JP2022042424A - Polyol-containing composition, expandable polyurethane composition, and polyurethane foam - Google Patents

Abstract

To provide a polyol-containing composition capable of forming polyurethane foam that is easily detached from an object when a building is demolished or construction is done over again while keeping powerful adhesiveness at usual times.SOLUTION: A polyol-containing composition is reacted with polyisocyanate to obtain polyurethane foam. The polyol-containing composition contains polyol, a foaming agent, a catalyst, and filler. The catalyst contains a metal catalyst including at least one kind selected from the group consisting of bismuth and tin. The polyol-containing composition is reacted with polyisocyanate by spraying to produce the polyurethane foam having an adhesive strength of 80 kPa or more and 250 kPa or less measured in accordance with JIS A 09526.SELECTED DRAWING: None

Description

The present invention relates to polyol-containing compositions, effervescent polyurethane compositions, and polyurethane foams.

Polyurethane foam is used as a heat insulating material for buildings such as condominiums and other condominiums, detached houses, various school facilities, and commercial buildings because of its excellent heat insulating properties and adhesiveness. The polyurethane foam can be obtained by mixing a polyol-containing composition and polyisocyanate, foaming them, and spraying them onto an object such as a ceiling, a wall, or a roof using a spray device or the like.

Polyurethane foam requires a certain level of adhesive strength in order to prevent it from peeling off from the object after being sprayed at the construction site of the building. As a means for imparting a certain adhesive strength, for example, after arranging an exterior material in a mold, a urethane resin composition is injected between the exterior materials, the mold is plugged, and foaming and curing are performed under pressure. There is a method to make it (Patent Document 1).

JP-A-2017-105188

However, the conventional polyurethane foam does not normally cause defects such as peeling, but has a problem that it is difficult to peel off from the object when the building is dismantled or the construction is redone.

Therefore, the present invention provides a polyol-containing composition capable of forming a polyurethane foam that can be easily peeled off from an object when dismantling a building or reconstructing a building while maintaining good adhesiveness in normal times. The challenge is to provide.

As a result of diligent studies, the present inventor has determined the adhesive strength of the polyurethane foam obtained by spraying using a polyol-containing composition containing a polyol, a foaming agent, a catalyst, and a filler and containing a specific metal catalyst as a catalyst. The present invention has been completed by finding that the above-mentioned problems can be solved by keeping the above range within the range of. That is, the present invention provides the following [1] to [11].
[1] A polyol-containing composition for reacting with a polyisocyanate to obtain a polyurethane foam, which contains a polyol, a foaming agent, a catalyst, and a filler, and the catalyst is selected from the group consisting of bismuth and tin. The polyurethane foam containing a metal catalyst containing at least one of the above and reacted with polyisocyanate by spraying is characterized by having an adhesive strength of 80 kPa or more and 250 kPa or less measured in accordance with JIS A 09526. Containing composition.
[2] The polyol-containing composition according to the above [1], wherein the filler ratio in the polyol-containing composition is 8% or more.
[3] The polyol-containing composition according to the above [1] or [2], wherein the filler ratio in the polyol-containing composition is 29% or less.
[4] The polyol-containing composition according to any one of [1] to [3] above, wherein the catalyst contains a trimerization catalyst.
[5] The polyol-containing composition according to any one of [1] to [4] above, wherein the trimerization catalyst contains a quaternary ammonium salt.
[6] The polyol-containing composition according to any one of [1] to [5] above, wherein the catalyst contains an imidazole derivative.
[7] The polyol-containing composition according to any one of [1] to [6] above, wherein the catalyst contains bismuth.
[8] The polyol-containing composition according to any one of the above [1] to [7], wherein the foaming agent contains a hydrofluoroolefin.
[9] A metal catalyst containing a polyol, a foaming agent, a catalyst, a filler, and a polyisocyanate, wherein the catalyst contains at least one selected from the group consisting of bismuth and tin, and is reacted by spraying. The polyurethane foam is a foamable polyurethane composition, characterized in that the adhesive strength measured in accordance with JIS A 09526 is 80 kPa or more and 250 kPa or less.
[10] The foamable polyurethane composition according to the above [9], which has an isocyanate index of 200 or more.
[11] A polyurethane foam obtained by reacting and foaming the effervescent polyurethane composition according to the above [9] or [10].

According to the present invention, a polyol-containing composition capable of forming a polyurethane foam that can be easily peeled off from an object when dismantling a building or reconstructing a building while maintaining good adhesiveness in normal times is provided. Can be provided.

[Polycarbonate-containing composition]
The polyol-containing composition of the present invention is a polyol-containing composition for reacting with polyisocyanate to obtain a polyurethane foam, and contains a polyol, a foaming agent, a catalyst, and a filler, and the catalysts include bismuth and tin. It contains a metal catalyst containing at least one selected from the group consisting of.

<Adhesive strength>
The polyol-containing composition of the present invention has a polyurethane foam formed by reacting the composition with a polyisocyanate and having an adhesive strength of 80 to 250 kPa measured in accordance with JIS A 09526. If the adhesive strength is less than 80 kPa, the problem of peeling from the object occurs. On the other hand, when the adhesive strength exceeds 250 kPa, it becomes difficult to peel off the building when dismantling or reconstructing the building. From these viewpoints, the adhesive strength is preferably 90 to 230 kPa, more preferably 100 to 200 kPa.
For the "adhesive strength" referred to here, 4,4'-diphenylmethane diisocyanate (4,4'-MDI) is used as the polyisocyanate, and the polyol-containing composition and the polyisocyanate are mixed at a volume ratio of 1: 1. It means the adhesive strength when a polyurethane foam is formed by spraying from the mixture. In addition, 4,4'-MDI is a polyisocyanate typically used by spraying, and the volume ratio adopted 1: 1 which is the condition most typically performed by spraying. The details of the method for forming the polyurethane foam and the method for measuring the adhesive strength are as shown in Examples.
The adhesive strength can be appropriately adjusted depending on the amount and type of catalyst, filler ratio, amount and type of foaming agent, and the like.

