JPWO2016010042A1 - Flame retardant polyurethane resin composition - Google Patents

Abstract

The flame retardant urethane resin composition contains a polyisocyanate compound, a polyol compound, a trimerization catalyst, a foaming agent, a foam stabilizer and an additive, and is measured by 13C NMR in a cured product of the flame retardant urethane resin composition The intensity ratio of the isocyanurate carbonyl peak to the urethane carbonyl peak is between 0.3 and 3.5.

Description

(Cross-reference of related fields)
This application claims the benefit of priority of Japanese Patent Application No. 2014-144008 filed on Jul. 14, 2014, which is hereby incorporated by reference in its entirety.
(Technical field)
The present invention relates to a flame retardant polyurethane resin composition.

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

  On the other hand, because concrete has heat storage and cold storage properties, the inside of the building is heated due to ripeness accumulated in the summer, and the inside of the building is cooled as a result of cooling the concrete in the cold season in 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.

  Patent Document 1 describes a polyol composition for rigid polyurethane foam containing a polyol compound, a water-soluble organic solvent, a catalyst, a flame retardant, a foaming agent, and a polyisocyanate compound. It is described that a rigid polyurethane foam formed by mixing and foaming these components is excellent in flame retardancy.

  Patent Document 2 describes a polyol composition for polyurethane foam containing 100 parts by weight of a polyol compound, 10-30 parts by weight of a phosphate ester flame retardant, a foaming agent, a foam stabilizer and a catalyst.

  Patent Document 3 describes a flame-retardant rigid polyurethane foam obtained by reacting and curing a polyhydroxyl compound, a polyisocyanate, a urethanization catalyst, a flame retardant, a foam stabilizer and a foaming agent.

  Patent Document 4 describes a catalyst composition for producing a rigid polyurethane foam and / or an isocyanurate-modified rigid polyurethane foam comprising a quaternary ammonium salt and a heterocyclic tertiary amine compound.

JP 2010-053267 A JP 2002-338651 A Japanese Patent Laid-Open No. 2001-200027 JP 2010-7079 A

  None of the above Patent Documents 1 to 4 disclose the relationship between the ratio of the carbonyl group derived from urethane and the carbonyl group derived from isocyanurate and the incombustibility of the flame retardant polyurethane composition.

  An object of the present invention is to provide a flame retardant polyurethane composition that can exhibit high flame retardancy and is excellent in handling.

  The flame-retardant urethane resin composition according to the present invention is as follows.

Item 1. A flame retardant urethane resin composition comprising a polyisocyanate compound, a polyol compound, a trimerization catalyst, a foaming agent, a foam stabilizer, and an additive, measured by ¹³ C NMR in a cured product of the flame retardant urethane resin composition A flame retardant urethane resin composition in which the intensity ratio of the peak of the carbonyl group of isocyanurate to the peak of the carbonyl group of urethane is between 0.3 and 3.5.

  Item 2. The additive contains red phosphorus as an essential component, and includes at least one selected from a phosphate ester, a phosphate-containing flame retardant, a bromine-containing flame retardant, an antimony-containing flame retardant, and a metal hydroxide in addition to the red phosphorus. Item 2. A flame retardant urethane resin composition according to item 1.

  Item 3. Item 3. The flame retardant urethane resin composition according to item 1 or 2, wherein the additive is in a range of 4.5 to 70 parts by weight based on 100 parts by weight of a urethane resin composed of the polyisocyanate compound and the polyol compound. object.

  Item 4. Item 4. The flame retardant urethane according to any one of Items 1 to 3, wherein the trimerization catalyst is in a range of 0.1 to 10 parts by weight based on 100 parts by weight of a urethane resin composed of the polyisocyanate compound and the polyol compound. Resin composition.

  Item 5. Item 5. The flame-retardant urethane resin according to any one of Items 1 to 4, wherein the foaming agent is in the range of 0.1 to 30 parts by weight based on 100 parts by weight of the urethane resin composed of the polyisocyanate compound and the polyol compound. Composition.

  Item 6. Item 6. The flame retardant urethane resin composition according to any one of Items 1 to 5, wherein an isocyanate index of the urethane resin is in a range of 125 to 1,000.

