CN113015757A - Foaming composition for non-combustible polyurethane foam - Google Patents

Foaming composition for non-combustible polyurethane foam Download PDF

Info

Publication number
CN113015757A
CN113015757A CN201980075408.6A CN201980075408A CN113015757A CN 113015757 A CN113015757 A CN 113015757A CN 201980075408 A CN201980075408 A CN 201980075408A CN 113015757 A CN113015757 A CN 113015757A
Authority
CN
China
Prior art keywords
composition
polyurethane foam
polyol
mass
organic
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
CN201980075408.6A
Other languages
Chinese (zh)
Other versions
CN113015757B (en
Inventor
关浩之
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Yukizai Corp
Original Assignee
Asahi Yukizai Corp
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 Asahi Yukizai Corp filed Critical Asahi Yukizai Corp
Publication of CN113015757A publication Critical patent/CN113015757A/en
Application granted granted Critical
Publication of CN113015757B publication Critical patent/CN113015757B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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

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

Provided is a foamable composition which can favorably form a nonflammable polyurethane foam having synergistically improved flame retardancy, and further provided is a foamable composition which can favorably form a nonflammable polyurethane foam having improved freedom of coloring without impairing the color of a polyurethane resin itself. A polyurethane foam-foamable composition containing a polyol-containing composition A, a polyisocyanate-containing composition B, and a blowing agent, wherein at least a trimerization catalyst is contained as a catalyst, and an organic phosphinic acid metal salt is contained in at least either one of the composition A and the composition B in a proportion of 30 parts by mass or more relative to 50 parts by mass of the polyol.

