JP2017105188A - Method for manufacturing frame-retardant heat insulation panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant heat insulation panel having excellent fire resistance and adhesive strength and/or compression strength.SOLUTION: A method for manufacturing a flame-retardant heat insulation panel 100 which is formed by laminating a fire-resistant heat insulation layer 10 obtained by curing and molding an urethane resin composition 5 containing a flame retardant and exterior materials 1 and 1 includes: a step of arranging the urethane resin composition 5 containing the flame retardant in a mold 2 having the exterior materials 1 and 1 arranged therein; and a step of curing the urethane resin composition 5 containing the flame retardant under pressurization.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a method for manufacturing a flame-retardant insulation panel.

  A polyurethane foam can be obtained by curing the urethane resin composition. Since this polyurethane foam is excellent in heat insulating properties, it is widely applied to heat insulating materials.

  Specifically, a heat insulating panel called a sandwich panel in which a polyisocyanurate foam is sandwiched between a metal surface material and a back material has been proposed (Patent Document 1).

  There has also been proposed a heat insulating panel in which a synthetic resin foam made of polyurethane foam is sandwiched between a front surface material and a back surface material (Patent Document 2).

  Although the polyisocyanurate foam of Patent Document 1 and the polyurethane foam of Patent Document 2 have excellent heat insulation properties, they have the disadvantage of being easily flammable, and there is a problem that the use of the obtained heat insulation panel is limited. The flame retardance of the heat insulation panel is improved by using the material and the back material together.

  However, when the metal surface material and the back material are used in combination to protect the flammable synthetic resin foam, there is a problem that the weight of the obtained heat insulating panel increases.

  For this reason, the applicant of the present application has previously developed a flame retardant insulation panel having excellent heat insulation and fire resistance, which is a combination of a urethane resin composition containing a flame retardant as a fire resistant thermal insulation layer and an exterior material ( Patent Document 3).

  However, the urethane resin composition of Patent Document 3 is foamed and cured freely at atmospheric pressure to achieve non-flammability performance, but between the fireproof heat insulating layer formed by curing the urethane resin composition and the exterior material. In some cases, the adhesive strength is insufficient, or the compressive strength of the refractory heat insulating layer is insufficient.

JP 2002-276072 A Japanese Patent Laid-Open No. 4-64659 JP-A-2015-78594

  The object of the present invention is to make it difficult to improve the adhesive strength between the fire-resistant and heat-insulating layer obtained by curing the urethane resin composition and the exterior material and / or the compressive strength of the fire-resistant and heat-insulating layer. It is to provide a fuel insulation panel.

  In order to solve the above-mentioned problems, as a result of intensive studies by the present inventors, after placing an exterior material in the mold, a urethane resin composition containing a flame retardant is injected between the exterior materials, and the mold is plugged. The present inventors have found that the adhesive strength and / or the compressive strength of the refractory heat insulating layer in the obtained flame-retardant heat insulating panel can be improved by foaming and curing under pressure.

  That is, the present invention is as follows.

Item 1. A method for producing a flame-retardant and heat-insulating panel obtained by laminating a fire-resistant heat-insulating layer obtained by curing and molding a urethane resin composition containing a flame retardant and an exterior material, wherein the flame retardant is contained in a mold in which the exterior material is disposed. Including a step of disposing a urethane resin composition containing, and curing a urethane resin composition containing the flame retardant under pressure,
The urethane resin composition containing the flame retardant includes a urethane resin composed of a polyol compound and a polyisocyanate compound,
The flame retardant includes red phosphorus and at least one selected from the group consisting of a phosphate-containing flame retardant, a phosphate ester, a bromine-containing flame retardant, a metal hydroxide, an acicular filler, and a boron-containing flame retardant,
The method wherein the red phosphorus is in the range of 1.0 to 30 parts by weight with respect to 100 parts by weight of the urethane resin.

  Item 2. Item 2. The method according to Item 1, wherein the step of curing the urethane resin composition containing the flame retardant under pressure includes pressurizing a mold to cure the urethane resin composition containing the flame retardant.

  Item 3. Item 3. The method according to Item 1 or 2, wherein the step of curing the urethane resin composition containing the flame retardant under pressure is performed by setting a curing temperature in a range of 20 to 120 ° C.

  Item 4. The step of disposing the urethane resin composition containing the flame retardant includes injecting the urethane resin composition between 1 and 1 of the two facing materials facing each other. The method described.

  Item 5. At least one selected from the group consisting of the phosphate-containing flame retardant, phosphate ester, bromine-containing flame retardant, metal hydroxide, and needle filler is 1.5 wt. Item 5. The method according to any one of Items 1-4, wherein the boron-containing flame retardant is in the range of 0.1-60 parts by weight with respect to 100 parts by weight of the urethane resin.

Item 6. Based on 100 parts by weight of urethane resin,
The phosphate-containing flame retardant used for the flame retardant is in the range of 1.5 to 20 parts by weight,
The phosphate used in the flame retardant is in the range of 2.5 to 50 parts by weight,
The bromine-containing flame retardant used for the flame retardant is in the range of 1.5 to 20 parts by weight,
The metal hydroxide used for the flame retardant is in the range of 1.5 to 20 parts by weight,
The needle filler used for the flame retardant is in the range of 3.0 to 30 parts by weight, and the boron-containing flame retardant used for the flame retardant is in the range of 0.1 to 60 parts by weight. 5. The method according to any one of 4.

Item 7. The urethane resin composition containing the flame retardant contains a trimerization catalyst that promotes a trimerization reaction of isocyanate groups contained in the urethane resin,
Item 7. The method according to any one of Items 1 to 6, wherein the trimerization catalyst is in a range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the urethane resin.

  Item 8. Item 8. The method according to any one of Items 1 to 7, wherein the urethane resin composition containing the flame retardant contains at least one of a foam stabilizer and a foaming agent.

  Item 9. Item 9. The method according to any one of Items 1 to 8, wherein a heat insulating layer is added in addition to the fireproof heat insulating layer.

  Item 10. Item 10. The method according to any one of Items 1 to 9, wherein the exterior material comprises at least one selected from the group consisting of an organic material, an inorganic material, and a metal material.

  The flame-retardant insulation panel produced by the method of the present invention can exhibit excellent fire resistance, adhesive strength and / or compressive strength.

It is a schematic sectional drawing for demonstrating the flame-retardant heat insulation panel structure of 1st Embodiment. It is a schematic sectional drawing for demonstrating the manufacturing process of the flame-retardant heat insulation panel of FIG. It is sectional drawing for demonstrating the structure of the flame-retardant heat insulation panel which concerns on 2nd Embodiment. It is sectional drawing for demonstrating the structure of the flame-retardant heat insulation panel which concerns on 3rd Embodiment.