<Polyol>
The polyol-containing composition of the present invention contains a polyol as a raw material for polyurethane foam.
Examples of the polyol used in the present invention include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, polymer polyols, and polyether polyols.

Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, polyvalerolactone glycol and the like.
Examples of the polycarbonate polyol include a polyol obtained by a dealcohol reaction between a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentandiol, hexanediol, octanediol, and nonanediol and ethylene carbonate, propylene carbonate, or the like. And so on.

Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolac, cresol novolak and the like.
Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, dimethyldicyclohexylmethanediol and the like.
Examples of the aliphatic polyol include alkanediols such as ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.

Examples of the polyester polyol include a polymer obtained by dehydration condensation of a polybasic acid and a polyhydric alcohol, and a condensate of a hydroxycarboxylic acid and the polyhydric alcohol or the like.
Examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, isophthalic acid (m-phthalic acid), terephthalic acid (p-phthalic acid), succinic acid and the like. Examples of the polyhydric alcohol include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexaneglycol, neopentyl glycol and the like.
Examples of the hydroxycarboxylic acid include castor oil, a reaction product of castor oil and ethylene glycol, and the like.

Examples of the polymer polyol include a polymer obtained by graft-polymerizing an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, and methacrylate with an aromatic polyol, an alicyclic polyol, an aliphatic polyol, a polyester polyol, or the like. , Polybutadiene polyols, or their hydrogenated additives and the like.

As the polyether polyol, for example, at least one kind of alkylene oxide such as ethylene oxide, propylene oxide and tetrahydrofuran is ring-opened polymerized in the presence of at least one kind such as a low molecular weight active hydrogen compound having two or more active hydrogens. Examples thereof include the obtained polymer. Examples of the low molecular weight active hydrogen compound having two or more active hydrogens include diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol and 1,6-hexanediol, and triols such as glycerin and trimethylolpropane. Pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol and the like, sucrose, glucose, mannose, fructose, methylglucoside and its derivatives such as tetra-octavalent alcohols, ethylenediamine, butylene diamine and the like. Examples include amines.

The polyol used in the present invention is preferably at least one selected from polyester polyols and polyether polyols. Polyester polyols are more preferred from the standpoint of foamability and reactivity. Further, a polyol having two hydroxyl groups is preferable. Of these, aromatic polyester polyols, which are polyester polyols having an aromatic ring, are preferable from the viewpoint of enhancing flame retardancy. Examples of the aromatic polyester polyol include polybasic acids having an aromatic ring such as isophthalic acid (m-phthalic acid) and terephthalic acid (p-phthalic acid), bisphenol A, ethylene glycol, 1,2-propylene glycol and the like. The one obtained by dehydration condensation with the dihydric alcohol of No. 1 is more preferable.

The hydroxyl value of the polyol is preferably 20 to 350 mgKOH / g, more preferably 50 to 300 mgKOH / g, and even more preferably 100 to 250 mgKOH / g. When the hydroxyl value of the polyol is not more than the upper limit, the viscosity of the polyol-containing composition tends to decrease, which is preferable from the viewpoint of handleability and the like. On the other hand, when the hydroxyl value of the polyol is at least the above lower limit value, the crosslink density of the polyurethane foam is increased and the strength is increased.
The hydroxyl value of the polyol can be measured according to JIS K 1557-1: 2007.

<Catalyst>
(Metal catalyst (resinized metal catalyst))
The catalyst used in the polyol-containing composition of the present invention contains a metal catalyst containing at least one selected from the group consisting of bismuth and tin. This metal catalyst is generally called a resinified metal catalyst. In the present invention, the inclusion of the metal catalyst promotes the reaction between the polyol and the polyisocyanate, and in particular, the initial reaction rate can be increased. Further, if a certain amount or more of a filler described later is contained, the reactivity of the polyurethane foam is hindered and the foamability tends to decrease. However, by containing a metal catalyst, it becomes easy to maintain good foamability of the polyurethane foam and adhesion is achieved. The strength is also easily maintained at a high value. The metal catalyst more preferably contains bismuth from the viewpoint of foamability, adhesive strength and the like.

The resinized metal catalyst is preferably a metal salt selected from bismuth and tin, and more preferably a bismuth salt. The metal salt is preferably an organic acid metal salt, more preferably a metal salt of a carboxylic acid having 5 or more carbon atoms. When the carboxylic acid has 5 or more carbon atoms, its stability with respect to a foaming agent, particularly a hydrofluoroolefin, becomes good. The carbon number of the carboxylic acid is preferably 18 or less, more preferably 12 or less, from the viewpoint of catalytic activity and the like. The carboxylic acid is preferably an aliphatic carboxylic acid, more preferably a saturated aliphatic carboxylic acid. The carboxylic acid may be linear or may have a branched structure, but it is preferable that the carboxylic acid has a branched structure.
Specific examples of the carboxylic acid include octyl acid, lauryl acid, versatic acid, pentanic acid, acetic acid and the like, and among these, octyl acid is preferable. That is, the transition metal salt is preferably a metal salt of octyl acid. These carboxylic acids may be linear as described above, but may have a branched structure. Examples of the octylic acid having a branched structure include 2-ethylhexanoic acid.
As the metal salt of carboxylic acid, a bismuth salt of carboxylic acid and a tin salt of carboxylic acid are preferable, and a bismuth salt of octyl acid is particularly preferable. Further, the metal salt of the carboxylic acid may be a carboxylate of an alkyl metal. For example, the carboxylic acid tin salt may be a dialkyltin carboxylate or the like, preferably a dioctyltin carboxylate or the like.
Specific examples of the metal salt of the carboxylic acid include bismuth trioctate, dioctyl tin versate, dibutyl tin dilaurate, dioctyl tin dilaurate, tin dioctylate and the like, preferably bismuth trioctate, dioctyl tin versate and more preferably. Bismuth Trioctate.

