CN113015757B - Foamable composition for nonflammable polyurethane foam - Google Patents

Foamable composition for nonflammable polyurethane foam Download PDF

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CN113015757B
CN113015757B CN201980075408.6A CN201980075408A CN113015757B CN 113015757 B CN113015757 B CN 113015757B CN 201980075408 A CN201980075408 A CN 201980075408A CN 113015757 B CN113015757 B CN 113015757B
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phosphinate
polyurethane foam
polyol
organic
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CN113015757A (en
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关浩之
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Asahi Yukizai Corp
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Asahi Yukizai Corp
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
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    • 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
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • 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
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    • 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
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    • 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
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    • 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
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    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
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    • C08J2203/00—Foams characterized by the expanding agent
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  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Provided is a foamable composition which can advantageously form a nonflammable polyurethane foam having synergistically improved flame retardancy, and which can advantageously form a nonflammable polyurethane foam having improved coloring freedom without impairing the color of a polyurethane resin itself. The polyurethane foam foamable composition containing the polyol-containing composition a, the polyisocyanate-containing composition B and the blowing agent contains at least a trimerization catalyst as a catalyst, and the metal organic phosphinate is contained in at least any 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

Foamable composition for nonflammable polyurethane foam
Technical Field
The present invention relates to a foamable composition for nonflammable polyurethane foam, and more particularly, to a foamable composition for forming polyurethane foam which favorably satisfies nonflammable characteristics prescribed in the japanese building standards method.
Background
Conventionally, polyurethane foam has been used mainly as a heat insulating material for heat insulation of inner and outer wall materials for construction, panels, etc., heat insulation of metal wall boards, refrigerators, etc., heat insulation of body wall surfaces of Gao Lou apartment houses, freezer houses, etc., heat insulation of ceilings, roofs, etc., condensation prevention, heat insulation of transfusion pipes, etc., and has been put to practical use as a back filling material for filling gaps generated in civil engineering, a reinforcing material in civil engineering, etc., by utilizing its excellent heat insulating properties, adhesiveness, light weight, etc. Such polyurethane foam is generally produced by continuously or intermittently mixing a composition a (formed of a polyol blend (premix) in which a foaming agent and, if necessary, various auxiliaries such as a catalyst, a foam stabilizer, and a flame retardant are blended with a composition B mainly containing a polyisocyanate) by a mixing device to prepare a foamable composition for polyurethane foam, and foaming and curing the foamable composition by a plate foaming method (slab foaming process), an injection foaming method, a spray foaming method, a laminated continuous foaming method, a lightweight soil filling method, an injection back burying method, or the like.
However, since flame retardancy is required for the polyurethane foam formed as described above in terms of its use, a foamable composition for flame-retardant polyurethane foam is proposed, which is prepared by blending various flame retardants, and for example, in japanese patent application laid-open No. 2014-524954 (patent document 1), it is proposed that a reactive complex comprising a polyisocyanate component (the polyisocyanate component comprising an isocyanate prepolymer and an optional flame retardant compound) and a polyol component (the polyol component comprising an aromatic polyester polyol, red phosphorus, a catalyst, and a further flame retardant) is used as a reactive complex for producing a sprayable elastic polyurethane coating material having improved flame retardant properties, and it is thereby clarified that an elastic polyurethane coating material having improved flame retardant properties can be formed. Among them, examples of the flame retardant additive that 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 polyurethane foam, and thus, when combustion occurs, smoke generation is significantly reduced, that is, it is clear that polyurethane foam having improved smoke suppressing characteristics can be obtained. Moreover, the following are also specified therein: for forming the polyurethane foam, urethane catalysts and isocyanate trimerization catalysts (Japanese: three-component catalysts) may be used, and metal-based inorganic fillers for easy processability, for example, zinc salts such as metal hydrate, zinc borate and zinc stannate, may be contained.
Further, japanese patent application laid-open No. 2015-193839 (patent document 3) discloses a flame-retardant polyurethane resin composition which is obtained by blending a polyol compound, a polyisocyanate compound, a trimerization catalyst, a foaming agent and a foam stabilizer, and further blending a predetermined amount of red phosphorus as one of additives, and it has been revealed that a flame-retardant polyurethane resin composition which can exhibit excellent flame retardancy and excellent handleability by adding a small amount of flame retardant (red phosphorus) can be provided. Further, it is clear that a metal hydroxide, an inorganic compound containing crystal water, a clay mineral, and other moisture releasing substances must be blended as one of the additives, and a flame retardant containing phosphate or phosphate, a flame retardant containing bromine, and the like can be blended.
However, in these patent documents, the flame retardant properties of the flame retardant polyurethane coating and the polyurethane foam having improved smoke suppression performance obtained in patent document 1 and patent document 2 are not sufficient to meet the recent strict flame retardant requirements. For example, the flame retardant polyurethane coating obtained in patent document 1 has only clarified the characteristics related to the coating layer having elasticity, and is not sufficient to satisfy the strict flame retardant characteristics required for polyurethane foam (foam), and even the polyurethane foam disclosed in patent document 2 is only aimed at improving the smoke suppressing performance, and is not sufficient to cope with the requirements related to the stricter flame retardant performance.
Further, although the red phosphorus used in patent documents 1 and 3 is an excellent flame retardant, if the amount of the red phosphorus used is increased in order to improve the flame retardancy of the polyurethane foam to be formed, there is a problem that the foam is easily burned, and there is a risk of the red phosphorus itself igniting, 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 operability is poor when the polyurethane foam is used. Further, since red phosphorus is a reddish color as its name implies, there is a problem that it is difficult to reflect the color of a target colorant when the resin (foam) as a whole is colored red by the color tone inherent to red phosphorus and the colorant is colored, and therefore, there is a demand to avoid the use of red phosphorus as much as possible.
