JP2018090721A - Flame-retardant urethane resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant urethane resin composition for providing a polyurethane foam that has improved brittleness and also has corrosion resistance while maintaining flame retardancy.SOLUTION: A flame-retardant urethane resin composition contains polyisocyanate, polyol, trimerization catalyst, foaming agent, foam stabilizer, powder flame retardant and alkali metal silicate. Based on urethane resin composed of polyol and polyisocyanate of 100 pts.wt., the content of alkali metal silicate is 0.1-50 pts.wt.SELECTED DRAWING: None

Description

  The present invention relates to a flame retardant urethane resin composition and a polyurethane foam.

  Concrete reinforced with reinforcing bars or the like is used as a structural material to enhance the strength of buildings, such as apartment buildings, detached houses, various facilities of schools, and outer walls of commercial buildings.

  On the other hand, since concrete has a heat storage property and a cold storage property, there is a disadvantage that the inside of the building is heated by the heat accumulated in summer, or the inside of the building is cooled as a result of cooling the concrete in the cold season of winter. In order to reduce the influence of the outside temperature on the interior of the building through such concrete for a long time, the concrete is usually insulated.

  Therefore, a rigid polyurethane foam having fire resistance to fire is used as a heat insulating layer.

JP-A-11-279398 JP 52-17598

  Conventionally, countermeasures such as blending a powdered flame retardant and accelerating the formation of isocyanurate foam have been used to make the polyurethane foam flame-retardant. However, when the above measures are implemented, the polyurethane foam becomes brittle, dust is caused, and there are problems in terms of safety and performance such as lack of chipping dimensions at the time of molding.

  In addition, the isocyanate which is a raw material for the flame retardant and isocyanurate contains a halogen compound, and when added in a large amount, there is a problem that it corrodes when a metal pipe or the like is insulated.

  An object of the present invention is to provide a flame-retardant urethane resin composition for improving the brittleness of polyurethane foam while maintaining flame retardancy and providing a polyurethane foam having corrosion resistance.

  The inventors of the present application have made various studies to achieve the above object, and found that the above-described problems can be solved by a flame retardant urethane resin composition containing a powder flame retardant and a predetermined amount of an alkali metal silicate. The present invention has been completed.

  That is, the present invention is as follows.

  Item 1. A flame retardant urethane resin composition comprising a polyisocyanate, a polyol, a trimerization catalyst, a foaming agent, a foam stabilizer, a powder flame retardant, and an alkali metal silicate, and 100 parts by weight of a urethane resin comprising a polyol and a polyisocyanate The flame retardant urethane resin composition is characterized in that the content of the alkali metal silicate is 0.1 to 50 parts by weight based on the above.

  Item 2. Item 2. The flame retardant urethane resin composition according to Item 1, wherein the powder flame retardant is at least one selected from the group consisting of red phosphorus, boron-containing flame retardant, and needle filler.

  Item 3. Item 3. A polyurethane foam obtained by curing the flame retardant urethane resin composition according to item 1 or 2.

  Item 4. Item 4. The polyurethane foam according to Item 3, which is a molded body.

  According to the present invention, there is provided a flame retardant urethane resin composition for providing a polyurethane foam having improved foam brittleness and also having corrosion resistance while maintaining flame retardancy.

  The present invention includes (i) a polyisocyanate, a polyol, a trimerization catalyst, a foaming agent, a foam stabilizer, a powder flame retardant, and an alkali metal silicate, based on 100 parts by weight of a urethane resin composed of a polyol and a polyisocyanate. Including a flame retardant urethane resin composition, wherein the content of alkali metal silicate is 0.1 to 50 parts by weight, and (ii) polyurethane foam obtained by curing the flame retardant urethane resin composition To do.

  The flame retardant urethane resin composition of the present invention contains polyisocyanate, polyol, trimerization catalyst, foaming agent, foam stabilizer, powder flame retardant, and alkali metal silicate.

  The polyisocyanate as the main component of the urethane resin and the polyol as the curing agent of the urethane resin are cured by a chemical reaction to form a urethane resin.

  Hereinafter, each component will be described.

1. Polyols Examples of polyols that are curing agents for urethane resins include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, polymer polyols, and polyether polyols.

