expansion ratio of the carbonized heat insulation layer was measured. Further, the denseness of the foam layer was visually evaluated. Then, the test body was made vertical and the strength of the carbonized heat insulating layer was visually evaluated. The evaluation criteria are as follows. The results are shown in Table 2, respectively.

<Foaming ratio>
A: Foaming ratio 20 times or more B: Foaming ratio 10 times or more and less than 20 times C: Foaming ratio 5 times or more and less than 10 times D: Foaming ratio less than 5 times <Denseness>
A: The inside of the carbonized thermal insulation layer is dense B: Some internal voids were observed in the carbonized thermal insulation layer

<Strength>
A: No dropout B: Partial dropout of surface layer C: All dropout

(Test Examples 2 to 10)
Test bodies 2 to 10 were produced in the same manner as in Test Example 1 except that the covering materials 2 to 10 were used instead of the covering material 1 of Test Example 1, and the same evaluation as that of the test body 1 was performed. The results are shown in Table 2.

Claims (3)

A covering material containing a binder, a flame retardant, a foaming agent, a carbonizing agent and a filler,
A coating material comprising TiO ₂ and an inorganic powder having a phase transition temperature of 1000 ° C. or higher as the filler. The coating material according to claim 1, wherein the inorganic powder contains SiO ₂ or Al ₂ O ₃ .   The said synthetic resin contains vinyl acetate resin, The coating | covering material of Claim 1 or Claim 2 characterized by the above-mentioned.