However, in the japanese building standard method, flame resistance and fire resistance of materials are classified into flame retardant materials, quasi-non-combustible materials and non-combustible materials, and more stringent fire resistance is required from the flame retardant materials to the quasi-non-combustible materials and to the non-combustible materials, and in order to impart high flame retardancy to a foam material (the foam material is formed of a polyurethane foam obtained by reacting a polyol with a polyisocyanate and foaming), it is difficult to satisfy the non-combustible performance of the non-combustible material requiring the most stringent fire resistance when the conventional flame retardant as disclosed in the above publication is used. In particular, if the required properties for the nonflammable material specified in the building standard method are obtained, namely, the radiation heat intensity: 50kW/m 2 The total heat release amount during heating within 20 minutes from the start of heating was 8.0MJ/m 2 The following problems arise when the amount of the known flame retardant to be blended is increased in the foamable composition for polyurethane foam due to the following non-combustibility: the reaction of the polyol and the polyisocyanate is hindered and the target foam is not obtained, or the physical or mechanical properties of the obtained foam are deteriorated and the color tone of the foam is limited.
In accordance with the above-mentioned specification of the building standard (execution ofLet clause 1, fifth) the incombustible material should satisfy the total heat release amount described above, and the highest heat release rate should not continuously exceed 200kW/m for more than 10 seconds 2 Further, the polyurethane foam material should not have cracks and holes penetrating to the back surface, which are harmful in terms of fire resistance, but the polyurethane foam material obtained by compounding the conventional flame retardant cannot secure physical or mechanical properties useful as a polyurethane resin and cannot sufficiently cope with such a requirement for incombustibility.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2014-524954
Patent document 2: japanese patent application laid-open No. 2014-532098
Patent document 3: japanese patent application laid-open No. 2015-193839
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 thereof is to provide a foamable composition that can advantageously form a nonflammable polyurethane foam having improved flame retardancy in cooperation with the polyurethane resin, and to provide a foamable composition that can advantageously form a nonflammable polyurethane foam having improved coloring freedom without impairing the color of the polyurethane resin itself.
Means for solving the problems
The present invention is also applicable to various embodiments as described below in order to solve the above-described problems. The aspects and technical features of the present invention are not limited to the following description, but should be understood to be recognized based on the inventive concept that can be understood from the description of the specification.
(1) A foamable composition for nonflammable polyurethane foam, characterized in that it comprises a composition A containing a polyol and a composition B containing a polyisocyanate, and a polyurethane foam is formed by the reaction of the polyol with the polyisocyanate and foaming by a foaming agent,
in the composition a, at least a trimerization catalyst is contained as a catalyst, and the metal organic phosphinate is contained in at least any 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 nonflammable polyurethane foam, characterized in that it comprises a composition A containing a polyol and a composition B containing a polyisocyanate, and a polyurethane foam is formed by the reaction of the polyol with the polyisocyanate and foaming by a foaming agent,
the foamable composition for nonflammable polyurethane foam is composed of: the composition a contains at least a trimerization catalyst as a catalyst, and the organic phosphinate 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 phosphinate metal salt and the organic phosphate are contained in a proportion of 30 parts by mass or more in total with respect to 50 parts by mass of the polyol, and the content of the organic phosphinate metal salt is 5 parts by mass or more with respect to 50 parts by mass of the polyol.
(3) The foamable composition for nonflammable polyurethane foam according to the above-mentioned aspect (2), wherein said organic phosphate is selected from the group consisting of monophosphate and condensed phosphate.
(4) The foamable composition for nonflammable polyurethane foam according to the above-mentioned item (2) or the above-mentioned item (3), wherein said organic phosphoric acid ester is tris (1-chloro-2-propyl) phosphate.
(5) The foamable composition for nonflammable polyurethane foam according to any one of the above-mentioned (1) to (4), wherein said metal salt of organic phosphinic acid is a salt of organic phosphinic acid having a structure in which methyl group, ethyl group or phenyl group is bonded to phosphorus atom and a metal selected from the group consisting of Mg, al, ca, ti and Zn.
(6) The foamable composition for nonflammable polyurethane foam according to any one of the above-mentioned (1) to the above-mentioned (5), wherein said composition A and/or said composition B further comprises a metal hydroxide.
(7) The foamable composition for nonflammable polyurethane foam according to any one of the above (1) to the above (6), wherein said trimerization catalyst is a quaternary ammonium salt.
(8) The foamable composition for nonflammable polyurethane foam according to any one of the above-mentioned (1) to the above-mentioned (6), wherein an alkali metal salt of a carboxylic acid and a quaternary ammonium salt are used in combination as the trimerization catalyst.
(9) The foamable composition for nonflammable polyurethane foam according to any one of the above (1) to (8), wherein said polyol is an aromatic polyester polyol.
(10) The foamable composition for nonflammable polyurethane foam according to the above-mentioned aspect (9), wherein said aromatic polyester polyol is a phthalic acid polyester polyol.
(11) The foamable composition for nonflammable polyurethane foam according to any of the above (1) to (10), wherein said foaming agent is an organic foaming agent selected from the group consisting of hydrocarbon, hydrofluoroolefin and hydrochlorofluoroolefin.
(12) The foamable composition for nonflammable polyurethane foam according to any of the above-mentioned (1) to (11), wherein water is used as said blowing agent together with a hydrofluoroolefin or hydrochlorofluoroolefin.
(13) The foamable composition for nonflammable polyurethane foam according to any one of the above-mentioned (1) to the above-mentioned (12), wherein the above-mentioned polyurethane foam has the following nonflammable characteristics: according to the exothermic test method specified in ISO-5660, the heat strength of radiation was 50kW/m 2 The total heat release amount during heating within 20 minutes from the start of heating was 8.0MJ/m 2 The following is given.
Effects of the invention
As described above, in the foamable composition for a nonflammable 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 is used alone or an organic phosphinate metal salt and an organic phosphate ester are used as a flame retardant, and are added in a prescribed ratio to be contained in at least any one of the composition a containing a polyol and the composition B containing a polyisocyanate, so that the synergistic flame retarding effect by the organic phosphinate metal salt or both the organic phosphinate metal salt and the organic phosphate ester in the presence of an isocyanurate structure introduced by the trimerization catalyst can be effectively exhibited, whereby the flame retardancy of the resulting polyurethane foam can be further improved, and a target nonflammable property can be advantageously imparted.