Description

Foaming composition for non-combustible polyurethane foam
Technical Field
The present invention relates to a foamable composition for a nonflammable polyurethane foam, and particularly to a foamable composition for forming a polyurethane foam which favorably satisfies the nonflammable characteristics specified in japanese building standards act.
Background
Polyurethane foams have been used as heat insulating materials mainly for heat insulation of inner and outer wall materials and panels for buildings, heat insulation of metal sidings and refrigerators, heat insulation of main wall surfaces of high buildings, apartments and freezing warehouses, heat insulation of ceilings and roofs, and heat insulation of condensation prevention and infusion pipes, and also as back filling materials for filling gaps generated in civil engineering, reinforcing materials in civil engineering, and the like, taking advantage of their excellent properties such as heat insulating properties, adhesiveness, and lightweight properties. Such a polyurethane foam is usually produced by continuously or intermittently mixing a composition a (formed from a polyol mixture (premix) in which a foaming agent and, if necessary, various additives such as a catalyst, a foam stabilizer, and a flame retardant are mixed with a polyol) and a composition B mainly containing a polyisocyanate by a mixing device to prepare an expandable composition for a polyurethane foam, and expanding and curing the expandable composition by a plate expansion method (slab foaming process), an injection expansion method, a spray expansion method, a laminated continuous expansion method, a light-weight filling construction method, an injection back construction method, and the like.
However, since the polyurethane foam formed as described above is required to have flame retardancy in view of its use, a foamable composition for flame-retardant polyurethane foam containing various flame retardants is proposed, and for example, japanese patent application laid-open No. 2014-524954 (patent document 1) proposes a reactive complex comprising a polyisocyanate component containing an isocyanate prepolymer and an optional flame-retardant compound and a polyol component containing an aromatic polyester polyol, red phosphorus, a catalyst, and further a flame retardant as a reactive complex for producing a sprayable elastic polyurethane coating having improved flame-retardant characteristics, thereby making it clear that an elastic polyurethane coating having improved flame-retardant characteristics can be formed. Examples of the flame retardant additive which may be added and contained include halogen-containing compounds, phosphates, inorganic fillers, antimony oxides, zinc, and the like.
In addition, in japanese patent application laid-open No. 2014-532098 (patent document 2), it is proposed to use trialkyl phosphate as a smoke suppressant for a polyurethane foam, whereby when combustion occurs, smoke generation is remarkably reduced, that is, it is clear that a polyurethane foam having improved smoke suppression characteristics can be obtained. Moreover, the following is also clear therein: for the formation of the polyurethane foam, a urethane catalyst or an isocyanate trimerization catalyst (Japanese: three-part catalyst) may be used, and a metal-based inorganic filler for easy processability, for example, a zinc salt such as a metal hydrate, zinc borate or zinc stannate, may be contained.
Furthermore, jp 2015-193839 a (patent document 3) discloses a flame-retardant polyurethane resin composition containing a polyol compound, a polyisocyanate compound, a trimerization catalyst, a blowing agent, and a foam stabilizer, and further containing a predetermined amount of red phosphorus as one of the additives, whereby a flame-retardant polyurethane resin composition which can exhibit excellent flame retardancy by adding a small amount of a flame retardant (red phosphorus) and has excellent handling properties can be provided. Further, it is clear that, in addition to a moisture-releasing substance such as a metal hydroxide, a crystal water-containing inorganic compound, and a clay mineral, which are one of the additives, a flame retardant containing phosphate ester or phosphate, a flame retardant containing bromine, and the like may be further blended.
However, in these patent documents, the flame retardant polyurethane foams having improved flame retardant polyurethane coatings and smoke suppression performance obtained in patent documents 1 and 2 do not have flame retardant properties sufficient to meet recent strict requirements for flame retardancy. For example, the flame-retardant polyurethane coating layer obtained in patent document 1 merely clarifies the characteristics relating to the covering layer having elasticity, and does not sufficiently satisfy the strict flame-retardant characteristics required for the polyurethane foam (foam), and even the polyurethane foam disclosed in patent document 2 merely aims at improving the smoke suppression performance, and does not sufficiently meet the requirements relating to the stricter flame-retardant performance.
Further, although red phosphorus used in patent documents 1 and 3 is an excellent flame retardant, when the amount of red phosphorus used is increased in order to improve the flame retardancy of the polyurethane foam formed, there is a problem that the foam is rather easily burned, and moreover, red phosphorus itself has a risk of ignition, so that there is a potential problem that an accident is easily caused when the polyurethane foam is produced, and there is a problem that the workability is poor when it is used. Further, since red phosphorus has a purple red color as its name implies, there is a problem that when a resin (foam) is colored in red as a whole with such a color tone inherent to red phosphorus and is colored with a colorant, it is difficult to reflect the color of the target colorant, and there is a demand for avoiding the use of red phosphorus as much as possible.
However, in the standard construction law of japan, regarding the fire resistance and fire resistance of materials, they are classified into a flame retardant material, a quasi-incombustible material, and an incombustible material, and from a flame retardant material to a quasi-incombustible material and further to an incombustible material, a more strict fire resistance is required, and when a conventional flame retardant such as that disclosed in the above-mentioned publication is used in order to impart a high degree of flame retardancy to a foam material (which is formed of a polyurethane foam obtained by foaming a polyol by reacting with a polyisocyanate), it is difficult to satisfy the incombustible performance of an incombustible material which requires the most strict fire resistance. In particular, in order to obtain the characteristics required for the incombustible material specified in the building standard law, that is, in the case of the radiant heat intensity: 50kW/m2The total heat release during heating within 20 minutes from the start of heating was 8.0MJ/m2When the amount of the known flame retardant is increased to the following incombustible characteristic in the foamable composition for polyurethane foam, the following problems arise: inhibition of the reaction of polyol and polyisocyanate to make the target foam not available, or deterioration of physical or mechanical properties of the obtained foam, and color tone of the foamTo a limit.
It should be noted that, according to the regulations of the building standard law (article 1, article five), the noncombustible material should satisfy the above-mentioned total heat release amount, and the maximum heat release rate should continuously exceed 200kW/m for not more than 10 seconds2Further, cracks and holes penetrating to the back surface, which are harmful in fire prevention, should not be present, but a polyurethane foam material containing a conventional flame retardant cannot sufficiently meet the requirement of such incombustibility while ensuring physical and mechanical properties useful as a polyurethane resin.
Documents of the prior art
Patent document
Patent document 1: japanese Kokai publication No. 2014-524954
Patent document 2: japanese Kokai publication Hei-2014-532098
Patent document 3: japanese patent laid-open publication No. 2015-
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a foamable composition capable of advantageously forming a nonflammable polyurethane foam which is synergistically improved in flame retardancy, and to provide a foamable composition capable of advantageously forming a nonflammable polyurethane foam which is improved in the degree of freedom of coloring without losing the color of a polyurethane resin itself.
Means for solving the problems
The present invention is also suitable for various embodiments as described below in order to solve the above problems. It should be noted that the aspects and technical features of the present invention are not limited to the following description, and should be understood as being recognizable based on the idea of the invention that can be understood from the description of the specification.
(1) A foamable composition for non-combustible polyurethane foam, which comprises a composition A containing a polyol and a composition B containing a polyisocyanate, wherein a polyurethane foam is formed by the reaction of the polyol with the polyisocyanate and foaming with a blowing agent,
the composition A contains at least a trimerization catalyst as a catalyst, and the organic phosphinic acid metal salt is contained in at least either one of the composition A and the composition B in a proportion of 30 parts by mass or more relative to 50 parts by mass of the polyol.
(2) A foamable composition for non-combustible polyurethane foam, which comprises a composition A containing a polyol and a composition B containing a polyisocyanate, wherein a polyurethane foam is formed by the reaction of the polyol with the polyisocyanate and foaming with a blowing agent,
the foamable composition for a non-combustible polyurethane foam comprises: the composition A contains at least a trimerization catalyst as a catalyst, and the organic phosphinic acid metal salt and the organic phosphate are contained in at least either one of the composition A and the composition B separately or together, and the organic phosphinic acid metal salt and the organic phosphate are contained in a ratio of 30 parts by mass or more in total relative to 50 parts by mass of the polyol, and the content of the organic phosphinic acid metal salt is 5 parts by mass or more relative to 50 parts by mass of the polyol.
