WO2020110332A1 - Composition expansible pour mousses de polyuréthane non inflammables - Google Patents

Composition expansible pour mousses de polyuréthane non inflammables Download PDF

Info

Publication number
WO2020110332A1
WO2020110332A1 PCT/JP2019/009967 JP2019009967W WO2020110332A1 WO 2020110332 A1 WO2020110332 A1 WO 2020110332A1 JP 2019009967 W JP2019009967 W JP 2019009967W WO 2020110332 A1 WO2020110332 A1 WO 2020110332A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
polyurethane foam
polyol
combustible
mass
Prior art date
Application number
PCT/JP2019/009967
Other languages
English (en)
Japanese (ja)
Inventor
関　浩之
Original Assignee
旭有機材株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 旭有機材株式会社 filed Critical 旭有機材株式会社
Priority to KR1020217007992A priority Critical patent/KR20210095852A/ko
Priority to JP2019538458A priority patent/JP6621571B1/ja
Priority to CN201980075408.6A priority patent/CN113015757B/zh
Publication of WO2020110332A1 publication Critical patent/WO2020110332A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0038—Use of organic additives containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/125—Water, e.g. hydrated salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/06—Polyurethanes from polyesters

Definitions

  • the present invention relates to a foamable composition for a non-combustible polyurethane foam, and more particularly to a foamable composition for forming a polyurethane foam that advantageously satisfies the non-combustible characteristics defined by the Building Standards Law of Japan.
  • polyurethane foam has been used mainly as a heat insulating material by utilizing its excellent heat insulating properties, adhesiveness, lightweight properties, and the like, as a heat insulating material for building interior and exterior wall materials and panels, metal siding, electric refrigerators, etc. It is used for heat insulation, insulation of building walls, ceilings, roofs, etc. of buildings, condominiums, frozen warehouses, etc., prevention of dew condensation, insulation of infusion pipes, etc., and backing material for filling voids generated in civil engineering work, civil engineering work It is also in practical use as a reinforcing material for such occasions.
  • such a polyurethane foam is generally a composition comprising a polyol compounding liquid (premix liquid) in which a foaming agent is further mixed with a polyol and, if necessary, various auxiliary agents such as a catalyst, a foam stabilizer and a flame retardant.
  • a and a composition B mainly containing polyisocyanate are continuously or intermittently mixed by a mixing device to obtain a foamable composition for polyurethane foam, which is slab foaming method, injection foaming method, spraying method. It is manufactured by foaming and curing by a method such as a foaming method, a continuous laminating foaming method, a lightweight embankment construction method, and an injection backfill construction method.
  • the polyurethane foam formed as described above is required to have flame retardancy in view of its use, and therefore, a foamable composition for a flame retardant polyurethane foam is proposed which is blended with various flame retardants.
  • Patent Document 1 as a reactive formulation for producing a sprayable elastic polyurethane coating having improved flame retardant properties, an isocyanate prepolymer is used.
  • a reactive formulation comprising a polyisocyanate component containing a polymer and any flame retardant compound and a polyol component containing components such as aromatic polyester polyol, red phosphorus and catalyst, and further flame retardant is proposed, whereby It has been demonstrated that elastic polyurethane coatings with improved flammability properties can be formed.
  • halogen-containing compounds, phosphates, inorganic fillers, antimony oxide, zinc and the like as flame-retardant additives to be further added and contained.
  • Patent Document 2 JP-T-2014-532098 (Patent Document 2), it is proposed to use trialkyl phosphate as a smoke suppressor for polyurethane foam, which significantly reduces smoke generation when burned. That is, it has been demonstrated that a polyurethane foam having improved smoke control properties is obtained. Then, there, for the formation of polyurethane foam, a urethane catalyst or a trimerization catalyst of isocyanate is used, and a metal-based inorganic filler for ease of processing, for example, a metal hydrate or zinc borate, It has been clarified that a zinc salt such as zinc stannate can be contained.
  • a predetermined amount of red phosphorus is compounded as one of additives together with a polyol compound, a polyisocyanate compound, a trimerization catalyst, a foaming agent and a foam stabilizer.
  • a flame-retardant urethane resin composition has been clarified, which makes it possible to exhibit excellent flame retardancy by adding a small amount of flame retardant (red phosphorus), and to make it easy to handle. It has been demonstrated that a flammable urethane resin composition may be provided.
  • a metal hydroxide an inorganic compound containing water of crystallization
  • a water-releasing substance such as a clay mineral is indispensable, as well as a phosphate ester or a phosphate-containing flame retardant. It has been clarified that bromine-containing flame retardants and the like can be further compounded as additives.
  • the flame-retardant polyurethane coating obtained in Patent Document 1 and Patent Document 2 and the polyurethane foam having improved smoke suppression performance have severe flame retardancy in recent years due to their flame retardant properties. It was not able to fully meet the request for realization.
  • the flame-retardant polyurethane coating obtained in Patent Document 1 merely reveals the characteristics of a coating layer having elasticity, and the severe flame-retardant characteristics required for polyurethane foam (foam).
  • the polyurethane foam disclosed in Patent Document 2 is merely intended to improve the smoke suppression performance, and the stricter flame retardant performance. It was not possible to fully meet the request concerning the above.
  • Red phosphorus used in Patent Documents 1 and 3 is an excellent flame retardant, but its amount is increased in order to increase the flame retardancy of the polyurethane foam formed. Then, there is a problem that the foam tends to burn easily due to warping, and further, since there is a risk of ignition of the red phosphorus itself, there is an inherent problem that it tends to cause an accident during the production of polyurethane foam, and its use In this case, there is a problem that handling is poor.
  • red phosphorus has a purple-red color as its name suggests, and therefore, due to such a unique hue of red phosphorus, the entire resin (foam) is dyed red and when colored with a colorant, Since there is a problem that the color of the coloring agent is difficult to be reflected, there is a demand to avoid the use of such red phosphorus as much as possible.
  • the total calorific value for 20 minutes from the start of heating is 8.0 MJ/