  Hereinafter, embodiments according to the present invention will be described with reference to the drawings.

FIG. 1 is a schematic cross-sectional view of the flame retardant insulation panel of the first embodiment. The flame retardant insulation panel 100 of the first embodiment is formed by laminating two exterior materials 1, 1 and a refractory heat insulation layer 10 sandwiched between the exterior materials 1, 1. The fireproof heat insulating layer 10 is a layer formed by curing and molding a urethane resin composition containing a flame retardant described later.
The manufacturing process of the flame-retardant heat insulation panel 100 of FIG. 1 will be described with reference to FIG. First, two exterior materials 1 and 1 are arranged facing each other in a mold 2 formed of a material such as metal, resin, wood, or cardboard. Next, the nozzle 4 connected to the urethane foaming device 6 of the low pressure foaming machine containing the urethane resin composition 5 containing the flame retardant before curing is connected to the two sheets in the mold 2 through the opening 2a of the mold 2. It inserts in the space 3 between the exterior materials 1 and 1, and inject | pours the urethane resin composition 5 containing the flame retardant before hardening through the nozzle 4 in the direction of the arrow. In the urethane foaming device 6, the polyisocyanate compound and the polyol compound are usually divided and accommodated separately so that curing does not start, and the divided liquid is mixed when passing through the nozzle 4. You may make it mix in one liquid within the apparatus 6. FIG.

  After injecting the urethane resin composition 5 in an amount necessary for constituting the fireproof heat insulating layer 10, the nozzle 4 is removed from the mold 2, and the opening 2a of the mold 2 is plugged with a plug member (not shown). The urethane resin composition 5 is foamed and cured in a state in which is pressed, and the fireproof heat insulating layer 10 is formed. At this time, the mold 2 may be in a state where air can enter and exit, or the mold 2 is completely sealed, and the pressurization in the mold 2 by foaming of the urethane resin composition 5 is promoted. There may be.

The curing pressure of the urethane resin composition is not particularly limited as long as it is a pressure higher than atmospheric pressure. For example, it exceeds atmospheric pressure and is about 0.5 MPa or less.
It is preferable to manufacture the flame retardant insulation panel 100 in a container that can withstand pressure, such as the mold 2, in order to suppress a change in dimensions when cured.

  Although the curing temperature of the urethane resin composition containing a flame retardant is not particularly limited, it is usually performed by setting the curing temperature in the range of 20 to 120 ° C, preferably 40 ° C or more and 100 ° C or less, and 40 ° C or more and 90 ° C. More preferably, the temperature is 50 ° C. or more and 80 ° C. or less, and most preferably 60 ° C. or more and less than 80 ° C. When cured at a temperature of 40 ° C. or higher, the urethane resin composition 5 reaches the corners of the mold 2, and the urethane resin composition 5 can be uniformly filled in the mold 2.

  After the urethane resin composition 5 is cured, the flame retardant insulation panel 100 is completed when the mold 2 is removed from the laminate composed of the exterior materials 1, 1 and the fireproof insulation layer 10.

  According to the above method for producing the flame-retardant heat insulating panel 100, the urethane resin composition 5 containing the flame retardant is foamed and cured under pressure in the mold 2 so that the produced flame-retardant heat insulating panel 100 is flame retardant. In particular, not only is it nonflammable, but also the adhesive strength between the fireproof heat insulating layer 10 which is a cured product of the urethane resin composition 5 and the exterior material 2 becomes good, and the compressive strength of the fireproof heat insulating layer 10 also increases.

  In addition, as a flame-resistant heat insulation panel, the flame retardant heat insulation panel 100 of the above-mentioned 1st Embodiment WHEREIN: Three layers of the exterior material 1, the fireproof heat insulation layer 10, and the exterior material 1 are comprised by the exterior material-fireproof heat insulation layer. -In addition to the three-layer structure in which the exterior materials are laminated in order, for example, two layers in which the fire-resistant and heat-insulating layer 10 and the exterior material 1 are laminated one by one as in the flame-retardant thermal insulation panel 110 of the second embodiment in FIG. As shown in the flame retardant thermal insulation panel 120 of the third embodiment in FIG. 4, the four layers in which the thermal insulation layer 20 is added in addition to the fireproof thermal insulation layer 10 between the exterior material 1 and the exterior material 1. A structure or a laminated structure of five or more layers including any additional layers can be exemplified. These flame-retardant heat insulation panels 110 and 120 are also arranged by placing the material constituting the exterior material 1 and the heat insulation layer 20 in the mold 2, pouring the urethane resin composition 5 into the mold 2, and curing and molding under pressure. It can manufacture similarly to the flame-retardant heat insulation panel 100 of 1st Embodiment.

  Next, each structural member of a flame-retardant heat insulation panel is demonstrated.

  Examples of the exterior material 1 include one formed by combining one or more of organic materials, inorganic materials, metal materials, and the like.

  The exterior material 1 is not limited to a plate material, and may be a thin material such as a sheet material or a film material.

  In addition, a board | plate material says what keeps a fixed shape, without bending at the location hold | maintained when holding with one end.

  Further, the sheet material is a material that is bent at the holding position when the sheet material is held with one end.

  A sheet material having a thickness of less than 100 μm is referred to as a film material.

  In the present invention, the exterior material 1 may be a laminate of at least one of a plate material, a sheet material, a film material, etc., or two or more.

  Examples of the organic material include synthetic resin, wood, paper, woven fabric, and non-woven fabric.

  Examples of the synthetic resin include polyethylene, polypropylene, polyamide, polyester, polycarbonate, and the like.

  Examples of the paper include craft paper and cardboard paper.

  Examples of the woven fabric include a fabric woven using polypropylene, polyester, nylon, cellulose fiber, and the like.

  Examples of the nonwoven fabric include wet nonwoven fabrics and long fiber nonwoven fabrics made of polypropylene, polyester, nylon, cellulose fibers, and the like.

  Examples of the inorganic material include a cement panel and an inorganic ceramic panel.

  Examples of the cement-based panel include a hard wood chip cement board, an inorganic fiber-containing slate board, a lightweight cellular concrete board, a mortar board, and a precast concrete board.

  Examples of the inorganic ceramic panel include a gypsum board, a calcium silicate board, a calcium carbonate board, a mineral wool board, and a ceramic board.

  Here, as the gypsum board, specifically, a lightweight material such as saw dust or pearlite is mixed into calcined gypsum, and cardboard is pasted on both sides and formed. For example, ordinary gypsum board (JIS A 6901 compliant: GB-R) ), Decorative gypsum board (JIS A6911 compliant: GB-D), waterproof gypsum board (JISA6912 compliant: GB-S), reinforced gypsum board (JIS A6913 compliant: GB-F), sound-absorbing gypsum board (JISA6301 compliant: GB-P) ) And the like.