(3) The foamable composition for noncombustible polyurethane foam according to the above aspect (2), wherein the organic phosphate is selected from the group consisting of monophosphates and condensed phosphates.
(4) The foamable composition for a nonflammable polyurethane foam according to the above aspect (2) or the above aspect (3), wherein the organic phosphate is tris (1-chloro-2-propyl) phosphate.
(5) The foamable composition for noncombustible polyurethane foam according to any one of the above aspects (1) to (4), wherein the metal salt of an organic phosphinic acid is a salt of 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 a metal selected from the group consisting of Mg, Al, Ca, Ti and Zn.
(6) The foamable composition for a non-combustible polyurethane foam according to any one of the above aspects (1) to (5), wherein the composition A and/or the composition B further contains a metal hydroxide.
(7) The foamable composition for noncombustible polyurethane foam according to any one of the above aspect (1) to aspect (6), wherein the trimerization catalyst is a quaternary ammonium salt.
(8) The foamable composition for noncombustible polyurethane foam according to any one of the above aspect (1) to the above aspect (6), wherein an alkali metal carboxylate and a quaternary ammonium salt are used in combination as the trimerization catalyst.
(9) The foamable composition for a non-combustible polyurethane foam according to any one of the above aspects (1) to (8), wherein the polyol is an aromatic polyester polyol.
(10) The foamable composition for a nonflammable polyurethane foam according to the above aspect (9), wherein the aromatic polyester polyol is a phthalic acid polyester polyol.
(11) The foamable composition for a non-combustible polyurethane foam according to any one of the above aspects (1) to (10), wherein the blowing agent is an organic blowing agent selected from the group consisting of hydrocarbons, hydrofluoroolefins and hydrochlorofluoroolefins.
(12) The foamable composition for noncombustible polyurethane foam according to any one of the above aspect (1) to the above aspect (11), characterized in that water is used as the blowing agent in combination with a hydrofluoroolefin or a hydrochlorofluoroolefin.
(13) The foamable composition for a non-combustible polyurethane foam according to any one of the above aspects (1) to (12), wherein the polyurethane foam has the following non-combustible characteristics: according to the exothermic test method specified in ISO-5660, the radiant heat intensity is 50kW/m2The total heat release during heating within 20 minutes from the start of heating was 8.0MJ/m2The following.
Effects of the invention
As described above, in the foamable composition for a non-combustible polyurethane foam according to the present invention, at least a trimerization catalyst is used as a reaction catalyst of a polyol and a polyisocyanate, and an organic phosphinate metal salt alone or in combination with the organic phosphinate metal salt and an organic phosphate ester as a flame retardant is added and contained in a prescribed ratio in at least either one of the polyol-containing composition a and the polyisocyanate-containing composition B, and therefore, in the presence of an isocyanurate structure introduced by the trimerization catalyst, a synergistic flame-retardant action by the organic phosphinate metal salt, or both the organic phosphinate metal salt and the organic phosphate ester can be effectively exhibited, whereby the flame retardancy of the resulting polyurethane foam can be further improved, and a target non-combustible property can be favorably imparted.
In particular, in the polyurethane foam formed from the foamable composition according to the present invention, the amount of heat generated during combustion can be effectively reduced, and combustion does not continue even if a fire occurs, and a high residual carbon ratio can be imparted, whereby a polyurethane foam which is extremely difficult to burn and has improved self-extinguishing properties can be advantageously provided.
Further, in the foamable composition for a nonflammable polyurethane foam of the present invention, red phosphorus is not used as a flame retardant, and therefore the color tone of the polyurethane foam formed from such a foamable composition can be completely prevented from being affected by the purple color inherent to red phosphorus, and the organic phosphinic acid metal salt and the organic phosphate ester used do not exert any influence on the color tone of the formed polyurethane foam, and therefore the formed polyurethane foam can be favorably colored to a desired color tone by a colorant, and therefore the degree of freedom of coloring of the polyurethane foam can be effectively increased.
Detailed Description
Hereinafter, the foamable composition for a non-combustible polyurethane foam of the present invention will be described in detail so that the specific structure thereof will be more apparent.
First, the foamable composition for a nonflammable polyurethane foam of the present invention is composed of a composition a mainly containing a polyol and a composition B mainly containing a polyisocyanate, and the target polyurethane foam is formed by the reaction of these polyols with a polyisocyanate and the foaming by a foaming agent, and various polyol compounds known to react with a polyisocyanate to form a polyurethane can be used alone or in an appropriate combination for the polyol which is the main component constituting the composition a used herein. Here, polyether polyol, polyester polyol and the like are preferably used as the polyol. Of course, it goes without saying that various known polyol compounds, for example, polyolefin-based polyols, acrylic polyols, polymer polyols, and the like may be used alone or in appropriate combinations in addition to the above polyols.
Specifically, among the above polyols, polyether polyols are obtained by reacting alkylene oxides with at least 1 initiator such as a polyol, a saccharide, an aliphatic amine, an aromatic amine, a phenol, and a mannich condensate. Here, as the alkylene oxide, propylene oxide, 1, 2-butylene oxide, 2, 3-butylene oxide, ethylene oxide, and the like can be given. The polyhydric alcohol as the initiator includes ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc., the saccharide includes sucrose, glucose (dextrose), sorbitol, etc., the aliphatic amine includes alkanolammonium such as diethanolamine, triethanolamine, etc., polyamine such as ethylenediamine, etc., the aromatic amine includes various methyl substituents of phenylenediamine collectively called tolylenediamine (tolylendiamine), derivatives obtained by introducing a substituent such as methyl, ethyl, acetyl, benzoyl, etc., to the amino group, 4' -diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine, etc., and the phenol includes bisphenol A, Novolac type phenol resin, etc. Examples of the mannich condensate include mannich condensates obtained by mannich condensation reaction of phenols, aldehydes, and alkanol ammonium salts.
Examples of the polyester polyol include polyols based on condensation of a polyol and a polycarboxylic acid, and polyols based on ring-opening polymers of cyclic esters. Here, as the polyol, the above-mentioned polyol can be used, and a diol is particularly preferably used. Examples of the polycarboxylic acid include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, isophthalic acid, and anhydrides thereof, and epsilon-caprolactone can be used as the cyclic ester.
Among these, as the polyester polyol, an aromatic polyester polyol is preferably used from the viewpoint of flame retardancy and compatibility, specifically, a phthalic polyester polyol is preferably used, and it is also effective to combine 2 or more of these polyester polyols. The phthalic polyester polyol is preferably a phthalic polyester polyol formed from a condensate of phthalic acid, terephthalic acid, isophthalic acid, or an anhydride thereof with a glycol such as ethylene glycol, propylene glycol, diethylene glycol, or dipropylene glycol. The use of such a phthalic acid polyester polyol has the following advantages: even when in-situ foaming is carried out at a low temperature (about-10 to 5 ℃), the resulting foam is less likely to peel off from the building body or the like, and a rigid polyurethane foam having flexibility to such an extent that the treatment of the foam end after in-situ foaming is easy can be obtained. In particular, when a hydrofluoroolefin-based blowing agent or a hydrochlorofluoroolefin-based blowing agent is contained, a composition having excellent storage stability can be provided.
On the other hand, the polyisocyanate in the composition B is a compound which is blended with the composition a and reacts with the polyol in the composition a to form a polyurethane (resin), and is an organic isocyanate compound having 2 or more isocyanate groups (NCO groups) in the molecule, and examples thereof include: aromatic polyisocyanates such as diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, toluene diisocyanate, polymethylene triisocyanate, xylylene diisocyanate, and naphthalene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, and alicyclic polyisocyanates such as isophorone diisocyanate; and urethane prepolymers having an isocyanate group at a molecular end, isocyanurate-modified products of polyisocyanates, carbodiimide-modified products, and the like. These polyisocyanate compounds may be used alone or in combination of 2 or more. In general, polymethylene polyphenylene polyisocyanate (polymeric mdi) is suitably used from the viewpoints of reactivity, economy, workability, and the like.
The ratio of the polyisocyanate in the composition B to the polyol in the composition a is appropriately determined depending on the type of foam to be formed (for example, polyurethane or polyisocyanurate), and is generally appropriately determined so that the NCO/OH index (equivalent ratio) indicating the ratio of the isocyanate group (NCO) of the polyisocyanate to the hydroxyl group (OH) of the polyol falls within a range of about 0.9 to 2.5.