  • the compounding amount of the above-mentioned known flame retardant is increased with respect to the foamable composition for polyurethane foam, the reaction between the polyol and the polyisocyanate is inhibited, This causes problems that the desired foam cannot be obtained, the physical or mechanical properties of the obtained foam are deteriorated, and the color tone of the foam is restricted. It will be.
  • the non-combustible material satisfies the above-mentioned total calorific value, and the maximum heat generation rate continuously exceeds 10 seconds. It is said that it does not exceed 200 kW/m 2 and that there are no cracks and holes penetrating to the back surface, which are harmful for flame prevention.
  • polyurethane foam materials containing conventional flame retardants are However, it has not been possible to sufficiently meet such demands of non-flammability while securing useful physical or mechanical properties as a polyurethane resin.
  • the present invention has been made in view of such circumstances, and the problem to be solved is to advantageously form a non-combustible polyurethane foam in which flame retardancy is synergistically enhanced. And a foamable composition capable of advantageously forming a non-combustible polyurethane foam having an increased degree of freedom of coloring without losing the color of the polyurethane resin itself. There is also a thing.
  • the present invention can be suitably implemented in various aspects as listed below in order to solve the above problems. It is understood that the aspects and technical features of the present invention are not limited to those described below and can be recognized based on the inventive idea that can be understood from the description of the specification. Should be.
  • a composition A containing a polyol and a composition B containing a polyisocyanate, and a reaction between the polyol and the polyisocyanate, A foamable composition for forming a polyurethane foam by foaming with a foaming agent is prepared.
  • the composition A is made to contain at least a trimerization catalyst as a catalyst, and an organic phosphinic acid metal salt is mixed with the above-mentioned polyolefin. 30 parts by mass or more with respect to 50 parts by mass of the resin, and at least one of the composition A and the composition B is contained in the non-combustible polyurethane foam foaming composition. object.
  • composition A containing a polyol and a composition B containing a polyisocyanate, and a reaction between the polyol and the polyisocyanate
  • a foamable composition for forming a polyurethane foam by foaming with a foaming agent wherein the composition A contains at least a trimerization catalyst as a catalyst, an organic phosphinic acid metal salt and an organic phosphate ester.
  • the organic phosphinic acid metal salt and the organic phosphate ester are contained in the above-mentioned polyol in a total amount.
  • a non-combustible foamable composition for polyurethane foams (3) The foamable composition for a non-flammable polyurethane foam according to the above aspect (2), wherein the organic phosphate ester is selected from the group consisting of a monophosphate ester and a condensed phosphate ester.
  • the organic phosphate is tris(1-chloro-2-propyl) Aspect (2) or Aspect (wherein it is a phosphate)
  • the organic phosphinic acid metal salt is an organic phosphinic acid having a structure in which a methyl group, an ethyl group or a phenyl group is bonded to a phosphorus atom, and Mg, A
  • the metal hydroxide is based on the composition A and/or the composition B, The foamable composition for non-combustible polyurethane foam according to any one of the aspects (1) to (5), which is further contained.
  • an alkali metal carboxylic acid salt and a quaternary ammonium salt are used in combination as the trimerization catalyst.
  • the foaming agent is an organic foaming agent selected from the group consisting of hydrocarbons, hydrofluoroolefins and hydrochlorofluoroolefins.
  • the non-combustible poly according to any one of the above aspects (1) to (11), characterized in that water is used together with a hydrofluoroolefin or a hydrofluorofluoroolefin as the foaming agent.
  • Foamable composition for urethane foam (13) When the polyurethane foam is heated at a radiant heat intensity of 50 kW/m 2 in accordance with the heat generation test method specified in ISO-5660, the total calorific value for 20 minutes from the start of heating is 8
  • a trimerization catalyst is used as a reaction catalyst of a polyol and a polyisocyanate
  • an organic phosphinic acid metal salt is used as a flame retardant.
  • the calorific value upon combustion thereof can be effectively reduced, and even if it ignites, it does not continue to burn and has a high residual value. It is possible to provide a charcoal rate, which makes it possible to advantageously provide a polyurethane foam which is extremely difficult to burn and has high self-extinguishing property.
  • the hue of the polyurethane foam formed from such a foamable composition is In addition to being completely avoidable from the effect of reddish-purple purple-red color, the organic phosphinic acid metal salt and organic phosphoric acid ester used have no effect on the hue of the polyurethane foam formed. Since the polyurethane foam thus formed can be advantageously colored in a desired hue with a colorant, the degree of freedom in coloring the polyurethane foam can be effectively increased.
  • a foamable composition for non-combustible polyurethane foam is composed of a composition A containing a polyol as a main component and a composition B containing a polyisocyanate as a main component, together with a reaction between the polyol and the polyisocyanate, A foamable composition in which a desired polyurethane foam is formed by foaming with a foaming agent.
  • a polyol which is a main component constituting the composition A used therein, reacts with a polyisocyanate.
  • Various publicly known polyol compounds which produce polyurethane will be used alone or in appropriate combination.
  • polyether polyol, polyester polyol, or the like is preferably used as the polyol.
  • polyols such as polyolefin-based polyols, acrylic-based polyols, polymer polyols and the like can be used alone or in an appropriate combination, as a matter of course.
  • the polyether polyol is an alkylene for at least one initiator such as a polyhydric alcohol, a saccharide, an aliphatic amine, an aromatic amine, a phenol, and a Mannich condensation product. It is obtained by reacting an oxide.
  • an initiator such as a polyhydric alcohol, a saccharide, an aliphatic amine, an aromatic amine, a phenol, and a Mannich condensation product. It is obtained by reacting an oxide.
  • the alkylene oxide propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, ethylene oxide and the like can be mentioned.
  • polyhydric alcohols as initiators include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.
  • saccharides include sucrose, dextrose, sorbitol, etc.
  • alkanolamines such as diethanolamine and triethanolamine
  • polyamines such as ethylenediamine
  • aromatic amine various methyl-substituted compounds of phenylenediamine generally called tolylenediamine.