The content of the metal catalyst in the polyol-containing composition is preferably 0.1 to 10 parts by mass, more preferably 1 to 8 parts by mass, and further preferably 1.5 to 6 parts by mass with respect to 100 parts by mass of the polyol. Preferably, 2 to 5 parts by mass is even more preferable. When the content of the metal catalyst is at least the above lower limit value, it becomes easy to adjust the adhesive strength of the polyurethane foam to 80 kPa or more, and it becomes easy to maintain good adhesiveness. On the other hand, when the content of the metal catalyst is not more than the upper limit value, the reaction can be easily controlled.

(Imidazole derivative)
The catalyst used in the polyol-containing composition of the present invention preferably contains a resinified amine catalyst, and more preferably contains an imidazole derivative as the resinified amine catalyst.
The imidazole derivative is less susceptible to the influence of hydrofluoroolefins, and makes it easier for the polyol to react with the polyisocyanate while increasing the stability of the polyol-containing composition. Therefore, when the polyol-containing composition contains an imidazole derivative in addition to the above-mentioned metal catalyst, the reactivity between the polyol and the isocyanate is enhanced, and the foamability is further improved.
The imidazole derivative is preferably an imidazole in which the 1-position and the 2-position are independently substituted with an alkyl group having 8 or less carbon atoms, and the alkyl group preferably has 6 or less carbon atoms, and more preferably 4 or less carbon atoms. A suitable specific example of the imidazole derivative is represented by the following general formula (1).

（一般式（１）中、Ｒ^１及びＲ^２は、それぞれ独立に炭素数１～８のアルキル基又は炭素数２～８のアルケニル基を表す。）

(In the general formula (1), R ¹ and R ² independently represent an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, respectively.)

R ¹ and R ² in the general formula (1) independently represent an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, respectively. The alkyl group and the alkenyl group may be linear or have a branched structure.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, isopentyl group, sec-pentyl group, hexyl group and heptyl. Groups, octyl groups and the like can be mentioned.
Specific examples of the alkenyl group include a vinyl group, a 1-propenyl group, an allyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group and the like.
When the carbon number of the alkyl group or the alkenyl group of R ¹ and R ² is at least the above lower limit value, steric hindrance becomes large and it is less likely to be affected by a foaming agent such as a hydrofluoroolefin, which is preferable. On the other hand, when the carbon number of the alkyl group of R ¹ and R ² is not more than the above upper limit value, the steric hindrance does not become extremely large, so that the reaction between the polyol and the polyisocyanate can be rapidly promoted, and the foamability becomes foamy. Will also be good.
From these viewpoints, R ¹ and R ² are each independently preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group.

Examples of the imidazole derivative represented by the general formula (1) include 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl. Examples thereof include -2-methylimidazole, among which 1,2-dimethylimidazole and 1-isobutyl-2-methyl are used from the viewpoint of improving the activity of the catalyst in the presence of hydrofluoroolefin and promptly advancing the reaction. Imidazole is preferred. Further, 1,2-dimethylimidazole is more preferable from the viewpoint of further enhancing the stability.

The content of the imidazole derivative in the polyol-containing composition is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the polyol. Up to 10 parts by mass is particularly preferable. When the content of the imidazole derivative is at least the above lower limit value, the formation of urethane bonds is likely to occur, the reaction proceeds rapidly, and the foamability becomes good. On the other hand, when the content of the imidazole derivative is not more than the above upper limit value, the reaction rate can be easily controlled, which is preferable.

(Triquantization catalyst)
The polyol-containing composition of the present invention preferably further contains a trimerization catalyst. The trimerization catalyst is a catalyst that promotes the formation of an isocyanurate ring by reacting an isocyanate group contained in polyisocyanate to trimerize it. There is an advantage that a good polyurethane foam can be obtained by completing the reaction of the unreacted isocyanate group by containing the trimerization catalyst. Examples of the trimerization catalyst include metal catalysts and ammonium salts.
Examples of the metal catalyst used as the trimerization catalyst (trimerization metal catalyst) include potassium organic acid, preferably potassium octylate such as potassium 2-ethylhexanoate, potassium acetate, potassium propionate, potassium butanoate, and the like. It is potassium carboxylate having 2 to 8 carbon atoms such as potassium benzoate.
As the ammonium salt, a tertiary ammonium salt such as triethylammonium salt and triphenylammonium salt, a quaternary ammonium salt such as tetramethylammonium salt, tetraethylammonium salt and tetraphenylammonium salt can be used. Of these, a quaternary ammonium salt is preferable. The ammonium salt is, for example, an ammonium salt of a carboxylic acid. Examples of the carboxylic acid in the ammonium salt include saturated fatty acids having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms. The saturated fatty acid may have a linear hydrocarbon group or may have a branch, but it is preferable that the saturated fatty acid has a branch. Specific examples of the carboxylic acid include 2-ethylhexanoic acid, 2,2-dimethylpropionic acid, acetic acid, and formic acid, and among these, 2,2-dimethylpropionic acid is preferable. The trimerization catalyst may be used alone or in combination of two or more. When two or more kinds are used in combination, it is preferable to use a quaternary ammonium salt and a metal catalyst in combination.

The content of the trimerization catalyst in the polyol-containing composition is preferably 0.4 to 30 parts by mass, more preferably 1 to 25 parts by mass, still more preferably 2 to 20 parts by mass, based on 100 parts by mass of the polyol. 4 to 18 parts by mass is even more preferable. When the content of the trimerization catalyst is at least the above lower limit value, there is no big difference in the activity between the resinification and the trimerization, the foaming can be suppressed from being in two stages, and the foaming property is improved. On the other hand, when the content of the quantification catalyst is not more than the above upper limit value, the resinification reaction proceeds to the activity, so that the activity of the quantification can be assisted by the heat of the resinification reaction, and the foaming property becomes good, which is good. Polyurethane foam can be formed.

