JP2018021142A - Flame-retardant urethane resin composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To clarify the relationship between a structure of a flame-retardant urethane resin composition and non-combustibility.SOLUTION: A flame-retardant urethane resin composition contains polyisocyanate, polyol, a trimerization catalyst, a foaming agent, a foam stabilizer and a phosphorus compound, where inP-NMR of a surface layer of 1 mm after heating a cured product of the flame-retardant urethane resin composition at 50 kW/mfor 20 minutes, an intensity ratio of a peak in the vicinity of -30 ppm with respect to a peak in the vicinity of 0 ppm is 0.3 or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a flame retardant urethane resin composition and a method for producing the same.

  Known methods of imparting flame retardancy to urethane include a method of increasing the isocyanurate skeleton and a method of adding a flame retardant such as red phosphorus and phosphate ester (see Patent Document 1).

  The flame retardant expression mechanism of the urethane resin composition containing red phosphorus is that red phosphorus reacts with water and oxygen to produce polyphosphoric acid, which forms a char to form a flame retardant. It is said to improve.

However, as well as detailed structural analysis of the polyphosphoric acid, it is not clear how the structure and flame retardancy are related. The structure of phosphorus in the urethane resin composition was analyzed by ³¹ P-NMR of the combustion residue, and the relationship between the structure and nonflammability was clarified.

JP2012-97169

  The objective of this invention is providing the flame-retardant urethane resin composition excellent in the flame retardance, and its manufacturing method.

In order to achieve the above object, the present inventors measured 0 ppm when ³¹ P-NMR of a surface layer of 1 mm after heating a cured product of a flame retardant urethane resin composition at 50 kW / m ² for 20 minutes. By adjusting the components of the flame retardant urethane resin composition so that the intensity ratio of the peak near -30 ppm with respect to the peak in the vicinity is 0.3 or more, a flame retardant urethane capable of solving the above problems can be obtained. The headline and the present invention were completed.