In the present invention, as described above, the composition a and the composition B are mixed and reacted in the presence of a catalyst, and the mixture is foamed and cured by a blowing agent to form a rigid polyurethane foam, and as a catalyst used herein, at least a trimerization catalyst, that is, a catalyst (isocyanotomizing catalyst) that causes the isocyanate groups of the polyisocyanate to react and trimerize to promote the formation of isocyanurate rings is contained in the composition a. As the trimerization catalyst, various known trimerization catalysts can be appropriately selected and used, but preferable examples thereof include: carboxylic acid alkali metal salts such as quaternary ammonium salts, potassium octylate, potassium 2-ethylhexanoate, and sodium acetate; nitrogen-containing aromatic compounds such as tris (dimethylaminomethyl) phenol, 2, 4-bis (dimethylaminomethyl) phenol, and tris (dimethylaminopropyl) hexahydrotriazine; tertiary ammonium salts such as trimethylammonium salts, triethylammonium salts, and triphenylammonium salts. Among them, quaternary ammonium salts are preferably used from the viewpoint of improving flame retardancy, and particularly, quaternary ammonium salts and alkali metal carboxylate salts are preferably used in combination from the viewpoint of further improving flame retardancy.
As the quaternary ammonium group (1-valent cation in the form of 4 organic groups covalently bonded to a nitrogen atom) in the quaternary ammonium salt used advantageously herein, there can be mentioned: aliphatic ammonium groups such as tetramethylammonium, methyltriethylammonium, ethyltrimethylammonium, propyltrimethylammonium, butyltrimethylammonium, pentyltrimethylammonium, hexyltrimethylammonium, heptyltrimethylammonium, octyltrimethylammonium, nonyltrimethylammonium, decyltrimethylammonium, undecyltrimethylammonium, dodecyltrimethylammonium, tridecyltrimethylammonium, tetradecyltrimethylammonium, heptadecyltrimethylammonium, hexadecyltrimethylammonium, heptadecyltrimethylammonium, and octadecyltrimethylammonium; hydroxylammonium groups such as (2-hydroxypropyl) trimethylammonium, hydroxyethyltrimethylammonium, trimethylaminoethoxyethanol, and hydroxyethyl-2-hydroxypropyldimethylammonium; 1-methyl-1-azonian-4-azabicyclo [2, 2, 2] octan-ium (Japanese: 1- メチル -1- アザ bis ア -4- アザ ビ シ ク [2, 2, 2] p ク bis ゥ ), 1-dimethyl-4-methylpiperidinium, 1-methylmorpholinium, 1-methylpiperidinium and other alicyclic ammonium groups. Among them, quaternary ammonium groups such as tetramethylammonium, methyltriethylammonium, ethyltrimethylammonium, butyltrimethylammonium, hexyltrimethylammonium, octyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium, tetradecyltrimethylammonium, hexadecyltrimethylammonium, octadecyltrimethylammonium, (2-hydroxypropyl) trimethylammonium, hydroxyethyltrimethylammonium, hydroxyethyl-2-hydroxypropyldimethylammonium, 1-methyl-1-1-azoniacation-4-azabicyclo [2, 2, 2] octanium, and 1, 1-dimethyl-4-methylpiperidinium can be preferably used from the viewpoint of providing excellent catalyst activity and being industrially available.
As the organic acid group or inorganic acid group which is a 1-valent anion ionically bonded to the quaternary ammonium group to form the quaternary ammonium salt as described above, there can be mentioned, for example: organic acid groups such as a formate group, an acetate group, an octanoate group, an oxalate group, a malonate group, a succinate group, a glutarate group, a adipate group, a benzoate group, a toluate group, an ethylbenzoate group, a methylcarbonate group, a phenol group, an alkylbenzenesulfonic group, a toluenesulfonate group, a benzenesulfonate group, and a phosphate group; inorganic acid groups such as halogen groups, hydroxyl groups, hydrogen carbonate groups, and carbonate groups. Among them, in view of excellent catalytic activity and industrial availability, it is preferable to use a formate group, an acetate group, an octanoate group, a methyl carbonate group, a halogen group, a hydroxyl group, a carbonate group, and a carbonate group.
Further, as the catalyst comprising the quaternary ammonium salt having the above-mentioned structure, various commercially available products are exemplified by U-CAT 18X, U-CAT 2313 (manufactured by San-Apro corporation), KAOLIZER No.410, KAOLIZER No.420 (manufactured by Kao corporation).
In order to effectively exhibit the function as a catalyst, the amount of the trimerization catalyst used as one of the catalysts may be selected from the range of 0.1 to 8 parts by mass, preferably 1 to 6 parts by mass, based on 50 parts by mass of the entire polyol in the composition A. If the amount of the trimerization catalyst used is less than 0.1 part by mass, the trimerization of the polyisocyanate cannot be sufficiently achieved, and thus there is a problem that it is difficult to sufficiently achieve the effect of improving the flame retardancy, while if it exceeds 8 parts by mass, the reaction proceeds excessively, and the curing becomes fast, and thus it is difficult to apply the coating.
In the present invention, a urethane-forming catalyst can be used in combination with the trimerization catalyst as a resinating catalyst. Examples of the urethane-forming catalyst include known catalysts such as dibutyltin dilaurate, bismuth octoate, (bismuth 2-ethylhexanoate), bismuth neodecanoate, bismuth neododecanoate, fatty acid bismuth salts such as bismuth naphthenate, and lead naphthenate.
The amount of the resin-forming catalyst to be used may be selected from the range of 0.1 to 5 parts by mass, preferably 0.5 to 3 parts by mass, based on 50 parts by mass of the entire polyol in the composition A, in order to effectively exhibit the function as the catalyst. When the amount of the resinification catalyst used is less than 0.1 part by mass, the obtained foam is sticky, dust and the like are attached, and the appearance is deteriorated, and when the amount is more than 5 parts by mass, the foam is sticky and the application property is deteriorated, and on the other hand, the foam is deteriorated in appearance due to the heat release during the resin conversion reaction, and the quaternary ammonium salt-containing catalyst contained in the foam generated during the foaming may deteriorate the working environment at the working site where the spray coating work is performed.
Further, in addition to the above-mentioned trimerization catalyst and resinification catalyst, a known catalyst conventionally used in the production of a polyurethane foam may be appropriately selected as necessary and included in the composition a mainly containing a polyol. For example, the amine-based catalyst can advantageously improve initial foamability of polyurethane, and has an action of lowering the density of foam as a whole without changing the density difference between the skin layer and the core layer, and also can improve stickiness of foam to favorably prevent deterioration in appearance due to adhesion of dust and the like, and also exhibits a characteristic of improving deterioration in workability due to stickiness of spray adhering to a floor or the like in a spray foaming method. As such an amine-based catalyst, a reactive amine compound having an OH group and an NH group in its chemical structure or a cyclic amine compound having a cyclic structure is recommended, and among these, by using a reactive amine compound as a catalyst, odor can be further reduced.
The reactive amine compound and the cyclic amine compound used as such an amine catalyst can be appropriately selected from known urethanization catalysts, and examples of the reactive amine compound include 2, 4, 6-tris (dimethylaminomethyl) phenol, tetramethylguanidine, N-dimethylaminoethanol, N-dimethylaminoethoxyethanol, ethoxylated hydroxylamine, N ' -tetramethyl-1, 3-diamino-2-propanol, N ' -trimethylaminoethylethanolamine, 1, 4-bis (2-hydroxypropyl), 2-methylpiperazine, 1- (2-hydroxypropyl) imidazole, 3-diamino-N-methyldipropylamine, N, N ' -trimethylaminoethylethanolamine, 1, 4-bis (2-hydroxypropyl) amine, N, N, N ' -trimethylaminoethylethanolamine, N, N ' -dimethylurethanol, N, N, N-dimethylurethanol, N-methyl-N' -hydroxyethylpiperazine, and the like. Examples of the cyclic amine compound include triethylenediamine, N ' -dimethylcyclohexylamine, N-dicyclohexylmethylamine, methylenebis (dimethylcyclohexyl) amine, N-dimethylbenzylamine, morpholine, N-methylmorpholine, N-ethylmorpholine, N- (2-dimethylaminoethyl) morpholine, 4 ' -oxydiethylenedimorpholine, N ' -diethylpiperazine, N ' -dimethylpiperazine, N-methyl-N ' -dimethylaminoethylpiperazine, and 1, 8-diazabicyclo (5, 4, 0) -undecene-7.
The amount of the amine catalyst used as one of the catalysts is selected from the range of 0.1 to 7 parts by mass, preferably 0.2 to 3 parts by mass, and more preferably 0.3 to 1 part by mass, based on 50 parts by mass of the entire polyol in the polyol composition, in order to effectively exhibit the function as the catalyst and to obtain effective foam characteristics by reducing problems such as odor and deterioration of working environment. When the amount of the amine-based catalyst used is less than 0.1 part by mass, it is difficult to sufficiently exhibit the function as a catalyst, and the resulting foam is sticky, dust and the like are attached, and the appearance is deteriorated. When the amount of the amine catalyst used is more than 7 parts by mass, the odor of the resulting polyurethane foam becomes conspicuous, and the amine catalyst volatilized during foaming causes a problem of deterioration of the spraying work environment. Therefore, the amine-based catalyst is preferably used in a small amount from the viewpoint of odor.
In the present invention, the polyurethane foam having high flame retardancy can be advantageously provided by including at least the above-mentioned trimerization catalyst as one of the catalysts in the composition a and reacting the polyol in the composition a with the polyisocyanate in the composition B to form polyurethane, and by using the organic phosphinate metal salt as the flame retardant and including the organic phosphinate metal salt in at least either one of the composition a and the composition B, the flame retardancy of the polyurethane foam to be formed can be synergistically improved.
The metal salt of an organophosphinic acid used herein is a compound in which various known metals are ionically bonded to an organophosphinic acid (having a structure in which 1 or 2 organic groups such as linear alkyl groups having 1 to 6 carbon atoms and phenyl groups are covalently bonded to phosphorus atoms constituting the phosphinic acid) to form a salt form, and generally, a methyl group, an ethyl group, or a phenyl group is preferably bonded to the phosphorus atom, and as the metal, Mg, Al, Ca, Ti, or Zn is preferable, and Al or Zn is particularly preferable. Specific examples thereof include zinc (mono-or di) -methylphosphinate, zinc (mono-or di) -ethylphosphinate, zinc (mono-or di) -phenylphosphinate, aluminum (mono-or di) -methylphosphinate, aluminum (mono-or di) -ethylphosphinate, and aluminum (mono-or di) -phenylphosphinate. These metal phosphinates are generally colorless or white powders and can therefore be advantageously used without any hindrance to the colorability of the polyurethane foam.