<Filler>
The polyol-containing composition of the present invention contains a filler. The filler is contained as a solid component in the polyol-containing composition, and is a component generally present as a granular or powdery component in the polyol-containing composition. In the present invention, the inclusion of the filler facilitates improvement of various physical properties such as flame retardancy and mechanical properties of the polyurethane foam.

The filler may be a component that is solid at room temperature (23 ° C.) and normal pressure (1 atm) and does not dissolve in the polyol-containing composition. The filler preferably has no hygroscopicity and deliquescent property from the viewpoint of reducing the water absorption rate of the polyurethane foam. The above-mentioned catalyst is not included in the filler.
As the filler, specifically, a solid flame retardant which is solid at normal temperature (23 ° C.) and normal pressure (1 atm) may be used. Specific solid flame retardants include red phosphorus flame retardants, phosphate-containing flame retardants, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, chlorine-containing flame retardants, metal hydroxides, and needle-like fillers. And so on. These solid flame retardants may be used alone or in combination of two or more.

(Red phosphorus flame retardant)
The red phosphorus flame retardant used as a filler may be composed of red phosphorus alone, may be a red phosphorus coated with a resin, a metal hydroxide, a metal oxide, or the like, or may be a red phosphorus coated with a resin or a metal. It may be a mixture of hydroxide, metal oxide and the like. The resin coated with red phosphorus or mixed with red phosphorus is not particularly limited, and examples thereof include thermosetting resins such as phenol resin, epoxy resin, unsaturated polyester resin, melamine resin, urea resin, aniline resin, and silicone resin. Be done. As the film or the compound to be mixed, a metal hydroxide is preferable from the viewpoint of flame retardancy. As the metal hydroxide, those described later may be appropriately selected and used.

(Phosphate-containing flame retardant)
As the phosphate-containing flame retardant, for example, at least selected from various phosphoric acids, metals of Group IA to IVB of the Periodic Table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring. Included are phosphates consisting of salts with one metal or compound. The term "various phosphoric acids" is a concept that includes not only phosphoric acid but also phosphorous acid, hypophosphoric acid and the like.
Examples of the metals of Group IA to Group IVB of the Periodic Table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum.
Examples of the aliphatic amine include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine and the like. Examples of the aromatic amine include aniline, o-triidin, 2,4,6-trimethylaniline, anicidin, 3- (trifluoromethyl) aniline and the like. Examples of the heterocyclic compound containing nitrogen in the ring include pyridine, triazine, melamine and the like.

Specific examples of the phosphate-containing flame retardant include monophosphate, polyphosphate and the like. The monophosphate is not particularly limited, but for example, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, monosodium phosphate, disodium phosphate, trisodium phosphate, and phosphite. Sodium salts such as monosodium, disodium phosphite, sodium hypophosphite, monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, hypophosphite Potassium salts such as potassium, monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphate, dilithium phosphate, lithium salts such as lithium hypophosphite, barium dihydrogen phosphate, phosphorus Barium salts such as barium hydrogen phosphate, tribarium phosphate, barium hypophosphite, magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, magnesium salts such as magnesium hypophosphite, calcium dihydrogen phosphate , Calcium hydrogen phosphate, tricalcium phosphate, calcium salts such as calcium hypophosphite, zinc salts such as zinc phosphate, zinc phosphite, zinc hypophosphite and the like.
Here, the polyphosphate is not particularly limited, and examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate, aluminum polyphosphate, and the like.
The phosphate-containing flame retardant may be used alone from the above-mentioned ones, or may be used in combination of two or more.

(Brominated flame retardant)
The bromine-containing flame retardant is not particularly limited as long as it is a compound containing bromine in its molecular structure and is solid at room temperature (23 ° C.) and normal pressure (1 atm). Examples include compounds.
Examples of the brominated aromatic ring-containing aromatic compound include hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (pentabromophenoxy) ethane, and ethylenebis (pentabromophenoxy). Examples thereof include monomer-based organic bromine compounds such as pentabromophenyl), ethylene bis (tetrabromophthalimide), and tetrabromobisphenol A.

Further, the brominated aromatic ring-containing aromatic compound may be a bromine compound polymer. Specifically, a polycarbonate oligomer produced from brominated bisphenol A as a raw material, a brominated polycarbonate such as a copolymer of this polycarbonate oligomer and bisphenol A, and a diepoxy compound produced by the reaction of brominated bisphenol A with epichlorohydrin. And so on. Furthermore, brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols with epichlorhydrin, condensates of brominated phenols of brominated polyphenylene ether, brominated bisphenol A and cyanur chloride, uncrosslinked or crosslinked. Examples include brominated polystyrene.
Further, it may be a compound other than a brominated aromatic ring-containing aromatic compound such as hexabromocyclododecane.
These brominated flame retardants may be used alone or in combination of two or more.

(Boron-containing flame retardant)
Examples of the boron-containing flame retardant used in the present invention include borax, boron oxide, boric acid, borate and the like. Examples of the boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, tetraboron pentoxide and the like.
Examples of the borate include alkali metals, alkaline earth metals, elements of Groups 4, 12, and 13 of the Periodic Table, and ammonium borates. Specifically, an alkali metal borate salt such as lithium borate, sodium borate, potassium borate, and cesium borate, an alkaline earth metal salt borate such as magnesium borate, calcium borate, and barium borate, boro Examples thereof include zirconium acid, zinc borate, aluminum borate, and ammonium borate.
The boron-containing flame retardant may be used alone or in combination of two or more.
The boron-containing flame retardant used in the present invention is preferably borate, more preferably zinc borate.