  Examples of the metal material include: any metal plate and plated steel plate used for a sandwich panel of building materials such as iron plate, stainless steel plate, galvanized steel plate, aluminum zinc alloy plated steel plate, aluminum plate, and Galvalume steel plate (registered trademark). Aluminum craft; metal foil such as aluminum foil, copper foil, and gold foil.

  The exterior material 1 can be obtained by appropriately laminating one or two or more of synthetic resin, wood, paper, woven fabric, nonwoven fabric, and the like.

  Although the exterior material 1 usually has a thick rectangular shape, the shape and thickness can be appropriately adjusted according to the purpose and application.

  Also for the frame material, the type of mold is not limited, and for example, an arbitrary metal such as the same metal as the exterior material 1 described above can be used.

  In addition to the metal frame, the material of the mold is not limited as long as no significant deformation occurs due to pressure, and any material such as resin, wood, or cardboard can be used.

  In the present invention, the “mold” also includes a “frame body” that can accommodate the urethane resin composition and has an open top.

  Moreover, in this invention, in addition to an exterior material and a fireproof heat insulation layer, a heat insulation layer can also be laminated | stacked as demonstrated previously.

  Examples of the material used for the heat insulating layer include a resin heat insulating material and an inorganic heat insulating material.

  Examples of the resin heat insulating material include those made of polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyethylene, acrylic, vinyl chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, cellulose triacetate, and the like. Polycarbonate and vinyl chloride are preferred because of their self-extinguishing properties and good compatibility as building materials.

  Since the resin-based heat insulating material is excellent in heat insulating properties, it is preferable to use a foam containing bubbles inside.

  Moreover, as an inorganic type heat insulating material, what contains inorganic fibers, such as rock wool, ceramic wool, glass wool other than a cement system panel and an inorganic ceramic system panel, etc. can be mentioned, for example.

  Next, the fireproof heat insulating layer 10 will be described.

  The fireproof heat insulating layer 10 is made of a urethane resin composition containing a flame retardant. First, the urethane resin used for the urethane resin composition containing the flame retardant will be described.

  Examples of the urethane resin include those containing a polyisocyanate compound as a main agent and a polyol compound as a curing agent.

  Examples of the polyisocyanate compound that is a main component of the urethane resin include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.

  Examples of the aromatic polyisocyanate include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and the like.

  Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

  Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

  One or more polyisocyanate compounds can be used.

  The main component of the urethane resin is preferably diphenylmethane diisocyanate for reasons such as ease of use and availability.

  One or two or more polyisocyanate compounds can be used.

  Examples of the polyol compound include polylactone polyol, polycarbonate polyol, aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, polymer polyol, and polyether polyol.

  Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol.

Examples of the polycarbonate polyol include a polyol obtained by a dealcoholization reaction of a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with diethylene carbonate, dipropylene carbonate, and the like. Etc.
Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolac, and cresol novolak.

  Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, dimethyldicyclohexylmethanediol, and the like.

  Examples of the aliphatic polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.

  Examples of the polyester polyol include a polymer obtained by dehydration condensation of a polybasic acid and a polyhydric alcohol, a polymer obtained by ring-opening polymerization of a lactone such as ε-caprolactone and α-methyl-ε-caprolactone, Examples thereof include condensates of hydroxycarboxylic acid and the above polyhydric alcohol.

  Specific examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, and succinic acid.

  Specific examples of the polyhydric alcohol include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, neopentyl glycol, and the like. .

  Specific examples of the hydroxycarboxylic acid include castor oil, a reaction product of castor oil and ethylene glycol, and the like.

  As the polymer polyol, for example, an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, and methacrylate is graft-polymerized to an aromatic polyol, an alicyclic polyol, an aliphatic polyol, a polyester polyol, a polyether polyol, and the like. Examples thereof include polymers, polybutadiene polyols, modified polyols of polyhydric alcohols, and hydrogenated products thereof.

  Examples of the modified polyol of the polyhydric alcohol include those modified by reacting the raw material polyhydric alcohol with an alkylene oxide.

Examples of polyhydric alcohols include trihydric alcohols such as glycerin and trimethylolpropane,
Pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc., tetra- to octavalent alcohols such as sucrose, glucose, mannose, fructose, methyl glucoside and derivatives thereof,
Phenol, phloroglucin, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene, 1,3,6,8-tetrahydroxynaphthalene, anthrol, 1,4,5 , 8-tetrahydroxyanthracene, phenols such as 1-hydroxypyrene,
Polybutadiene polyol,
Castor oil polyol,
Examples thereof include (co) polymers of hydroxyalkyl (meth) acrylates and polyfunctional polyols (for example, 2 to 100 functional groups) such as polyvinyl alcohol, and condensates (novolaks) of phenol and formaldehyde.

  The method for modifying the polyhydric alcohol is not particularly limited, but a method of adding alkylene oxide (hereinafter abbreviated as AO) is preferably used.

  As AO, C2-C6 AO, for example, ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), 1,3-propyloxide, 1,2- Examples include butylene oxide and 1,4-butylene oxide.

Among these, PO, EO, and 1,2-butylene oxide are preferable from the viewpoint of properties and reactivity, and PO and EO are more preferable.

  When two or more types of AO are used (for example, PO and EO), block addition or random addition may be used, or a combination thereof may be used.

  As the polyether polyol, for example, in the presence of at least one low molecular weight active hydrogen compound having two or more active hydrogens, at least one alkylene oxide such as ethylene oxide, propylene oxide, and tetrahydrofuran is subjected to ring-opening polymerization. The obtained polymer is mentioned.

Examples of the low molecular weight active hydrogen compound having two or more active hydrogens include diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, and 1,6-hexanediol,
Triols such as glycerin and trimethylolpropane,
Examples include amines such as ethylenediamine and butylenediamine.

  As the polyol, it is preferable to use a polyester polyol or a polyether polyol, and a polyester polyol is more preferable because a polyurethane foam obtained by curing the urethane resin composition is difficult to ignite.

  Next, the compounding ratio of the main component of urethane resin and the curing agent will be described.

In the present invention, the isocyanate index (INDEX) is calculated by the following method.
INDEX = isocyanate equivalent number / (polyol equivalent number + water equivalent number) × 100

here,
Number of equivalents of isocyanate = number of parts used of polyisocyanate × NCO content (%) ÷ 100 ÷ molecular weight of NCO,

  Equivalent number of polyol = OHV × number of used parts of polyol ÷ molecular weight of KOH, OHV is hydroxyl value of polyol (mg KOH / g),

Equivalent number of water = number of water used × number of OH groups in water / molecular weight of water.
In the above formula, the unit of the number of parts used is weight (g), the molecular weight of the NCO group is 42, and the NCO content is the percentage of the NCO group in the polyisocyanate compound expressed by mass%. For convenience of unit conversion, the molecular weight of KOH is 56100, the molecular weight of water is 18, and the number of OH groups in water is 2.