In particular, in the polyurethane foam formed from the foamable composition according to the present invention, the amount of heat released upon combustion can be effectively reduced, and combustion is not continued even when a fire is generated, and a high carbon residue can be imparted, whereby a polyurethane foam which is extremely difficult to burn and has improved self-extinguishing properties can be advantageously provided.
Further, since red phosphorus is not used as a flame retardant in the foamable composition for a nonflammable polyurethane foam of the present invention, the color tone of a polyurethane foam formed from such a foamable composition can be completely prevented from being affected by the reddish color inherent to red phosphorus, and the metal salt of organic phosphinic acid or organic phosphate used does not affect the color tone of the formed polyurethane foam at all, so that the formed polyurethane foam can be colored favorably to a desired color tone by a colorant, and thus the degree of freedom in coloring of the polyurethane foam can be effectively improved.
Detailed Description
The foamable composition for nonflammable polyurethane foam of the present invention will be described in detail below, and the specific constitution thereof will be more clearly understood.
First, the foamable composition for a nonflammable polyurethane foam of the present invention comprises a composition a containing a polyol as a main component and a composition B containing a polyisocyanate as a main component, 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 known polyol compounds which react with a polyisocyanate to form polyurethane can be used alone or in combination as appropriate for the polyol which is the main component constituting the composition a used herein. Further, polyether polyols, polyester polyols, and the like are suitably used herein as the polyol. Of course, it goes without saying that various known polyol compounds, for example, polyolefin-based polyols, acrylic polyols, polymer polyols, etc., may be used alone or in appropriate combination in addition to the above-mentioned polyols.
Specifically, in such polyols, the polyether polyol is obtained by reacting an alkylene oxide (alkylene oxide) with at least 1 initiator such as a polyol, a saccharide, an aliphatic amine, an aromatic amine, phenols, and a mannich condensate (mannich condensate). Here, examples of the alkylene oxide include propylene oxide, 1, 2-butylene oxide, 2, 3-butylene oxide, and ethylene oxide. Further, the polyhydric alcohol used as the initiator includes ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, and the like, the saccharide includes sucrose, glucose (dextrose), sorbitol, and the like, the aliphatic amine includes alkanolamines such as diethanolamine, triethanolamine, and the like, polyamines such as ethylenediamine, and the like, the aromatic amine includes various methyl substituents of phenylenediamine generally called tolylenediamine (tolylenediamine), derivatives of which substituents such as methyl, ethyl, acetyl, benzoyl are introduced into the amino group thereof, 4' -diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalene diamine, and the like, and the phenol is bisphenol A, novolac type phenol resin, and the like. The mannich condensate may be obtained by subjecting phenols, aldehydes, and alkanolammonium to a mannich condensation reaction.
Examples of the polyester polyol include polyol based on polyol-polycarboxylic acid condensation system, and polyol based on cyclic ester ring-opening polymer. The above-mentioned polyhydric alcohol can be used as the polyhydric alcohol, and a dihydric alcohol 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, anhydrides thereof, and the like, and as the cyclic ester, epsilon-caprolactone and the like can be used.
Among them, from the viewpoint of flame retardancy and compatibility, aromatic polyester polyols are preferably used, and specifically, phthalic acid polyester polyols are preferably used, and it is also effective to further combine 2 or more of such polyester polyols. The phthalic acid-based polyester polyol is preferably a phthalic acid-based polyester polyol formed from a condensate of phthalic acid, terephthalic acid, isophthalic acid, anhydrides thereof, and the like, with a glycol such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and the like. If such a phthalic acid-based polyester polyol is used, the following advantages are obtained: even when in-situ foaming is carried out at a low temperature (-10 ℃ to 5 ℃), the foam produced is less likely to peel from the building body or the like, and a rigid polyurethane foam having flexibility such that handling of the foam ends after in-situ foaming is easy can be obtained. In particular, when a hydrofluoroolefin-based foaming agent or a hydrochlorofluoroolefin-based foaming agent is contained, a composition excellent in storage stability can be provided.
On the other hand, the polyisocyanate in the composition B is a compound which is compounded with the composition a and reacts with the polyol in the composition a to form 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, 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 terminal, isocyanurate modified polyisocyanates, carbodiimide modified polyisocyanates, and the like. These polyisocyanate compounds may be used alone or in combination of 2 or more. In general, polymethylene polyphenylene polyisocyanate (polymerization MDI (polymeric MDI)) is suitably used from the viewpoints of reactivity, economy, handleability, 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 and polyisocyanurate), and is generally determined so that the NCO/OH index (equivalent ratio) representing the ratio of the isocyanate groups (NCO) of the polyisocyanate to the hydroxyl groups (OH) of the polyol is in the range of about 0.9 to 2.5.
In the present invention, the composition a and the composition B are mixed and reacted in the presence of a catalyst as described above, and foamed and cured by a foaming agent to form a rigid polyurethane foam, and as the catalyst used herein, at least the composition a contains a trimerization catalyst, in other words, a catalyst (isocyanurate catalyst) that promotes formation of isocyanurate rings by reacting and trimerizing isocyanate groups of a polyisocyanate. As the trimerization catalyst, various known trimerization catalysts can be appropriately selected and used, but preferable examples include: alkali metal salts of carboxylic acids such as quaternary ammonium salts, potassium octoate, potassium 2-ethylhexanoate, and sodium acetate; nitrogen-containing aromatic compounds such as tris (dimethylaminomethyl) phenol, 2, 4-bis (dimethylaminomethyl) phenol, tris (dimethylaminopropyl) hexahydrotriazine; tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt and triphenylammonium salt. Among them, from the viewpoint of improving flame retardancy, a quaternary ammonium salt is preferably used, and from the viewpoint of further improving flame retardancy, a quaternary ammonium salt and an alkali metal carboxylate salt are particularly preferably used in combination.