(Antimony-containing flame retardant)
Examples of the antimony-containing flame retardant include antimony oxide, antimony acid salt, pyroantimony acid salt and the like. Examples of antimony oxide include antimony trioxide and antimony pentoxide. Examples of the antimonate include sodium antimonate, potassium antimonate and the like. Examples of the pyroantimonate include sodium pyroantimonate, potassium pyroantimonate and the like.
The antimony-containing flame retardant may be used alone or in combination of two or more. The antimony-containing flame retardant used in the present invention is preferably antimony oxide.

(Chlorine-containing flame retardant)
Examples of the chlorine-containing flame retardant include those commonly used for polyurethane foam, such as polynaphthalene chloride, chlorendic acid, and dodecachlorododecahydrodimethanodibenzocyclooctene sold under the trade name of "Dechloran Plus". Be done.

(Metal hydroxide)
Examples of the metal hydroxide used in the present invention include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, and copper hydroxide. Examples thereof include vanadium hydroxide and tin hydroxide. The metal hydroxide may be used alone or in combination of two or more. As the metal hydroxide, aluminum hydroxide is preferable.

(Needle-shaped filler)
Examples of the needle-shaped filler include potassium titanate whisker, aluminum borate whisker, magnesium-containing whisker, silicon-containing whisker, wollastonite, sepiolite, zonolite, elestadite, boehmite, rod-shaped hydroxyapatite, glass fiber, carbon fiber, and graphite fiber. , Metal fiber, slag fiber, gypsum fiber, silica fiber, alumina fiber, silica alumina fiber, zirconia fiber, boron nitride fiber, boron fiber, stainless fiber and the like.
These needle-shaped fillers may be used alone or in combination of two or more.
The range of the aspect ratio (length / diameter) of the needle-shaped filler used in the present invention is preferably in the range of 5 to 50, and more preferably in the range of 10 to 40. The aspect ratio can be obtained by observing the needle-shaped filler with a scanning electron microscope and measuring its length and width.

In addition, an inorganic filler other than the above-mentioned solid flame retardant may be used, and such inorganic fillers include alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, ferrites, and basic materials. Magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, talc, mica, montmorillonite, bentonite, active white clay, imogolite, sericite, glass beads, Aluminum nitride, boron nitride, silicon nitride, various metal powders, magnesium sulfate, lead zirconate titanate, molybdenum sulfide, silicon carbide, various magnetic powders, fly ash and the like can be appropriately used. These inorganic fillers may be used alone or in combination of two or more.
These fillers may be used alone or in combination of two or more.

The filler ratio in the polyol-containing composition is preferably 8% or more, more preferably 13% or more, further preferably 19% or more, still more preferably 29% or less, still more preferably 27% or less, still more preferably 25% or less. .. When the filler ratio is at least the above lower limit value, it becomes easy to suppress the adhesive strength of the polyurethane foam to 250 kPa or less, and it becomes easy to peel it off from the object. In addition, various performances such as flame retardancy tend to be improved. On the other hand, when the filler ratio is not more than the upper limit value, it becomes easy to adjust the adhesive strength to 80 kPa or more, and it becomes easy to maintain good adhesiveness.
The filler ratio in the polyol-containing composition means the mass% of the total amount of filler contained in the polyol-containing composition with respect to the total amount of the polyol-containing composition.

<Phosphate ester>
The polyol-containing composition of the present invention may contain a flame retardant other than the above-mentioned solid flame retardant. Examples of such a flame retardant include flame retardants that are liquid at normal temperature (23 ° C.) and normal pressure (1 atm), and specific examples thereof include phosphoric acid esters. By using the phosphoric acid ester, it becomes easy to improve the flame retardancy of the polyurethane foam without lowering the fluidity of the polyol-containing composition.

As the phosphoric acid ester, a monophosphate ester, a condensed phosphoric acid ester and the like can be used. The monophosphate ester is a phosphate ester having one phosphorus atom in the molecule. Examples of the monophosphate ester include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate and tri (2-ethylhexyl) phosphate, halogen-containing phosphate esters such as tris (β-chloropropyl) phosphate, and tributoxyethyl phosphate. Arocyclic-containing phosphoric acid esters such as trialkoxy phosphate, tricredyl phosphate, trixilenyl phosphate, tris (isopropylphenyl) phosphate, cresyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, monoisodecyl phosphate, diisodecyl, etc. Examples thereof include acidic phosphoric acid esters such as phosphate.

Examples of the condensed phosphate ester include aromatic condensed phosphate esters such as trialkylpolyphosphate, resorcinol polyphenyl phosphate, bisphenol A polycresyl phosphate, and bisphenol A polyphenyl phosphate.
Commercially available products of condensed phosphoric acid ester include, for example, "CR-733S", "CR-741" and "CR747" manufactured by Daihachi Chemical Industry Co., Ltd., and "ADEKA STUB PFR" and "FP-600" manufactured by ADEKA. And so on.

As the phosphoric acid ester, one of the above-mentioned ones may be used alone, or two or more of them may be used in combination. Among these, monophosphate ester is preferable from the viewpoint of facilitating the appropriate viscosity of the polyol-containing composition and improving the flame retardancy of polyurethane foam, and halogen-containing phosphoric acid such as tris (β-chloropropyl) phosphate is preferable. Esters are more preferred.
The content of the phosphoric acid ester in the polyol-containing composition is preferably 5 to 100 parts by mass, more preferably 12 to 90 parts by mass, further preferably 20 to 75 parts by mass, and 30 to 60 parts by mass with respect to 100 parts by mass of the polyol. Parts by mass are even more preferred.