That is, the present invention is as follows.
[1] A flame retardant urethane resin composition containing a polyisocyanate, a polyol, a trimerization catalyst, a foaming agent, a foam stabilizer, and a phosphorus compound, and 50 kW / m ² of a cured product of the flame retardant urethane resin composition A flame retardant urethane resin composition, wherein the intensity ratio of the peak near −30 ppm to the peak near 0 ppm is ³¹ or more in ³¹ P-NMR of 1 mm of the surface layer after heating for 20 minutes.
[2] The phosphorus compound is at least selected from red phosphorus, phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant, antimony-containing flame retardant, metal hydroxide, and needle filler. The flame-retardant urethane resin composition according to [1], including one.
[3] Based on 100 parts by weight of urethane resin, a foam stabilizer in the range of 0.1 to 10 parts by weight, a catalyst in the range of 0.3 to 10 parts by weight, and 0.1 to 30 parts by weight The flame retardant urethane resin composition according to [1] or [2], comprising a foaming agent and a flame retardant in the range of 6 to 70 parts by weight.
[4] The flame retardancy according to any one of [1] to [3], wherein the content of the trimerization catalyst is in the range of 0.6 to 10 parts by weight with respect to 100 parts by weight of the urethane resin. Urethane resin composition.
[5] Any of [1] to [4], further comprising a urethanization catalyst, wherein the content of the urethanization catalyst is in the range of 0.6 to 10 parts by weight with respect to 100 parts by weight of the urethane resin. The flame retardant urethane resin composition described in 1.
[6] The flame-retardant urethane resin composition according to any one of [1] to [5], wherein the foaming agent content is in the range of 1 to 20 parts by weight with respect to 100 parts by weight of the urethane resin.
[7] The foaming agent contains water, and the water content is in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the urethane resin. Flame retardant urethane resin composition.
[8] The flame retardant is 3 to 35 parts by weight of red phosphorus, phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant, antimony-containing flame retardant, metal hydroxide, and acicular shape. The flame retardant urethane resin composition according to any one of [1] to [7], comprising at least one filler selected from 3 to 35 parts by weight selected from fillers.
[9] A method for producing a flame-retardant urethane resin composition,
A polyisocyanate, a polyol, a trimerization catalyst, a foaming agent, a foam stabilizer, and a phosphorus compound are mixed to produce a flame retardant urethane resin composition, and 50 kW of a cured product of the flame retardant urethane resin composition In the ³¹ P-NMR of 1 mm surface layer after heating for 20 minutes at / m ² , polyisocyanate, polyol, trimerization catalyst, so that the intensity ratio of the peak near −30 ppm to the peak near 0 ppm is 0.3 or more, Adjusting the composition of the foaming agent, foam stabilizer and phosphorus compound.
[10] The phosphorus compound is at least selected from red phosphorus, phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant, antimony-containing flame retardant, metal hydroxide, and needle filler. The method according to [9], including one.
[11] Based on 100 parts by weight of urethane resin, a foam stabilizer in the range of 0.1 to 10 parts by weight, a catalyst in the range of 0.3 to 10 parts by weight, and 0.1 to 30 parts by weight The method according to [9] or [10], comprising a foaming agent and a flame retardant in the range of 6 to 70 parts by weight.
[12] The flame retardancy according to any one of [1] to [11], wherein the content of the trimerization catalyst is in the range of 0.6 to 10 parts by weight with respect to 100 parts by weight of the urethane resin. Urethane resin composition.
[13] Any of [1] to [12], further including a urethanization catalyst, wherein the content of the urethanization catalyst is in the range of 0.6 to 10 parts by weight with respect to 100 parts by weight of the urethane resin. The method described in 1.
[14] The method according to any one of [1] to [13], wherein the foaming agent content is in the range of 1 to 20 parts by weight with respect to 100 parts by weight of the urethane resin.
[15] The foaming agent contains water, and the water content is in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the urethane resin. Method.
[16] The flame retardant is 3 to 35 parts by weight of red phosphorus, phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant, antimony-containing flame retardant, metal hydroxide, and needle-like The method according to any one of [1] to [15], comprising 3 to 35 parts by weight of at least one filler selected from fillers.

According to the present invention, the nonflammability of a flame retardant urethane resin composition can be evaluated by measuring the ³¹ P-NMR value after heating of the flame retardant urethane resin composition. Moreover, the flame-retardant urethane resin composition which has the outstanding flame retardance can be manufactured based on this ³¹ P-NMR value.

(A) Example 1, (B) Example 2, and (C) a graph showing the ³¹ P-NMR measurements after heating the cured product of the flame-retardant urethane resin composition of Comparative Example 1.

The present invention is a flame retardant urethane resin composition comprising a polyisocyanate, a polyol, a trimerization catalyst, a foaming agent, a foam stabilizer, and a phosphorus compound, and 50 kW / m of a cured product of the flame retardant urethane resin composition Including a flame retardant urethane resin composition characterized in that, in ³¹ P-NMR of 1 mm surface layer after heating at ² for 20 minutes, the intensity ratio of the peak near -30 ppm to the peak near 0 ppm is 0.3 or more To do.

  First, the urethane resin used for the flame retardant urethane resin composition will be described.

  The urethane resin is composed of polyisocyanate as a main agent and polyol as a curing agent.

  As polyisocyanate, aromatic polyisocyanate, alicyclic polyisocyanate, aliphatic polyisocyanate etc. are mentioned, for example.

  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 two or more polyisocyanates can be used. The main component of the urethane resin is preferably diphenylmethane diisocyanate for reasons such as ease of use and availability.

  Examples of the polyol which is a curing agent for the urethane resin include polylactone polyol, polycarbonate polyol, aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, polymer polyol, polyether polyol, and the like.

  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 polyhydric alcohol include trihydric alcohols such as glycerin and trimethylolpropane; pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc., sucrose, glucose, mannose, fructose, methyl glucoside 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 , Antrol, phenol such as 1,4,5,8-tetrahydroxyanthracene, 1-hydroxypyrene; polybutadiene polyol; 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.