  • phenols include bisphenol A and novolac type phenol resin.
  • Mannich condensation products include Mannich condensation products obtained by subjecting phenols, aldehydes and alkanolamines to a Mannich condensation reaction.
  • polyester polyol examples include polyhydric alcohol-polyhydric carboxylic acid condensation type polyol, cyclic ester ring-opening polymerization type polyol and the like.
  • polyhydric alcohol examples include the above-mentioned ones can be used, and the dihydric alcohol is particularly preferably used.
  • polycarboxylic acid examples include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, isophthalic acid, and their anhydrides.
  • ⁇ -caprolactone or the like is used as the cyclic ester.
  • polyester polyol it is preferable to use an aromatic polyester polyol from the viewpoint of flame retardancy and compatibility, and specifically, it is preferable to use a phthalic acid polyester polyol, and further, such polyester It is also effective to combine two or more kinds of polyols.
  • the phthalic acid-based polyester polyol is a phthalic acid composed of a condensation product of phthalic acid, terephthalic acid, isophthalic acid and their anhydrides with a dihydric alcohol such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol.
  • a system polyester polyol will be used preferably.
  • the polyisocyanate in the composition B is blended with the composition A and reacts with the polyol in the composition A to form a polyurethane (resin).
  • An organic isocyanate compound having the above isocyanate group (NCO group) for example, an aromatic polyisocyanate such as diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, tolylene diisocyanate, polytolylene triisocyanate, xylylene diisocyanate, naphthalene diisocyanate,
  • aromatic polyisocyanate such as diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, tolylene diisocyanate, polytolylene triisocyanate, xylylene diisocyanate, naphthalene diisocyanate
  • aliphatic polyisocyanates such as hexamethylene diisocyanate
  • alicyclic polyisocyanates
  • polystyrene resin examples include polyethylene polyphenylene polyisocyanate (polymeric MDI) and polyethylene polyphenylene polyisocyanate (polymeric MDI).
  • polymeric MDI polymethylene polyphenylene polyisocyanate
  • the proportion of the polyisocyanate in the composition B and the polyol in the composition A described above is appropriately determined depending on the type of foam to be formed (for example, polyurethane or polyisocyanurate).
  • the NCO/OH index equivalent ratio
  • the proportion of the isocyanate group (NCO) of the polyisocyanate to the hydroxyl group (OH) of the polyol falls within the range of about 0.9 to 2.5, It will be decided as appropriate.
  • the composition A and the composition B as described above are mixed, reacted in the presence of a catalyst, foamed by a foaming agent, and cured to give a hard Polyurethane foam is formed, but as a catalyst used therein, at least a trimerization catalyst, in other words, an isocyanate group of polyisocyanate is reacted to cause trimerization and promote formation of an isocyanurate ring.
  • the catalyst isocyanurate-forming catalyst
  • the trimerization catalyst various known catalysts can be appropriately selected and used, and preferably, a quaternary ammonium salt, potassium octylate, potassium 2-ethylhexanoate, sodium acetate is used.
  • Alkali metal salts of carboxylic acids such as; Tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, tris(dimethylaminopropyl)hexahydrotriazine and other nitrogen-containing aromatic compounds; Trimethylammonium salt, triethyl Examples thereof include tertiary ammonium salts such as ammonium salts and triphenylammonium salts. Of these, it is preferable to use a quaternary ammonium salt from the viewpoint of improving flame retardancy, and above all, it is preferable to use a quaternary ammonium salt in combination with an alkali metal carboxylic acid salt. From the viewpoint of further improvement, it is particularly preferable.
  • Examples of the quaternary ammonium group (monovalent cation in the form in which four organic groups are covalently bonded to a nitrogen atom) in the quaternary ammonium salt advantageously used herein include tetramethylammonium, methyltriethylammonium, and ethyltrimethyl.
  • tetramethylammonium, methyltriethylammonium, ethyltrimethylammonium, butyltrimethylammonium, hexyltrimethylammonium, octyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium have excellent catalytic activity and are industrially available.
  • Examples of the organic acid group or inorganic acid group, which is a monovalent anion that is ionically bonded to the quaternary ammonium group to form the quaternary ammonium salt include, for example, a formic acid group, an acetic acid group, and an octyl acid group.
  • oxalic acid group oxalic acid group, malonic acid group, succinic acid group, glutaric acid group, adipic acid group, benzoic acid group, toluic acid group, ethyl benzoic acid group, methyl carbonic acid group, phenol group, alkylbenzene sulfonic acid group, toluene sulfonic acid group
  • organic acid groups such as benzenesulfonic acid group and phosphoric acid ester group
  • inorganic acid groups such as halogen group, hydroxyl group, hydrogen carbonate group and carbonate group.
  • formic acid group acetic acid group, octylic acid group, methyl carbonate group, halogen group, hydroxyl group, hydrogen carbonate group, and carbonate group are preferably adopted because they have excellent catalytic activity and are industrially available. .
  • the amount of the trimerization catalyst used as one of the catalysts is 0 with respect to 50 parts by mass of the entire polyol in the composition A in order to effectively exhibit the function as the catalyst. It will be selected in the range of 1 to 8 parts by mass, preferably 1 to 6 parts by mass. If the amount of the trimerization catalyst used is less than 0.1 parts by mass, the trimerization of the polyisocyanate cannot be sufficiently realized, which makes it difficult to sufficiently achieve the flame retardancy improving effect. On the other hand, when the amount is more than 8 parts by mass, the reaction proceeds too much and the solidification is accelerated, which makes spraying difficult.
  • urethane-forming catalyst which is a resin-forming catalyst
  • trimerization catalyst examples include known ones such as dibutyltin dilaurate, bismuth octylate (bismuth 2-ethylhexylate), bismuth neodecanoate, bismuth neododecanoate, bismuth naphthenate, and fatty acid bismuth salts, and lead naphthenate.
  • dibutyltin dilaurate bismuth octylate (bismuth 2-ethylhexylate), bismuth neodecanoate, bismuth neododecanoate, bismuth naphthenate, and fatty acid bismuth salts, and lead naphthenate.