Examples of the quaternary ammonium group (1-valent cation having 4 organic groups covalently bonded to a nitrogen atom) in the quaternary ammonium salt that is advantageously used herein include: aliphatic ammonium groups such as tetramethylammonium, methyltriethylammonium, ethyltrimethylammonium, propyltrimethylammonium, butyltrimethylammonium, pentylmethylammonium, hexyltrimethylammonium, heptyltrimethylammonium, octyltrimethylammonium, nonyltrimethylammonium, decyltrimethylammonium, undecyltrimethylammonium, dodecyltrimethylammonium, tridecyltrimethylammonium, tetradecyltrimethylammonium, heptadecyltrimethylammonium, hexadecyltrimethylammonium, heptadecyltrimethylammonium, octadecyltrimethylammonium and the like; hydroxylammonium groups such as (2-hydroxypropyl) trimethylammonium, hydroxyethyl trimethylammonium, trimethylaminoethoxyethanol, and hydroxyethyl-2-hydroxypropyl dimethylammonium; alicyclic ammonium groups such as 1-methyl-1-azocation-4-azabicyclo [2, 2] octanium (1-in Japanese) can be used as a base for 1-in Japanese-1-in-two-in-one, 2-in-two-in-one, ) and 1, 1-dimethyl-4-methylpiperidinium, 1-methylmorpholinium, and 1-methylpiperidinium. Among them, quaternary ammonium groups such as tetramethyl ammonium, methyltriethyl ammonium, ethyltrimethyl ammonium, butyltrimethyl ammonium, hexyltrimethyl ammonium, octyltrimethyl ammonium, decyltrimethyl ammonium, dodecyltrimethyl ammonium, tetradecyltrimethyl ammonium, hexadecyltrimethyl ammonium, octadecyl trimethyl ammonium, (2-hydroxypropyl) trimethyl ammonium, hydroxyethyl-2-hydroxypropyl dimethyl ammonium, 1-methyl-1-1-azocation-4-azabicyclo [2, 2] octane onium and 1, 1-dimethyl-4-methylpiperidinium are preferable from the viewpoint of making the catalyst excellent in activity and industrially available.
As the organic acid group or inorganic acid group which is a 1-valent anion which is bonded to the quaternary ammonium group to form the quaternary ammonium salt as described above, for example: organic acid groups such as formate group, acetate group, octanoate group, oxalate group, malonate group, succinate group, glutarate group, adipate group, benzoate group, toluate group, ethylbenzoate group, methylcarbonate group, phenol group, alkylbenzenesulfonate group, toluenesulfonate group, benzenesulfonate group, and phosphate group; inorganic acid groups such as halogen groups, hydroxyl groups, hydrogen carbonate groups, and carbonate groups. Among them, from the viewpoint of excellent catalyst activity and industrially available, a formate group, an acetate group, a octanoate group, a methylcarbonate group, a halogen group, a hydroxyl group, a hydrogencarbonate group and a carbonate group are preferably used.
As a catalyst comprising the quaternary ammonium salt having the above-described constitution, various commercial products are commercially available, and examples thereof include U-CAT 18X, U-CAT 2313 (manufactured by San-Apro Co., ltd.), KAOLIZER No.410, KAOLIZER No.420 (manufactured by Kao Co., ltd.), and the like.
In this way, the amount of the trimerization catalyst used as one of the catalysts may be selected in the range of 0.1 to 8 parts by mass, preferably 1 to 6 parts by mass, relative to 50 parts by mass of the entire polyol in the composition a, in order to effectively perform the function as the catalyst. If the amount of the trimerization catalyst is less than 0.1 part by mass, the trimerization of the polyisocyanate is not sufficiently achieved, and thus the flame retardancy improving effect is difficult to sufficiently achieve, while if it is more than 8 parts by mass, the reaction excessively proceeds to accelerate the curing, and thus the spray application is difficult.
In the present invention, a urethane catalyst which is a resin catalyst can be used in combination with the trimerization catalyst. Examples of the urethanization catalyst include known catalysts such as dibutyltin dilaurate, bismuth octoate, (2-ethylhexyl bismuth), bismuth neodecanoate, bismuth neododecanoate, bismuth salts of fatty acids such as bismuth naphthenate, and lead naphthenate.
The amount of the resinifying catalyst used may be selected in 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. If the amount of the resin catalyst used is less than 0.1 part by mass, there is a problem that the obtained foam is sticky and dust or the like adheres to the foam, and the appearance is poor, and if it exceeds 5 parts by mass, there is a problem that the workability is poor because the foam adhering to the floor or the like is sticky in the spray foaming operation, and if it exceeds 5 parts by mass, the heat is released during the resin reaction, the appearance is abnormal such as yellowing of the foam, and there is a risk that the working environment at the working site where the spray application is performed is deteriorated due to the catalyst containing quaternary ammonium salt contained in the foam generated during the foaming.
Further, in addition to the above-described trimerization catalyst and resinification catalyst, a known catalyst conventionally used in the production of polyurethane foam may be appropriately selected as required, and contained in the composition a mainly containing a polyol. For example, the amine-based catalyst can advantageously improve the initial foamability of polyurethane, can reduce the foam density as a whole without changing the density difference between the skin layer and the core layer, can improve the tackiness of foam, can advantageously prevent deterioration of appearance due to adhesion of dust or the like, and can improve the handleability deterioration due to tackiness of a spray attached to a floor or the like in a spray foaming method. Further, as such an amine-based catalyst, a reactive amine compound having an OH group or an NH group in the chemical structure and a cyclic amine compound having a cyclic structure are recommended, and the use of the reactive amine compound as a catalyst can further reduce odor.