Item 7. (A) 1st liquid containing polyisocyanate compound, (B) 2nd liquid containing polyol compound, (C) trimerization catalyst, (D) foaming agent, (E) foam stabilizer and (F) additive In the cured product of the flame retardant urethane resin composition, the intensity ratio of the peak of the carbonyl group of isocyanurate to the peak of the carbonyl group of urethane when measured by ¹³ C NMR is 0.3 to 3.5 A combination for forming a flame retardant urethane resin composition.

  According to the present invention, there is provided a flame retardant polyurethane composition that can exhibit high flame retardancy and is excellent in handling.

The graph which shows the measurement result of the solid NMR of the flame-retardant urethane resin composition of Example 1-3 and Comparative Example 1. The graph which shows the solid NMR measurement result of the flame-retardant urethane resin composition of Examples 1 and 4.

  The flame retardant urethane resin composition according to the present invention will be described.

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

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

  As a polyisocyanate compound, 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 more polyisocyanate compounds can be used. The main component of the urethane resin is preferably diphenylmethane diisocyanate for reasons such as ease of use and availability.

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

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

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

  Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolac, and cresol novolak.

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

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

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

  Specific examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, and succinic acid. Specific examples of the polyhydric alcohol include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, neopentyl glycol, and the like. .

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

  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 , Antrol, 1,4,5,8-tetrahydroxyanthracene, 1-hydroxypyrene, etc., phenol polybutadiene polyol; castor oil polyol; hydroxyalkyl (meth) a Polyfunctional (e.g. functionality 2 to 100) polyol such as (co) polymers and polyvinyl alcohol Relate include condensates of phenol and formaldehyde (novolac) it 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, 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, 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.

  The isocyanate index is a percentage of the equivalent ratio of the isocyanate group of the polyisocyanate compound to the hydroxyl group of the polyol compound. When the value exceeds 100, 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 preferably in the range of 125 to 1000, more preferably in the range of 200 to 800, and even more preferably in the range of 300 to 700. 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 parts used of polyisocyanate × NCO content (%) × 100 / NCO molecular weight Number of equivalents of polyol = OHV × number of parts used of polyol ÷ molecular weight of KOH, OHV is hydroxyl value of polyol (mg KOH / g) ,
Equivalent number of water = number of water used × number of OH groups in water / molecular weight of water. In the above formula, the unit of the number of parts used is weight (g), the molecular weight of the NCO group is 42, and the NCO content is the percentage of the NCO group in the polyisocyanate compound expressed by mass%.
For convenience of unit conversion in the above formula, 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 catalyst, a foaming agent, and a foam stabilizer.

  Examples of the catalyst include triethylamine, N-methylmorpholine bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N′-trimethylaminoethyl- Nitrogen atom-containing catalysts such as ethanolamine, bis (2-dimethylaminoethyl) ether, N-methyl, N′-dimethylaminoethylpiperazine, imidazole compounds in which the secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group, etc. Is mentioned.

  The addition amount of the catalyst used in the flame retardant urethane resin composition is preferably in the range of 0.1 to 10 parts by weight, and 0.1 to 8 parts by weight with respect to 100 parts by weight of the urethane resin. Is more preferably in the range of 0.1 to 6 parts by weight, and most preferably in the range of 0.1 to 3.0 parts by weight.

  When the amount is 0.1 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 handling is easy.

  Preferable catalysts include a trimerization catalyst that causes the isocyanate group contained in the polyisocyanate compound, which is the main component of the polyurethane resin, to react and trimerize to promote the formation of an isocyanurate ring.

  In order to promote the formation of the isocyanurate ring, for example, as a catalyst, tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, 2,4,6-tris (dialkylaminoalkyl) hexahydro Nitrogen-containing aromatic compounds such as -S-triazine; carboxylic acid alkali metal salts such as potassium acetate, potassium 2-ethylhexanoate and potassium octylate; tertiary ammonium such as trimethylammonium salt, triethylammonium salt and triphenylammonium salt Salt: Quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, and tetraphenylammonium salt can be used.

  The addition amount 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 0.1 to 8 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, more preferably in the range of 0.1 parts by weight to 6 parts by weight, and most preferably in the range of 0.1 parts by weight to 3.0 parts by weight. When the amount is 0.1 parts by weight or more, there is no problem that the trimerization of the isocyanate is inhibited. When the amount is 10 parts by weight or less, an appropriate foaming rate can be maintained and the handling is easy.