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

  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 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, and ethylenediamine. And amines such as 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.

  The isocyanate index is an equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyol in percentage. A value exceeding 100 means that the isocyanate group is in excess of the hydroxyl group.

  The range of the isocyanate index of the urethane resin used in the present invention is not particularly limited, but is preferably in the range of 150 to 1000, more preferably in the range of 200 to 800, and even more preferably in the range of 250 to 700. preferable. The isocyanate index (INDEX) is calculated by the following method.

INDEX = isocyanate equivalent number / (polyol equivalent number + water equivalent number) × 100

Here, the equivalent number of isocyanate = molecular weight of NCO ÷ NCO content (%) × 100,
Equivalent number of polyol = OHV x number of parts used / molecular weight of KOH, OHV is hydroxyl value of polyol (mg KOH / g),
Equivalent number of water = number of parts used / molecular weight of water × number of OH groups of water. In the above formula, the molecular weight of NCO is 42, the molecular weight of KOH is 56100, the molecular weight of water is 18, and the number of OH groups in water is 2.

  Moreover, a flame-retardant urethane resin composition contains a foam stabilizer, a catalyst, a foaming agent, and a flame retardant.

  Examples of the foam stabilizer used in the flame-retardant urethane resin composition include surfactants such as polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ether, silicone foam stabilizers such as organopolysiloxane, and the like. .

  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, A range of 0.1 to 10 parts by weight is preferable.

  Examples of the catalyst used in the flame retardant urethane resin composition include 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′-dimethylaminoethylpiperazine, secondary amine functional group in imidazole ring replaced with cyanoethyl group And nitrogen atom-containing catalysts such as imidazole compounds.

  The content of the catalyst used in the flame retardant urethane resin composition is preferably in the range of 0.6 to 10 parts by weight, and 0.6 to 8 parts by weight with respect to 100 parts by weight of the urethane resin. More preferred is the range of parts.

  When the amount is 0.6 parts by weight or more, there is no problem that the formation of urethane bonds is hindered. When the amount is 10 parts by weight or less, an appropriate foaming rate can be maintained and the handling is easy.

  Preferred catalysts include trimerization catalysts and urethanization catalysts.

  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.

  Trimerization catalysts include nitrogen-containing aromatic compounds such as tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, 2,4,6-tris (dialkylaminoalkyl) hexahydro-S-triazine ; Potassium acetate, potassium 2-ethylhexanoate, alkali metal carboxylate; tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, triphenylammonium salt; tetramethylammonium salt, tetraethylammonium salt, tetraphenylammonium salt, etc. And quaternary ammonium salts.

  The content of the trimerization catalyst used in the flame retardant urethane resin composition is preferably in the range of 0.6 to 10 parts by weight, and 0.6 to 6 parts by weight with respect to 100 parts by weight of the urethane resin. More preferably, it is in the range of parts by weight. In the case of 0.6 parts by weight or more, there is no problem that the trimerization of isocyanate is inhibited, and in the case of 10 parts by weight or less, an appropriate foaming rate can be maintained and the handling is easy.

  The urethanization catalyst catalyzes the reaction between the isocyanate compound and the polyol.

  The urethanization catalyst is preferably a tertiary amine, and examples of the tertiary amine include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N ′, N ″, N ″ Pentamethyldipropylenetriamine, N, N, N ′, N′-tetramethylguanidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, 1,8-diazabicyclo [5 4.0] undecene-7, triethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N′-dimethylpiperazine, dimethyl Chlorhexylamine, N-methylmorpholine, N-ethylmorpholine, bis (2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropyl Tertiary amine compounds such as imidazole and N-methyl-N- (N, N-dimethylaminoethyl) ethanolamine are exemplified.

  The urethanization catalyst includes a resinification catalyst and a foaming catalyst.