  The range of the index is not particularly limited, but is preferably in the range of 100 to 1000, more preferably 120 to 700, still more preferably 150 to 500, and most preferably 250 to 400. Yes.

  When the index is 1000 or less, foaming failure can be prevented, and when the index is 100 or more, good heat resistance can be obtained.

  In the present invention, a urethane resin curing catalyst can be used in addition to the urethane resin.

  Examples of the urethane curing catalyst include amino compounds, tin compounds, and acetylacetone metal salts.

Examples of amino compounds include pentamethyldiethylenetriamine, triethylamine, N-methylmorpholine bis (2-dimethylaminoethyl) ether, bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″, N ″ — Pentamethyldiethylenetriamine, N, N, N′-trimethylaminoethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N-methyl, N′-dimethylaminoethylpiperazine, secondary amine functional group in imidazole ring Is substituted with a cyanoethyl group, N, N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylhexamethylenediamine, N-methylimidazole, trimethylaminoethylpiperazine, tripropylamine Min,
Examples thereof include tetramethylammonium salt, tetraethylammonium salt, and triphenylammonium salt.

  Examples of the tin compound include stannous octylate, dibutyltin diacetate, dibutyltin dilaurate, and the like.

  Examples of the acetylacetone metal salt include acetylacetone aluminum, acetylacetone iron, acetylacetone copper, acetylacetone zinc, acetylacetone beryllium, acetylacetone chromium, acetylacetone indium, acetylacetone manganese, acetylacetone molybdenum, acetylacetone titanium, acetylacetone cobalt, acetylacetone vanadium, and acetylacetone zirconium. .

  One or two or more urethane resin curing catalysts can be used.

  The addition amount of the urethane resin curing catalyst used in the urethane resin composition according to the present invention is not particularly limited, but is preferably in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the urethane resin. The range is more preferably 0.01 to 8.0 parts by weight, still more preferably 0.01 to 6.0 parts by weight, and more preferably 0.01 to 1.5 parts by weight. Most preferred.

  In the case of 0.01 parts by weight or more and 10 parts by weight or less, it is easy to handle and the reaction can be easily controlled.

  As the polyurethane resin, those obtained by reacting an isocyanate group contained in a polyisocyanate compound, which is the main component of the polyurethane resin, to trimerize and promoting the formation of an isocyanurate ring can be used.

  In order to promote the formation of an isocyanurate ring, for example, as a catalyst, tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, 2,4,6-tris (dialkylaminoalkyl) hexahydro Aromatic compounds such as -S-triazine, potassium acetate, sodium acetate, potassium 2-ethylhexanoate, sodium 2-ethylhexanoate, quaternary ammonium compounds such as tertiary amine carboxylates, 2-ethylaziridine, etc. Amine compounds such as aziridines, lead compounds such as diazabicycloundecene, lead naphthenate and lead octylate, alcoholate compounds such as sodium methoxide, phenolate compounds such as potassium phenoxide, quaternary ammonium salts of carboxylic acids, etc. Can be used.

  The addition amount of the trimerization catalyst used in the urethane resin composition according to the present invention is not particularly limited, but is preferably in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the urethane resin. It is more preferably in the range of ˜8 parts by weight, still more preferably in the range of 0.01 to 6 parts by weight, and most preferably in the range of 0.5 to 1.5 parts by weight.

  When the amount is 0.01 parts by weight or more, the problem that the trimerization of isocyanate is inhibited does not occur, and when the amount is 10 parts by weight or less, the problem that the urethane bond is inhibited can be reduced.

  One or two or more trimerization catalysts can be used.

Examples of the foaming agent include water;
Low boiling point hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane;
Chlorinated aliphatic hydrocarbon compounds such as dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride;
Fluorine compounds such as trichloromonofluoromethane, trichlorotrifluoroethane, CHF ₃ , CH ₂ F ₂ , CH ₃ F;
Hydrochlorofluorocarbons such as dichloromonofluoroethane (e.g., HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane);
Hydrofluorocarbons such as HFC-245fa (1, 1, 1, 3, 3-pentafluoropropane), HFC-365mfc (1, 1, 1, 3, 3-pentafluorobutane);
Hydrofluoroolefins such as HFO-1233zd (E) (trans-1-chloro-3,3,3-trifluoropropene), HFO-1234yf (2,3,3,3-tetrafluoro-1-propene);
Ethers such as diisopropyl ether; or organic physical blowing agents such as mixtures of these compounds;
And inorganic physical foaming agents such as nitrogen gas, oxygen gas, argon gas and carbon dioxide gas.

  The blowing agent is preferably cyclopentane, hydrofluorocarbon, hydrofluoroolefin, or water, and more preferably, water and hydrofluorocarbon or hydrofluoroolefin are used in combination.

  Moreover, 1 type, or 2 or more types can be used for a foaming agent.

  The amount of the foaming agent used in the urethane resin composition according to the present invention is not particularly limited, but is preferably in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the urethane resin. More preferably, it is in the range of ˜15 parts by weight, further preferably in the range of 1.0 to 15 parts by weight, and most preferably in the range of 1.5 to 10 parts by weight.

  When the range of water is 0.1 parts by weight or more, foaming is promoted, and the density of the obtained molded body can be reduced. When the water content is 20 parts by weight or less, bubbles continuous with each other in the obtained molded body. Can be introduced.

  A foam stabilizer can also be used in the urethane resin composition according to the present invention.

  Examples of the foam stabilizer include surfactants such as a polyoxyalkylene foam stabilizer such as polyoxyalkylene alkyl ether and a silicone foam stabilizer such as organopolysiloxane.

  The amount of the foam stabilizer used for the urethane resin cured by the chemical reaction is appropriately set depending on the urethane resin cured by the chemical reaction used. For example, for 100 parts by weight of the urethane resin, The amount is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 4.0 parts by weight, and still more preferably 1.0 to 3.0 parts by weight.

  One or more foam stabilizers can be used.

  Next, the flame retardant added to a urethane resin composition is demonstrated.

  The flame retardant includes red phosphorus and at least one selected from the group consisting of a phosphate-containing flame retardant, a phosphate ester, a bromine-containing flame retardant, a metal hydroxide, an acicular filler, and a boron-containing flame retardant. First, red phosphorus will be described.

  There is no limitation to red phosphorus, and a commercially available product can be appropriately selected and used.