<Effervescent agent>
The foaming agent promotes the foaming of the effervescent polyurethane composition described below. Examples of the foaming agent include water, propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and other low boiling hydrocarbons, dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, and the like. Chlorinated aliphatic hydrocarbon compounds such as isobutyl chloride, pentyl chloride and isopentyl chloride, hydrofluoroolefins (hereinafter sometimes referred to as "HFO"), ether compounds such as diisopropyl ether, or mixtures of these compounds, etc. Examples thereof include organic physical foaming agents, nitrogen gas, oxygen gas, argon gas, carbon dioxide gas and other inorganic physical foaming agents.
Among these, it is preferable to contain hydrofluoroolefin (HFO), which has high stability as a foaming agent, is less likely to reduce catalytic activity, and has a low environmental load.

Examples of the HFO which is a suitable foaming agent include fluoroalkenes having about 3 to 6 carbon atoms. Further, the HFO may be a hydrochlorofluoroolefin having a chlorine atom, and therefore may be a chlorofluoroalkene having about 3 to 6 carbon atoms.
Examples of the HFO include trifluoropropene, tetrafluoropropene such as HFO-1234, pentafluoropropene such as HFO-1225, chlorodifluoropropene, chlorotrifluoropropene such as HFO-1233, and chlorotetrafluoropropene. Will be.
More specifically, 3,3,3-trifluoropropene (HFO-1243zf), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), cis-1,3,3 , 3-Tetrafluoropropene (HFO-1234ze (Z)), 2,3,3,3-Tetrafluoropropene (HFO-1234yf), 1,1,3,3-Tetrafluoropropene, Sis-1,3,3 3,3-tetrafluoropropene (HFO-1234ze (Z)), trans-1,2,3,3,3-pentafluoropropene (HFO-1225ye (E)), cis-1,2,3,3 3-Pentafluoropropene (HFO-1225ye (Z),), 1,1,3,3,3-pentafluoropropene (HFO-1225zc), 1,1,2,3,3-pentafluoropropene (HFO-) 1225yc), trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd (E)), 1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz). ) Etc. can be mentioned. Among these, HFO-1233zd (E) is preferable.

The content of the foaming agent is not particularly limited, and is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and even more preferably 35 to 60 parts by mass with respect to 100 parts by mass of the polyol. When the content of the foaming agent is at least the above lower limit value, foaming is promoted, foamability is improved, and the density of the polyurethane foam can be reduced. On the other hand, when the content of the foaming agent is not more than the upper limit, it is possible to prevent the foaming from progressing excessively. Further, by setting the content of the foaming agent within the above range, it becomes easy to adjust the adhesive strength within a predetermined range.

The above-mentioned foaming agent may be used alone or in combination of two or more. In the foamable polyurethane composition of the present invention, it is preferable to use the above-mentioned HFO and other foaming agents in combination. For example, HFO may be used in combination with water, oxygen gas, or carbon dioxide gas having excellent handleability. .. In particular, water is preferable from the viewpoint of adjusting the isocyanate index and from the viewpoint of ease of handling.

<Foam control agent>
The polyol-containing composition of the present invention may contain a defoaming agent. By containing a foam stabilizer, the foamability of the polyurethane foam can be improved, and for example, foaming can be promoted when reacting with polyisocyanate in a spray spray.
Specific examples of the defoaming agent include a surfactant, more specifically, a nonionic surfactant, a cationic surfactant, an anionic surfactant and the like. Specific examples of the nonionic surfactant include a polyoxyalkylene defoaming agent such as polyoxyalkylene alkyl ether and a silicone defoaming agent such as organopolysiloxane. The defoaming agent used in the present invention is not particularly limited, but a silicone defoaming agent is preferable from the viewpoint of foamability. The foam stabilizer may be used alone or in combination of two or more.

The content of the defoaming agent in the polyol-containing composition of the present invention is preferably 0.1 to 12 parts by mass, more preferably 1 to 10 parts by mass, and 2 to 8 parts by mass with respect to 100 parts by mass of the polyol. More preferred. When the content of the defoaming agent is at least the above lower limit value, the mixture of the polyol-containing composition and the polyisocyanate can be easily foamed, so that a homogeneous polyurethane foam can be obtained. Further, when the content of the defoaming agent is not more than the upper limit value, the balance between the manufacturing cost and the obtained effect is optimized.

<Other ingredients>
The polyol-containing composition may be a phenol-based, amine-based, sulfur-based or other antioxidant, heat stabilizer, metal damage inhibitor (metal inactivating agent), if necessary, as long as the object of the present invention is not impaired. It can contain one or more selected from additives such as antistatic agents, stabilizers, cross-linking agents, lubricants, softeners, plasticizers, pigments, tackifier resins, and tackifiers such as polybutene and petroleum resin. ..

<Manufacturing method of polyol-containing composition>
The method for producing the polyol-containing composition of the present invention is not particularly limited, and for example, each component can be produced by stirring at about 20 to 40 ° C. using a homodisper or the like for about 30 seconds to 20 minutes.

[Effervescent polyurethane composition and polyurethane foam]
The effervescent polyurethane composition of the present invention comprises a polyol, a foaming agent, a catalyst, a filler, and a polyisocyanate, and the catalyst contains a metal catalyst containing at least one selected from the group consisting of bismuth and tin. In addition, the effervescent polyurethane composition may appropriately contain a phosphoric acid ester, a defoaming agent, and other components. The details of the polyol, the foaming agent, the catalyst, the filler, the phosphoric acid ester, the foam stabilizer, and other components in the effervescent polyurethane composition according to the present invention are as described above, and the description thereof will be omitted.
The effervescent polyurethane composition of the present invention preferably contains the above-mentioned polyol-containing composition and polyisocyanate, and is obtained by mixing these. Further, the polyurethane foam of the present invention is a reaction product obtained by reacting and foaming a foamable polyurethane composition.
In the present invention, the foamable polyurethane composition is a polyurethane foam obtained by reacting by spraying, and the adhesive strength measured in accordance with JIS A 09526 is 80 kPa or more and 250 kPa or less. If the adhesive strength is less than 80 kPa, the problem of peeling from the object occurs. On the other hand, when the adhesive strength exceeds 250 kPa, it becomes difficult to peel off the building when dismantling or reconstructing the building. From these viewpoints, the adhesive strength is preferably 90 to 230 kPa, more preferably 100 to 200 kPa.
The term "adhesive strength" as used herein means that a polyurethane foam is formed by spraying from a foamable polyurethane composition (usually a mixture of the above-mentioned polyol-containing composition and polyisocyanate) used for forming the polyurethane foam. It means the adhesive strength when it is used. The details of the method for forming the polyurethane foam and the method for measuring the adhesive strength are as shown in Examples.