  • the amount of such a resinification catalyst used is 0.1 to 5 parts by mass, preferably 50 parts by mass with respect to 50 parts by mass of the entire polyol in the composition A, so that the function as the catalyst can be effectively exhibited. Will be selected within the range of 0.5 to 3 parts by mass. If the amount of the resinification catalyst used is less than 0.1 parts by mass, the resulting foam may be sticky, dust, etc. may adhere to the foam, and the appearance may be deteriorated. There is a problem that the workability deteriorates because the droplets that adhere to the surface become sticky. On the other hand, if it exceeds 5 parts by mass, the heat generated during the resinification reaction will increase and the appearance of the foam will become yellow and other abnormalities will occur. However, the catalyst containing the quaternary ammonium salt contained in the droplets generated during foaming may deteriorate the work environment at the work site where the spraying work is performed.
  • a known catalyst conventionally used in the production of polyurethane foam is appropriately selected, and a composition containing a polyol as a main component. It will be contained in the product A.
  • an amine-based catalyst can advantageously improve the initial foamability of polyurethane, and also has the effect of reducing the foam density as a whole without changing the density difference between the skin layer and the core layer. It improves the stickiness of the foam and can advantageously prevent the deterioration of the appearance due to the adhesion of dust, etc., and in the spray foaming method, it has the characteristics of improving the workability due to the stickiness of the droplets adhering to the floor etc. To do.
  • an amine-based catalyst it is recommended to use a reactive amine compound having an OH group or an NH group in the chemical structure, or a cyclic amine compound having a cyclic structure. By using it as a catalyst, the odor can be further reduced.
  • the reactive amine compound or cyclic amine compound used as such an amine-based catalyst can be appropriately selected from known urethanization catalysts.
  • the reactive amine compound 4,6-Tri(dimethylaminomethyl)phenol, tetramethylguanidine, N,N-dimethylaminoethanol, N,N-dimethylaminoethoxyethanol, ethoxylated hydroxylamine, N,N,N',N'-tetramethyl -1,3-diamino-2-propanol, N,N,N'-trimethylaminoethylethanolamine, 1,4-bis(2-hydroxypropyl), 2-methylpiperazine, 1-(2-hydroxypropyl)imidazole , 3,3-diamino-N-methyldipropylamine, N-methyl-N′-hydroxyethylpiperazine and the like.
  • cyclic amine compound examples include triethylenediamine, N,N′-dimethylcyclohexylamine, N,N-dicyclohexylmethylamine, methylenebis(dimethylcyclohexyl)amine, N,N-dimethylbenzylamine, morpholine, N-methyl.
  • Morpholine N-ethylmorpholine, N-(2-dimethylaminoethyl)morpholine, 4,4'-oxydiethylenedimorpholine, N,N'-diethylpiperazine, N,N'-dimethylpiperazine, N- Methyl-N′-dimethylaminoethylpiperazine, 1,8-diazobicyclo(5,4,0)-undecene-7 and the like can be mentioned.
  • the amount of the amine-based catalyst used as one of such catalysts while effectively exhibiting its function as a catalyst, problems such as odor and deterioration of working environment are reduced, and effective foam characteristics are obtained.
  • the amount of the amine-based catalyst used is less than 0.1 parts by mass, it becomes difficult to sufficiently exhibit the function as a catalyst, and the resulting foam becomes sticky and dust adheres, resulting in poor appearance.
  • the droplets adhered to the floor and the like become sticky, which causes problems such as poor workability.
  • the amount of the amine-based catalyst used is more than 7 parts by mass, the odor of the obtained polyurethane foam becomes remarkable, and the amine-based catalyst volatilized during foaming causes a problem that the working environment for spraying is deteriorated.
  • the amine catalyst is used in a small amount.
  • the trimerization catalyst as described above is contained in the composition A as at least one of the catalysts to react the polyol in the composition A with the polyisocyanate in the composition B.
  • an organic phosphinic acid metal salt is used as a flame retardant, and the flame retardance of a polyurethane foam produced by containing it in at least one of composition A and composition B.
  • organic phosphinic acid metal salt used here, one or two organic groups such as a linear alkyl group having 1 to 6 carbon atoms and a phenyl group are covalently bonded to a phosphorus atom constituting phosphinic acid.
  • organic phosphinic acid having the structure described above various known metals are ionically bonded to form a salt form, and in general, the phosphorus atom has a methyl group, an ethyl group or a phenyl group bonded thereto.
  • the metal is preferably Mg, Al, Ca, Ti or Zn, and particularly preferably Al or Zn.
  • zinc (mono or di)methylphosphinate zinc (mono or di)ethylphosphinate, zinc (mono or di)phenylphosphinate, aluminum (mono or di)methylphosphinate, (mono or di) Examples thereof include aluminum ethylphosphinate, (mono- or di)phenylphosphinate aluminum, and the like. Since these metal salts of phosphinic acid are usually colorless or white powder, they can be advantageously used without impairing the coloring property of the polyurethane foam.
  • organic phosphinic acid metal salt needs to be used in a ratio of 30 parts by mass or more, preferably 35 parts by mass or more, and more preferably, 50 parts by mass of the polyol in the composition A. Will be preferably used at a ratio of 40 parts by mass or more. This is because if the amount of the organic metal phosphinic acid salt used is too small, it becomes difficult to sufficiently exert the synergistic effect of flame retardancy. Further, when the amount used is too large, the viscosity of the composition to which it is added increases, causing problems such as poor stirring, and also causes problems such as reduced workability.
  • the upper limit of the amount of the organic metal phosphinic acid salt used is 100 parts by mass or less, preferably 75 parts by mass or less, and more preferably 50 parts by mass or less with respect to 50 parts by mass of the polyol. It will be.
  • the organic phosphoric acid ester is used in combination with the organic phosphinic acid metal salt as described above so that they are present in the foamable composition according to the present invention.
  • the flame-retardant property of a polyurethane foam formed from such a foamable composition can be improved more advantageously, and a non-combustible polyurethane foam that conforms to the non-combustible material specified by the above-mentioned Building Standards Act is obtained. It will be advantageously formed.
  • the organic phosphinic acid metal salt and the organic phosphoric acid ester are separately or together contained in at least one of the composition A and the composition B described above.
  • the organic phosphoric acid ester used here is not particularly limited, and known ones such as monophosphoric acid ester and condensed phosphoric acid ester can be used alone or in combination.
  • the organophosphate ester also acts as a viscosity reducer that can effectively reduce the viscosity of the chemical liquid (composition A or composition B) and improve workability such as spraying.