  The content of the urethanization catalyst used in the flame retardant urethane resin composition is preferably in the range of 0.6 parts by weight to 10 parts by weight, and 0.6 parts by weight to 6 parts by weight with respect to 100 parts by weight of the urethane resin. More preferably, it is in the range of parts by weight. When the amount is 0.6 parts by weight or more, there is no problem that the formation of urethane bonds is hindered. When the amount is 10 parts by weight or less, an appropriate foaming rate can be maintained and the handling is easy.

  The foaming agent used for the flame retardant urethane resin composition promotes foaming of the urethane resin.

Specific examples of the blowing agent include, for example, water; hydrocarbons having a low boiling point such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane; dichloroethane, propyl chloride, isopropyl chloride, Chlorinated aliphatic hydrocarbon compounds such as butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride; Fluorine compounds such as CHF ₃ , CH ₂ F ₂ , CH ₃ F; trichloromonofluoromethane, trichlorotrifluoroethane, dichloromono Hydrochlorofluorocar, such as fluoroethane (for example, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)) Bon compounds; hydrofluorocarbons such as HFC-245fa (1,1,1,3,3-pentafluoropropane) and HFC-365mfc (1,1,1,3,3-pentafluorobutane); ethers such as diisopropyl ether Examples thereof include organic physical foaming agents such as compounds or mixtures of these compounds, and inorganic physical foaming agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas.

  The range of the foaming agent is preferably in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the urethane resin. The foaming agent is more preferably in the range of 1 to 20 parts by weight, and still more preferably in the range of 5 to 18 parts by weight with respect to 100 parts by weight of the urethane resin.

  When a foaming agent contains water, it is preferable that content of water is the range of 0.1 weight part-5 weight part with respect to 100 weight part of urethane resins.

  When the range of the foaming agent is 0.1 parts by weight or more, the formation of bubbles is promoted and a good foam is obtained. When the range is 30 parts by weight or less, the vaporization power is increased and the bubbles are prevented from becoming coarse. Can do.

  One or two or more foam stabilizers, catalysts, and foaming agents can be used.

  Next, the flame retardant used in the flame retardant urethane resin composition of the present invention will be described.

  According to the present invention, the flame retardant contains red phosphorus as an essential component. In one embodiment, the flame retardant is comprised of red phosphorus, phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant, antimony-containing flame retardant, metal hydroxide, and acicular filler. And at least one selected.

  The content of the flame retardant used in the present invention is preferably in the range of 6 to 70 parts by weight with respect to 100 parts by weight of the urethane resin, preferably 6 to 40 parts by weight. More preferred is a range, 6 to 30 parts by weight is still more preferred, and 6 to 20 parts by weight is most preferred.

  When the range of the flame retardant is 6 parts by weight or more, the compact made of the flame retardant urethane resin composition can be prevented from cracking the dense residue formed by the heat of the fire, and when the range is 70 parts by weight or less, it is difficult. Foaming of the flammable urethane resin composition is not inhibited.

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

  The content of red phosphorus used in the fireproof urethane resin composition according to the present invention is preferably in the range of usually 3.5 parts by weight to 30 parts by weight with respect to 100 parts by weight of the urethane resin. The range is more preferably 20 parts by weight, and more preferably in the range of 6.0 parts by weight to 18 parts by weight.

  When the range of red phosphorus is 3.5 parts by weight or more, the self-extinguishing property of the flame retardant urethane resin composition is maintained, and when it is 20 parts by weight or less, foaming of the flame retardant urethane resin composition is inhibited. Not.

  In one preferred embodiment, red phosphorus is 2 to 18% by weight based on the weight of the flame retardant urethane resin composition.

  The phosphate ester used in the present invention is not particularly limited, but it is preferable to use a monophosphate ester, a condensed phosphate ester, or the like.

  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, di- Phenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, Resorcinol 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 is preferably in the range of 2.5 to 50 parts by weight and more preferably in the range of 2.5 to 40 parts by weight with respect to 100 parts by weight of the urethane resin. The range is preferably from 2.5 parts by weight to 30 parts by weight.

  When the range of the phosphate ester is 2.5 parts by weight or more, the self-extinguishing property is maintained, and when it is 50 parts by weight or less, foaming of the flame retardant urethane resin composition is not inhibited.