<Polyisocyanate>
In the present invention, examples of the polyisocyanate include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.
Examples of the aromatic polyisocyanate include phenylenediocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate (polymeric MDI). Will be.

Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate and the like.

Among these, aromatic polyisocyanate is preferable, diphenylmethane diisocyanate, polypeptide MDI, or a mixture thereof is more preferable, and diphenylmethane diisocyanate is more preferable, and particularly 4, 4'-diphenylmethane diisocyanate is preferred. As the polyisocyanate, one type may be used alone, or two or more types may be mixed and used.
Further, the polyisocyanate may be appropriately blended with a known additive to be blended with the polyisocyanate before being mixed with the polyol-containing composition.

It is preferable that the volume of the polyol-containing composition and the polyisocyanate mixed in the polyol-containing composition are substantially the same. Specifically, the volume ratio of the polyisocyanate to the polyol-containing composition is preferably 0.8 to 1.2, more preferably 0.9 to 1.1, and even more preferably 0.95 to 1.05.

<Isocyanate index>
The isocyanate index in the effervescent polyurethane composition of the present invention is not particularly limited, but is preferably 200 or more. When the isocyanate index is at least the lower limit value, the amount of polyisocyanate with respect to the polyol becomes excessive, and isocyanurate bonds are easily generated by the trimericized polyisocyanate, and as a result, the flame retardancy of the polyurethane foam is improved. It is also possible to impart nonflammability. Further, when the above lower limit value or more is set, a polyurethane foam having a sufficient isocyanurate bond, that is, a polyurethane foam having a high level of flame retardancy and heat insulating property, is produced in combination with the combined use of the above-mentioned various catalysts. Easy to manufacture. From these viewpoints, the isocyanate index is more preferably 250 or more, and further preferably 300 or more.
The isocyanate index is preferably 1,000 or less, more preferably 800 or less, and even more preferably 600 or less. When the isocyanate index is not more than the upper limit value, flame retardancy sufficiently commensurate with the manufacturing cost can be obtained. Further, when the isocyanate index is within the above range, the adhesive strength of the foamable polyurethane composition can be easily adjusted within the predetermined range.

The isocyanate index can be calculated by the following method.
Isocyanate index = equivalent number of polyisocyanate ÷ (equivalent number of polyol + equivalent number of water) × 100
Here, each equivalent number can be calculated as follows.
Equivalent number of polyisocyanate = amount of polyisocyanate used (g) x NCO content (mass%) / molecular weight of NCO (mol) x 100
Equivalent number of polyol = OHV × amount of polyol used (g) ÷ molecular weight of KOH (mmol)
OHV is the hydroxyl value (mgKOH / g) of the polyol.
Equivalent number of water = molecular weight of water (g) / molecular weight of water (mol) x number of OH groups of water In each of the above formulas, the molecular weight of NCO is 42 (mol) and the molecular weight of KOH is 56,100 (mmol). ), The molecular weight of water is 18 (mol), and the number of OH groups in water is 2.

<Manufacturing method of polyurethane foam>
The method for producing polyurethane foam is not particularly limited, but the polyol-containing composition is mixed with polyisocyanate in a foaming machine or the like, and the obtained mixture (foamable polyurethane composition) is reacted and foamed to obtain polyurethane. It is good to manufacture foam. As the foaming machine, it is preferable to use a spray device or the like having a spray gun.
The polyol-containing composition may be fed to a foaming machine and collision-mixed with polyisocyanate sent from another container or the like inside the foaming machine. Then, the mixed liquid (foamable polyurethane composition) may be discharged from a discharge port of a spray gun or the like, and the polyurethane foam may be molded by the discharged foamable polyurethane composition.

This manufacturing method can preferably be applied to spraying applications. Therefore, it is preferable to form the polyurethane foam on the surface to be constructed by spraying the mixed liquid discharged from the foaming machine onto the surface to be constructed with a constant discharge pressure and foaming the mixture.

<Use of polyurethane foam>
The use of the polyurethane foam of the present invention is not particularly limited, but since it is excellent in flame retardancy and heat insulating property, it can be suitably used for buildings such as walls, ceilings, roofs, and floors of buildings. Polyurethane foam may be molded using the roof, floor, etc. as the spray target surface.

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

[Material used]
<Polycarbonate-containing composition>
(Polyol)
-P-Phthalic acid polyester polyol (manufactured by Kawasaki Kasei Chemicals, product name: Maximol RLK-087, hydroxyl value = 200 mgKOH / g)

(catalyst)
-Resinylated amine catalyst, 1,2-dimethylimidazole (manufactured by Tosoh Corporation, product name: TOYOCAT (registered trademark) -DM70) concentration 65-75% by mass
・ Resinized metal catalyst, bismuth trioctate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-600) concentration 55-58% by mass
・ Resinized metal catalyst, dioctyl tin versatate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-830) concentration approx. 99% by mass
-Ammonium salt (triquantization catalyst), 2,2-dimethylpropanoic acid tetramethylammonium salt (Air Products, Chemicals, product name: DABCO (registered trademark) TMR7) concentration 45-55% by mass
-Metal catalyst (triquantization catalyst), potassium 2-ethylhexanoate (manufactured by Air Products and Chemicals, product name: DABCO (registered trademark) K-15) concentration 70-80% by mass