  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.

  Examples of the polymer polyol include a polymer obtained by graft polymerization of an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, and methacrylate on an aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, or the like, polybutadiene Examples thereof include 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 the polyhydric alcohol include trihydric alcohols such as glycerin and trimethylolpropane; pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc., sucrose, glucose, mannose, fructose, methylglucoside and Tetravalent to octavalent alcohols such as derivatives thereof; phenol, phloroglucin, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene, 1,3,6,8-tetrahydroxynaphthalene Phenol polybutadiene polyols such as anthrol, 1,4,5,8-tetrahydroxyanthracene, 1-hydroxypyrene; castor oil polyol; hydroxyalkyl (meth) acrylate Polyfunctional (e.g. functionality 2 to 100) polyol such as (co) polymers and polyvinyl alcohol rate, and condensation products of phenol and formaldehyde (novolac) is.

  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, from the viewpoints of properties and reactivity, PO, EO, and 1,2-butylene oxide are preferable, 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 or tetrahydrofuran is subjected to ring-opening polymerization. The polymer obtained by making it contain 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, and triols such as glycerol and trimethylolpropane. And amines such as ethylenediamine and butylenediamine.

  The polyol used in the present invention is preferably a polyester polyol or a polyether polyol because the effect of reducing the total calorific value upon combustion is great.

  Among them, it is more preferable to use a polyester polyol having a molecular weight of 200 to 800, and it is more preferable to use a polyester polyol having a molecular weight of 300 to 500.

2. Polyisocyanate compound 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 an aromatic polyisocyanate such as diphenylmethane diisocyanate because it is easy to use and easily available.

  In the composition of the present invention, the isocyanate index is preferably 250 or more, more preferably 260 or more and 700 or less, further preferably 280 or more and 600 or less, and most preferably 300 or more and 500 or less.

  The isocyanate index (INDEX) is calculated by the following method.

INDEX = isocyanate equivalent number / (polyol equivalent number + water equivalent number) × 100
here,
Equivalent number of isocyanate = number of polyisocyanate used × NCO content (%) ÷ 100 / NCO molecular weight,
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 used parts of water × number of OH groups of 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.

3. Catalyst The composition of the present invention includes a trimerization catalyst as a catalyst.

  The trimerization catalyst causes the isocyanate group contained in polyisocyanate, which is the main component of the polyurethane resin, to react and trimerize, thereby promoting the formation of an isocyanurate ring.

Nitrogen-containing aromatic compounds such as tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, 2,4,6-tris (dialkylaminoalkyl) hexahydro-S-triazine as a trimerization catalyst; Carboxylic acid alkali metal salts such as potassium acetate, potassium 2-ethylhexanoate and potassium octylate; tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt and triphenylammonium salt; tetramethylammonium salt, tetraethylammonium and tetraphenyl A quaternary ammonium salt such as an ammonium salt can be used.

  The blending amount of the trimerization catalyst can be in the range of 0.6 to 10 parts by weight and more preferably in the range of 0.6 to 8 parts by weight with respect to 100 parts by weight of the urethane resin. Preferably, it is in the range of 0.6 to 6 parts by weight, and more preferably in the range of 0.6 to 3.0 parts by weight. When the amount is not less than the above lower limit value, the formation of an isocyanurate ring is sufficiently promoted, and when it is not more than the above upper limit value, an appropriate foaming rate can be maintained and the handling is easy.

  One or two or more trimerization catalysts can be used.

  The composition of the present invention may further contain a urethane catalyst as a catalyst. A urethane catalyst is a catalyst that promotes the reaction between a polyol or the like and an isocyanate.

  Examples of the urethane catalyst include tertiary amines, tin compounds, and acetylacetone metal salts.

  Examples of the tertiary amine include pentamethyldiethylenetriamine, triethylamine, N-methylmorpholine bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ′. -Trimethylaminoethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N-methyl-N'N'-dimethylaminoethylpiperazine, an imidazole compound in which the secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group N, N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylhexamethylenediamine, N-methylimidazole, trimethylaminoethylpiperazine, tripropylamine and the like.

  Examples of the tin compound include dibutyltin diacetate and dibutyltin dilaurate.

  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. It is done.