  • the monophosphoric acid ester is not particularly limited, and examples thereof include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, tributoxyethyl phosphate, Triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl)phosphate, tris(phenylphenyl)phosphate, trinaphthylphosphate, cresyldiphenylphosphate, xylenyldiphenylphosphate, diphenyl(2-ethylhexyl)phosphate , Di(isopropylphenyl)phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, di
  • the condensed phosphoric acid ester is not particularly limited, and examples thereof include trialkyl polyphosphate, resorcinol polyphenyl phosphate, resorcinol poly(di-2,6-xylyl) phosphate (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.). ), hydroquinone poly(2,6-xylyl) phosphate, and condensed phosphoric acid esters such as condensation products thereof.
  • condensed phosphoric acid esters examples include resorcinol polyphenyl phosphate (CR-733S), bisphenol A polycresyl phosphate (CR-741), aromatic condensed phosphoric acid ester (CR747), resorcinol polyphenyl phosphate (CR ADEKA STAB PFR manufactured by ADEKA Co., Ltd., bisphenol A polycresyl phosphate (FP-600, FP-700), and the like.
  • monophosphoric acid ester is preferably used because it has a high effect of lowering the viscosity of the composition before curing and a high effect of decreasing the initial amount of heat generation, and tris(1-chloro-2-propyl) is particularly preferable. It is more preferred to use phosphates.
  • the amount of the organic phosphate ester used is 30 parts by mass based on 50 parts by mass of the polyol in the composition A in the total amount with the amount of the organic phosphinic acid metal salt used at the same time. It is necessary to use a proportion of at least 35 parts by weight, and it is preferable to use a proportion of at least 35 parts by weight, more preferably at least 40 parts by weight. In addition, in the total amount of such an organic phosphinic acid metal salt and an organic phosphoric acid ester, the organic phosphinic acid metal salt needs to be configured in a ratio of 5 parts by mass or more with respect to 50 parts by mass of the polyol.
  • the organic phosphinic acid metal salt and the organic phosphoric acid ester becomes too small, or if the used amount of the organic phosphinic acid metal salt becomes too small, the organic phosphinic acid metal salt and the organic phosphoric acid ester The effect of improving the flame retardancy due to the synergistic effect becomes difficult to be sufficiently exerted.
  • the amount used is too large, the catalytic effect for forming a polyurethane foam is lowered, and problems such as foam inhibition are caused. Therefore, these organic phosphinic acid metal salts and organic phosphoric acid are used.
  • the upper limit of the total amount of the ester is generally 180 parts by mass or less, preferably 150 parts by mass or less, and more preferably 120 parts by mass or less with respect to 50 parts by mass of the polyol. Become.
  • metal hydroxides include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, Vanadium hydroxide, tin hydroxide, etc.
  • the amount of the metal hydroxide used is generally in the range of about 5 to 50 parts by mass, preferably 10 to 40 parts by mass with respect to 50 parts by mass of the polyol in the composition A. preferable.
  • foaming for further foaming the polyurethane to be produced is provided.
  • the agent may be added, and in addition, if necessary, various conventionally known auxiliary agents such as known foam stabilizers and other flame retardants may be appropriately selected and added. It is possible.
  • non-CFC type/CFC type foaming agents various known non-CFC type/CFC type foaming agents can be appropriately selected.
  • the non-CFC type foaming agent And/or its source
  • an organic foaming agent such as hydrocarbon (HC), hydrofluoroolefin (HFO), hydrochlorofluoroolefin (HCFO), etc. is contained.
  • hydrofluorocarbons as freon-based foaming agents include difluoromethane (HFC32), 1,1,1,2,2-pentafluoroethane (HFC125).
  • 1,1,1-trifluoroethane HFC143a
  • 1,1,2,2-tetrafluoroethane HFC134
  • 1,1,1,2-tetrafluoroethane HFC134a
  • 1,1-difluoroethane HFC152a
  • 1,1,1,2,3,3,3-heptafluoropropane HFC227ea
  • 1,1,1,3,3-pentafluoropropane HFC245fa
  • 1,1,1,3,3 -Pentafluorobutane HFC365mfc
  • 1,1,1,2,2,3,4,5,5,5-decafluoropentane HFC4310mee
  • hydrocarbon (HC) which is one of the non-fluorocarbon-based foaming agents preferably used in the present invention, include normal pentane, isopentane, cyclopentane, and isobutane.
  • hydrofluoroolefin examples include pentafluoropropene such as 1,2,3,3,3-pentafluoropropene (HFO1225ye), 1,3,3,3-tetrafluoropropene (HFO1234ze), 2,3,3,3-Tetrafluoropropene (HFO1234yf), 1,2,3,3-Tetrafluoropropene (HFO1234ye) and other tetrafluoropropenes, 3,3,3-Trifluoropropene (HFO1243zf) and other trifluoropropenes Hexafluorobutene isomers such as fluoropropene, tetrafluorobutene (HFO1345), pentafluorobutene isomer (HFO1354), 1,1,1,4,4,4-hexafluoro-2-butene (HFO1336mzz) ( HFO1336), heptafluorobutene
  • these hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs) are chemically unstable and therefore have a low global warming potential. Therefore, they are suitably used as environmentally friendly foaming agents. To get. Then, together with these hydrofluoroolefins (HFO) or hydrochlorofluoroolefins (HCFO), water described below will be advantageously used as a foaming agent.
  • water as a foaming agent is advantageously used together with or instead of the above organic foaming agent. Due to the presence of such water in the composition A containing the polyol, when the composition A and the polyisocyanate-containing composition B are mixed and reacted with each other, the water and the polyisocyanate are separated from each other. Since it reacts to generate carbon dioxide, this carbon dioxide can effectively contribute to the foaming of the polyurethane formed by the reaction between the polyol and the polyisocyanate. Moreover, since heat of reaction is generated during the generation of carbon dioxide, the heat can cause the urethanization reaction and isocyanurate reaction to proceed effectively, and the resulting polyurethane foam. The compressive strength of the can be further increased.
  • the amount of water used is generally 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 50 parts by weight of the total polyol in the composition A. It is contained in the composition A. If the amount of water used is more than 5 parts by mass, the strength of the polyurethane foam produced on the contrary will be reduced. That is, the urea bond generated by the reaction between water and polyisocyanate increases in the resin, and the polyisocyanate used for the isocyanurate-forming reaction is consumed by the reaction with water, and the polyisocyanate in the reaction system decreases. This is because. If the amount used is less than 0.1 part by mass, the effect as a foaming agent due to the use of water cannot be sufficiently obtained.
  • the foam stabilizer is used to evenly arrange the cell structure of the polyurethane foam, and here, a silicone type or a nonionic surfactant is preferably adopted.
  • a silicone type or a nonionic surfactant is preferably adopted.