  Moreover, the foaming agent used for a flame-retardant urethane resin composition accelerates | stimulates foaming of a 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, Hydrochloric compounds such as chlorinated aliphatic hydrocarbon compounds such as butyl chloride, isobutyl chloride, pentyl chloride and isopentyl chloride, fluorine compounds such as trichloromonofluoromethane and trichlorotrifluoroethane, and hydrous such as CHF ₃ , CH ₂ F ₂ and CH ₃ F Fluorocarbon; dichloromonofluoroethane (for example, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)), Hydrochlorofluorocarbon compounds such as HFC-245fa (1,1,1,3,3-pentafluoropropane) and HFC-365mfc (1,1,1,3,3-pentafluorobutane); ether compounds such as diisopropyl ether Or organic physical foaming agents such as mixtures of these compounds, 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 0.1 to 18 parts by weight, still more preferably in the range of 0.5 to 18 parts by weight with respect to 100 parts by weight of the urethane resin. Most preferably, it is in the range of 5 to 10 parts by weight.

  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.

  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.

  One or two or more of the catalyst, the foaming agent and the foam stabilizer can be used.

  Next, the additive used for this invention is demonstrated.

  In one embodiment, the additive includes at least one selected from the group consisting of red phosphorus, phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant, antimony-containing flame retardant, and metal hydroxide. In another embodiment, the additive comprises red phosphorus and at least one selected from the group consisting of phosphate esters, phosphate-containing flame retardants, bromine-containing flame retardants, antimony-containing flame retardants and metal hydroxides. . In another embodiment, the additive includes at least one selected from the group consisting of phosphate esters, phosphate-containing flame retardants, bromine-containing flame retardants, antimony-containing flame retardants, and metal hydroxides.

The additive preferably includes red phosphorus. Examples of preferable combinations of additives to be used include any of the following (a) to (i). The additive more preferably includes red phosphorus and a phosphate-containing flame retardant.
(a) Red phosphorus and phosphate
(b) Red phosphorus and phosphate containing flame retardant
(c) Red phosphorus and bromine containing flame retardants
(d) Red phosphorus and antimony containing flame retardant
(e) Red phosphorus and metal hydroxide
(f) Red phosphorus, phosphate ester and phosphate containing flame retardant
(g) Red phosphorus, phosphate ester and bromine containing flame retardant
(h) Red phosphorus, phosphate-containing flame retardant and bromine-containing flame retardant
(i) Red phosphorus, phosphate ester, phosphate-containing flame retardant and bromine-containing flame retardant The additive amount used in the present invention is the total amount of additives other than urethane resin with respect to 100 parts by weight of urethane resin. The range is preferably 4.5 to 70 parts by weight, more preferably 4.5 to 40 parts by weight, and 4.5 to 30 parts by weight. More preferably, the range is 4.5 to 20 parts by weight.

  When the range of the additive is 4.5 parts by weight or more, the molded product made of the flame retardant urethane resin composition can prevent the dense residue formed by the heat of the fire from cracking, and when the additive is 70 parts by weight or less Does not inhibit foaming of the flame retardant urethane resin composition.

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

  When red phosphorus is included as an additive, the amount of red phosphorus used in the refractory urethane resin composition according to the present invention is in the range of 3.0 to 18 parts by weight with respect to 100 parts by weight of the urethane resin. Preferably there is.

  When the range of red phosphorus is 3.0 parts by weight or more, the self-extinguishing property of the flame retardant urethane resin composition is maintained, and when it is 18 parts by weight or less, foaming of the flame retardant urethane resin composition is inhibited. Not.

  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, 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. Polyphenyl phosphate (trade name ADEKA STAB PFR, manufactured by ADEKA), bisphenol A polycresyl phosphate (trade names FP-600, FP-700, manufactured by ADEKA) and the like can be mentioned.

  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 addition amount of the phosphate ester is preferably in the range of 1.5 to 52 parts by weight, 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 1.5 parts by weight or more, the self-extinguishing property is maintained, and when it is 52 parts by weight or less, foaming of the flame retardant urethane resin composition is not inhibited.

The phosphate-containing flame retardant used in the present invention contains phosphoric acid.
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, magnesium salt such as trimagnesium phosphate, magnesium hypophosphite, calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, calcium hypophosphite calcium salt, zinc phosphate, zinc phosphite, Examples thereof include zinc salts such as zinc hypophosphite.

  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 addition amount of the phosphate-containing flame retardant used in the present invention is preferably 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.