  The content of the urethanization catalyst in the composition of the present invention is preferably in the range of 0.01 to 1 part by weight with respect to 100 parts by weight of the urethane resin, and 0.05 to 1 part by weight. The range is more preferable, and the range of 0.1 to 1 part by weight is still more preferable. In the case of the above lower limit or more, the dimerization reaction occurs sufficiently, and sufficient heat is generated to cause the trimerization reaction, so that flame retardancy is improved. When the amount is not more than the above upper limit value, the foaming start is sufficiently slow, so that a uniform foam can be formed.

  One or two or more urethane catalysts can be used.

4). 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.

  If an example is shown, content of a foam stabilizer can be made into the range of 0.1 weight part-10 weight part with respect to 100 weight part of urethane resins.

  One or more foam stabilizers can be used.

5. Foaming agent Foaming agent promotes foaming of urethane resin. Examples of the blowing agent include water; low-boiling hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane; dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, Chlorinated aliphatic hydrocarbon compounds such as isobutyl chloride, pentyl chloride, isopentyl chloride; fluorine compounds such as CHF ₃ , CH ₂ F ₂ , CH ₃ F; trichloromonofluoromethane, trichlorotrifluoroethane, dichloromonofluoroethane, (For example, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)), etc. Orocarbon compounds; hydrofluorocarbons such as HFC-245fa (1,1,1,3,3-pentafluoropropane) and HFC-365mfc (1,1,1,3,3-pentafluorobutane); HFO-1233zd ( Hydrofluoroolefins such as 1-chloro-3,3,3-trifluoropropene); ether type compounds such as diisopropyl ether, or organic physical foaming agents such as mixtures of these compounds, nitrogen gas, oxygen gas, argon gas, Examples include inorganic physical foaming agents such as carbon dioxide gas.

  Although content of a foaming agent is not specifically limited, It can be set as the range of 0.1 weight part-30 weight part with respect to 100 weight part of urethane resins, and is the range of 0.1 weight part-18 weight part. More preferably, it is in the range of 0.5 to 18 parts by weight, more preferably in the range of 1 to 10 parts by weight.

  When the range of the foaming agent is equal to or higher than the lower limit, foaming is promoted, and the density of the obtained molded body can be reduced. When the range is equal to or lower than the upper limit, the foam does not foam and no foam is formed. Can be prevented.

  One or two or more foaming agents can be used.

6). Silicate Alkali Metal Salt Examples of the alkali metal silicate include alkali metal orthosilicate and alkali metal metasilicate. Examples of the alkali metal salt include sodium salt and potassium salt.

  The content of the alkali metal silicate in the composition of the present invention is in the range of 0.1 to 50 parts by weight and in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the urethane resin. Is preferable, and the range of 0.1 to 5 parts by weight is more preferable. In the case of the above lower limit or more, the corrosivity is improved while improving the brittleness. In the case of the upper limit or less, there is no adverse effect on urethane foaming.

7). Flame retardant The composition of the present invention contains a powder flame retardant in order to impart flame retardancy to the resulting foam.

  Examples of the powder flame retardant include red phosphorus, needle filler, boron-containing flame retardant, phosphate-containing flame retardant, bromine-containing flame retardant, antimony-containing flame retardant, metal hydroxide and the like. The powder flame retardant is preferably at least one selected from the group consisting of red phosphorus, boron-containing flame retardant and needle filler. One or more powder flame retardants can be used.

  There is no limitation in red phosphorus used for this invention, A commercial item can be selected suitably and can be used.

  Further, the content of red phosphorus used in the present invention can be in the range of 1.5 to 52 parts by weight and in the range of 1.5 to 20 parts by weight with respect to 100 parts by weight of the urethane resin. More preferably, the range is from 2.0 parts by weight to 15 parts by weight, and most preferably from 2.0 parts by weight to 10 parts by weight.

  When the range of the red phosphorus is not less than the above lower limit, the self-extinguishing property of the foam is maintained, and when it is not more than the above upper limit, the foaming of the flame retardant urethane resin composition is not inhibited.