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

  The phosphate-containing flame retardant is selected from, for example, the various phosphoric acids and metals in groups IA to IVB of the periodic table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring. Mention may be made of phosphates composed of salts with at least one metal or compound.

  Examples of the metals in 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.

  Examples of the aromatic amine include aniline, o-triidine, 2,4,6-trimethylaniline, anisidine, and 3- (trifluoromethyl) aniline.

  Examples of the heterocyclic compound containing nitrogen in the ring include pyridine, triazine, melamine and the like.

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

Although not particularly limited as the monophosphate, for example, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen 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 the like can be mentioned.

  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-digestibility of the phosphate-containing flame retardant is improved, it is preferable to use a monophosphate, and it is preferable to use ammonium dihydrogen phosphate.

  The said phosphate containing flame retardant can use 1 type, or 2 or more types.

  Although there is no limitation in particular in content of the phosphate containing flame retardant used for this invention, It is preferable that it is the range of 0.1 weight part-60 weight part with respect to 100 weight part of urethane resins, More preferably, the range is from 50 parts by weight to 50 parts by weight, still more preferably from 0.1 part by weight to 40 parts by weight, and most preferably from 3.0 parts by weight to 10 parts by weight. .

  When the range of the phosphate-containing flame retardant is 0.1 parts by weight or more, the self-extinguishing property of the fire-resistant urethane resin composition according to the present invention is maintained, and when it is 60 parts by weight or less, the present invention is applied. Foaming of such a refractory 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 a brominated aromatic ring-containing aromatic compound.

Specific examples of the brominated aromatic ring-containing aromatic compound include, for example, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, Monomeric organic bromine compounds such as bis (pentabromophenoxy) ethane, ethylenebis (pentabromophenyl), ethylenebis (tetrabromophthalimide), tetrabromobisphenol A,
A polycarbonate oligomer produced from brominated bisphenol A as a raw material, a brominated polycarbonate such as a copolymer of the polycarbonate oligomer 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,
A condensate 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 controlling the calorific value at the initial stage of combustion, ethylene bis (pentabromophenyl), ethylene bis (tetrabromophthalimide), hexabromobenzene and the like are preferable, and hexabromobenzene is more preferable.

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

  Although there is no limitation in particular in content of the bromine containing flame retardant used for this invention, It is preferable that it is the range of 0.1 weight part-60 weight part with respect to 100 weight part of urethane resins, 0.1 weight part More preferably, it is in the range of ˜50 parts by weight, more preferably in the range of 0.1 part by weight to 40 parts by weight, and most preferably in the range of 3.0 parts by weight to 5.0 parts by weight. .

  When the range of the bromine-containing flame retardant is 0.1 parts by weight or more, the self-extinguishing property of the fire-resistant 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.

  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.

  Content of the boron containing flame retardant used for this invention is the range of 0.1-60 weight part with respect to 100 weight part of urethane resins. The content of the boron-containing flame retardant is preferably in the range of 0.1 to 50 parts by weight, more preferably in the range of 0.1 to 40 parts by weight, and in the range of 1.0 to 10 parts by weight. More preferably it is.

  When the range of the boron-containing flame retardant is 0.1 parts by weight or more, the self-extinguishing property of the urethane resin composition according to the present invention is maintained, and when it is 60 parts by weight or less, the urethane resin composition according to the present invention. The foaming of objects is not hindered.

  Examples of the antimony-containing flame retardant 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 the pyroantimonate include sodium pyroantimonate and potassium pyroantimonate.

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

  Although there is no limitation in particular in content of the antimony containing flame retardant used for this invention, It is preferable that it is the range of 0.1 weight part-60 weight part with respect to 100 weight part of urethane resins, 0.1 weight part It is more preferably in the range of ˜50 parts by weight, still more preferably in the range of 0.1 part by weight to 40 parts by weight, and most preferably in the range of 1 part to 10 parts.

  When the range of the antimony-containing flame retardant is 0.1 parts by weight or more, the self-extinguishing property of the fire-resistant 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.