  When the range of the phosphate-containing flame retardant is 1.5 parts by weight or more, the self-extinguishing property of the flame retardant urethane resin composition is maintained, and when it is 52 parts by weight or less, the flame retardant urethane resin composition Foaming is not hindered.

  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, hexapromobiphenyl, decapromobiphenyl, hexapromocyclodecane, decapromodiphenyl ether, octabromodiphenyl ether, hexapromodiphenyl ether, bis (pentabromo Monomeric organic bromine compounds such as phenoxy) ethane, ethylene-bis (tetrapromophthalimide), tetraprobisbisphenol A; polycarbonate oligomers produced from brominated bisphenol A as a raw material, copolymer of polycarbonate oligomer and bisphenol A Brominated polycarbonates such as diepoxy compounds produced by the reaction of brominated bisphenol A and 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 amount of bromine-containing flame retardant used in the present invention is preferably in the range of 1.5 parts by weight to 52 parts by weight with respect to 100 parts by weight of the urethane resin, and 1.5 parts by weight 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.

  When the range of the bromine-containing flame retardant is 0.1 part by weight or more, the self-extinguishing property of the flame retardant urethane resin composition is maintained, and when the range is 52 parts by weight or less, foaming of the flame retardant urethane resin composition Is not disturbed.

  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 addition amount of the antimony-containing flame retardant is preferably 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. 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.

  When the range of the antimony-containing flame retardant is 1.5 parts by weight or more, the self-extinguishing property of the flame retardant urethane resin composition is maintained, and when it is 52 parts by weight or less, foaming of the flame retardant urethane resin composition Is not disturbed.

  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, zinc hydroxide, copper hydroxide. , Vanadium hydroxide, tin hydroxide and the like.

  One or two or more metal hydroxides can be used.

  The addition amount of the metal hydroxide is preferably in the range of 1.5 parts by weight to 52 parts by weight and more preferably in the range of 1.5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the urethane resin. 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.

  When the range of the metal hydroxide is 1.5 parts by weight or more, the self-extinguishing property of the flame retardant urethane resin composition is maintained, and when it is 52 parts by weight or less, the foam of the flame retardant urethane resin composition is maintained. Is not disturbed.

  The flame retardant urethane resin composition can be used in combination with 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, zinc carbonate, barium carbonate, dosonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, potassium salt, 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, zirconate titanate Lead, aluminum port rate, 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.

  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.

The present invention includes (A) a first liquid containing a polyisocyanate compound, (B) a second liquid containing a polyol compound, (C) a trimerization catalyst, (D) a foaming agent, (E) a foam stabilizer and ( F) A system that is a combination or reaction system for forming a flame retardant urethane resin composition, including an additive, comprising a polyisocyanate compound, a polyol compound, a trimerization catalyst, a foaming agent, a foam stabilizer, and an additive The intensity ratio of the peak of the carbonyl group of isocyanurate to the peak of the carbonyl group of urethane as measured by ¹³ C NMR in the cured product of the flame retardant urethane resin composition produced by mixing 0.3 to 3. Also included is a system for forming a flame retardant urethane resin composition that is between 5.

  Each of (C) trimerization catalyst, (D) foaming agent, (E) foam stabilizer and (F) additive may be contained in the first liquid or the second liquid, and the first liquid and It may be provided separately from the second liquid. Preferably, (C) the trimerization catalyst, (D) the foaming agent, (E) the foam stabilizer and (F) the additive are each contained in the second liquid. A system for forming a flame retardant urethane resin composition includes a first container that contains the first liquid and a second container that contains the second liquid, such as a caulking gun or a spray-type container. Provided.

  Details of the components (A) to (F) and the flame-retardant urethane resin composition formed therefrom are as described above.

The flame retardant urethane resin composition of the present invention has a carbonyl group peak of isocyanurate with respect to a peak (B) of the carbonyl group of urethane when the flame retardant urethane resin composition after curing is measured by solid state ¹³ C NMR ( It is characterized by an intensity ratio (A / B) of A) between 0.3 and 3.5.

When the above ratio is less than 0.3, the flame retardant polyurethane composition is soft and flammable, resulting in poor shape retention. If the above ratio exceeds 3.5, the strength of the foam becomes hard and tends to be brittle. According to the present application, solid-state ¹³ C NMR makes it possible for the first time to quantify the nulation rate in a flame retardant polyurethane composition, and when the above ratio is in the range of 0.3 to 3.5, the flame retardant polyurethane composition Since the product can exhibit high flame retardancy and is excellent in shape retention, it is excellent in handling.