The reactive amine compound and the cyclic amine compound used as the amine-based catalyst may 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, 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-diamino-N-methyldipropylamine, N-methyl-N' -hydroxyethylpiperazine, and the like. Examples of the cyclic amine compound include triethylenediamine, N ' -dimethylcyclohexylamine, N-dicyclohexylmethylamine, methylenebis (dimethylcyclohexyl) amine, and N, N-dimethylbenzylamine, morpholine, N-methylmorpholine, N-ethylmorpholine, N- (2-dimethylaminoethyl) morpholine, 4' -oxydiethylenediphorpholine, N ' -diethylpiperazine, N ' -dimethylpiperazine, N-methyl-N ' -dimethylaminoethylpiperazine, 1, 8-diazabicyclo (5, 4, 0) -undecene-7, and the like.
The amount of the amine-based catalyst used as one of the catalysts may be selected in 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 reduce problems such as odor and deterioration of the working environment. If the amount of the amine-based catalyst used is less than 0.1 part by mass, it is difficult to sufficiently exert the function as a catalyst, and there are problems such as tackiness of the obtained foam, adhesion of dust and the like, deterioration in appearance and the like, and in addition, in the spray foaming operation, the adhesion of droplets adhering to floors and the like causes problems such as deterioration in workability. If the amount of the amine-based catalyst used is more than 7 parts by mass, the odor of the polyurethane foam obtained becomes remarkable, and the amine-based catalyst volatilized during foaming causes a problem of deterioration of the working environment of the spraying operation. Therefore, the amine-based catalyst is preferably used in a small amount from the viewpoint of odor.
In the present invention, at least one of the above-mentioned trimerization catalysts is contained in the composition a as a catalyst, and the polyol in the composition a and the polyisocyanate in the composition B are reacted to form polyurethane, and the metal salt of an organic phosphinic acid is used as a flame retardant and is contained in at least either of the composition a and the composition B, whereby the flame retardancy of the polyurethane foam to be formed can be synergistically improved, whereby a polyurethane foam having high flame retardancy can be advantageously provided.
The metal salt of an organic phosphinic acid used herein is a compound having a salt form in which a known metal is ionically bonded to an organic phosphinic acid (the structure of which is that 1 or 2 of 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 the phosphinic acid), and in general, it is preferable that a methyl group, an ethyl group or a phenyl group is bonded to a phosphorus atom, and further, as a metal, mg, al, ca, ti or Zn is preferable, and Al or Zn is particularly preferable. Specifically, 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, aluminum (mono or di) phenylphosphinate, and the like can be cited. These metal phosphinates are generally colorless or white powders and can therefore be used advantageously without any impediment to the colorability of the polyurethane foam.
Such an organic phosphinate needs to be used in a proportion of 30 parts by mass or more, and is preferably used in a proportion of 35 parts by mass or more, more preferably 40 parts by mass or more, relative to 50 parts by mass of the polyol in the composition a. This is due to: if the amount of the metal organic phosphinate used is too small, it is difficult to sufficiently exert the synergistic effect of flame retardancy. Further, if the amount of the organic phosphinate is too large, the viscosity of the composition containing the organic phosphinate increases, which causes problems such as stirring failure and also causes problems such as a decrease in operability, and therefore, in general, the upper limit of the amount of the organic phosphinate is usually 100 parts by mass or less, preferably 75 parts by mass or less, and more preferably 50 parts by mass or less, relative to 50 parts by mass of the polyol.
In addition, in the present invention, it is desirable that: the organic phosphate is used in combination with the above-mentioned metal salts of organic phosphinic acid, and they are allowed to be present in the foamable composition of the invention. Thus, the flame retardancy of the polyurethane foam formed from such a foamable composition can be further advantageously improved, and a nonflammable polyurethane foam satisfying the nonflammable materials specified in the aforementioned building standard can be advantageously formed. Moreover, these metal salts of organic phosphinic acid and organic phosphate esters may be contained in at least any one of the aforementioned composition a and composition B, separately or together.
The organic phosphate used herein is not particularly limited, and known organic phosphates such as monophosphate and condensed phosphate may be used alone or in combination. The organic phosphate can effectively reduce the viscosity of the chemical solution (composition a and/or composition B), and can also function as a viscosity reducing agent that can improve the handling properties such as spraying.
Specifically, among these organic phosphoric acid esters, as the monophosphate ester, there are exemplified, but not particularly limited to, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, tris (butoxyethyl) phosphate, triphenyl phosphate, tricresyl phosphate, tri (isopropylphenyl) phosphate, tricresyl phosphate, trinaphthyl phosphate, tolyldiphenyl phosphate, xylyldiphenyl 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, melamine phosphate, di (melamine) phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methane phosphonate, diethyl phenyl phosphonate, resorcinol bis (diphenyl phosphate), bisphenol A), bisphenol-bisphenol A, bisphenol-3-phenylphosphine phosphate, and the like.
Examples of the condensed phosphoric acid ester include, but are not particularly limited to, a trialkyl polyphosphate, a resorcinol polyphenyl phosphoric acid ester, a resorcinol poly (di-2, 6-xylyl) phosphoric acid ester (PX-200 manufactured by daba chemical industries, ltd.), a hydroquinone poly (2, 6-xylyl) phosphoric acid ester, and a condensed phosphoric acid ester of these. Further, examples of commercially available condensed phosphates include resorcinol polyphenyl phosphate (CR-733S), bisphenol A polytolyl phosphate (CR-741), aromatic condensed phosphate (CR 747), resorcinol polyphenyl phosphate (ADK STAB PFR manufactured by ADEKA, co., ltd.), bisphenol A polytolyl phosphate (FP-600, FP-700), and the like.
Among the above, in order to make the effect of reducing the viscosity in the composition before curing and the effect of reducing the initial exotherm high, it is preferable to use a monophosphate ester, and in particular, it is more preferable to use tris (1-chloro-2-propyl) phosphate.