The organic phosphinic acid metal salt is used in a proportion of 30 parts by mass or more relative to 50 parts by mass of the polyol in the composition a, and is preferably used in a proportion of 35 parts by mass or more, more preferably 40 parts by mass or more. This is due to: if the amount of the organic phosphinic acid metal salt used is too small, it is difficult to sufficiently exhibit the synergistic effect of flame retardancy. Further, since an excessive amount of the organic phosphinic acid metal salt increases the viscosity of the composition containing the organic phosphinic acid metal salt, causes problems such as poor stirring and the like, and causes problems such as poor workability, the upper limit of the amount of the organic phosphinic acid metal salt is generally 100 parts by mass or less, preferably 75 parts by mass or less, and more preferably 50 parts by mass or less, based on 50 parts by mass of the polyol.
In addition, in the present invention, it is desirable that: the organic phosphate ester is used in combination with the organic phosphinic acid metal salt as described above, and is present in the foamable composition of the invention. Thus, the flame retardancy of the polyurethane foam formed from the foamable composition can be further advantageously improved, and a nonflammable polyurethane foam satisfying the nonflammable materials specified in the building standards act can be advantageously formed. Further, these organic phosphinic acid metal salt and organic phosphoric acid ester may be contained in at least either one of the composition a and the composition B described above, separately or together.
The organic phosphate used herein is not particularly limited, and known organic phosphates such as monophosphates and condensed phosphates may be used alone or in combination. The organic phosphate ester is effective in reducing the viscosity of the chemical solution (composition A and/or composition B) and also acts as a viscosity reducing agent for improving the workability such as spraying.
Specific examples of the monophosphoric acid ester include, but are not particularly limited to, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, tris (butoxyethyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, tri (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, tolyldiphenyl phosphate, ditolyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, and the like, Melamine phosphate, di (melamine) phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, methanephosphonic acid biphenyl, phenylphosphonic acid diethyl ester, resorcinol bis (diphenylphosphate), bisphenol a bis (diphenylphosphate), phosphaphenanthrene, tris (1-chloro-2-propyl) phosphate, and the like.
The condensed phosphate ester is not particularly limited, and examples thereof include condensed phosphate esters such as trialkyl polyphosphate, resorcinolphenylpolyphenyl phosphate, resorcinolic poly (di-2, 6-xylyl) phosphate (PX-200 manufactured by Dai chemical industries Co., Ltd.), hydroquinone poly (2, 6-xylyl) phosphate, and condensates thereof. Further, examples of commercially available condensed phosphates include resorcinol polyphenyl phosphate (CR-733S), bisphenol A polytoluene phosphate (CR-741), aromatic condensed phosphate (CR747), resorcinol polyphenyl phosphate (ADK STAB PFR manufactured by ADEKA Co., Ltd.), and bisphenol A polytoluene phosphate (FP-600, FP-700).
Among the above, monophosphoric acid esters are preferably used, and particularly, tris (1-chloro-2-propyl) phosphate is more preferably used in order to make the effect of reducing the viscosity in the composition before curing and the effect of reducing the initial exotherm higher.
The amount of the organic phosphate ester to be used is preferably 30 parts by mass or more relative to 50 parts by mass of the polyol in the composition A, and more preferably 35 parts by mass or more, particularly 40 parts by mass or more, in terms of the total amount of the organic metal phosphinate to be used together with the organic metal phosphinate. The total amount of the metal organophosphinate and the organophosphate needs to be 5 parts by mass or more relative to 50 parts by mass of the polyol, and may be preferably 7 parts by mass or more, more preferably 10 parts by mass or more. If the total amount of the metal organophosphinate and the organic phosphate is too small and the amount of the metal organophosphinate used is too small, it is difficult to sufficiently exhibit the flame retardancy-improving effect due to the synergistic effect of the metal organophosphinate and the organic phosphate. On the other hand, if the amount of the organic phosphinic acid metal salt is too large, the effect of the catalyst for forming the polyurethane foam is lowered, and problems such as inhibition of foaming are caused, so that the upper limit of the total amount of the organic phosphinic acid metal salt and the organic phosphoric acid ester is usually favorably 180 parts by mass or less, preferably 150 parts by mass or less, and more preferably 120 parts by mass or less, relative to 50 parts by mass of the polyol.
Further, in the present invention, in addition to the use of the metal salt of organic phosphinic acid alone or the use of the metal salt of organic phosphinic acid and the organic phosphate in combination as described above, a metal hydroxide can be further compounded as one of the additives and contained in the above-mentioned composition A and/or composition B, whereby the incombustibility of the polyurethane foam can be further improved. Examples of such 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, and the like, and 2 or more of these may be blended singly or in combination in the composition a and/or the composition B. The amount of the metal hydroxide used is preferably about 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass, based on 50 parts by mass of the polyol in the composition A.
In addition to the above-mentioned compounding ingredients or components contained, a foaming agent for foaming the polyurethane to be produced and, if necessary, various conventionally known auxiliary agents such as a known foam stabilizer and further other flame retardants may be appropriately selected and compounded in the composition a or the composition B constituting the foamable composition for a nonflammable polyurethane foam of the present invention.
Further, as the foaming agent used herein, various known non-freon-based or freon-based foaming agents can be appropriately selected, and particularly, in the present invention, a non-freon-based foaming agent (and/or a generation source thereof) can be favorably used, and specifically, an organic foaming agent such as Hydrocarbon (HC), Hydrofluoroolefin (HFO), Hydrochlorofluoroolefin (HCFO), or the like can be contained.
Among the blowing agents usable in the present invention, examples of Hydrofluorocarbons (HFC) as the chlorofluorocarbon blowing agent 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), and 1, 1, 1, 2, 2, 3, 4, 5, 5, 5-decafluoropentane (HFC4310 mee).
On the other hand, as a Hydrocarbon (HC) which is one of the non-freon blowing agents suitably used in the present invention, n-pentane, isopentane, cyclopentane, isobutane and the like are exemplified. Further, as Hydrofluoroolefin (HFO), for example: pentafluoropropene such as 1, 2, 3, 3, 3-pentafluoropropene (HFO1225ye), tetrafluoropropene such as 1, 3, 3, 3-tetrafluoropropene (HFO1234ze), 2, 3, 3, 3-tetrafluoropropene (HFO1234yf), 1, 2, 3, 3-tetrafluoropropene (HFO1234 ye); trifluoropropene such as 3, 3, 3-trifluoropropene (HFO1243 zf); hexafluorobutene isomers (HFO1336) such as tetrafluorobutene (HFO1345), pentafluorobutene isomers (HFO1354), and 1, 1, 1, 4, 4, 4-hexafluoro-2-butene (HFO1336 mzz); heptafluorobutene isomers (HFO1327), heptafluoropentene isomers (HFO 1447), octafluoropentene isomers (HFO1438), nonafluoropentene isomers (HFO1429), and the like. Examples of the Hydrochlorofluoroolefin (HCFO) include 1-chloro-3, 3, 3-trifluoropropene (HCFO-1233zd), 2-chloro-3, 3, 3-trifluoropropene (HCFO-1233xf), and dichlorotrifluoropropene (HCFO 1223). In particular, these Hydrofluoroolefins (HFOs) and Hydrochlorofluoroolefins (HCFO) are chemically unstable and therefore have a low global warming potential, and therefore can be suitably used as environmentally friendly blowing agents. Further, water described later can be advantageously used as a blowing agent in combination with these Hydrofluoroolefin (HFO) or Hydrochlorofluoroolefin (HCFO).
In the present invention, water as a blowing agent may be advantageously used in addition to or in place of the organic blowing agent. When such water is present in the polyol-containing composition a, the water reacts with the polyisocyanate to generate carbon dioxide when the composition a and the polyisocyanate-containing composition B are mixed and reacted, and therefore the carbon dioxide can effectively participate in the polyurethane foam formed by the reaction of the polyol and the polyisocyanate. Further, since the generation of carbon dioxide generates reaction heat, the heat can be utilized to efficiently carry out the urethanization reaction and the isocyanurated reaction, and the compressive strength of the resulting polyurethane foam can be further improved. The amount of water used is generally 0.1 to 5 parts by mass, preferably 0.5 to 3 parts by mass, based on 50 parts by mass of the total polyol in the composition a. If the amount of water used is more than 5 parts by mass, the strength of the polyurethane foam produced is rather lowered. This is due to: the urea bond formed by the reaction of water with the polyisocyanate increases in the resin, and the polyisocyanate used in the isocyanuric acid esterification reaction is consumed by the reaction with water, resulting in a decrease in the polyisocyanate content in the reaction system. If the amount is less than 0.1 part by mass, the effect of the blowing agent due to the use of water cannot be sufficiently obtained.