In one embodiment, the flame retardant urethane resin composition comprises a trimerization catalyst 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 compound and the polyol compound; 1 to 30 parts by weight of foaming agent, 0.1 to 10 parts by weight of foam stabilizer, and 4.5 to 70 parts by weight of additive, measured by ¹³ C NMR The intensity ratio of the isocyanurate carbonyl group peak to the urethane carbonyl group peak is between 0.3 and 3.5.

The measurement method for solid state ¹³ C NMR is as follows: The apparatus is operated by attaching an 8 mm MAS probe to an ECX400 NMR apparatus manufactured by JEOL RESONANCE. The measurement is performed using a single pulse method (DD / MAS method) at a 90 ° pulse of 6.6 μs and a magic angle rotation number of 7.0 kHz. For the calculation of chemical shift, the methyl group of hexamethylbenzene is used as an external standard (17.3 ppm). The probe to be used is not particularly limited, and is selected according to the capacity and outer diameter of the sample tube. The pulse irradiation delay time is based on the T1 relaxation time of the ¹³ C nucleus of each peak obtained in advance by the saturation recovery method or the like. The value when the flip angle of each peak component is 90 ° is 5 for the peak with the longest T1. Set to double the value.

  The number of integration depends on each sample, but is at least once, preferably 64 times or more, more preferably 640 times or more in order to obtain an S / N sufficient for analysis.

A peak broadening ratio of various peaks is calculated from an NMR spectrum obtained by applying 20 Hz line broadening to the spectrum and then performing a Fourier transform.
The peak intensity is the height from the baseline to the peak top.

  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, etc., and a reaction curable resin component contained in a flame retardant urethane resin composition at a temperature of 25 ° C. When the component which is is contained, a flame-retardant urethane resin composition can be obtained by methods, such as melting a 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.

  When obtaining a molded body comprising the flame retardant urethane resin composition, ripening or pressure can be applied.

  The molded body made of the flame retardant urethane resin composition preferably has a specific gravity in the range of 0.020 to 0.130 because it is easy to handle, and more preferably in the range of 0.030 to 0.100. , 0.030-0.080 is more preferable, and 0.040-0.060 is most preferable.

The solid-state ¹³ C NMR shows the peak of the carbonyl group of isocyanurate and the peak of the carbonyl group of urethane in the obtained flame-retardant urethane resin composition after curing, that is, a sample of the cured product of the flame-retardant urethane resin composition. When measuring, the skin layer of the upper surface in the hardened | cured material of a flame-retardant urethane resin composition is avoided, and the part below a skin layer is measured. When measuring the hardened | cured material of the flame-retardant urethane resin composition applied to the wall surface etc., it is preferable to scrape off a sample from the part of 10% depth from the surface of hardened | cured material.

  Moreover, as a method for analyzing the trimerization catalyst contained in the sample of the cured flame retardant urethane resin composition obtained after curing, that is, the cured product of the flame retardant urethane resin composition, for example, a water-soluble component of the cured product There is a method of analyzing the water extracted from using ion chromatography.

Next, application examples of the flame retardant urethane resin composition according to the present invention will be described.
By blowing the flame retardant urethane resin composition onto a structure such as a building, furniture, automobile, train, ship, etc., a foam layer made of the flame retardant urethane resin composition is formed on the surface of the structure. be able to.

  For example, the flame retardant urethane resin composition is divided into a polyisocyanate compound and other components, mixed while spraying both, and sprayed onto the surface of the structure, the polyisocyanate compound, Examples thereof include a method of spraying the surface of the structure after mixing with other components. By the above method, a foam layer can be formed on the surface of the structure.

  Next, a fire resistance test performed on the fiber-reinforced resin molded article of the present invention will be described.

  A molded product made of the flame retardant urethane 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 corn calorimeter test.

Using the sample for corn calorimeter test, the total calorific value by the corn calorimeter test when heated at a radiant heat intensity of 50 kW / m ^{2 for} 20 minutes can be measured in accordance with the test method of ISO-5660.