Further, as the amount of the organic phosphate, a ratio of 30 parts by mass or more to 50 parts by mass of the polyol in the composition a is required as the total amount of the organic phosphinate and the organic phosphinate used simultaneously, and among these, a ratio of 35 parts by mass or more, more preferably 40 parts by mass or more is desirable. The total amount of the metal organophosphate and the organic phosphate is required 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 these metal salts of organic phosphinic acid and organic phosphate is too small and the amount of metal salts of organic phosphinic acid to be used is too small, it is difficult to sufficiently exhibit the flame retardancy-improving effect due to the synergistic effect of these metal salts of organic phosphinic acid and organic phosphate. On the other hand, if the amount of these is too large, the effect of the catalyst for forming a polyurethane foam will be reduced, and problems such as inhibition of foaming will arise, so that as the upper limit of the total amount of these metal salts of organic phosphinic acid and organic phosphate, a proportion of 180 parts by mass or less, preferably 150 parts by mass or less, more preferably 120 parts by mass or less, relative to 50 parts by mass of polyol, is usually advantageously employed.
In the present invention, in addition to the metal organic phosphinate alone or in combination with the metal organic phosphinate and the organic phosphate, the metal hydroxide may be further blended as one of the additives and contained in the composition a and/or the composition B, as described above, 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, and tin hydroxide, and 2 or more of these may be blended into the composition a and/or the composition B, singly or in combination. The amount of the metal hydroxide to be used is preferably about 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, based on 50 parts by mass of the polyol in the composition a.
In addition, in addition to the above-mentioned compounding ingredients or components, a foaming agent for foaming the produced polyurethane is compounded in the composition a or composition B constituting the foamable composition for nonflammable polyurethane foam of the present invention, and various conventionally known auxiliary agents such as a known foam stabilizer, further other flame retardant and the like can be appropriately selected and compounded as required.
As the foaming agent used herein, various known non-freon-based and 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 advantageously used, and specifically, an organic foaming agent such as Hydrocarbon (HC), hydrofluoroolefin (HFO), hydrochlorofluoroolefin (HCFO) or the like can be contained.
For example, among the blowing agents usable in the present invention, hydrofluorocarbon (HFC) as a fluorocarbon-based blowing agent, examples thereof include difluoromethane (HFC 32), 1, 2-pentafluoroethane (HFC 125), 1-trifluoroethane (HFC 143 a) 1, 2-tetrafluoroethane (HFC 134), 1, 2-tetrafluoroethane (HFC 134 a), 1-difluoroethane (HFC 152 a) 1, 2-tetrafluoroethane (HFC 134), 1, 2-tetrafluoroethane (HFC 134 a) 1, 1-difluoroethane (HFC 152 a).
On the other hand, as the Hydrocarbon (HC) which is one of the non-freon-based blowing agents suitable for use in the present invention, n-pentane, isopentane, cyclopentane, isobutane and the like are exemplified. In addition, as the Hydrofluoroolefin (HFO), there may be mentioned, for example: pentafluoropropene such as 1,2, 3-pentafluoropropene (HFO 1225 ye), 1, 3-tetrafluoropropene (HFO 1234 ze) tetrafluoropropenes such as 2, 3-tetrafluoropropene (HFO 1234 yf) and 1,2, 3-tetrafluoropropene (HFO 1234 ye); trifluoropropenes such as 3, 3-trifluoropropene (HFO 1243 zf); hexafluorobutene isomers (HFO 1336) such as tetrafluorobutene (HFO 1345), pentafluorobutene isomers (HFO 1354), and 1, 4-hexafluoro-2-butene (HFO 1336 mzz); heptafluorobutene isomers (HFO 1327), heptafluoropentene isomers (HFO 1447), octafluoropentene isomers (HFO 1438), nonafluoropentene isomers (HFO 1429), and the like. Examples of the Hydrochlorofluoroolefin (HCFO) include 1-chloro-3, 3-trifluoropropene (HCFO-1233 zd), 2-chloro-3, 3-trifluoropropene (HCFO-1233 xf), and dichlorotrifluoropropene (HCFO 1223). In particular, these Hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (hcfcs) are unstable in chemical properties and therefore have a low global warming potential, and thus are suitable for use as environmentally friendly blowing agents. Moreover, water, which will be described later, can be advantageously used as a blowing agent together with these Hydrofluoroolefins (HFOs) or Hydrochlorofluoroolefins (HCFOs) described above.
In the present invention, water as a foaming agent may be advantageously used together with the organic foaming agent or in place of the organic foaming agent. By having such water present in the polyol-containing composition a, when the composition a and the polyisocyanate-containing composition B are mixed and reacted, the water will react with the polyisocyanate to form carbon dioxide, which can thus be effectively involved in polyurethane foaming formed by the reaction of the polyol with the polyisocyanate. Further, since reaction heat is generated when such carbon dioxide is generated, the urethane reaction and the isocyanurate reaction can be efficiently performed by using the heat, and the compressive strength of the polyurethane foam obtained 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 entire polyol in the composition a. If the amount of water is more than 5 parts by mass, the strength of the polyurethane foam produced is rather lowered. This is due to: urea bonds formed by the reaction of water and polyisocyanate become more in the resin, and the polyisocyanate used in the isocyanation reaction is consumed by the reaction with water, so that the polyisocyanate in the reaction system becomes less. If the amount 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 uniformly conform the cell structure of the polyurethane foam, and a silicone surfactant or a nonionic surfactant may be suitably used. Specific examples thereof include polyoxyalkylene-modified dimethylpolysiloxane, polysiloxane-oxyalkylene copolymer, polyoxyethylene sorbitan fatty acid ester, castor oil ethylene oxide adduct, lauryl fatty acid ethylene oxide adduct, and the like, and 1 or 2 or more thereof may be used alone or in combination. The amount of the foam stabilizer to be blended may be appropriately determined depending on the desired foam characteristics, the type of foam stabilizer to be used, etc., but may be selected in the range of 0.1 to 10 parts by mass, preferably 1 to 8 parts by mass, relative to 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, various known polyurethane foam production methods can be suitably employed, 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 plate-like shape, an injection foaming method in which a space portion requiring heat insulation such as a refrigerator, a honeycomb structure of a lightweight and high-strength plate, a void generated in civil engineering, or the like is injected, filled and foamed and cured, or a spray foaming method in which a predetermined object (structure) to be adhered is sprayed from a gun head of an in-situ foaming machine and foamed and cured, and a polyurethane foam obtained by imparting high flame retardancy to the object is produced, and a flame retardant material defined by the above-mentioned building standard is advantageously formed from the foam.