  • Specific examples include polyoxyalkylene-modified dimethyl polysiloxane, polysiloxane oxyalkylene copolymer, polyoxyethylene sorbitan fatty acid ester, castor oil ethylene oxide adduct, lauryl fatty acid ethylene oxide adduct, and the like.
  • One type may be used alone, or two or more types may be used in combination.
  • the amount of this foam stabilizer is appropriately determined according to the desired foam characteristics, the type of foam stabilizer to be used, etc., but is 50 parts by mass of the entire polyol in the composition A. On the other hand, it is selected in the range of 0.1 to 10 parts by mass, preferably 1 to 8 parts by mass.
  • composition A containing a polyol and the composition B containing a polyisocyanate obtained as described above are reacted in the presence of at least a trimerization catalyst to cause foaming/curing
  • a known method is used.
  • the method for producing various polyurethane foams can be appropriately adopted.
  • Continuous foaming method injection foaming method that foams and hardens by injecting and filling into spaces such as electric refrigerators that require heat insulation, honeycomb structures of lightweight and high-strength boards, and voids that occur during civil engineering work.
  • the foamable composition according to the present invention is foamed and cured by a spray foaming method of spraying from a spray gun head of an in-situ foaming machine onto a predetermined adherend (structure) to foam and cure the composition.
  • a non-combustible material defined by the above-mentioned Building Standard Law is advantageously formed in a polyurethane foam provided with flame retardancy.
  • the density, the maximum heat generation rate, the total heat generation amount, the state of the residue, and the colorability of the polyurethane foams obtained in the following Examples and Comparative Examples were evaluated or measured as follows, respectively.
  • Polyol compound phthalic acid type polyester polyol (RFK505 manufactured by Kawasaki Kasei Kogyo Co., Ltd.) : Mannich-based polyether polyol (DK Polyol 3776 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.; hydroxyl value: 35 0 mgKOH/g, viscosity: 500 mPa ⁇ s/25°C )
  • Trimerization catalyst potassium octylate (Da, manufactured by Evonik Japan Co., Ltd. bco K-15) : Quaternary ammonium salt (KAOLYZER No.
  • Resinization catalyst Bismuth octylate (Pucat 2 manufactured by Nippon Kagaku Sangyo Co., Ltd. 5) Flame retardant: Aluminum diethylphosphinate (Client Chemicals Co., Ltd.
  • EXOLIT OP930, EXOLIT OP935 Phosphate ester [TCPP: tris(1-chloro-2-propyl) phosphate] : Phosphate ester (Polyphosphate ester: ADEKA STAB PFR manufactured by ADEKA Corporation) : Red phosphorus (Nova Excel 140 manufactured by Rin Chemical Industry Co., Ltd.) : Aluminum hydroxide (B1403 manufactured by Nippon Light Metal Co., Ltd., average particle diameter: 2 ⁇ m) Blowing agent: HCFO-1233zd (1-chloro-produced by Honeywell) 3,3,3-trifluoropropene) : HFC365mfc (SOLVAY 1,1,1,3,3-pentafluorobutane) : HFC245fa (Central Glass Co., Ltd.
  • Water Foam stabilizer Silicone type foam stabilizer (SH-1 manufactured by Toray Dow Corning Co., Ltd. 93)
  • Dye Red dye (OIL RED RR manufactured by Orient Chemical Industry Co., Ltd. ) : Blue dye (OIL BLUE 2 manufactured by Orient Chemical Industry Co., Ltd. N) : Green dye (OIL GREEN manufactured by Orient Chemical Industry Co., Ltd. 502)
  • composition A Preparation of polyol composition (composition A)-
  • the various raw materials prepared above namely, the polyol, the trimerization catalyst, the resinification catalyst, the flame retardant, the foaming agent, the foam stabilizer and the dye, in various combinations and blending ratios shown in Tables 1 to 3 below, By uniformly mixing, various polyol compositions according to Examples 1 to 12 and Comparative Examples 1 to 8 were prepared.
  • composition B Preparation of Polyisocyanate Composition (Composition B)— As the polyisocyanate, a polymeric MDI (Wannate PM-130 manufactured by Wanka Chemical Japan Co., Ltd.) was prepared, and the composition B was composed of only this polyisocyanate.
  • composition A 80 parts of the various polyol compositions obtained above and 120 parts of the composition B consisting only of polyisocyanate (mass ratio 1:1.5) were adjusted to a liquid temperature of 20° C., respectively. Then, the mixture was placed in a polypropylene container of 300 parts by volume and mixed for 10 seconds using a stirrer: TK Homo Disper (manufactured by PRIMIX Corporation). Then, the mixed liquid was poured into a polypropylene container of 2000 parts by volume, foamed and cured to obtain a desired foamed body.
  • a foamable composition comprising a combination of the polyol composition (composition A) and polyisocyanate (composition B) adopted in Examples 1 to 12 according to the present invention.
  • composition A polyol composition
  • composition B polyisocyanate
  • the product it is possible to obtain a polyurethane foam having a high degree of flame retardance with a total calorific value (20 minutes) of 8 MJ/m 2 or less in a combustion test method according to ISO-5660, and a flame retardant. It is recognized that the hue does not change, and that a colored foam having a desired hue can be easily obtained by using a predetermined coloring dye.
  • Comparative Example 3 in which the amount of the organic phosphinic acid metal salt used is small.
  • Comparative Example 4 and Comparative Example 4 the effect of improving the flame retardancy was not sufficient, and even in the case of Comparative Example 5 in which only organic phosphate was blended as the flame retardant, It is obvious that the total calorific value (20 minutes) that satisfies the above standard cannot be satisfied.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne une composition expansible qui est capable de former avantageusement une mousse de polyuréthane non inflammable qui a une ininflammabilité améliorée de façon synergique. La présente invention concerne également une composition expansible qui est capable de former avantageusement une mousse de polyuréthane non inflammable qui a un degré de liberté amélioré dans la coloration sans perdre la couleur d'une résine de polyuréthane elle-même. Selon la présente invention, une composition expansible pour des mousses de polyuréthane, qui contient une composition A contenant un polyol, une composition B contenant un polyisocyanate et un agent d'expansion, est conçue pour contenir, en tant que catalyseur, au moins un catalyseur de trimérisation, tout en étant conçue de manière à ce qu'au moins l'une de la composition A et de la composition B contienne un sel de phosphinate métallique organique en une quantité de 30 parties en masse ou plus par rapport à 50 parties en masse du polyol.
PCT/JP2019/009967 2018-11-26 2019-03-12 Composition expansible pour mousses de polyuréthane non inflammables WO2020110332A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020217007992A KR20210095852A (ko) 2018-11-26 2019-03-12 불연성 폴리우레탄 폼용 발포성 조성물
JP2019538458A JP6621571B1 (ja) 2018-11-26 2019-03-12 不燃性ポリウレタンフォーム用発泡性組成物
CN201980075408.6A CN113015757B (zh) 2018-11-26 2019-03-12 不燃性聚氨酯泡沫用发泡性组合物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018220175 2018-11-26
JP2018-220175 2018-11-26