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

1. Production of Flame Retardant Urethane Resin Composition According to the formulation shown in Table 1, flame retardant urethane resin compositions according to Examples 1 to 13 and Comparative Examples 1 to 3 were prepared. Details of each component in the table are as follows.
(1) Polyol composition / polyol compound (A-1) p-phthalic acid polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RFK-505, hydroxyl value = 250 mgKOH / g)
・ Foam stabilizer Polyalkylene glycol foam stabilizer (manufactured by Toray Dow Corning, product name: SH-193)
Trimerization catalyst (A-1) Potassium 2-ethylhexanoate (Tokyo Chemical Industry Co., Ltd., product code: P0048)
(A-2) Trimerization catalyst (product name: TOYOCAT-TR20, manufactured by Tosoh Corporation)
(A-3) Trimerization catalyst (product name: TOYOCAT-TRX, manufactured by Tosoh Corporation)
-Urethane catalyst (B-1) Pentamethyldiethylenetriamine (manufactured by Tosoh Corporation, product name: TOYOCAT-DT)
(B-2) Urethane catalyst (manufactured by Tosoh Corporation, product name: TOYOCAT-TT)
-Foaming agent water HFC HFC-365mfc (1,1,1,3,3-pentafluorobutane, manufactured by Nippon Solvay) and HFC-245fa (1,1,1,3,3-pentafluoropropane, Central Glass Co., Ltd.) Manufactured), mixing ratio HFC-365mfc: HFC-245fa = 7: 3, hereinafter referred to as “HFC”)

(2) Isocyanate compound (hereinafter referred to as “polyisocyanate”)
MDI (manufactured by Nippon Urethane Industry Co., Ltd., product name: Millionate MR-200) Viscosity: 167 mPa · s
(3) Additive (C-1) Red phosphorus (Rin Chemical Industry Co., Ltd., product name: Nova Excel 140)
(C-2) Ammonium dihydrogen phosphate (manufactured by Taihei Chemical Industrial Co., Ltd.)
(C-3) Tris (β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP, hereinafter referred to as “TMCPP”)
(C-4) Hexabromobenzene (manac, product name: HBB-b, hereinafter referred to as “HBB”).
(C-5) Aluminum hydroxide (Almorix, product name: B-325)
(C-6) Antimony trioxide (Nippon Seika Co., Ltd., product name: Patox C)
In accordance with the composition shown in Table 1 below, the polyol compound, foam stabilizer, various catalysts, the foaming agent excluding the HFC component, and the additive were weighed in a 1000 mL polypropylene beaker and stirred with a hand mixer at 25 ° C. for 10 seconds. A polyisocyanate compound and HFC were added to the kneaded material after stirring, and a foam was made by worshiping with a hand mixer for about 10 seconds. The obtained flame-retardant urethane resin composition lost fluidity with the passage of time, and the foams of the cured flame-retardant urethane resin compositions of Examples 1 to 13 and Comparative Examples 1 to 3 were obtained.
2. Evaluation of Foam The above foam was evaluated according to the following criteria, and the results are shown in Table 1 (the ratio of each component is shown in parts by weight relative to 100 parts by weight of the polyisocyanurate resin).
[Measurement of calorific value]
A sample for corn calorimeter test is cut out from the cured product so as to be 10 cm × 10 cm × 5 cm, and the maximum heat generation rate and the total heat generation amount when heated for 20 minutes at a radiant heat intensity of 50 kW / m ² in accordance with ISO-5660. The measured results are shown in Table 1.

  This measurement method is a test method stipulated as corresponding to the standard by the cone calorimeter method at the Building Research Institute, which is a public institution stipulated in Article 108-2 of the Building Standard Law Enforcement Ordinance. It conforms to the test method of ISO-5660.

When the total heating value of the cone calorimeter is 9 mJ / m ² or less at 8 MJ / m ² or less and 20 minutes at a heating for 10 minutes it is acceptable. This × what is in excess of 8 MJ / m ² at a heating 10 minutes at the test, the 8 MJ / m ² or less and exceeding the 8 MJ / m ² at 20 minutes heating 9 mJ / m ² or less in 10 minutes as the △, 8 MJ 10 min / m ² or less and those with heating for 20 minutes 8 MJ / m ² or less ○, 8 MJ / m ² or less and at 20 min heating 6 mJ / m ² or less of those were the ◎ 10 minutes.
[Measurement of expansion]
When the test of ISO-5660 was carried out, it was described in Table 1 as x when the molded body after expansion was in contact with the igniter, and ◯ when it was not in contact.
[Measurement of deformation (cracking)]
When the test of ISO-5660 is carried out, x is shown when deformation reaching the back surface of the test sample is observed, and ○ is shown when deformation reaching the back surface is not seen. did.
[Measurement of shrinkage]
When the test of ISO-5660 was carried out, the test sample was evaluated as x when a deformation of 1 cm or more in the lateral direction and 5 mm or more was observed in the thickness direction, and ○ when no deformation was observed. It was described in.
[Comprehensive judgment]
In the measurement of calorie, expansion, deformation, and contraction, the case where all were good or bad was judged as OK, and the others were judged as NG.