  Examples of the metal hydroxide include calcium hydroxide, sodium hydroxide, magnesium hydroxide, aluminum hydroxide, lithium hydroxide, and potassium hydroxide.

  The said metal hydroxide can use 1 type, or 2 or more types.

  Content of the metal hydroxide used for this invention is the range of 0.1 weight part-50 weight part with respect to 100 weight part of urethane resins. The content of the metal hydroxide is preferably in the range of 0.5 to 40 parts by weight, more preferably in the range of 0.5 to 30 parts by weight, and 1.5 to 10 parts by weight. More preferably, it is in the range of parts.

  When the range of the metal hydroxide is 0.1 parts by weight or more, the self-extinguishing property of the flame retardant urethane resin composition according to the present invention is maintained, and when it is 10 parts by weight or less, the present invention is concerned. Foaming of the flame retardant urethane resin composition is not inhibited.

  The needle-like filler refers to a filler whose 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.

  The acicular filler may be an organic filler or an inorganic filler, but is preferably an inorganic filler. The aspect ratio of the filler is preferably 5-50. Filler aspect ratio refers to the ratio (diameter / thickness) of the maximum filler length to the minimum thickness (perpendicular to the maximum length) confirmed in an image obtained by observing the filler with a scanning electron microscope. It is also referred to as a ratio), which is a sufficient number of fillers and an average of 250 or more. The average particle size of the filler is preferably 0.1 μm or more and less than 15 μm. The average particle size is determined by an X-ray transmission type sedimentation method particle size distribution analyzer. The melting point of the filler is preferably 750 ° 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. Preferred acicular inorganic fillers are wollastonite or potassium titanate whiskers.

  The content of the acicular filler is preferably in the range of 3 to 30 parts by weight, more preferably in the range of 3 to 25 parts by weight, with respect to 100 parts by weight of the urethane resin. More preferably, it is in the range of 18 parts by weight.

  Furthermore, the flame retardant urethane resin composition is within a range that does not impair the object of the present invention, as necessary, such as phenol-based, amine-based, sulfur-based antioxidants, heat stabilizers, metal harm-preventing agents, charging agents. An inhibitor, a stabilizer, a crosslinking agent, a lubricant, a softener, a pigment, an auxiliary component such as a tackifier resin, and a tackifier such as polybutene and a petroleum resin can be included.

  Since the flame retardant urethane resin composition reacts and cures, its viscosity changes over 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. And when using a flame-retardant urethane resin composition, a flame-retardant urethane resin composition is obtained by putting together the flame-retardant urethane resin composition divided | segmented into two or more.

  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.

  In one embodiment, the flame retardant urethane resin composition comprises a foam stabilizer in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the urethane resin composed of the polyisocyanate and the polyol; 3 to 10 parts by weight of catalyst, 0.1 to 30 parts by weight of blowing agent, and 6 to 70 parts by weight of flame retardant. In this flame retardant urethane resin composition, preferably the trimerization catalyst is 0.6 to 10 parts by weight, red phosphorus is 3 to 35 parts by weight, and phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant, At least one filler selected from a boron-containing flame retardant, an antimony-containing flame retardant, a metal hydroxide, and an acicular filler is 3 to 35 parts by weight.

The flame retardant urethane resin composition of the present invention has a peak around 0 ppm when a cured product of the flame retardant urethane resin composition is heated at 50 kW / m ² for 20 minutes and then 1 mm of the surface layer is measured by ³¹ P-NMR. The intensity ratio of the peak in the vicinity of −30 ppm to is not less than 0.3. For this reason, the flame-retardant urethane resin composition of the present invention is excellent in flame retardancy.

  Without being bound by theory, the peak near 0 ppm is derived from phosphoric acid, the peak near −30 ppm is derived from condensed phosphoric acid (hereinafter, condensed phosphoric acid), and the ratio of condensed phosphoric acid to phosphoric acid is It is considered that the flame retardancy increases as the value increases. Surprisingly, the inventors have found that the ratio of condensed phosphoric acid to phosphoric acid is an indicator of flame retardancy in the ratio of condensed phosphoric acid to phosphoric acid.