(Effervescent agent)
-Hydrofluoroolefin (HFO), trans-1-chloro-3,3,3-trifluoropropene (manufactured by Honeywell Japan, product name: Saltis LBA)
·water

(Phosphoric acid ester (liquid flame retardant))
-Tris (β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP)

(Filler)
・ Wollastonite (SiO ₂・ CaO) (manufactured by Kinsei Matek Co., Ltd., product name: SH-1250)

<Polyisocyanate>
・ 4,4'-Diphenylmethane diisocyanate (4,4'-MDI) (manufactured by Manka Chemical Japan Co., Ltd., product name: PM200)

[Manufacturing of polyurethane foam]
Each component was mixed according to the formulation shown in Table 1 to prepare a polyol-containing composition. Using the polyol-containing composition and polyisocyanate, a polyurethane foam was produced under the following conditions.
<Manufacturing conditions>
-Sprayer: Graco sprayer H-25
・ Setting (heater setting)
Isocyanate heater: 38 ° C
Premix heater (for heating polyol-containing composition): 38 ° C.
Hose heater (for pre-mixing heating of polyisocyanate and polyol-containing compositions): 38 ° C.
Pressure: Adjust appropriately so that the mist has a wide circular shape ・ Base material temperature (temperature of the surface to be sprayed): 20 ° C ± 1 ° C

[Evaluation method of polyurethane foam]
1. 1. Adhesive strength Polyurethane foam is sprayed onto a 30 cm square plywood (wooden board) under the above manufacturing conditions. A test piece is collected so that the bottom surface is a square with a side of 50 ± 1 mm and the thickness of the polyurethane foam is 30 ± 1 mm. Attach the jig. Use a metal jig with a hook so that it can be attached to the test piece.
Using a tensile test device (Tencilon universal testing machine, manufactured by A & D Co., Ltd.) at 23 ° C, hook the metal jig in the direction perpendicular to the plywood at a constant speed of 10 mm / min. The pressure is obtained from the load and cross-sectional area when the polyurethane foam is broken or the polyurethane foam and the plywood are peeled off by grasping and pulling the portion.
The number of test pieces was three, the average value of the above pressures was calculated, and the integers were rounded off. The numerical results are shown in Table 1.

2. 2. Presence or absence of peeling The above 50 mm square test piece was placed in an oven and left in an environment with a temperature of 40 ° C. and a humidity of 95 RH% for one week. Then, the presence or absence of peeling of the polyurethane foam from the plywood was evaluated visually and by palpation. The evaluation criteria are as follows.
〇: Not peeled off ×: Peeled off

3. 3. Ease of peeling The 30 cm test piece was manually peeled off onto plywood and polyurethane foam. Then, the ease of peeling off the polyurethane foam was evaluated by palpation. The evaluation criteria are as follows.
〇: Polyurethane foam can be removed from the plywood by peeling it off several times.
X: Polyurethane foam remains on the plywood and cannot be peeled off cleanly.

[Examples 1 to 7, Comparative Examples 1 and 2]
Each component was mixed according to the formulation shown in Table 1 to prepare a polyol-containing composition. A polyurethane foam was produced using the polyol-containing composition and polyisocyanate, and the above evaluation methods 1 to 3 were evaluated. The results are shown in Table 1. The mixing ratio of the polyol-containing composition and the polyisocyanate was 1: 1 by volume.

触媒の各含有量は、製品としての含有量である。

Each content of the catalyst is the content as a product.

As is clear from the results of the above Examples and Comparative Examples, the polyurethane foam using the polyol-containing composition of the present invention has a predetermined adhesive strength, does not peel off under normal conditions, and is a target. It can be seen that it is easy to peel off from an object, that is, it has both good adhesiveness and ease of peeling.
On the other hand, none of the polyurethane foams using the polyol-containing composition of the comparative example had a predetermined adhesive strength, and could not achieve both good adhesiveness and ease of peeling.

Claims (11)

A polyol-containing composition for reacting with a polyisocyanate to obtain a polyurethane foam.
Contains polyols, foaming agents, catalysts, and fillers,
The catalyst contains a metal catalyst containing at least one selected from the group consisting of bismuth and tin.
The polyurethane foam obtained by reacting with polyisocyanate by spraying is a polyol-containing composition characterized by having an adhesive strength of 80 kPa or more and 250 kPa or less measured in accordance with JIS A 09526. The polyol-containing composition according to claim 1, wherein the filler ratio in the polyol-containing composition is 8% or more. The polyol-containing composition according to claim 1 or 2, wherein the filler ratio in the polyol-containing composition is 29% or less. The polyol-containing composition according to any one of claims 1 to 3, wherein the catalyst comprises a trimerization catalyst. The polyol-containing composition according to any one of claims 1 to 4, wherein the trimerization catalyst contains a quaternary ammonium salt. The polyol-containing composition according to any one of claims 1 to 5, wherein the catalyst contains an imidazole derivative. The polyol-containing composition according to any one of claims 1 to 6, wherein the catalyst contains bismuth. The polyol-containing composition according to any one of claims 1 to 7, wherein the foaming agent contains a hydrofluoroolefin. Contains polyols, foaming agents, catalysts, fillers, and polyisocyanates.
The catalyst contains a metal catalyst containing at least one selected from the group consisting of bismuth and tin.
The polyurethane foam obtained by reacting by spraying is a foamable polyurethane composition characterized in that the adhesive strength measured in accordance with JIS A 09526 is 80 kPa or more and 250 kPa or less. The foamable polyurethane composition according to claim 9, wherein the isocyanate index is 200 or more. A polyurethane foam obtained by reacting and foaming the effervescent polyurethane composition according to claim 9 or 10.