JP2009208355A - Fire proof resin foaming laminate - Google Patents

Abstract

Provided is a fire resistant resin foam laminate having excellent fire resistance when the roof passes a roof fire resistance 30 minute certification test when used as a heat insulating material attached to the back of a roof steel plate.
A fireproof resin foam laminate comprising a resin foam sheet containing an inorganic flame retardant and a coating agent containing a phosphorus compound, a nitrogen-containing compound and a low-melting glass applied to the surface of the resin foam sheet. 16
[Selection] Figure 1

Description

  The present invention relates to a fire-resistant resin foam laminate that is suitably used as a roof steel plate-backed heat insulating material.

  Polyolefin resin foams are used in a wide range of fields such as building materials, home appliances, automobiles, energy, and toys because of their excellent light weight, heat insulation, water resistance, and chemical resistance. Since polyolefin-based resins themselves are easily flammable, in an area where flame retardancy is required, inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide are blended to impart flame retardancy. Yes.

  As a use of the polyolefin resin foam in which an inorganic flame retardant is blended to impart flame retardancy as described above, there is a roof steel sheet backing heat insulating material. This heat insulating material is obtained by applying a primer to the surface of a polyolefin resin foam sheet, and bonding the primer-coated surface to a roof steel plate. However, this heat insulating material has a problem in that the thickness and the adhesion to a steel plate are insufficient in the roof fire resistance 30 minute certification test, which may not pass the roof fire resistance 30 minute certification test.

  In order to solve the above-mentioned problems, it is conceivable to use a foamable fire-resistant paint as a primer for the above-described roof steel sheet backing heat insulating material. As such a foamable fireproof paint, there exist some which were described in patent documents 1-3, for example.

JP 2005-97509 A Japanese Patent Laid-Open No. 2004-155889 JP 2005-314893 A

  However, these foam fire-resistant paints are directly applied to steel materials for building materials (beams, columns, etc.), leading to an increase in cost. Also, due to the difference in fire resistance performance depending on the building material part, it is premised on a thick coating of about 2 mm, and there is a problem in that the fire resistance performance is greatly reduced if it is thinly coated for cost reduction.

  The present invention has been made in view of the above-described circumstances, and can be used as a heat insulating material attached to the roof of a steel sheet, and can effectively adhere an inorganic flame retardant contained in the foam to the roof steel sheet at the time of fire resistance evaluation. Thus, an object of the present invention is to provide a fire-resistant resin foam laminate having excellent fire resistance that suppresses the temperature rise of the roof steel plate and the roof passes the roof fire resistance 30-minute certification test.

In order to achieve the above object, the present invention provides the following fire-resistant resin foam laminates (1) to (6).
(1) A fire-resistant resin foam laminate comprising a resin foam sheet containing an inorganic flame retardant and a coating agent containing a phosphorus compound, a nitrogen-containing compound, and a low-melting glass.
(2) The fire-resistant resin foam laminate according to (1), wherein the coating agent is an emulsion-based paint, or an adhesive or pressure-sensitive adhesive primer containing a phosphorus compound, a nitrogen-containing compound, and a low-melting glass. body.
(3) The coating agent comprises 20 to 300 parts by weight of a phosphorus compound, 5 to 300 parts by weight of a nitrogen-containing compound, and a low-melting-point glass with respect to 100 parts by weight of the solid content of the emulsion paint or adhesive or pressure-sensitive adhesive primer. The fire-resistant resin foam laminate according to (2), wherein 5 to 100 parts by weight are blended.
(4) The fire resistant resin foam laminate according to any one of (1) to (3), wherein the nitrogen-containing compound has one or more hydroxyl groups.
(5) The refractory resin foam laminate according to (1) to (4), wherein the yield point of the low-melting glass is 300 to 750 ° C.
(6) The fire-resistant resin foam laminate according to (1) to (5), wherein the phosphorus compound is microencapsulated with a nitrogen-containing compound.

  The 30-minute roof fire resistance test heats the inside of the furnace according to the heating curve of ISO834 and measures the amount of bending and the bending speed of the roof specimen installed in the upper part of the furnace. It is necessary to keep the amount and the bending speed within a certain standard. The fire-resistant resin foam laminate of the present invention has the above-described configuration, so that the combustion residue of the inorganic flame retardant originally contained in the resin foam at the time of combustion is efficiently fixed to the steel plate and the roof at the time of heating. In order to form the heat insulation layer for suppressing the temperature rise of the roof steel plate itself that affects the bending (strength) of the roof, excellent fire resistance that passes the 30-minute roof fire resistance certification test can be obtained.