The present invention is a method for producing a flame retardant urethane resin composition, which comprises a polyisocyanate, a polyol, a trimerization catalyst, a foaming agent, a foam stabilizer, and a phosphorus compound to produce a flame retardant urethane resin composition. In the ³¹ P-NMR of the surface layer 1 mm after heating for 20 minutes at 50 kW / m ² of the cured product of the flame retardant urethane resin composition, the intensity ratio of the peak near −30 ppm to the peak near 0 ppm is The method includes adjusting the composition of the polyisocyanate, the polyol, the trimerization catalyst, the foaming agent, the foam stabilizer and the phosphorus compound so as to be 0.3 or more.

  Flame retardant urethane resin composition is, for example, a method of mixing each component of the flame retardant urethane resin composition, suspending the flame retardant urethane resin composition in an organic solvent, or heating and melting it. A method of preparing a slurry by dispersing in a solvent, preparing a slurry, etc., and a component that is solid at room temperature (about 25 ° C.) in a reaction curable resin component contained in a 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.

  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 flame-retardant urethane resin composition of the present invention is particularly suitable as a flame-retardant urethane resin composition for spraying which is sprayed on a structure to form a spray layer.

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

Example 1 Production of Foam Molded Body Consisting of Flame Retardant Urethane Resin Composition and Performance Evaluation Production of Foam Molded Body Composed of Flame Retardant Urethane Resin Composition With the formulation shown in Table 1, flame retardant urethane resin compositions according to Example 1, Example 2 and Comparative Example 1 were prepared. Details of each component in the table are as follows.
(A) component: Polyol premix composition Polyol p-phthalic polyester polyol (Kawasaki Chemical Industries, product name: Maximol RLK-087, hydroxyl value = 200 mgKOH / g)
2. Foam stabilizer Polyalkylene glycol foam stabilizer (Toray Dow Corning, product name: SH-193)
3. Catalyst Trimerization catalyst (Tosoh Corporation, product name: TOYOCAT-TRX)
Trimerization catalyst (potassium octylate, Air Products, product name: DABCO K-15)
Urethane catalyst (alkylated polyalkylene polyamine, Tosoh Corporation, product name: TOYOCAT-TT)
Urethane catalyst (tertiary amine mixture, Tosoh Corporation, product name: TOYOCAT-DM70)
4). Blowing agent Pure water HFC HFC-365mfc (1,1,1,3,3-pentafluorobutane, Nippon Solvay)
HFC-245fa (1,1,1,3,3-pentafluoropropane, Honeywell Japan Co., Ltd.))
(B) Component: Isocyanate Compound Diphenylmethane Diisocyanate (Wanhua Chemical Co., Ltd., product name: WANnate PM-200)
Component (C): Flame retardant Red phosphorus (Rin Chemical Industry Co., Ltd., product name: Nova Excel 140)
Tris (β-chloropropyl) phosphate (Daihachi Chemical Co., Ltd., product name: TMCPP, hereinafter referred to as “TMCPP”)
Wollastonite (SiO ₂ · CaO) (Kinsei Matec Co., Ltd., product name: SH-1250) Aspect ratio 10-16, average particle size 4.5-6.5 μm
According to the composition of Table 1 below, the polyol premix composition of component (A) excluding the HFC component and the flame retardant of component (C) were weighed in a 1000 mL polypropylene beaker and stirred with a hand mixer at 25 ° C. for 10 seconds. (B) component polyisocyanate and HFC component are added to the kneaded product after stirring, and the mixture is stirred for about 10 seconds with a hand mixer. The flame-retardant urethane resin compositions of Examples 1, 2 and Comparative Example 1 A foam made of
2. Spraying of polyurethane resin composition The formulations described in Examples 1 and 2 and Comparative Example 1 were sprayed onto a gypsum board having a thickness of 12.5 mm to prepare a cured product of the polyurethane resin composition. As the sprayer, “H-VR” manufactured by Graco Co., Ltd. was used. The temperature of the isocyanate and polyol liquid was 35 ° C., the temperature of the hose was 33 ° C., the discharge pressure of the liquid from the spraying machine was 30 bar, the air pressure was 4 MPa, and a D gun made by Gasmer was used.
3. Fire resistance test Sample for corn calorimeter test so that it becomes 100 mm x 100 mm x 20 mm (length direction x width direction x thickness direction) from the cured product of the polyurethane resin composition blended as described in Examples 1 and 2 and Comparative Example 1. Was cut out and heated at a radiant heat intensity of 50 kW / m ^{2 for} 20 minutes in accordance with ISO-5660, and the total calorific value was measured. The results are shown in Table 1.