  The acicular filler may be an organic filler or an inorganic filler, but is preferably an inorganic filler. The aspect ratio of the acicular filler is 5 to 50, preferably 8 to 40, more preferably 10 to 40, still more preferably 10 to 35, and most preferably 8 to 25. Here, the aspect ratio of the filler in the present specification is the minimum thickness of the maximum length of the filler that is confirmed by an image obtained by observing the acicular filler with a scanning electron microscope (relative to the maximum length). (The vertical direction) (also referred to as the diameter / thickness ratio), a sufficient number of fillers, an average of 250 or more.

  The average particle diameter of the acicular filler is 0.1 μm or more and less than 15 μm, preferably 0.1 μm or more and 14 μm or less, more preferably 0.3 to 10 μm. The average particle size is determined by an X-ray transmission type sedimentation method particle size distribution analyzer. The melting point of the acicular filler is 750 ° C. or higher, preferably 800 ° C. or higher, more preferably 1,000 ° C. or higher.

  As the needle-like inorganic filler, basic magnesium sulfate, aluminum borate, wollastonite, zonolite, dosonite, elastadite, boehmite, rod-like hydroxyapatite, potassium titanate whisker, aluminum borate whisker, magnesium-based whisker, Silicon-based whisker, acicular alumina, acicular ceramic, asbestos, acicular calcium carbonate, gypsum fiber, glass fiber, asbestos fiber, silica fiber, alumina fiber, silica / alumina fiber, zirconia fiber, carbon fiber (fiber such as carbon nanotube) , Needle-like or spherical new carbon such as fullerene), graphite fiber, boron nitride fiber, boron fiber, metal fiber and the like.

  The acicular filler prevents at least one of shrinkage and deformation. In this specification, “shrinkage” refers to changes in length including length in the length direction, length in the width direction, and length in the thickness direction, and “deformation” refers to a shape such as warpage. It refers to a change, particularly a change in shape in the thickness direction. The needle shape means that the major axis is three times or more the minor axis, and includes not only a so-called needle shape but also a spindle shape, a cylindrical shape, and the like.

  In one embodiment, the acicular filler is an acicular inorganic filler having an aspect ratio of 5 to 50 and an average particle diameter of 0.1 μm or more and less than 15 μm. Preferred acicular fillers are wollastonite or potassium titanate whiskers.

  The content of the acicular filler is preferably 1 to 30 parts by weight, more preferably 1 to 25 parts by weight, and preferably 2 to 18 parts by weight with respect to 100 parts by weight of the urethane resin. More preferably it is.

  Examples of the boron-containing flame retardant include borax, boron oxide, boric acid, and borate.

  Examples of boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide.

  Examples of borates include alkali metals, alkaline earth metals, Group 4 elements, Group 12 elements, Group 13 elements, and ammonium borates.

  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, aluminum borate, and ammonium borate.

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

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

  The content of the boron-containing flame retardant used in the present invention can be in the range of 1.5 to 52 parts by weight with respect to 100 parts by weight of the urethane resin, and 1.5 to 20 parts by weight. The range is more preferable, the range of 2.0 parts by weight to 15 parts by weight is still more preferable, and the range of 2.0 parts by weight to 10 parts by weight is most preferable.

  The phosphate-containing flame retardant used in the present invention contains a phosphate. 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, pyrophosphoric acid, polyphosphoric acid, and combinations thereof.

  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 Groups 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, pyrophosphate, polyphosphate, and the like.

  Although it does not specifically limit as monophosphate, For example, ammonium salts, such as ammonium phosphate, ammonium dihydrogen phosphate, and hydrogen ammonium phosphate, phosphoric acid-sodium, disodium phosphate, trisodium phosphate, phosphorous acid -Sodium salts such as sodium, disodium phosphite, sodium hypophosphite, monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, hypophosphorous acid Potassium salts such as potassium, lithium salts such as phosphoric acid-lithium phosphate, dilithium phosphate, trilithium phosphate, phosphorous acid-lithium, dilithium phosphite, lithium hypophosphite, etc., barium dihydrogen phosphate, phosphorus Barium salts such as barium oxyhydrogen, tribarium phosphate, barium hypophosphite, magnesium monohydrogen phosphate, hydrogen phosphate Magnesium, trimagnesium phosphate, magnesium salts such as magnesium hypophosphite, calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, calcium salts such as calcium hypophosphite, and the like.