  The fire-resistant resin foam laminate of the present invention has excellent fire resistance when the roof passes the roof fire resistance 30-minute certification test when used as a roof steel sheet backing heat insulating material.

  Hereinafter, the present invention will be described in more detail. The fire resistant resin foam laminate of the present invention comprises a coating agent containing a phosphorus compound, a nitrogen-containing compound (for example, a compound having a triazine ring) and a low-melting glass on the surface of a resin foam sheet containing an inorganic flame retardant. As the coating agent, an emulsion-based paint or a primer blended with a phosphorus compound, a nitrogen-containing compound and a low-melting glass can be suitably used as the coating agent. Hereinafter, each component in the present invention will be described.

  As a material for the resin foam sheet, a polyolefin-based resin can be suitably used. For example, a low density polyethylene, a linear low density polyethylene, a high density polyethylene, an ethylene-α olefin copolymer, an ethylene-propylene copolymer. A polymer, an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-vinyl acetate-vinyl chloride copolymer, an ethylene-acrylic acid copolymer or the like is used alone or in a mixture of two or more. be able to. Among these, an ethylene-vinyl acetate copolymer is particularly preferable. Moreover, as a resin foam, a resin crosslinked foam is preferable.

  Examples of inorganic flame retardants include aluminum hydroxide, magnesium hydroxide, antimony trioxide, titanium oxide, zinc oxide, aluminum oxide, calcium carbonate, lithium carbonate, magnesium carbonate, talc, mica, kaolin, shirasu balloon, and hollow ceramic. Etc. can be used. Among these, aluminum hydroxide, magnesium hydroxide, and antimony trioxide are particularly preferable.

  Examples of coating emulsion paints include polyester paints, acrylic paints, urethane paints, epoxy paints, vinyl acetate paints, polybutadiene paints, alkyd resin paints, vinyl chloride paints, and melamine resin paints. Etc. can be used. Among these, polyester paints, acrylic paints, and epoxy paints are particularly preferable.

  As a coating agent adhesive or pressure-sensitive adhesive primer (adhesive or pressure-sensitive adhesive coating primer), for example, a primer such as chloroprene rubber, SBR, ionomer, polyester, acrylic or urethane is used. be able to. Among these, a chloroprene rubber-based primer is particularly preferable.

  The phosphorus compound of the coating agent has a role as a foaming agent and a role of promoting dehydration carbonization. Examples of phosphorus compounds include phosphorus, ammonium polyphosphate, melamine phosphate, guanidine phosphate, guanyl urea phosphate, zinc phosphate, calcium phosphate, magnesium phosphate, polyphosphate amide, triphenyl phosphate, cresyl phenyl phosphate, etc. Can be used. Among these, ammonium polyphosphate and melamine phosphate are particularly preferable. In addition, it is preferable that the phosphorus compound is microencapsulated with a nitrogen-containing resin in terms of enhancing the water resistance of the phosphorus compound when added to the emulsion paint or primer.

  The nitrogen-containing compound of the coating agent has a role as a carbonizing foaming agent. The nitrogen-containing compound preferably has one or more hydroxyl groups. Examples of such a compound include melamine cyanurate, tris (2-hydroxyethyl) isocyanurate, nitrilotrismethylenephosphonic acid melamine salt, Dimethylol dihydroxyethylene urea or the like can be used. Among these, tris (2-hydroxyethyl) isocyanurate is particularly preferable.

The low melting point glass of the coating agent has a role of stabilizing carbides. Examples of the low melting point glass include B ₂ O ₃ system, Na ₂ O system, K ₂ O system, P ₂ O ₅ system, Al ₂ O ₃ system, BaO system, CaO system, MgO system, Li ₂ O system, SrO-based, CuO-based low-melting glass, or the like can be used. Of these, B ₂ O-based, Na ₂ O-based, and P ₂ O ₅ -based low melting glass are particularly preferable. The low-melting glass has a yield point of 300 to 750 ° C., more preferably 500 to 650 ° C., and preferably has a large volume expansion coefficient at the yield point. The low melting point glass is suitably blended into the coating agent in the form of a glass frit in the form of flakes or powder.

  The compounding amount of each component in the coating agent is 20 to 300 parts by weight of the phosphorus compound, more preferably 100 to 200 parts by weight, and 5 to 300 of the nitrogen-containing compound with respect to 100 parts by weight of the solid content of the emulsion paint or primer. Part by weight, more preferably 50 to 200 parts by weight, and the low melting point glass is 5 to 100 parts by weight, more preferably 40 to 80 parts by weight.