  The addition amount of red phosphorus used in the urethane resin composition is in the range of 1.0 to 30 parts by weight with respect to 100 parts by weight of the urethane resin. The amount of red phosphorus added is preferably in the range of 1.0 to 20 parts by weight, more preferably in the range of 3.2 to 20 parts by weight, and in the range of 3.2 to 18 parts by weight. More preferably, it is in the range of 6.0 to 18 parts by weight.

  When the range of red phosphorus is 1.0 part by weight or more, the self-extinguishing property of the urethane resin composition is maintained, and when it is 30 parts by weight or less, foaming of the urethane resin composition is not inhibited.

  In addition to the red phosphorus described above as a flame retardant, the urethane resin composition includes a phosphate-containing flame retardant, a phosphate ester, a bromine-containing flame retardant, a metal hydroxide, an acicular filler, and a boron-containing flame retardant. At least two selected from the group consisting of can be used.

  The phosphoric acid used for the phosphate-containing flame retardant is not particularly limited, and examples thereof include various phosphoric acids such as monophosphoric acid and pyrophosphoric acid.

  Examples of the phosphate-containing flame retardant include phosphorus composed of salts of various phosphoric acids and at least one metal or compound selected from metals of Group IA to IVB of the periodic table, ammonia, aliphatic amines, and aromatic amines. There may be mentioned acid salts.

  Examples of the metals of Group IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum.

  Examples of the aliphatic amine include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine and the like.

  Aromatic amines include pyridine, triazine, melamine, ammonium and the like.

  The phosphate-containing flame retardant may be subjected to a known water resistance improving treatment such as silane coupling agent treatment or coating with a melamine resin, and a known foaming aid such as melamine or pentaerythritol may be added. May be.

  Specific examples of the phosphate-containing flame retardant include monophosphate and pyrophosphate.

Although it does not specifically limit as monophosphate, For example, ammonium salts, such as ammonium phosphate, ammonium dihydrogen phosphate, hydrogen diammonium phosphate;
Sodium salts such as monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, disodium phosphite, sodium hypophosphite;
Potassium salts such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, potassium hypophosphite;
Lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, lithium hypophosphite;
Barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, tribarium phosphate, barium hypophosphite;
Magnesium salts such as magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, magnesium hypophosphite;
Calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, calcium hypophosphite;
Zinc salts such as zinc phosphate, zinc phosphite, zinc hypophosphite;
And aluminum salts such as primary aluminum phosphate, secondary aluminum phosphate, tertiary aluminum phosphate, aluminum phosphite, and aluminum hypophosphite.

  Among these, since the self-extinguishing property of the phosphate-containing flame retardant is improved, it is preferable to use a monophosphate, and ammonium dihydrogen phosphate, diammonium hydrogen phosphate, primary aluminum phosphate, monophosphate It is more preferable to use at least one selected from the group consisting of sodium and tertiary aluminum phosphate, and it is more preferable to use ammonium dihydrogen phosphate and primary aluminum phosphate.

  One or two or more monophosphate-containing flame retardants can be used.

  The addition amount of the phosphate-containing flame retardant is preferably in the range of 1.5 to 20 parts by weight with respect to 100 parts by weight of the urethane resin. The addition amount of the phosphate-containing flame retardant is more preferably in the range of 1.5 to 10 parts by weight, further preferably in the range of 3.0 to 10 parts by weight, and 3.0 to 8.0 parts by weight. The range of parts is most preferable.

  When the range of the monophosphate-containing flame retardant is 1.5 parts by weight or more, the self-extinguishing property of the urethane resin composition is maintained, and when it is 20 parts by weight or less, foaming of the urethane resin composition is not inhibited.

  Urethane resin composition also contains phosphate ester, bromine-containing flame retardant, metal hydroxide, needle filler and boron in addition to or in place of phosphate-containing flame retardant as flame retardant At least one selected from the group consisting of flame retardants can be used.

  Although there is no limitation in particular as phosphate ester, it is preferable to use monophosphate ester, condensed phosphate ester, etc.

  The monophosphate ester is not particularly limited, and examples thereof include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, Tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate Fate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, phenylphosphonic acid Examples include diethyl, resilsinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), phosphaphenanthrene, tris (β-chloropropyl) phosphate, and the like.

  Although it does not specifically limit as condensed phosphate ester, For example, a trialkyl polyphosphate, a resorcinol polyphenyl phosphate, a resorcinol poly (di-2,6- xylyl) phosphate (made by Daihachi Chemical Industry Co., Ltd., brand name PX-200) ), Hydroquinone poly (2,6-xylyl) phosphate, and condensed phosphates such as condensates thereof.

  Examples of commercially available condensed phosphate esters include resorcinol polyphenyl phosphate (trade name CR-733S), bisphenol A polycresyl phosphate (trade name CR-741), aromatic condensed phosphate ester (trade name CR747), and resorcinol. Examples thereof include polyphenyl phosphate (manufactured by ADEKA, trade name ADK STAB PFR), bisphenol A polycresyl phosphate (trade names FP-600, FP-700), and the like.

  Among these, it is preferable to use a monophosphate ester because it is highly effective in reducing the viscosity in the composition before curing and reducing the initial calorific value, and using tris (β-chloropropyl) phosphate. Is more preferable.

  Phosphoric acid ester can use 1 type, or 2 or more types.

  Moreover, it is preferable that the addition amount of phosphate ester is the range of 2.5-50 weight part with respect to 100 weight part of urethane resins. The addition amount of the phosphate ester is more preferably in the range of 3.0 to 50 parts by weight, further preferably in the range of 3.0 to 30 parts by weight, and in the range of 7.0 to 30 parts by weight. Is most preferable.

  When the range of the phosphate ester is 2.5 parts by weight or more, the molded article made of the urethane resin composition is difficult to ignite, and when it is 50 parts by weight or less, foaming of the urethane resin composition is not inhibited.

  The bromine-containing flame retardant is not particularly limited as long as it is a compound containing bromine in the molecular structure, and examples thereof include aromatic brominated compounds.

Specific examples of aromatic brominated compounds include, for example, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (pentabromo Monomeric organic bromine compounds such as phenoxy) ethane, ethylene-bis (tetrabromophthalimide), tetrabromobisphenol A;
Brominated polycarbonates such as polycarbonate oligomers produced from brominated bisphenol A as a raw material, copolymers of polycarbonate oligomers and bisphenol A;
Brominated epoxy compounds such as diepoxy compounds produced by reaction of brominated bisphenol A with epichlorohydrin, monoepoxy compounds obtained by reaction of brominated phenols with epichlorohydrin;
Poly (brominated benzyl acrylate);
Brominated polyphenylene ether;
Condensates of brominated bisphenol A, cyanuric chloride and brominated phenol;
Brominated polystyrene such as brominated (polystyrene), poly (brominated styrene), cross-linked brominated polystyrene;
Halogenated bromine compound polymers such as crosslinked or non-crosslinked brominated poly (-methylstyrene).