3. Measurement by Solid State ¹³ C NMR ¹³ C NMR measurement was performed on samples of cured products of the flame retardant polyurethane resin compositions of Examples 1 to 4 and Comparative Example 1. This measurement is performed by attaching an 8 mm MAS probe to an ECX400 NMR apparatus manufactured by JEOL RESONANCE, Inc., using a single pulse method (DD / MAS method), 90 ° pulse 6.6 μs, magic angle rotation speed 7.0 kHz. Measured with For the calculation of chemical shift, the methyl group of hexamethylbenzene was used as an external standard (17.3 ppm). The pulse irradiation delay time is based on the T1 relaxation time of the ¹³ C nucleus of each peak obtained in advance by the saturation recovery method or the like. The value when the flip angle of each peak component is 90 ° is 5 for the peak with the longest T1. It was set to be a double value. 20 Hz line broadening was applied to the spectrum, and then the peak intensity ratio of various peaks was calculated from the NMR spectrum obtained by performing Fourier transform. The peak intensity was the height from the baseline to the peak top.

  The measurement results are shown in FIGS. In FIG. 1, (a) is a peak derived from the carbonyl group of isocyanurate, (b) is a peak derived from the carbonyl group of urethane, (c) is a peak of ester derived from polyol, (d ) Is a peak derived from an aromatic ring, and (e) is a peak derived from an ester. In FIG. 2, (a) is a peak derived from the carbonyl group of isocyanurate, and (b) is a peak derived from the carbonyl group of urethane. The intensity ratio of the carbonyl group peak of isocyanurate to the carbonyl group peak of urethane of the flame retardant polyurethane resin compositions of Examples 1 to 4 is 1.16, 2.19, 3.08 and 2.29, respectively. The intensity ratio of the carbonyl group peak of isocyanurate to the carbonyl group peak of urethane in the flame-retardant polyurethane resin composition of Comparative Example 1 was 0.20 (Table 2).

Claims (7)

A ¹³ C NMR in a flame retardant urethane resin composition comprising a polyisocyanate compound, a polyol compound, a trimerization catalyst, a foaming agent, a foam stabilizer and an additive, and a cured product of the flame retardant urethane resin composition A flame retardant urethane resin composition having an intensity ratio of a peak of a carbonyl group of isocyanurate to a peak of a carbonyl group of urethane when measured is between 0.3 and 3.5.   The additive contains red phosphorus as an essential component, and includes at least one selected from a phosphate ester, a phosphate-containing flame retardant, a bromine-containing flame retardant, an antimony-containing flame retardant, and a metal hydroxide in addition to the red phosphorus. The flame-retardant urethane resin composition according to claim 1.   The flame retardant urethane resin according to claim 1 or 2, wherein the additive is in the range of 4.5 parts by weight to 70 parts by weight based on 100 parts by weight of the urethane resin composed of the polyisocyanate compound and the polyol compound. Composition.   The flame retardant according to any one of claims 1 to 3, wherein the trimerization catalyst is in a range of 0.1 to 10 parts by weight based on 100 parts by weight of a urethane resin composed of the polyisocyanate compound and the polyol compound. Urethane resin composition.   The flame-retardant urethane according to any one of claims 1 to 4, wherein the foaming agent is in a range of 0.1 to 30 parts by weight based on 100 parts by weight of a urethane resin composed of the polyisocyanate compound and the polyol compound. Resin composition.   The flame-retardant urethane resin composition according to any one of claims 1 to 5, wherein an isocyanate index of the urethane resin is in a range of 125 to 1,000. (A) 1st liquid containing polyisocyanate compound, (B) 2nd liquid containing polyol compound, (C) trimerization catalyst, (D) foaming agent, (E) foam stabilizer and (F) additive In the cured product of the flame retardant urethane resin composition, the intensity ratio of the peak of the carbonyl group of isocyanurate to the peak of the carbonyl group of urethane when measured by ¹³ C NMR is 0.3 to 3.5 A combination for forming a flame retardant urethane resin composition.

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