Examples
In the following, several examples of the present invention are shown and compared with comparative examples, and thus the features of the present invention are more specifically clarified, and the present invention is not limited to the description of such examples. In addition, in the present invention, it should be understood that, in addition to the following examples: in addition to the above specific description, various alterations, modifications, improvements, and the like can be made based on the knowledge of those skilled in the art without departing from the gist of the present invention. The percentages (%) and parts shown below are percentages and parts shown on a mass basis unless otherwise specified.
The density, maximum heat release rate, total heat release amount, state of residue, and colorability of the polyurethane foam obtained in the examples and comparative examples below were evaluated or measured as follows.
(1) Determination of maximum Heat Release Rate and Total Heat release
A sample for a cone calorimeter test having dimensions of 100mm X50 mm was cut from a heat sink to be measured, and the heat radiation intensity of 50kW/m was measured according to the combustion test method defined in ISO-5660 2 Maximum heat release rate and total heat release amount at 20 minutes of heating. And, the maximum heat release rate was set to 200kW/m 2 The total heat release was 8MJ/m in the following cases 2 The following cases were evaluated as acceptable.
(2) Determination of Density
The above-mentioned sample for cone calorimeter test cut from the foam was measured for its size using a vernier caliper, on the other hand, its mass was measured using an electronic balance, and the density of the sample (foam) was calculated from these obtained measured values.
(3) Evaluation of residue State
The test sample obtained when the combustion test according to the above ISO-5660 was performed and after the test was completed, was evaluated as "X" when deformation and cracking were observed to reach the back surface, and as "O" when deformation was not observed to reach the back surface.
(4) Evaluation of colorability
For each polyol composition of examples and comparative examples, 0.016 parts by mass of a predetermined coloring dye was added, and a colored foam (foam) was produced according to a method for producing a polyurethane foam described later. Then, the color tone of the obtained colored foam was compared with the color tone of the colored foam obtained from the polyol composition (comparative example 8) not fully blended with the flame retardant, and if there was no difference between the two, the colored foam was evaluated as "o", and if the difference was confirmed, the colored foam was evaluated as "x".
First, as the components used in the following examples and comparative examples, the following various raw materials were prepared.
Polyol compound: phthalic acid polyester polyol (RFK 505 manufactured by Kawasaki chemical industry Co., ltd.)
: mannich polyether polyol (DK polyol 3776 (DK polyethylene 3776, japanese) of Mannich series, hydroxyl value: 350mgKOH/g, viscosity: 500 mPa.s/25 ℃ C.)
Trimerization catalyst: potassium octoate (Evonik JAPAN K.K. Dabco K-15)
: quaternary ammonium salt (KAOLIZER No.420 manufactured by Hua Wang Co., ltd.)
Resinification catalyst: bismuth octoate (PUCAT 25 manufactured by Japanese chemical industry Co., ltd.)
Flame retardant: aluminum diethylphosphinate (EXOLIT OP930, EXOLIT OP935, manufactured by Clariant Chemicals Co., ltd.)
: phosphate [ TCPP: phosphoric acid tris (1-chloro-2-propyl) ester
: phosphate (polyphosphate: ADK STAB PFR manufactured by ADEKA Co., ltd.)
: red phosphorus (Nova Excel140 manufactured by phosphorus chemical industry Co., ltd.)
: aluminum hydroxide (average particle diameter: 2 μm, manufactured by Japanese light metals Co., ltd. B1403)
Foaming agent: HCFO-1233zd (1-chloro-3, 3-trifluoropropene manufactured by Honeywell Co., ltd.)
: HFC365mfc (1, 3-pentafluorobutane manufactured by SOLVAY Co., ltd.)
: HFC245fa (1, 3-pentafluoropropane manufactured by Central Nitro Co., ltd.)
: water and its preparation method
Foam stabilizer: organosilicon foam stabilizer (SH-193 manufactured by Toli-Dow Corning Co., ltd.)
Dye: red dye (ORIENT CHEMICAL INDUSTRIES CO., LTD. OIL RED RR)
: blue dye (ORIENT CHEMICAL INDUSTRIES CO., LTD. OIL BIUE 2N)
: green dye (ORIENT CHEMICAL INDUSTRIES CO., LTD. OIL GREEN 502)
Preparation of polyol composition (composition A)
The above-prepared polyol, trimerization catalyst, resinification catalyst, flame retardant, foaming agent, foam stabilizer and dye were uniformly mixed in accordance with the respective combinations and blending ratios shown in tables 1 to 3 below to prepare respective polyol compositions according to examples 1 to 12 and comparative examples 1 to 8.
Preparation of the polyisocyanate composition (composition B)
Polymeric MDI (Wannate PM-130 manufactured by JAPAN corporation) was prepared as the polyisocyanate, and only the polyisocyanate was used to form the composition B.
Production of polyurethane foam
80 parts of each polyol composition (composition A) and 120 parts (mass ratio: 1.5) of the composition B composed only of the polyisocyanate obtained above were each adjusted to a liquid temperature of 20℃and then stored in a polypropylene container of 300 parts by volume, and the mixture was stirred: the mixture was mixed with a TK homogenizer (PRIMIX Co.) for 10 seconds. Then, the mixed liquid was poured into a 2000-volume part polypropylene container, and foamed and cured to obtain a target foam.