The foam stabilizer is used to uniformly adjust the cell structure of the polyurethane foam, and a silicone surfactant or a nonionic surfactant can be suitably used. Specific examples thereof include polyoxyalkylene-modified dimethylpolysiloxane, a polysiloxane-oxyalkylene copolymer, a polyoxyethylene sorbitan fatty acid ester, a castor oil ethylene oxide adduct, a lauryl fatty acid ethylene oxide adduct and the like, and 1 of these may be used alone or 2 or more may be used in combination. The amount of the foam stabilizer to be blended is appropriately determined depending on the desired foam characteristics, the type of the foam stabilizer to be used, and the like, but may be selected from the range of 0.1 to 10 parts by mass, preferably 1 to 8 parts by mass, based on 50 parts by mass of the entire polyol in the composition A.
When the composition A containing a polyol and the composition B containing a polyisocyanate obtained as described above are reacted and foamed and cured at least in the presence of a trimerization catalyst, the foamable composition of the present invention can be foamed and cured to produce a polyurethane foam to which a high degree of flame retardancy is imparted as an object by appropriately employing known various polyurethane foam production methods, for example, a laminated continuous foaming method in which a mixture of the composition A and the composition B is applied to a surface material and foamed and cured into a sheet form, an injection foaming method in which the mixture is injected, filled and foamed and cured into a space portion requiring heat insulation such as a refrigerator, into a honeycomb structure of a light and high-strength board, into a void space generated in civil engineering, or a spray foaming method in which the mixture is sprayed from a spray gun head of an in-situ foaming machine onto a predetermined object (structure) and foamed and cured, from which a non-combustible material as specified by the aforementioned building reference act is advantageously formed.
Examples
It is needless to say that the present invention is not limited to the description of the examples, and the features of the present invention will be more specifically clarified by the examples of the present invention shown below by comparing with comparative examples. In addition, in the present invention, in addition to the following examples, it should be understood that: in addition to the specific description above, various alterations, modifications, improvements, and the like can be applied based on the knowledge of those skilled in the art without departing from the spirit of the present invention. Unless otherwise specified, the percentages (%) and parts shown below are percentages and parts on a mass basis.
The density, maximum heat release rate, total heat release amount, state of residue, and coloring property of the polyurethane foam obtained in the following examples and comparative examples were evaluated or measured as follows.
(1) Determination of maximum exothermic Rate and Total exothermic amount
The cone calorimeter test specimens having a size of 100 mm. times.100 mm. times.50 mm were cut from the heat-releasing material to be measured, and the respective specimens were measured for radiant heat intensity of 50kW/m according to the combustion test method specified in ISO-56602Maximum heat release rate and total heat release at 20 minutes of heating. The maximum heat release rate was set to 200kW/m2The following cases and total heat release were 8MJ/m2The following cases were evaluated as passed.
(2) Determination of Density
The dimensions of the cone calorimeter test sample cut out of the foam were measured with a vernier caliper, while the mass thereof was measured with an electronic balance, and the density of the sample (foam) was calculated from the obtained measurement values.
(3) Evaluation of residue State
The test sample obtained after the completion of the test when the burning test according to ISO-5660 was performed was evaluated as "X" when deformation and cracking were observed on the back surface, and as "O" when no deformation was observed on the back surface.
(4) Evaluation of coloring Properties
To the polyol compositions in the examples and comparative examples, 0.016 part by mass of a predetermined coloring dye was added, and a colored foam (foam) was prepared according to the method for producing a polyurethane foam described later. Then, the color tone of the obtained colored foam was compared with the color tone of a colored foam obtained from a polyol composition (comparative example 8) in which a flame retardant was not completely blended, and when there was no difference between the two, the color tone was evaluated as "o", and when a difference was confirmed, the color tone was evaluated as "x".
First, the following raw materials were prepared as components used in the following examples and comparative examples.
Polyol compound (b): phthalic acid polyester polyol (RFK 505, Kawasaki chemical Co., Ltd.)
: mannich polyether polyol (DK polyol 3776 (DK ポリ - ル 3776, Japanese) having a hydroxyl value of 350mgKOH/g and a viscosity of 500 mPas/25 ℃ C.)
Trimerization catalyst: potassium caprylate (Dabco K-15, Evonik JAPAN Co., Ltd.)
: quaternary ammonium salt (Kaoli ZER No.420, product of Kallizer Co., Ltd.)
Resinification catalyst: bismuth octylate (PUCAT 25 manufactured by Nippon chemical industry Co., Ltd.)
Flame retardant: aluminum diethylphosphinate (EXOLIT OP930, EXOLIT OP935, manufactured by Clariant Chemicals Co., Ltd.)
: phosphate ester [ TCPP: phosphoric acid tris (1-chloro-2-propyl) ester ]
: phosphoric acid ester (polyphosphate ADK STAB PFR manufactured by ADEKA corporation)
: red phosphorus (Nova Excel140 available from phosphorus chemical industry Co., Ltd.)
: aluminum hydroxide (B1403, made by Nippon light Metal Co., Ltd., average particle diameter: 2 μm)
Foaming agent: HCFO-1233zd (1-chloro-3, 3, 3-trifluoropropene, manufactured by Honeywell Co., Ltd.)
: HFC365mfc (1, 1, 1, 3, 3-pentafluorobutane available from SOLVAY Co., Ltd.)
: HFC245fa (1, 1, 1, 3, 3-pentafluoropropane, Mitsui Kabushiki Kaisha)
: water (W)
Foam stabilizer: silicone foam stabilizer (SH-193, manufactured by Tooli-Dow Corning Co., Ltd.)
Dye: red dye (ORIENT CHEMICAL INDUSTRIES CO., LTD. manufactured OIL RED RR)
: blue dye (ORIENT CHEMICAL INDUSTRIES CO., LTD. manufactured OIL BIUE 2N)
: green dye (ORIENT CHEMICAL INDUSTRIES CO., LTD. manufactured OIL GREEN 502)
Preparation of the polyol composition (composition A) -
The prepared raw materials, that is, the polyol, the trimerization catalyst, the resinification catalyst, the flame retardant, the blowing agent, the foam stabilizer and the dye were uniformly mixed in various combinations and blending ratios shown in tables 1 to 3 below, to prepare various polyol compositions according to examples 1 to 12 and comparative examples 1 to 8, respectively.
Preparation of the polyisocyanate composition (composition B)
Polymeric MDI (Wannate PM-130, manufactured by Wanhua chemical JAPAN Co., Ltd.) was prepared as a polyisocyanate, and composition B was composed only of this polyisocyanate.
Production of polyurethane foams
After 80 parts of each of the polyol compositions (composition a) obtained above and 120 parts of composition B composed only of polyisocyanate (mass ratio 1: 1.5) were adjusted to a liquid temperature of 20 ℃, they were stored in a 300-part by volume polypropylene container, and the contents of the composition were mixed with each other using a mixer: a TK homomixer (manufactured by PRIMIX Co., Ltd.) was used for mixing for 10 seconds. Then, the mixed liquid was poured into a 2000 parts by volume polypropylene container, and foamed and cured to obtain a target foam.
Then, using the polyurethane foams thus obtained, the density, the maximum heat release rate, the total heat release amount, the state of residue and the coloring property were measured or evaluated, and the results are summarized in tables 1 to 3 below.
[ Table 1]
Figure BDA0003066194600000211
[ Table 2]
Figure BDA0003066194600000221
[ Table 3]
Figure BDA0003066194600000231
As can be seen from the results of table 1 and table 2, it can be confirmed that: just about the original hairAs to the foamable compositions comprising the combination of the polyol composition (composition A) and the polyisocyanate (composition B) used in examples 1 to 12, the total heat release (20 minutes) of 8MJ/m was obtained in the flame test method according to ISO-56602The following polyurethane foam having high flame retardancy can easily obtain a colored foam having a desired color tone by using a predetermined colored dye without changing the color tone by a flame retardant.
On the other hand, as is clear from the results shown in Table 3, in comparative examples 1 and 2 in which the amount of the organic phosphinic acid metal salt used as the flame retardant and the total amount of the organic phosphinic acid metal salt and the organic phosphoric acid ester used were small, the total heat release (20 minutes) became much larger than 8MJ/m2It was confirmed that it was difficult to form a polyurethane foam as a nonflammable material, of course, this was particularly the case of comparative example 8 in which no flame retardant was used. Even when the total amount of the organic phosphinic acid metal salt and the organic phosphoric acid ester is larger than the value defined in the present invention, the effect of improving the flame retardancy is not sufficient in comparative examples 3 and 4 in which the amount of the organic phosphinic acid metal salt is small, and the total amount of heat release (20 minutes) required to satisfy the standard as a nonflammable material is not remarkably satisfied in comparative example 5 in which only the organic phosphoric acid ester is blended as a flame retardant. In addition, in the case of comparative example 6 in which only a resinification catalyst was used without using a trimerization catalyst in forming a polyurethane foam, curing of the foam did not sufficiently proceed, and thus a sample that could be used in the test according to ISO-5660 was not obtained. Further, it is also known that: in the case of comparative example 7 in which red phosphorus was used as a flame retardant and an organic phosphate was used in combination therewith, although the conditions of the total heat release amount (20 minutes) were satisfied, the colored foams obtained by using a blue dye and a green dye in the coloring test could not realize the original blue and green hues, and the degree of freedom of coloring was limited.