Publications (1)

Publication Number Publication Date
WO2020110332A1 true WO2020110332A1 (fr) 2020-06-04

Family

ID=70852744

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/009967 WO2020110332A1 (fr) 2018-11-26 2019-03-12 Composition expansible pour mousses de polyuréthane non inflammables

Country Status (3)

Country Link
KR (1) KR20210095852A (fr)
CN (1) CN113015757B (fr)
WO (1) WO2020110332A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020172604A (ja) * 2019-04-12 2020-10-22 積水ソフランウイズ株式会社 発泡性ウレタン樹脂組成物及びポリウレタン発泡体
WO2021125237A1 (fr) * 2019-12-17 2021-06-24 日清紡ケミカル株式会社 Composition polyol, mousse dure de polyurethanne ignifuge et procede de production de celle-ci
CN113088210A (zh) * 2021-04-25 2021-07-09 东莞澳中新材料科技股份有限公司 一种可用于包裹锂离子电池的阻燃胶带及其制备方法
WO2022260363A1 (fr) * 2021-06-07 2022-12-15 미쓰이케미칼앤드에스케이씨폴리우레탄 주식회사 Mousse de polyuréthane et son procédé de fabrication

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116285306B (zh) * 2023-05-24 2023-08-18 北京宇极科技发展有限公司 一种发泡组合物、聚氨酯泡沫以及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010195920A (ja) * 2009-02-25 2010-09-09 Ube Ind Ltd フェノール性水酸基含有ポリウレタン
JP2012236874A (ja) * 2011-05-10 2012-12-06 Dic Corp 難燃性熱硬化性ポリウレタン樹脂組成物及びそれを用いて成形されたウレタンエラストマー成形品
WO2016010042A1 (fr) * 2014-07-14 2016-01-21 積水化学工業株式会社 Composition de résine de polyuréthane ignifuge