  From the viewpoint of enhancing the self-extinguishing property of the urethane resin composition, a brominated aromatic ring-containing aromatic compound in which a bromine atom is substituted on the aromatic ring is preferable, brominated polystyrene, hexabromobenzene and the like are more preferable, and hexabromobenzene is further preferable.

  One or more bromine-containing flame retardants can be used.

  Although there is no limitation in particular in the addition amount of a bromine containing flame retardant, it is preferable that it is the range of 1.5-20 weight part with respect to 100 weight part of urethane resins. The addition amount of the bromine-containing flame retardant is more preferably in the range of 1.5 to 10 parts by weight, still more preferably in the range of 3.0 to 10 parts by weight, and 3.0 to 8.0 parts by weight. The range is most preferable.

  When the range of the bromine-containing flame retardant is 1.5 parts by weight or more, the self-extinguishing property of the urethane resin composition is maintained, and when it is 20 parts by weight or less, foaming of the urethane resin composition is not inhibited.

Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dawsonite, calcium aluminate, dihydrate gypsum, calcium hydroxide and the like.
Since the metal hydroxide has high fire resistance, it is preferable to use aluminum hydroxide, magnesium hydroxide, or a combination thereof.

  One or two or more metal hydroxides can be used.

  Although there is no limitation in particular in the addition amount of a metal hydroxide, it is preferable that it is the range of 1.5-20 weight part with respect to 100 weight part of urethane resins. The addition amount of the metal hydroxide is more preferably in the range of 1.5 to 10 parts by weight, further preferably in the range of 3.0 to 10 parts by weight, and 3.0 to 8.0 parts by weight. The range is most preferable.

  When the range of the metal hydroxide is 1.5 parts by weight or more, the self-extinguishing property of the urethane resin composition is maintained, and when it is 20 parts by weight or less, foaming of the urethane resin composition is not inhibited.

  Examples of the acicular filler include potassium titanate whisker, aluminum borate whisker, magnesium-containing whisker, silicon-containing whisker, wollastonite, sepiolite, zonolite, elestadite, boehmite, rod-like hydroxyapatite, glass fiber, asbestos fiber, carbon Examples thereof include fiber, graphite fiber, metal fiber, slag fiber, gypsum fiber, silica fiber, alumina fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, boron fiber, and stainless steel fiber.

  The aspect ratio (length / diameter) of the acicular filler is preferably in the range of 5.0 to 50, more preferably in the range of 10 to 40.

  One or two or more acicular fillers can be used.

  Although there is no limitation in particular in the addition amount of an acicular filler, it is preferable that it is the range of 3.0-30 weight part with respect to 100 weight part of urethane resins, and it is the range of 3.0-20 weight part. More preferably, it is in the range of 3.0 to 18 parts by weight, and most preferably in the range of 6.0 to 18 parts by weight.

  When the range of the acicular filler is 3.0 parts by weight or more, the shape after combustion of the molded article of the urethane resin composition containing the flame retardant used in the present invention is retained. The foaming of the urethane resin composition containing the flame retardant used in the invention is not inhibited.

Examples of the boron-containing flame retardant include borax, boron oxide, boric acid, and borate. Examples of the boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide.

  Examples of the borate include alkali metals, alkaline earth metals, elements of Group 4, Group 12, and Group 13 of the periodic table, and ammonium borate.

  Specifically, alkali metal borate such as lithium borate, sodium borate, potassium borate, cesium borate, alkaline earth metal borate such as magnesium borate, calcium borate, barium borate, boron Examples thereof include zirconium acid, zinc borate, aluminum borate, and ammonium borate.

  The boron-containing flame retardant used in the present invention is preferably a borate, and more preferably zinc borate.

  One or more boron-containing flame retardants can be used.

  The addition amount of the boron-containing flame retardant used in the present invention is not particularly limited, but is preferably 0.1 to 60 parts by weight with respect to 100 parts by weight of the urethane resin.

  When the range of the boron-containing flame retardant is 0.1 parts by weight or more, the self-extinguishing property of the refractory urethane resin composition according to the present invention is maintained, and when it is 60 parts by weight or less, the fire resistance according to the present invention is maintained. Foaming of the conductive urethane resin composition is not inhibited.

At least one selected from the group consisting of a phosphate-containing flame retardant, a phosphate ester, a bromine-containing flame retardant, a metal hydroxide, and an acicular filler is 1.5 wt. The amount of the boron-containing flame retardant is preferably in the range of 0.6 to 60 parts by weight with respect to 100 parts by weight of the urethane resin.
In one embodiment, the total amount of phosphate-containing flame retardant, phosphate ester, bromine-containing flame retardant, metal hydroxide, needle filler and boron-containing flame retardant is 9 to 200 parts by weight, A more preferable total amount is 10 to 50 parts by weight. A more preferred upper limit is 40 parts by weight, 30 parts by weight, 25 parts by weight, or 20 parts by weight, and a more preferred lower limit is 15 parts by weight.
As the flame retardant other than the above-mentioned red phosphorus, it is preferable to use a flame retardant selected from a phosphate ester, a bromine-containing flame retardant, an acicular filler, and a boron-containing flame retardant, and a phosphate ester, an acicular filler, and It is more preferable to use a flame retardant selected from boron-containing flame retardants, and it is more preferable to use a phosphate ester in combination with an acicular filler and / or a boron-containing flame retardant, and a phosphate ester, an acicular filler, and Most preferably, a boron-containing flame retardant is used in combination.

  Moreover, an inorganic filler can be used for the urethane resin composition containing the flame retardant used in the present invention.

  The inorganic filler is not particularly limited. For example, silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, carbonate Zinc, barium carbonate, hydrotalcite, potassium salts such as calcium sulfate, barium sulfate, calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, imogolite, sericite, glass beads, silica-based balloon, aluminum nitride Boron nitride, silicon nitride, carbon black, graphite, carbon balloon, charcoal powder, various metal powders, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, various magnetic powders, fly ash, none Systems phosphorus compounds and the like.

  One or two or more inorganic fillers can be used.

  Furthermore, the urethane resin composition is within a range that does not impair the purpose of the present invention, as necessary, phenolic, amine-based, sulfur-based antioxidants, heat stabilizers, metal damage inhibitors, antistatic agents, Stabilizers, crosslinking agents, lubricants, softeners, pigments, additives such as tackifying resins, and tackifiers such as polybutene and petroleum resins can be included.

  Since the urethane resin composition reacts and cures, its viscosity changes over time.