Then, the density, maximum heat release rate, total heat release amount, state of residue and colorability of each polyurethane foam obtained in this manner were measured or evaluated, and the obtained results are summarized in tables 1 to 3 below.
TABLE 1
TABLE 2
TABLE 3
From the results of tables 1 and 2, it can be confirmed that: the polyol composition (composition A) and the polyisocyanate (composition B) used in examples 1 to 12 of the present invention were combined to form a polyol compositionThe foamable composition was found to have a total heat release (20 minutes) of 8MJ/m in the combustion test method according to ISO-5660 2 The following polyurethane foams having high flame retardancy and no change in color tone due to the flame retardant can easily give colored foams of a desired color tone by using a predetermined coloring dye.
On the other hand, as can be seen from the results shown in Table 3, in comparative examples 1 and 2 in which the amount of the organic phosphinate metal salt used as the flame retardant and the total amount of the organic phosphinate metal salt and the organic phosphate used were small, the total heat release amount (20 minutes) became much larger than 8MJ/m 2 It was confirmed that it was difficult to form polyurethane foam as a nonflammable material, of course, even in the case of comparative example 8 in which a flame retardant was not used. Even when the total amount of the organic phosphinate and the organic phosphate is larger than the value defined in the present invention, the effect of improving the flame retardancy is insufficient in the case of comparative examples 3 and 4 in which the amount of the organic phosphinate is small, and the total heat release amount (20 minutes) as the standard of the non-combustible material is not satisfied in the case of comparative example 5 in which only the organic phosphate is blended as the flame retardant. In the case of comparative example 6 in which the trimerization catalyst was not used but only the resinification catalyst was used in the formation of the polyurethane foam, the curing of the foam did not proceed sufficiently, and therefore, there was a problem that a sample that could be used in the test according to ISO-5660 could not be obtained. Further, it is also known that: in the case of comparative example 7 in which red phosphorus was used as the flame retardant and the organic phosphate was used in combination therewith, the total heat release amount (20 minutes) was satisfied, but the colored foam obtained by using the blue dye and the green dye in the coloring test could not achieve the original blue and green hues, and the degree of freedom of coloring was limited.

Claims (10)

1. A foamable composition for nonflammable polyurethane foam, characterized in that it comprises a composition A containing a polyol and a composition B containing a polyisocyanate, and a polyurethane foam is formed by the reaction of the polyol with the polyisocyanate and foaming by a foaming agent,
in the composition A, at least a trimerization catalyst is contained as a catalyst, and an organic phosphinate 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,
the trimerization catalyst is a quaternary ammonium salt or a combination of the quaternary ammonium salt and carboxylic acid alkali metal salt,
the organic phosphinate metal salt is monomethyl phosphinate zinc, dimethyl phosphinate zinc, monoethyl phosphinate zinc, diethyl phosphinate zinc, monophenyl phosphinate zinc, diphenyl phosphinate zinc, monomethyl phosphinate aluminum, dimethyl phosphinate aluminum, monoethyl phosphinate aluminum, diethyl phosphinate aluminum, monophenyl phosphinate aluminum or diphenyl phosphinate aluminum.
2. A foamable composition for nonflammable polyurethane foam, characterized in that it comprises a composition A containing a polyol and a composition B containing a polyisocyanate, and a polyurethane foam is formed by the reaction of the polyol with the polyisocyanate and foaming by a foaming agent,
The foamable composition for nonflammable polyurethane foam comprises: in the composition A, at least a trimerization catalyst is contained as a catalyst, and an organic phosphinate metal salt and an organic phosphate are contained in at least either one of the composition A and the composition B separately or together, and the organic phosphinate metal salt and the organic phosphate are contained in a proportion of 30 parts by mass or more in total with respect to 50 parts by mass of the polyol, and the content of the organic phosphinate metal salt is 5 parts by mass or more with respect to 50 parts by mass of the polyol,
the trimerization catalyst is a quaternary ammonium salt or a combination of the quaternary ammonium salt and carboxylic acid alkali metal salt,
the organic phosphinate metal salt is monomethyl phosphinate zinc, dimethyl phosphinate zinc, monoethyl phosphinate zinc, diethyl phosphinate zinc, monophenyl phosphinate zinc, diphenyl phosphinate zinc, monomethyl phosphinate aluminum, dimethyl phosphinate aluminum, monoethyl phosphinate aluminum, diethyl phosphinate aluminum, monophenyl phosphinate aluminum or diphenyl phosphinate aluminum.
3. The foamable composition for nonflammable polyurethane foam according to claim 2, wherein said organic phosphate is selected from the group consisting of monophosphate and condensed phosphate.
4. A foamable composition for nonflammable polyurethane foam according to claim 2 or 3, wherein said organic phosphoric acid ester is tris (1-chloro-2-propyl) phosphate.
5. The foamable composition for nonflammable polyurethane foam according to any one of claims 1 to 3, wherein said composition A and/or said composition B further comprises a metal hydroxide.
6. The foamable composition for nonflammable polyurethane foam according to any one of claims 1 to 3, wherein said polyol is an aromatic polyester polyol.
7. The foamable composition for nonflammable polyurethane foam according to claim 6, wherein said aromatic polyester polyol is a phthalic acid polyester polyol.
8. The foamable composition for nonflammable polyurethane foam according to any one of claims 1 to 3, wherein said foaming agent is an organic foaming agent selected from the group consisting of hydrocarbon, hydrofluoroolefin and hydrochlorofluoroolefin.
9. The foamable composition for nonflammable polyurethane foam according to any one of claims 1 to 3, wherein water is used as said blowing agent together with a hydrofluoroolefin or hydrochlorofluoroolefin.
10. According to the weightsThe foamable composition for nonflammable polyurethane foam of any one of claims 1 to 3, wherein said polyurethane foam has the following nonflammable characteristics: according to the exothermic test method specified in ISO-5660, the heat strength of radiation was 50kW/m 2 The total heat release amount during heating within 20 minutes from the start of heating was 8.0MJ/m 2 The following is given.
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