Claims (13)

1. A foamable composition for non-combustible polyurethane foam, which comprises a composition A containing a polyol and a composition B containing a polyisocyanate, wherein a polyurethane foam is formed by the reaction of the polyol with the polyisocyanate and foaming with a blowing agent,
in the composition a, at least a trimerization catalyst is contained as a catalyst, and an organic phosphinic acid metal salt is contained in at least either one of the composition a and the composition B in a proportion of 30 parts by mass or more with respect to 50 parts by mass of the polyol.
2. A foamable composition for non-combustible polyurethane foam, which comprises a composition A containing a polyol and a composition B containing a polyisocyanate, wherein a polyurethane foam is formed by the reaction of the polyol with the polyisocyanate and foaming with a blowing agent,
the foaming composition for the non-combustible polyurethane foam comprises the following components: the composition A contains at least a trimerization catalyst as a catalyst, and an organic phosphinic acid metal salt and an organic phosphoric acid ester are contained individually or collectively in at least either one of the composition A and the composition B, and the organic phosphinic acid metal salt and the organic phosphoric acid ester are contained in a ratio of 30 parts by mass or more in total relative to 50 parts by mass of the polyol, and the content of the organic phosphinic acid metal salt is 5 parts by mass or more relative to 50 parts by mass of the polyol.
3. The foamable composition for noncombustible polyurethane foam according to claim 2, wherein the organic phosphate is selected from the group consisting of monophosphates and condensed phosphates.
4. The foamable composition for noncombustible polyurethane foam according to claim 2 or 3, wherein the organic phosphate is tris (1-chloro-2-propyl) phosphate.
5. The foamable composition for noncombustible polyurethane foam according to any one of claims 1 to 4, wherein the metal salt of an organic phosphinic acid is a salt of 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 a metal selected from the group consisting of Mg, Al, Ca, Ti and Zn.
6. The foamable composition for noncombustible polyurethane foam according to any one of claims 1 to 5, wherein a metal hydroxide is further contained in the composition A and/or the composition B.
7. The foamable composition for noncombustible polyurethane foam according to any one of claims 1 to 6, wherein the trimerization catalyst is a quaternary ammonium salt.
8. The foamable composition for noncombustible polyurethane foam according to any one of claims 1 to 6, wherein an alkali metal carboxylate and a quaternary ammonium salt are used in combination as the trimerization catalyst.
9. The foamable composition for noncombustible polyurethane foam according to any one of claims 1 to 8, wherein the polyol is an aromatic polyester polyol.
10. The foamable composition for noncombustible polyurethane foam according to claim 9, wherein the aromatic polyester polyol is a phthalic acid polyester polyol.
11. The foamable composition for noncombustible polyurethane foam according to any one of claims 1 to 10, wherein the blowing agent is an organic blowing agent selected from the group consisting of hydrocarbons, hydrofluoroolefins and hydrochlorofluoroolefins.
12. The foamable composition for noncombustible polyurethane foam according to any one of claims 1 to 11, wherein water is used as the blowing agent in combination with a hydrofluoroolefin or a hydrochlorofluoroolefin.
13. The foamable composition for noncombustible polyurethane foam according to any one of claims 1 to 12, wherein the polyurethane foam has the following noncombustible characteristics: according to the exothermic test method specified in ISO-5660, the radiant heat intensity is 50kW/m2The total heat release during heating within 20 minutes from the start of heating was 8.0MJ/m2The following.
CN201980075408.6A 2018-11-26 2019-03-12 Foamable composition for nonflammable polyurethane foam Active CN113015757B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2018-220175 2018-11-26
JP2018220175 2018-11-26
PCT/JP2019/009967 WO2020110332A1 (en) 2018-11-26 2019-03-12 Expandable composition for non-flammable polyurethane foams