  Therefore, before using the urethane resin composition, the urethane resin composition is divided into two or more to prevent the urethane resin composition from reacting and curing. And when using a urethane resin composition, a urethane resin composition is obtained by putting together the urethane resin composition divided | segmented into two or more.

  In addition, when dividing the urethane resin composition into two or more, each component of the urethane resin composition divided into two or more does not start to cure, and after the respective components of the urethane resin composition are mixed, the curing reaction occurs. Each component can be divided to start.

  The urethane resin composition mixes the components of the urethane resin composition, suspends the urethane resin composition in an organic solvent, heats and melts it to form a paint, and disperses the slurry in a solvent. It can be obtained by a method such as preparation.

  Alternatively, the main component of urethane resin and the curing agent may be separately kneaded together with fillers and kneaded with a mixer or the like immediately before injection.

  Further, the components of the urethane resin composition excluding the catalyst and the catalyst can be kneaded in the same manner immediately before injection.

  The casting method of the urethane resin composition is not particularly limited. For example, the urethane resin composition is stirred using an arbitrary apparatus such as a low-pressure foaming machine or a high-pressure foaming machine usually used for foaming urethane, and a nozzle is used. It may be poured directly or poured into a cup before it is cured. The casting method is not particularly limited even when foaming is not performed by the apparatus. For example, there is a method in which a mechanical stirrer is used to manually pour the material stirred in the cup.

  In the above embodiment, the urethane resin composition is injected into the mold, and the mold is pressurized to cure under pressure by foaming of the urethane resin composition itself. The urethane resin composition may be cured by applying pressure.

  A urethane resin composition can be obtained by the method described above.

  When the respective components of the urethane resin composition are mixed, the reaction starts, the viscosity increases with the passage of time, and the fluidity is lost. By injecting the urethane resin composition into a mold and curing and molding, the fireproof heat insulating layer 10 made of the urethane resin composition can be obtained.

There is no particular limitation on the specific gravity of the fireproof heat insulating layer 10 made of the urethane resin composition, but it is preferably in the range of 0.02 to 0.20, more preferably in the range of 0.02 to 0.10, A range of 0.03 to 0.08 is more preferable, and a range of 0.03 to 0.06 is most preferable.
Since the urethane resin composition of the present invention is produced by applying pressure, a urethane resin composition having a high specific gravity relative to the specific gravity produced without pressure is obtained. The specific gravity of the resulting urethane resin composition is not particularly limited, but is preferably 101 to 200%, more preferably 110 to 180%, compared to the urethane resin composition produced by non-pressurization foaming. 110 to 160% is more preferable, and 120 to 150% is most preferable.

  Such a refractory heat insulating layer 10 is easy to handle because of its low specific gravity. The fireproof heat insulating layer 10 obtained by curing the urethane resin composition is made of polyurethane foam and has bubbles inside. It is preferable that the air bubbles are independent air bubbles in the polyurethane foam.

  Hereinafter, the present invention will be described in detail by examples. In addition, this invention is not limited at all by the following examples.

A urethane resin composition according to Example 1 was prepared according to the formulation shown in Table 1. The details of each component shown in Table 1 are as follows.
(A) Polyol compound A-1: p-phthalic acid-based polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RFK-505, hydroxyl value: 250 mgKOH / g, number of functional groups: 2 [per molecule])
A-2: p-phthalic acid-based polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: RLK-087, hydroxyl value: 200 mgKOH / g, number of functional groups: 2 [per molecule])
(B) Catalyst B-1: Potassium octylate (manufactured by Momentive Performance Materials, product name: K-zeroG)
B-2: Trimerization catalyst (product name: TOYOCAT-TR20, manufactured by Tosoh Corporation)
B-3: Pentamethyldiethylenetriamine (manufactured by Tosoh Corporation, product name: TOYOCAT-DT)
(C) Foam stabilizer Polyalkylene glycol foam stabilizer (manufactured by Dow Corning Toray, product name: SH-193, foam stabilizer of Table 1)
(D) Foaming agent D-1: Water D-2: HFC-365mfc (1,1,1,3,3-pentafluorobutane, manufactured by Nippon Solvay)
HFC-245fa (1,1,1,3,3-pentafluoropropane, manufactured by Central Glass Co., Ltd.)
Mixing ratio HFC-365mfc: HFC-245fa = 7: 3 (described as “HFC” in Table 1)
D-3: Solstice 1233Zd (Honeywell, product name: Soltis LBA)
(E) Polyisocyanate compound MDI (manufactured by Nippon Polyurethane Industry Co., Ltd., product name: Millionate MR-200, isocyanate content 30.5-32.0%)
(F) Flame retardant F-1: Red phosphorus (Rin Chemical Industry Co., Ltd., product name: Nova Excel 140)
F-2: Tris (β-chloropropyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., product name: TMCPP, hereinafter referred to as “TMCPP”)
F-3: Zinc borate (product name: FIREbrake ZB, manufactured by Hayakawa Shoji)
F-4: Hexabromobenzene (manac Co., Ltd., product name: HBB-B)
F-5: primary aluminum phosphate (manufactured by Taihei Chemical Industrial Co., Ltd.)
F-6: Magnesium hydroxide (Kyowa Chemical Industry Co., Ltd., product name: Kisuma 5A)
F-7: Wollastonite (SiO ₂ · CaO; acicular filler) (manufactured by Kinsei Matec, product name: SH-1250)
Preparation of polyol premix The polyol compound, catalyst, foam stabilizer, foaming agent, and flame retardant shown in Table 1 were weighed so that the total amount was 10 kg, and stirred for 10 minutes to prepare a polyol premix.
The polyol premix and polyisocyanate compound prepared above were put into separate tanks of a low pressure foaming machine (A310 type low pressure foaming machine manufactured by Toho Machine Industry Co., Ltd.).

Two SUS304 steel plates are placed inside the mold so as to face each other, a low-pressure foaming machine containing a urethane resin composition component is connected to the nozzle, and the nozzle is connected through the opening of the mold. The urethane resin composition was inserted into the space between the steel plates and injected into the mold through the nozzle under the following conditions.
Mold size (inner dimensions): 30cm x 30cm x 5cm (height)
Mold temperature: 70 ° C
Mold material: Aluminum polyol premix liquid temperature: 25 ° C
Isocyanate temperature: 25 ° C
Mixing method: Using a low-pressure urethane foaming machine, the polyol premix and isocyanate are mixed at a flow rate of 10 kg / min and a rotational speed of 3000 rpm / min. Injected.