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3127914A1 (de) * 1981-07-15 1983-02-03 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von flammwidrigen polyutheran- und/oder polyisocyanuratgruppen enthaltenden schaumstoffen
DE10317487A1 (de) * 2003-04-16 2004-01-22 Ticona Gmbh Flammschutzmittel-Kombination und flammgeschützte thermoplastische Formmassen
US20100324183A1 (en) * 2008-02-21 2010-12-23 Basf Se Halogen-free flame-retardant tpu
KR20120008441A (ko) * 2010-07-16 2012-01-30 디아이씨 가부시끼가이샤 열경화성 폴리우레탄 수지 조성물 및 그것을 사용하여 성형된 우레탄 엘라스토머 성형품
BR112013033460A2 (pt) 2011-06-28 2017-03-14 Dow Global Technologies Llc formulação reativa para confeccionar um revestimento de poliuretano elastomérico pulverizável e processo para revestir uma superfície de um substrato
JP2014532098A (ja) 2011-09-29 2014-12-04 ダウ グローバル テクノロジーズ エルエルシー ポリウレタンフォームにおける煙抑制剤としてのリン酸トリアルキルの使用
EP2687534A1 (fr) * 2012-07-20 2014-01-22 LANXESS Deutschland GmbH Poly(alkylphosphate) sans halogène
JP6423140B2 (ja) * 2012-09-04 2018-11-14 Dic株式会社 非ハロゲン系難燃性樹脂組成物および成形体
JP6564160B2 (ja) * 2013-03-05 2019-08-21 積水化学工業株式会社 耐火性ウレタン樹脂組成物
CN103709432B (zh) * 2013-12-18 2015-10-21 南京师范大学 一种高阻燃硬质聚氨酯泡沫塑料及其制备方法
CN103804626B (zh) * 2014-01-27 2016-07-06 中国科学技术大学 一种无卤阻燃硬质聚氨酯泡沫体及其制备方法
WO2015128213A1 (fr) * 2014-02-26 2015-09-03 Basf Se Polyuréthane thermoplastique ignifugé
JP6730003B2 (ja) 2014-03-27 2020-07-29 積水化学工業株式会社 難燃性ウレタン樹脂組成物
CN105330818B (zh) * 2015-12-01 2018-05-04 中国科学技术大学苏州研究院 一种阻燃聚氨酯硬质泡沫材料及其制备方法
CN105860504A (zh) * 2016-04-27 2016-08-17 安徽广燕新材料科技有限责任公司 一种聚氨酯保温复合板

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010195920A (ja) * 2009-02-25 2010-09-09 Ube Ind Ltd フェノール性水酸基含有ポリウレタン
JP2012236874A (ja) * 2011-05-10 2012-12-06 Dic Corp 難燃性熱硬化性ポリウレタン樹脂組成物及びそれを用いて成形されたウレタンエラストマー成形品
WO2016010042A1 (fr) * 2014-07-14 2016-01-21 積水化学工業株式会社 Composition de résine de polyuréthane ignifuge

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020172604A (ja) * 2019-04-12 2020-10-22 積水ソフランウイズ株式会社 発泡性ウレタン樹脂組成物及びポリウレタン発泡体
JP7442271B2 (ja) 2019-04-12 2024-03-04 積水化学工業株式会社 発泡性ウレタン樹脂組成物及びポリウレタン発泡体
WO2021125237A1 (fr) * 2019-12-17 2021-06-24 日清紡ケミカル株式会社 Composition polyol, mousse dure de polyurethanne ignifuge et procede de production de celle-ci
CN113088210A (zh) * 2021-04-25 2021-07-09 东莞澳中新材料科技股份有限公司 一种可用于包裹锂离子电池的阻燃胶带及其制备方法
CN113088210B (zh) * 2021-04-25 2022-09-06 东莞澳中新材料科技股份有限公司 一种可用于包裹锂离子电池的阻燃胶带及其制备方法
WO2022260363A1 (fr) * 2021-06-07 2022-12-15 미쓰이케미칼앤드에스케이씨폴리우레탄 주식회사 Mousse de polyuréthane et son procédé de fabrication

Also Published As

Publication number Publication date
KR20210095852A (ko) 2021-08-03
CN113015757B (zh) 2023-07-18
CN113015757A (zh) 2021-06-22

Similar Documents

Publication Publication Date Title
JP6626590B2 (ja) 難燃性ウレタン樹脂組成物
EP3112388B1 (fr) Système d'expansion in situ pour la formation d'une mousse polyuréthanne ignifuge
WO2020110332A1 (fr) Composition expansible pour mousses de polyuréthane non inflammables
JP6725606B2 (ja) ウレタン樹脂組成物および建築物の断熱方法
JP7034020B2 (ja) 難燃性ポリウレタンフォーム用発泡性組成物
US20220073691A1 (en) Flame retardant composition for polyurethane foam and flame-retarded polyurethane foam containing the same
JP2021130801A (ja) ポリウレタンフォーム用難燃剤組成物及びこれを配合した難燃性ポリウレタンフォーム
JP6978396B2 (ja) ポリウレタンフォームの製造方法
JP6621571B1 (ja) 不燃性ポリウレタンフォーム用発泡性組成物
JP2020128459A (ja) ポリウレタンフォームの製造方法
JP7039438B2 (ja) 建築物の断熱方法および建築物用断熱材のリサイクル方法
JP6987803B2 (ja) ポリウレタンフォームの製造方法
JP7305504B2 (ja) 不燃性ポリウレタンフォーム用発泡性組成物
JP2022155370A (ja) 難燃性発泡体用組成物
JP7263495B2 (ja) ポリウレタンフォームの製造方法
JP7263496B2 (ja) ポリウレタンフォームの製造方法
JP6978397B2 (ja) ポリウレタンフォームの製造方法
JP6987732B2 (ja) ポリウレタンフォームの製造方法
WO2021255958A1 (fr) Composition de mousse pour mousse de polyisocyanurate ignifuge et procédé de production de mousse de polyisocyanurate ignifuge à l'aide de ladite mousse
JP2022155368A (ja) 難燃性発泡体用組成物
JP2022155369A (ja) 難燃性発泡体用組成物

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2019538458

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19889457

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19889457

Country of ref document: EP

Kind code of ref document: A1