  The polyphosphate is not particularly limited, and examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, and aluminum polyphosphate.

  Among these, since the self-extinguishing property of the phosphate-containing flame retardant is improved, it is preferable to use a monophosphate, and it is more preferable to use ammonium dihydrogen phosphate.

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

  The content of the phosphate-containing flame retardant used in the present invention can be in the range of 1.5 to 52 parts by weight with respect to 100 parts by weight of the urethane resin, and 1.5 to 20 parts by weight. More preferably, it is in the range of 2.0 parts by weight to 15 parts by weight, and most preferably in the range of 2.0 parts by weight to 10 parts by weight.

  The bromine-containing flame retardant used in the present invention 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 the aromatic brominated compound 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; polycarbonate oligomers produced from brominated bisphenol A as raw materials, copolymers of polycarbonate oligomers and bisphenol A, etc. Brominated polycarbonates: diepoxy compounds produced by the reaction of brominated bisphenol A with epichlorohydrin, brominated phenols and epichlorohydrin Brominated epoxy compounds such as monoepoxy compounds obtained by reaction with poly; brominated benzyl acrylate; brominated polyphenylene ether; condensates of brominated bisphenol A, cyanuric chloride and brominated phenol; brominated (polystyrene), Brominated polystyrenes such as poly (brominated styrene), crosslinked brominated polystyrene; halogenated bromine compound polymers such as crosslinked or non-crosslinked brominated poly (-methylstyrene).

  From the viewpoint of controlling the calorific value at the initial stage of combustion, brominated polystyrene, hexabromobenzene and the like are preferable, and hexabromobenzene is more preferable.

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

  The content of the bromine-containing flame retardant used in the present invention can be in the range of 1.5 to 52 parts by weight with respect to 100 parts by weight of the urethane resin, and 1.5 to 20 parts by weight. The range is more preferable, the range of 2.0 parts by weight to 15 parts by weight is still more preferable, and the range of 2.0 parts by weight to 10 parts by weight is most preferable.

  Examples of the antimony-containing flame retardant used in the present invention include antimony oxide, antimonate, pyroantimonate and the like.

  Examples of the antimony oxide include antimony trioxide and antimony pentoxide.

  Examples of the antimonate include sodium antimonate and potassium antimonate.

  Examples of pyroantimonate include sodium pyroantimonate and potassium pyroantimonate.

  The antimony-containing flame retardant used in the present invention is preferably antimony oxide.

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

  The content of the antimony-containing flame retardant can be in the range of 1.5 to 52 parts by weight with respect to 100 parts by weight of the urethane resin, and can be in the range of 1.5 to 20 parts by weight. More preferably, it is in the range of 2.0 to 15 parts by weight, and most preferably in the range of 2.0 to 10 parts by weight.

  Examples of the metal hydroxide used in the present invention include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, copper hydroxide, and vanadium hydroxide. And tin hydroxide.

  One or two or more metal hydroxides can be used.

  The content of the metal hydroxide can be in the range of 1.5 to 52 parts by weight with respect to 100 parts by weight of the urethane resin, and is in the range of 1.5 to 20 parts by weight. More preferably, it is in the range of 2.0 to 15 parts by weight, and most preferably in the range of 2.0 to 10 parts by weight.

  The total content of the powder flame retardant used in the present invention can be in the range of 4.5 to 70 parts by weight with respect to 100 parts by weight of the urethane resin, and 4.5 to 40 parts by weight. The range is more preferable, and the range of 4.5 to 30 parts by weight is still more preferable.

  When the range of the powder flame retardant is not less than the above lower limit, the molded product made of the flame retardant resin composition can be prevented from cracking the dense residue formed by the heat of the fire, Foaming of the flame retardant resin composition is not inhibited.

  In the present invention, a flame retardant other than the powder flame retardant can also be used.

  Examples of such flame retardants include phosphate esters.

  Although the phosphate ester used for this invention is not specifically limited, It is preferable to use a 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, trixylyl 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, diphen Nyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, Resylcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), phosphaphenanthrene, tris (β-chloropropyl) phosphate and the like.