After injection of the urethane resin composition, the nozzle is removed from the mold, the opening of the mold is plugged, the urethane resin composition is foamed at 65 ° C. under pressure, and cured and cured at the same temperature for 30 minutes. By removing the mold, a 30 cm × 30 cm × 5 cm flame-retardant heat insulation panel of Example 1 comprising two steel plates and a fireproof heat insulation layer of a cured urethane resin composition sandwiched between them was obtained.
Examples 2 to 6 are flame retardant insulation panels created by the same manufacturing method as in Example 1, but the components were changed as shown in Table 1.

  Comparative Example 1 is the same as in Example 1 and the flame retardant insulation panel, and when the urethane resin composition is foamed and cured in the mold, the opening remains open and no atmospheric pressure is applied. It was foamed and cured below. The urethane resin composition overflowing from the opening after curing was cut to obtain a flame retardant insulation panel of 30 cm × 30 cm × 5 cm.

  Comparative Examples 2 to 11 are flame retardant insulation panels produced by the same manufacturing method as Comparative Example 1, but the components were changed as shown in Table 1.

[Measurement of total calorific value]
To specimens flame燃断heat panel was cut to be 10 cm × 10 cm × 2 cm of Examples 1 to 6 and Comparative Examples 1 to 11, conforming to ISO-5660, in radiant heat intensity 50 kW / ^{m 2} 20 The total calorific value when heated for minutes was measured.

  This measurement method is a test method stipulated as corresponding to the standard according to the corn calorimeter method at the Building Comprehensive Testing Laboratory, which is a public institution stipulated in Article 108-2 of the Building Standards Act Enforcement Ordinance. It conforms to the test method of ISO-5660.

The case where the total calorific value was 8.0 MJ / m ² or less was regarded as acceptable. The results are shown in Table 1.

Although the flame-retardant heat insulation panels of Examples 1 to 6 and Comparative Examples 1 to 10 were acceptable, those of Comparative Example 11 were used. The thermal panel failed. Moreover, in the flame-retardant heat insulation panels of Example 1 and Comparative Examples 1 and 2, the above test was performed using a test piece obtained by removing the steel plate and cutting out only the fireproof heat insulation layer of the cured urethane resin composition to be 10 cm × 10 cm × 2 cm. Also, the total calorific value of the sample was 8.0 MJ / m ² or less, which was acceptable.

[Measurement of adhesive strength]
The adhesiveness of the steel plate and the fireproof heat insulating layer of the flame-retardant heat insulating panels of Examples 1 to 6 and Comparative Examples 1 to 11 was evaluated by the two-layer adhesiveness when the steel plate was manually peeled from the fireproof heat insulating layer. When the material of the refractory thermal insulation layer is destroyed when trying to peel off the steel plate (ie, part of the refractory thermal insulation layer remains unbonded to the steel plate and does not peel off), and the steel plate can be easily separated from the refractory thermal insulation layer Was marked with x.
As a result, in the flame-retardant heat insulating panels of Examples 1 to 6 and Comparative Example 11, the two-layer adhesion was good, and in Comparative Examples 1 to 10, the two-layer adhesion was poor.

[Measurement of compressive strength]
Based on JIS K 7220, the compressive strength of 10 cm x 10 cm x 5 cm was measured for the compressive strength of the steel plate of the flame-retardant heat insulation panel of Examples 1-6 and Comparative Examples 1-11 and a fireproof heat insulation layer.
The compressive strength is preferably 40 N / cm ² or more in order to suppress deformation when the panel is formed.

As a result, the flame retardant insulation panels of Examples 1 to 6 and Comparative Example 11 were excellent in compressive strength, but the flame retardant insulation panels of Comparative Examples 1 to 10 had low compression strength.

DESCRIPTION OF SYMBOLS 1 ... Exterior material, 2 ... type | mold, 5 ... Urethane resin composition, 10 ... Fireproof heat insulation layer, 100,110,120 ... Flame-resistant heat insulation panel.

Claims (10)

A method for producing a flame-retardant and heat-insulating panel obtained by laminating a fire-resistant and heat-insulating layer formed by curing and molding a urethane resin composition containing a flame retardant, and an exterior material,
Including a step of placing a urethane resin composition containing a flame retardant in a mold in which an exterior material is placed, and a step of curing the urethane resin composition containing the flame retardant under pressure,
The urethane resin composition containing the flame retardant includes a urethane resin composed of a polyol compound and a polyisocyanate compound,
The flame retardant includes red phosphorus and at least one selected from the group consisting of a phosphate-containing flame retardant, a phosphate ester, a bromine-containing flame retardant, a metal hydroxide, an acicular filler, and a boron-containing flame retardant,
The method wherein the red phosphorus is in the range of 1.0 to 30 parts by weight with respect to 100 parts by weight of the urethane resin.   The method according to claim 1, wherein the step of curing the urethane resin composition containing the flame retardant under pressure includes pressurizing a mold to cure the urethane resin composition containing the flame retardant.   The method according to claim 1 or 2, wherein the step of curing the urethane resin composition containing the flame retardant under pressure is performed by setting a curing temperature in a range of 20 to 120 ° C.   The process of arrange | positioning the urethane resin composition containing the said flame retardant includes inject | pouring a urethane resin composition between 1 and 1 of two facing exterior materials. The method described in 1.   At least one selected from the group consisting of the phosphate-containing flame retardant, phosphate ester, bromine-containing flame retardant, metal hydroxide, and needle filler is 1.5 wt. 5 to 50 parts by weight, and the boron-containing flame retardant is in the range of 0.1 to 60 parts by weight with respect to 100 parts by weight of the urethane resin. The method according to any one of claims 1 to 4. Based on 100 parts by weight of urethane resin,
The phosphate-containing flame retardant used for the flame retardant is in the range of 1.5 to 20 parts by weight,
The phosphate used in the flame retardant is in the range of 2.5 to 50 parts by weight,
The bromine-containing flame retardant used for the flame retardant is in the range of 1.5 to 20 parts by weight,
The metal hydroxide used for the flame retardant is in the range of 1.5 to 20 parts by weight,
The acicular filler used for the flame retardant is in the range of 3.0 to 30 parts by weight,
The method in any one of Claims 1-4 the boron containing flame retardant used for the said flame retardant is the range of 0.1-60 weight part. The urethane resin composition containing the flame retardant contains a trimerization catalyst that promotes a trimerization reaction of isocyanate groups contained in the urethane resin,
The method according to any one of claims 1 to 6, wherein the trimerization catalyst is in a range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the urethane resin.   The method according to claim 1, wherein the urethane resin composition containing the flame retardant contains at least one of a foam stabilizer and a foaming agent.   The method according to claim 1, wherein a heat insulating layer is added in addition to the fireproof heat insulating layer.   The method according to claim 1, wherein the exterior material is made of at least one selected from the group consisting of an organic material, an inorganic material, and a metal material.