  Moreover, arbitrary components, such as a carbonization catalyst, can be mix | blended with a coating agent other than the component mentioned above. In this case, as the carbonization catalyst, for example, zinc oxide, zinc sulfate, zinc acetate, zinc borate, manganese sulfate, manganese acetate, magnesium oxide, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum oxide, or the like is used. it can.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example and a comparative example, this invention is not limited to the following Example.

  A coating agent having the composition shown in Table 1 below was prepared, and this coating agent was applied to one side of a polyolefin-based foam sheet (Furukawa Electric Co., Ltd., Funenace) containing an inorganic flame retardant (aluminum hydroxide or magnesium hydroxide). It coated and produced the fireproof resin foaming laminated body of Examples 1-8 and a comparative example. The comparative example is a conventional example. As a primer in Table 1, a chloroprene rubber-based primer, ammonium polyphosphate as a phosphorus compound, and tris (2-hydroxyethyl) isocyanurate as a nitrogen-containing compound were used. The flame retardant coating amount in Table 1 is the amount of flame retardant solid content in the coating agent coating amount, and is the content per unit area of ammonium polyphosphate, tris (2-hydroxyethyl) isocyanurate and glass frit. is there.

The following experiment was conducted using the above fire-resistant resin foam laminate.
(experimental method)
As shown in FIG. 1, the primer 12 of an Example and a comparative example is applied to one side of a resin foam to form a fireproof resin foam laminate 14, and the primer surface of this laminate and one side of a steel plate are bonded together with spray glue. After producing the experimental sample, the experimental sample was placed in contact with the outer surface of the door of the electric furnace 16 so that the fire-resistant resin foam laminate 14 was on the electric furnace 16 side. The temperature inside the furnace was raised to 0 to 5 min: 237 ° C., 5 to 8 min: 435 ° C., 8 to 11 min: 549 ° C., and 11 to 35 min: 850 ° C., and the refractory resin foam laminate 14 at that time The temperature of the steel sheet 10 surface on the non-bonding side was measured with a K thermocouple, and the heat resistance test was performed by confirming the temperature change.
(Criteria)
1. The heat resistance was determined according to the following criteria based on the time required for the steel plate temperature to reach 550 ° C. (550 ° C. is the time when the decrease in steel plate strength is considered to increase).
：: 20 minutes or more ○: 15 minutes or more ×: less than 15 minutes 2.35 minutes After the heating, the heat resistance was determined according to the following criteria.
A: Less than 700 ° C. ○: 700-749 ° C.
×: 750 ° C. or higher

  The experimental results are shown in Tables 1 and 2. From Tables 1 and 2, it can be seen that the laminates of the examples in which the phosphorus compound, the nitrogen-containing compound, and the low-melting glass were blended in the coating agent have excellent fire resistance. On the other hand, the comparative example in which none of the phosphorus compound, the nitrogen-containing compound and the low-melting glass was blended in the coating agent was inferior in fire resistance as compared with the laminates of the examples.

It is explanatory drawing which shows the experiment in an Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Steel plate 12 Primer 14 Fire resistant resin foam laminated body 16 Electric furnace

Claims (6)

  A fire-resistant resin foam laminate comprising a resin foam sheet containing an inorganic flame retardant and a coating agent containing a phosphorus compound, a nitrogen-containing compound and a low-melting glass applied to the surface of the resin foam sheet.   2. The fire-resistant resin foam laminate according to claim 1, wherein the coating agent is an emulsion-based paint, or an adhesive or pressure-sensitive adhesive primer containing a phosphorus compound, a nitrogen-containing compound, and a low-melting glass. .   The coating agent comprises 20 to 300 parts by weight of a phosphorus compound, 5 to 300 parts by weight of a nitrogen-containing compound, and 5 to 100 parts of a low-melting glass with respect to 100 parts by weight of the solid content of the emulsion paint or adhesive or pressure-sensitive adhesive primer. The fire-resistant resin foam laminate according to claim 2, wherein the fire-resistant resin foam laminate is blended with parts by weight.   The refractory resin foam laminate according to any one of claims 1 to 3, wherein the nitrogen-containing compound has one or more hydroxyl groups.   The refractory resin foam laminate according to any one of claims 1 to 4, wherein a yield point of the low-melting glass is 300 to 750 ° C.   The fire resistant resin foam laminate according to any one of claims 1 to 5, wherein the phosphorus compound is microencapsulated with a nitrogen-containing compound.

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