The total calorific value of the corn calorimeter when heated for 20 minutes was 8 MJ / m ² or less in the molded articles of Example 1 and Example 2, and the molded article was nonflammable. In the molded body of Comparative Example 1, the total calorific value of the corn calorimeter when heated for 20 minutes exceeded 8 MJ / m ² .
4). About ³¹ samples after the cone calorimeter test of the cured product of the P-NMR measurement in Example 1-2 and the polyurethane resin composition of Comparative Example 1 was measured for ³¹ P-NMR. This measurement is based on JEOL
An 8 mm MAS probe was attached to an ECX400 NMR apparatus manufactured by RESONANCE Co., Ltd., and measurement was performed using a single pulse method (DD / MAS method) at a 90 ° pulse of 12 μs and a magic angle rotation speed of 7.0 kHz. For the calculation of chemical shift, the largest peak of ammonium dihydrogen phosphate was used as an external standard (1.3 ppm). The delay time of the pulse irradiation is based on the T1 relaxation time of ³¹ P nuclei of each peak obtained in advance by the saturation recovery method or the like, and the value when the flip angle of each peak component is 90 ° is calculated for the peak around −30 ppm. The value was set to 5 times the longitudinal relaxation time T1. The peak intensity ratio of the peak near −30 ppm to the peak near 0 ppm (the peak intensity near −30 ppm / the peak intensity near 0 ppm) was calculated from the NMR spectrum obtained by subjecting the obtained free induction decay to Fourier transform. . The peak intensity was the height from the baseline to the peak top.

As shown in Table 1 and FIG. 1, the peak intensity ratio in ³¹ P-NMR of Example 1 is 0.97, the peak intensity ratio in ³¹ P-NMR of Example 2 is 0.57, and Comparative Example 1 The peak intensity ratio in ³¹ P-NMR was 0.12.

Claims (4)

A flame retardant urethane resin composition comprising a polyisocyanate, a polyol, a trimerization catalyst, a foaming agent, a foam stabilizer, and a phosphorus compound, and 20 minutes at 50 kW / m ² of a cured product of the flame retardant urethane resin composition In the ³¹ P-NMR of 1 mm surface layer after heating, the intensity ratio of the peak near -30 ppm to the peak near 0 ppm is 0.3 or more.   The phosphorus compound is red phosphorus, and at least one selected from phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant, antimony-containing flame retardant, metal hydroxide, and needle filler. The flame-retardant urethane resin composition according to claim 1. A method for producing a flame retardant urethane resin composition,
A polyisocyanate, a polyol, a trimerization catalyst, a foaming agent, a foam stabilizer, and a phosphorus compound are mixed to produce a flame retardant urethane resin composition, and 50 kW of a cured product of the flame retardant urethane resin composition In the ³¹ P-NMR of 1 mm surface layer after heating for 20 minutes at / m ² , polyisocyanate, polyol, trimerization catalyst, so that the intensity ratio of the peak near −30 ppm to the peak near 0 ppm is 0.3 or more, Adjusting the composition of the foaming agent, foam stabilizer and phosphorus compound. The phosphorus compound is red phosphorus, and at least one selected from phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant, antimony-containing flame retardant, metal hydroxide, and needle filler. 4. The method of claim 3, comprising.