  The condensed phosphate ester is not particularly limited, and examples thereof include trialkyl polyphosphate, resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate (trade name PX-200, manufactured by Daihachi Chemical Industry Co., Ltd.). ), Hydroquinone poly (2,6-xylyl) phosphate, and condensed phosphate esters 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 (trade name ADK STAB PFR manufactured by ADEKA), bisphenol A polycresyl phosphate (trade names FP-600, FP-700), and the like.

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

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

  The content of the phosphate ester can be in the range of 1.5 to 52 parts by weight and more preferably in the range of 1.5 to 20 parts by weight with respect to 100 parts by weight of the urethane resin. The range is preferably 2.0 parts by weight to 15 parts by weight, and more preferably 2.0 parts by weight to 10 parts by weight.

  When the range of the phosphate ester is not less than the above lower limit value, it is possible to prevent the molded product made of the flame retardant resin composition from cracking the dense residue formed by the ripening of the fire. Foaming of the flammable resin composition is not inhibited.

8). Other Components The composition of the present invention may further contain an inorganic filler. The inorganic filler is not particularly limited. For example, silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate, carbonate Magnesium, barium carbonate, dosonite, hydrotalcite, calcium sulfate, barium sulfate, potassium salts such as gypsum fiber, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, Silica parun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon parun, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum porate Molybdenum sulfide, silicon carbide, stainless steel fiber, various magnetic powder, slag fibers, fly ash, silica alumina fiber, alumina fiber, silica fiber, zirconia fiber, and the like.

  One or more inorganic fillers can be used.

  The composition of the present invention is within a range that does not impair the object of the present invention, as necessary, phenolic, amine-based, sulfur-based antioxidants, heat stabilizers, metal harm-preventing agents, antistatic agents, A stabilizer, a crosslinking agent, a lubricant, a softening agent, a pigment, an auxiliary component such as a tackifier resin, and a tackifier such as a polybutene and a petroleum resin can be included.

  Above 1. ~ 8. Since the above components are mixed and the flame retardant urethane resin composition reacts and cures, its viscosity changes with time. Therefore, before using the flame retardant urethane resin composition, the flame retardant urethane resin composition is divided into two or more to prevent the flame retardant urethane resin composition from reacting and curing (foamable polyurethane). Premix composition). And when using a flame-retardant urethane resin composition, a flame-retardant urethane resin composition is obtained by mixing the flame-retardant urethane resin composition divided | segmented into two or more, and putting them together.

  In addition, when dividing the flame retardant urethane resin composition into two or more, each component of the flame retardant urethane resin composition divided into two or more does not start to cure, and each of the flame retardant urethane resin composition Each component may be divided so that the curing reaction starts after the components are mixed.

  Although the flame retardant urethane resin composition may be cured and mixed at room temperature, each component may be heated in advance.

  The trimerization catalyst, foam stabilizer, foaming agent, flame retardant and alkali metal silicate may be mixed with either a polyol or polyisocyanate, or may be provided separately from the polyol and polyisocyanate, Preferably, the trimerization catalyst, foam stabilizer, foaming agent, flame retardant and alkali metal silicate are provided as a polyol premix containing a polyol and these components (reacted with a polyisocyanate compound to obtain a polyurethane foam). Polyol solution composition). In addition, the above 8. These other components may also be mixed with either the polyol or polyisocyanate, or may be provided separately from the polyol and polyisocyanate, but are preferably included in the polyol premix.

  The method for producing the flame retardant urethane resin composition is not particularly limited. For example, the method of mixing the components of the flame retardant urethane resin composition, the flame retardant urethane resin composition suspended in an organic solvent, A method of heating and melting to form a paint, a method of preparing a slurry by dispersing in a solvent, and the reaction curable resin component contained in the flame retardant urethane resin composition at room temperature (about 25 ° C.) When a component that is solid at the temperature is contained, the flame retardant urethane resin composition can be obtained by a method such as melting the flame retardant urethane resin composition under heating.

  The flame retardant urethane resin composition is a known component such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader mixer, a kneading roll, a laika machine, a planetary stirring machine, etc. It can be obtained by kneading using an apparatus.

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

  Further, the components of the flame retardant urethane resin composition excluding the catalyst and the catalyst can be kneaded in the same manner immediately before injection. A flame-retardant urethane resin composition can be obtained by the method described above.

  Next, the curing method of the flame retardant urethane resin composition according to the present invention will be described.

  When the respective components of the flame retardant urethane resin composition are mixed, the reaction starts, the viscosity increases with the passage of time, and the fluidity is lost.

  For example, the molded body made of the flame retardant urethane resin composition can be obtained as a foam by injecting the flame retardant urethane resin composition into a container such as a mold or a frame material and curing it. Or the molded object which consists of the said flame-retardant urethane resin composition can be obtained as a foam by spraying the said flame-retardant urethane resin composition on a to-be-coated structure, and making it harden | cure.

  When obtaining the molded object which consists of the said flame-retardant urethane resin composition, heat can be applied or a pressure can be applied.

  Although the thickness of the molded object of this invention is not specifically limited, For example, it is 1-50 mm. Particularly in the case of 20 mm or more, the effect of suppressing deformation during the exothermic test is exhibited, which is advantageous. In one embodiment, the molded article of the present invention was heated for 20 minutes at a radiant heat intensity of 50 kW / m 2 according to the ISO-5660 test method, the molded article of 100 mm × 100 mm × 20 mm (length direction × width direction × thickness direction). The dimension in the length direction and the width direction of the molded body after heating with respect to before heating is greater than 95 mm, and the deformation in the thickness direction is less than 10 mm.

  The molded body made of the flame retardant urethane resin composition of the present invention is preferably in the range of 0.020 to 0.130 because the specific gravity is in the range of 0.020 to 0.130, and preferably in the range of 0.020 to 0.100. More preferably, it is in the range of 0.030 to 0.080, more preferably in the range of 0.030 to 0.060.

  The molded body comprising the flame retardant urethane resin composition of the present invention is preferably heated at a rate of 10 ° C./min from 30 ° C. to 900 ° C., and the measurement atmosphere is an air flow at a flow rate of 100 mL / min. The weight reduction rate (1-sample weight after heating / sample weight before heating) × 100 (%)) in the TG / DTA measurement under air conditions is 5% or less. For this reason, a molded object can hold | maintain high shape retainability after a heating.

  Next, application examples of the flame retardant urethane resin composition according to the present invention will be described.

  The flame-retardant urethane resin composition can be molded into a thin panel and placed on structures such as buildings, furniture, automobiles, trains, and ships. Or the foam layer which consists of a flame-retardant urethane resin composition can be formed in the surface of the said structure by spraying the said flame-retardant urethane resin composition on the said structure.

The fire resistance of the urethane foam composition and polyurethane foam of the present invention can be evaluated by a cone calorimeter test based on the test method of ISO-5660. Specifically, in this fire resistance test, a polyurethane foam made of a flame retardant resin composition is cut into a length of 10 cm, a width of 10 cm, and a thickness of 5 cm to prepare a sample for a corn calorimeter test. Next, the total calorific value when heated at a radiant heat intensity of 50 kW / m ^{2 for} 20 minutes is measured with a corn calorimeter using a sample for corn calorimeter test according to the test method of ISO-5660.

In the present specification, “flame retardant” means (1) a total calorific value of 20 MJ / m ² or less after starting heating at a radiant heat intensity of 50 kW / m ² , and (2) 20 minutes after starting heating. (1) to (3) that the heat generation rate exceeding 200 kW / m ² does not continue for more than 10 seconds, and (3) deformation such as cracks or holes harmful to fire prevention does not occur in 20 minutes after the start of heating. The one that has all the conditions.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

1. Production of Foam Molded Body Composed of Flame Retardant Urethane Resin Composition According to the formulation shown in Table 1, flame retardant urethane resin compositions according to Examples 1 to 3 and Comparative Examples 1 to 2 were prepared. Details of each component in the table are as follows.

(1) Polyol composition (A-1) p-phthalic acid polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RFK-505, hydroxyl value = 250 mgKOH / g).

(2) Foam stabilizer (B-1) Polyalkylene glycol foam stabilizer (manufactured by Toray Dow Corning, product name: SH-193).

(3) Trimerization catalyst (C-1) 2-ethylhexanoic acid potassium (manufactured by MOMENTIVE, product name: K-zeroG),
(C-2) Trimerization catalyst (product name: TOYOCAT-TRX, manufactured by Tosoh Corporation).

(4) Urethane catalyst (D-1) pentamethyldiethylenetriamine (manufactured by Tosoh Corporation, product name: TOYOCAT-DT).

(5) Alkali metal silicate (E-1) Sodium metasilicate 1 type (Fuji Chemical Co., Ltd.).

(6) Foaming agent water HFC: HFC-365mfc (1,1,1,3,3-pentafluorobutane, manufactured by Central Glass Co., Ltd.), HFC-245fa (1,1,1,3,3-pentafluoropropane, (Made by Solvay Japan) Mixing ratio HFC-365fa: HFC-245fa = 7: 3 (hereinafter referred to as “HFC”).

(7) Polyisocyanate (F-1) MDI (manufactured by Nippon Urethane Industry Co., Ltd., product name: Millionate MR-200) Viscosity: 167 mPa · s.

(8) Additive (G-1) Red phosphorus (Rin Chemical Industry Co., Ltd., product name: Nova Excel 140)
(G-2) Tris (β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP, hereinafter referred to as “TMCPP”).

  In accordance with the composition shown in Table 1 below, the polyol compound, foam stabilizer, various catalysts, foaming agent, and additives were weighed into a 1000 mL polypropylene beaker and stirred with a hand mixer at 25 ° C. for 10 seconds (Liquid B). A polyisocyanate compound (liquid A) was added to the kneaded product after stirring, and the mixture was stirred for about 10 seconds with a hand mixer to prepare a foam. The obtained flame-retardant urethane resin composition lost fluidity with the passage of time, and foamed molded articles of the flame-retardant urethane resin compositions of Examples 1 to 3 and Comparative Examples 1 to 2 were obtained.

2. Evaluation of Molded Body Performances of the flame retardant urethane resin compositions of Examples 1 to 3 and Comparative Examples 1 and 2 and the foamed molded body were evaluated by the following methods. The results are shown in Table 1.

(1) Total calorific value It evaluated by the cone calorimeter test based on the test method of ISO-5660. Specifically, a polyurethane foam of the flame retardant resin composition was cut into a length of 10 cm, a width of 10 cm, and a thickness of 5 cm to prepare a sample for a corn calorimeter test. Next, the total calorific value when heated at a radiant heat intensity of 50 kW / m ^{2 for} 20 minutes was measured with a corn calorimeter using a sample for corn calorimeter test according to the test method of ISO-5660.

When the total calorific value was 8 MJ / m ² or less, it was evaluated as having flame retardancy.

(2) Compressive strength In order to evaluate brittleness, the compressive strength of the polyurethane foam was measured. The measurement of compressive strength was based on JISK7220.

When the compressive strength of the polyurethane foam is 20 N / cm ² or more, it is evaluated as ○ (foam brittleness is improved), and when it is less than 20 N / cm ² , x (foam brittleness is not improved) and evaluated.

(3) Corrosivity Corrosivity was evaluated according to ASTM C795.

  This standard is based on the idea that metal corrosion is promoted by water-soluble chloride and fluoride ions and suppressed by silicate and sodium ions. Measure the amount of water-soluble chlorine ion, fluorine ion, silicate ion, and sodium ion, ○ if it is below the total allowable amount of chlorine ion and fluorine ion determined by the total amount of silicate ion and sodium ion, × if it exceeds It was.

Claims (4)

  A flame retardant urethane resin composition comprising a polyisocyanate, a polyol, a trimerization catalyst, a foaming agent, a foam stabilizer, a powder flame retardant, and an alkali metal silicate, and 100 parts by weight of a urethane resin comprising a polyol and a polyisocyanate The flame retardant urethane resin composition is characterized in that the content of the alkali metal silicate is 0.1 to 50 parts by weight based on the above.   The flame retardant urethane resin composition according to claim 1, wherein the powder flame retardant is at least one selected from the group consisting of red phosphorus, boron-containing flame retardant and needle filler.   A polyurethane foam obtained by curing the flame retardant urethane resin composition according to claim 1. The polyurethane foam according to claim 3, wherein the polyurethane foam is a molded body.