Publications (2)

Publication Number Publication Date
CN113015757A true CN113015757A (en) 2021-06-22
CN113015757B CN113015757B (en) 2023-07-18

Family

ID=70852744

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201980075408.6A Active CN113015757B (en) 2018-11-26 2019-03-12 Foamable composition for nonflammable polyurethane foam

Country Status (3)

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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116285306A (en) * 2023-05-24 2023-06-23 北京宇极科技发展有限公司 Foaming composition, polyurethane foam and preparation method thereof

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7442271B2 (en) * 2019-04-12 2024-03-04 積水化学工業株式会社 Expandable urethane resin composition and polyurethane foam
JPWO2021125237A1 (en) * 2019-12-17 2021-06-24
CN113088210B (en) * 2021-04-25 2022-09-06 东莞澳中新材料科技股份有限公司 Flame-retardant adhesive tape for wrapping lithium ion battery and preparation method thereof
KR102695062B1 (en) * 2021-06-07 2024-08-13 에스케이피유코어 주식회사 Polyurethane foam and preperation method thereof

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0069975A1 (en) * 1981-07-15 1983-01-19 BASF Aktiengesellschaft Process for preparing fire retarding foams containing polymethane and/or polyisocyanurate groups
DE10317487A1 (en) * 2003-04-16 2004-01-22 Ticona Gmbh Fire retardant combination for thermoplastics, e.g. in coating materials, comprises a magnesium, calcium, aluminum or zinc salt of a phosphinic or diphosphinic acid plus another organophosphorus compound
JP2010195920A (en) * 2009-02-25 2010-09-09 Ube Ind Ltd Phenolic hydroxyl group-containing polyurethane
JP2011512449A (en) * 2008-02-21 2011-04-21 ビーエーエスエフ ソシエタス・ヨーロピア Halogen free flame retardant TPU
CN102336888A (en) * 2010-07-16 2012-02-01 Dic株式会社 Heat-curable polyurethane resin composition and urethane elastomer molded article using the same
EP2687534A1 (en) * 2012-07-20 2014-01-22 LANXESS Deutschland GmbH Halogen-free poly(alkylene phosphate)
WO2014038595A1 (en) * 2012-09-04 2014-03-13 Dic株式会社 Halogen-free fire-resistant resin composition and molded body
CN103709432A (en) * 2013-12-18 2014-04-09 南京师范大学 High-flame retardant rigid polyurethane foaming plastic and preparation method thereof
CN103804626A (en) * 2014-01-27 2014-05-21 中国科学技术大学 Halogen-free flame-retardant hard polyurethane foam and preparation method thereof
JP2014196476A (en) * 2013-03-05 2014-10-16 積水化学工業株式会社 Fire-resistant urethane resin composition
WO2016010042A1 (en) * 2014-07-14 2016-01-21 積水化学工業株式会社 Flame-retardant polyurethane resin composition
CN105330818A (en) * 2015-12-01 2016-02-17 中国科学技术大学苏州研究院 Flame retardant rigid polyurethane foam material and preparation method thereof
CN105860504A (en) * 2016-04-27 2016-08-17 安徽广燕新材料科技有限责任公司 Polyurethane thermal-insulation composite board
CN106255717A (en) * 2014-02-26 2016-12-21 巴斯夫欧洲公司 Flame-proof thermoplastic polyurethane

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5733008B2 (en) * 2011-05-10 2015-06-10 Dic株式会社 Flame retardant thermosetting polyurethane resin composition and urethane elastomer molded article molded using the same
BR112013033460A2 (en) 2011-06-28 2017-03-14 Dow Global Technologies Llc reactive formulation for making a sprayable elastomeric polyurethane coating and process for coating a surface of a substrate
EP2760928B1 (en) 2011-09-29 2018-12-26 Dow Global Technologies LLC Use of trialkyl phosphate as a smoke suppressant in polyurethane foam
JP6730003B2 (en) 2014-03-27 2020-07-29 積水化学工業株式会社 Flame-retardant urethane resin composition

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0069975A1 (en) * 1981-07-15 1983-01-19 BASF Aktiengesellschaft Process for preparing fire retarding foams containing polymethane and/or polyisocyanurate groups
DE10317487A1 (en) * 2003-04-16 2004-01-22 Ticona Gmbh Fire retardant combination for thermoplastics, e.g. in coating materials, comprises a magnesium, calcium, aluminum or zinc salt of a phosphinic or diphosphinic acid plus another organophosphorus compound
JP2011512449A (en) * 2008-02-21 2011-04-21 ビーエーエスエフ ソシエタス・ヨーロピア Halogen free flame retardant TPU
JP2010195920A (en) * 2009-02-25 2010-09-09 Ube Ind Ltd Phenolic hydroxyl group-containing polyurethane
CN102336888A (en) * 2010-07-16 2012-02-01 Dic株式会社 Heat-curable polyurethane resin composition and urethane elastomer molded article using the same
EP2687534A1 (en) * 2012-07-20 2014-01-22 LANXESS Deutschland GmbH Halogen-free poly(alkylene phosphate)
WO2014038595A1 (en) * 2012-09-04 2014-03-13 Dic株式会社 Halogen-free fire-resistant resin composition and molded body
JP2014196476A (en) * 2013-03-05 2014-10-16 積水化学工業株式会社 Fire-resistant urethane resin composition
CN103709432A (en) * 2013-12-18 2014-04-09 南京师范大学 High-flame retardant rigid polyurethane foaming plastic and preparation method thereof
CN103804626A (en) * 2014-01-27 2014-05-21 中国科学技术大学 Halogen-free flame-retardant hard polyurethane foam and preparation method thereof
CN106255717A (en) * 2014-02-26 2016-12-21 巴斯夫欧洲公司 Flame-proof thermoplastic polyurethane
WO2016010042A1 (en) * 2014-07-14 2016-01-21 積水化学工業株式会社 Flame-retardant polyurethane resin composition
CN105330818A (en) * 2015-12-01 2016-02-17 中国科学技术大学苏州研究院 Flame retardant rigid polyurethane foam material and preparation method thereof
CN105860504A (en) * 2016-04-27 2016-08-17 安徽广燕新材料科技有限责任公司 Polyurethane thermal-insulation composite board

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
（德）厄特尔（OERTEL，GUNTER）编著；阎家宾等译校: "《聚氨酯手册》", 30 September 1992, 中国石化出版社 *
卞军 等: "《聚合物共混改性基础》", 31 January 2018, 西南交通大学出版社 *
韩喜林: "《聚氨酯硬泡节能建筑保温系统应用技术》", 31 May 2010, 中国建材工业出版社 *
黄发荣 等: "《高分子材料的循环利用》", 31 January 2000, 化学工业出版社 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116285306A (en) * 2023-05-24 2023-06-23 北京宇极科技发展有限公司 Foaming composition, polyurethane foam and preparation method thereof
CN116285306B (en) * 2023-05-24 2023-08-18 北京宇极科技发展有限公司 Foaming composition, polyurethane foam and preparation method thereof

Also Published As

Publication number Publication date
WO2020110332A1 (en) 2020-06-04
KR20210095852A (en) 2021-08-03
CN113015757B (en) 2023-07-18

Similar Documents

Publication Publication Date Title
JP6626590B2 (en) Flame retardant urethane resin composition
CN113015757B (en) Foamable composition for nonflammable polyurethane foam
EP3112388B1 (en) In-situ foaming system for forming flame-retardant polyurethane foam in situ
JP6725606B2 (en) Urethane resin composition and method for heat insulation of building
JP7034020B2 (en) Effervescent composition for flame-retardant polyurethane foam
JP6978396B2 (en) Polyurethane foam manufacturing method
US20220073691A1 (en) Flame retardant composition for polyurethane foam and flame-retarded polyurethane foam containing the same
JP2021130801A (en) Flame retardant composition for polyurethane foam, and flame-retardant polyurethane foam having the same mixed therein
JP6621571B1 (en) Foamable composition for nonflammable polyurethane foam
JP2020128459A (en) Method for producing polyurethane foam
JP6987803B2 (en) Polyurethane foam manufacturing method
JP7233400B2 (en) Raw material for urethane resin composition and method for insulating buildings
JP7305504B2 (en) Foaming composition for non-combustible polyurethane foam
JP7263495B2 (en) Method for manufacturing polyurethane foam
JP6978397B2 (en) Polyurethane foam manufacturing method
JP7263496B2 (en) Method for manufacturing polyurethane foam
JP6987732B2 (en) Polyurethane foam manufacturing method
WO2021255958A1 (en) Foam composition for flame-retardant polyisocyanurate foam and method for producing flame-retardant polyisocyanurate foam using said foam
JP2024146096A (en) Polyol composition, polyurethane foam composition and foam
JP2024146097A (en) Polyol composition, polyurethane foam composition and foam
JP2024146593A (en) Polyol composition, foamable urethane resin composition, and polyurethane foam
JP2022155368A (en) Composition for flame-retardant foam

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant