JP2022030312A - Polyol composition, foamable polyurethane composition, and polyurethane foam - Google Patents

Abstract

To enable a polyol composition charged into containers such as a drum, to be blended with an isocyanate after a filler has been uniformly dispersed therein, practically easily at a construction site.SOLUTION: The present invention discloses a polyol composition that is reacted with a polyisocyanate to make a polyurethane foam, the polyol composition charged into a container, containing a polyol, a foamer, catalyst, and a filler and having a viscosity of 300-2000 mPa s at 25°C.SELECTED DRAWING: None

Description

The present invention relates to a polyol composition and a foamable polyurethane composition used for producing a polyurethane foam, and further to a polyurethane foam formed from a foamable polyurethane composition.

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. Polyurethane foam is obtained by mixing a polyol composition and polyisocyanate and foaming them.

As a construction method, it is common to mix a polyol composition and a polyisocyanate at a construction site, react and foam, and spray the mixture. For example, in Patent Document 1, the polyol composition and the polyisocyanate are separately stored in a container such as a drum can, and immediately before construction, the liquid is sent from each container to a mixing device equipped with an injection gun via a line and mixed. It is known that the mixture is mixed by an apparatus and the mixed solution is sprayed by an injection gun (see, for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2016-145360

In recent years, polyurethane foam has been studied to contain a filler in order to impart various performances such as flame retardancy. Of the polyol composition and polyisocyanate, the filler is generally blended with the polyol composition. When the polyol composition containing a filler is stored in a container such as a drum can, the filler may settle in the container, and therefore it has been considered to stir immediately before use.

However, at the construction site, the method of stirring the polyol composition filled in a container such as a drum can is limited, and it is practically easy to mix the polyol composition with isocyanate after uniformly dispersing the filler. is not it.

Therefore, according to the present invention, even if the polyol composition is filled in a container such as a drum can, the filler can be easily and uniformly dispersed at the construction site and then mixed with isocyanate. The challenge is to provide things.

As a result of diligent studies to solve the above problems, the present inventor has determined the viscosity at 25 ° C. of a polyol composition filled in a container such as a drum can and containing a polyol, a foaming agent, a catalyst, and a filler. We have found that the above problems can be solved by adjusting to a predetermined range, and have completed the following invention. That is, the present invention provides the following [1] to [11].
[1] A polyol composition for reacting with polyisocyanate to obtain a polyurethane foam.
A polyol composition that is filled in a container, contains a polyol, a foaming agent, a catalyst, and a filler, and has a viscosity at 25 ° C. of 300 to 2000 mPa · s.
[2] The polyol composition according to the above [1], wherein the catalyst contains a trimerization catalyst.
[3] The polyol composition according to the above [2], wherein the trimerization catalyst contains a quaternary ammonium salt.
[4] The polyol composition according to any one of the above [1] to [3], wherein the catalyst contains a metal catalyst containing at least one selected from the group consisting of bismuth and tin.
[5] The polyol composition according to any one of the above [1] to [4], wherein the catalyst contains an imidazole derivative.
[6] The polyol composition according to any one of the above [1] to [5], wherein the foaming agent contains a hydrofluoroolefin.
[7] The polyol composition according to any one of the above [1] to [6], wherein the filler contains a thickener.
[8] The polyol composition according to any one of the above [1] to [7] for spraying construction.
[9] A foamable polyurethane composition containing the polyol composition according to any one of the above [1] to [8] and a polyisocyanate.
[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, even a polyol composition used by being filled in a container such as a drum can can be practically easily uniformly dispersed at a construction site and then mixed with isocyanate. ..

[Polyform composition]
The polyol composition of the present invention is a polyol composition for reacting with polyisocyanate to obtain a polyurethane foam. The polyol composition of the present invention is filled in a container such as a drum and contains a polyol, a foaming agent, a catalyst, and a filler. Hereinafter, each component in the polyol composition will be described in detail.

<Polyol>
The polyol 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. The polyol usually becomes a liquid at normal temperature (23 ° C.) and normal pressure (1 atm).

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, pentandiol, and hexanediol.

Examples of the polyester polyol include a polymer obtained by dehydrating and condensing a polybasic acid and a polyhydric alcohol, and a condensate of a hydroxycarboxylic acid and the polyhydric alcohol and 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 and reaction products of castor oil and ethylene glycol.

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 polymer, for example, at least one kind of alkylene oxide such as ethylene oxide, propylene oxide and tetrahydrofuran is ring-opened 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 a polymer obtained by polymerization. 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, etc., sucrose, glucose, mannose, fructose, methyl glucoside and its derivatives, tetra-octavalent alcohols, ethylenediamine, butylene diamine, etc. Examples of amines and the like.

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. An aromatic polyester polyol obtained by dehydration condensation with the dihydric alcohol of No. 1 is more preferable. By using an aromatic polyester polyol, flame retardancy can be easily improved.

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 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.

The content of the polyol in the polyol composition of the present invention is preferably 15 to 80% by mass, more preferably 20 to 70% by mass, and further preferably 25 to 60% by mass. When the content of the polyol is at least the above lower limit value, the polyol and the polyisocyanate are likely to react with each other, which is preferable. On the other hand, when the content of the polyol is not more than the upper limit, the viscosity of the polyol composition does not become too high, which is preferable from the viewpoint of handleability.

<Effervescent agent>
The polyol composition of the present invention preferably contains a hydrofluoroolefin as a foaming agent. Hydrofluoroolefins have good foamability, have a low global warming potential, and are preferable from the viewpoint of environmental protection. Even when a hydrofluoroolefin is used as the foaming agent, the stability of the foaming agent is enhanced and the catalytic activity is less likely to be lowered by adjusting the composition of each component as described later. Examples of the hydrofluoroolefin include fluoroalkenes having about 3 to 6 carbon atoms. The hydrofluoroolefin may be a hydrochlorofluoroolefin having a chlorine atom, and therefore may be a chlorofluoroalkene having about 3 to 6 carbon atoms.
More specifically, trifluoropropene, tetrafluoropropene such as HFO-1234, pentafluoropropene such as HFO-1225, chlorotrifluoropropene such as HFO-1233, chlorodifluoropropene, chlorotrifluoropropene, and chlorotetra. Fluoropropene and the like can be mentioned. More specifically, 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene (HFO). -1225ye), 1,1,1-trifluoropropene, 1,1,1,3,3-pentafluoropropene (HFO-1225zc), 1,1,1,3,3,3-hexafluorobut-2 -En, 1,1,2,3,3-pentafluoropropene (HFO-1225yc), 1,1,1,2,3-pentafluoropropene (HFO-1225yez), 1-chloro-3,3,3 -Trifluoropropene (HFO-1233zd), 1,1,1,4,4,4-hexafluorobut-2-ene and the like can be mentioned. Of these, HFO-1233zd is preferred.
These hydrofluoroolefins may be used alone or in combination of two or more.

The content of the hydrofluoroolefin in the polyol composition is preferably 20 to 70 parts by mass, more preferably 25 to 60 parts by mass, and even more preferably 30 to 50 parts by mass with respect to 100 parts by mass of the polyol. When the content of the hydrofluoroolefin is at least the above lower limit value, foaming is promoted and the density of the obtained polyurethane foam can be reduced. On the other hand, when the content of the hydrofluoroolefin is not more than the above upper limit value, it is possible to suppress the excessive progress of foaming.

Further, the polyol composition of the present invention may contain a foaming agent other than the hydrofluoroolefin. Examples of the foaming agent other than the hydrofluoroolefin include water, an organic physical foaming agent, and an inorganic physical foaming agent. Examples of the organic physical foaming agent include low boiling hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane, dichloroethane, propyl chloride, isopropyl chloride, and butyl chloride. Examples thereof include chlorinated aliphatic hydrocarbon compounds such as isobutyl chloride, pentyl chloride, and isopentyl chloride, and ether compounds such as dimethyl ether and diisopropyl ether. Examples of the inorganic physical foaming agent include nitrogen gas, oxygen gas, argon gas, carbon dioxide gas and the like. Among these, water, oxygen gas, and carbon dioxide gas are preferable from the viewpoint of handleability, and water is more preferable from the viewpoint of adjusting the isocyanate index and from the viewpoint of ease of handling.

The content of the foaming agent other than the hydrofluoroolefin (HFO) such as water is preferably 0.01 to 25 parts by mass, more preferably 0.1 to 20 parts by mass, and 0.5 parts by mass with respect to 100 parts by mass of the polyol. Up to 15 parts by mass is more preferable. When the content of the foaming agent other than HFO is at least the above lower limit value, foaming is promoted and the density of the obtained polyurethane foam can be reduced. On the other hand, when the content of the foaming agent other than HFO is not more than the upper limit, it is possible to suppress the excessive progress of foaming.

<Catalyst>
Examples of the catalyst used in the polyol composition of the present invention include a resinification catalyst, a trimerization catalyst and the like, and preferably both a resinification catalyst and a trimerization catalyst are used. Examples of the resinification catalyst include a resinified metal catalyst, a resinified amine catalyst, and the like, as described later, and both of them may be used.

<< Metal catalyst (resinized metal catalyst) >>
Specifically, the catalyst preferably contains a metal catalyst containing at least one selected from 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. Further, if a filler described later is contained in a certain amount or more, the reactivity of the polyurethane foam is hindered and the foamability tends to decrease, but by containing a metal catalyst, the foamability of the polyurethane foam can be easily maintained. The metal catalyst more preferably contains bismuth from the viewpoint of foamability 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 octylic acid. These carboxylic acids may be linear as described above, but may have a branched structure. Examples of the octyl 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 composition is preferably 0.1 to 10 parts by mass, more preferably 1 to 8 parts by mass, still more preferably 1.5 to 6 parts by mass with respect to 100 parts by mass of the polyol. 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, the curing reaction speed of the effervescent polyurethane composition is improved and the effervescent property is improved. 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 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 composition. Therefore, when the polyol 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 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 composition is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, still more preferably 2 to 15 parts by mass, and 3 to 3 to 100 parts by mass with respect to 100 parts by mass of the polyol. 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 composition of the present invention preferably 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. The inclusion of the trimerization catalyst has the advantage that a good foam can be obtained by completing the reaction of the unreacted isocyanate group. Examples of the trimerization catalyst include a metal catalyst, an ammonium salt and the like, and these may be used in combination.
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, but preferably contains at least a quaternary ammonium salt. 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 composition is preferably 0.5 to 30 parts by mass, more preferably 1 to 25 parts by mass, and even more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the polyol. ~ 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. A foam can be formed.

<Filler>
The polyol composition of the present invention contains a filler. The filler is contained as a solid component in the polyol composition, and is a component generally present as a granular or powdery component in the polyol composition. In the present invention, by containing a filler, it becomes easy to improve various physical properties such as flame retardancy and mechanical properties of the obtained 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 composition. The filler preferably has no hygroscopicity and deliquescent property from the viewpoint of reducing the water absorption rate of the polyurethane foam.
Specifically, as the filler, it is preferable to use a solid flame retardant that is solid at normal temperature (23 ° C.) and normal pressure (1 atm). The solid flame retardant is selected from 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, needle-like fillers and the like. It is preferable that the number is at least one. By using a solid flame retardant as a filler, the flame retardancy of urethane foam is improved. The solid flame retardant may be used alone or in combination of two or more.

(Red phosphorus flame retardant)
The red phosphorus-based flame retardant used as a filler may be composed of red phosphorus alone, may be 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)
The phosphate-containing flame retardant is at least selected from various phosphates, metals of the Group IA to IVB of the Periodic Table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring. Phosphates consisting of salts with one metal or compound can be mentioned. 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 epichlorohydrin, 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, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide and vanadium hydroxide. Examples include 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.

The content of the solid flame retardant is, for example, preferably 10 parts by mass or more, more preferably 25 parts by mass or more, still more preferably 35 parts by mass or more, and 45 parts by mass with respect to 100 parts by mass of the polyol. It is particularly preferable that the content is by mass or more. By setting the content of the solid flame retardant to the above lower limit value or more, the flame retardancy of the polyurethane foam can be enhanced. The content of the solid flame retardant is preferably 110 parts by mass or less, more preferably 97 parts by mass or less, and further preferably 87 parts by mass or less with respect to 100 parts by mass of the polyol. By setting the content of the solid flame retardant to these upper limit values or less, it becomes easy to obtain good foamability without lowering the reactivity.

(Thickener)
The polyol composition of the present invention preferably contains a thickener as a filler. By containing the thickener, it becomes easy to adjust the viscosity of the polyol composition within a predetermined range. As the thickener, inorganic particles such as silica, fumed silica, calcium oxide, titanium oxide, metal oxide such as aluminum oxide (alumina), metal hydroxide salt such as calcium hydroxide, and metal carbonate such as calcium carbonate. Among these, alumina particles are preferable.
The alumina is preferably fumed alumina, and more preferably fumed alumina having a hydrophobic surface treatment. Examples of the hydrophobic surface treatment include a method of surface treatment with a silicon-based organic compound such as alkylsilane.
The content of the thickener is, for example, preferably 0.2 to 15 parts by mass, more preferably 0.4 to 10 parts by mass, and further preferably 0.8 to 6 parts by mass with respect to 100 parts by mass of the polyol. be. By setting the content of the thickener within the above range, it becomes easy to adjust the viscosity of the polyol composition within a predetermined range.

As the filler, an inorganic filler (other inorganic filler) other than the above-mentioned flame retardant and thickener may be used. Such inorganic fillers include ferrites, dosonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, talc, mica, montmorillonite, bentonite, activated clay, imogolite, sericite, glass beads, aluminum nitride, nitride. Boron, 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.

When a thickener is used as the filler, the thickener is preferably used in combination with a filler other than the thickener. The thickener may be used in combination with the above-mentioned solid flame retardant, or may be used in combination with an inorganic filler other than the thickener and the solid flame retardant, or may be used in combination with both of them. By using the thickener in combination with a solid flame retardant or an inorganic filler other than the thickener and the solid flame retardant, the polyurethane foam is imparted with functions such as flame retardancy, and the viscosity of the polyol composition is appropriate. It becomes easy to adjust within a reasonable range. Further, the thickener is preferably used in combination with the solid flame retardant from the viewpoint of adjusting the viscosity of the polyol composition within an appropriate range while imparting flame retardancy to the polyurethane foam.

The content of the filler in the polyol composition is preferably, for example, 10 parts by mass or more, more preferably 30 parts by mass or more, and further preferably 40 parts by mass or more with respect to 100 parts by mass of the polyol. , 50 parts by mass or more is particularly preferable. By setting the content of the filler to the above lower limit value or more, it becomes easy to impart various functions such as flame retardancy to the polyurethane foam. The content of the filler is preferably 120 parts by mass or less, more preferably 100 parts by mass or less, and further preferably 90 parts by mass or less with respect to 100 parts by mass of the polyol. By setting the content of the filler to these upper limit values or less, it becomes easy to obtain good foamability without lowering the reactivity.

<Phosphate ester>
The polyol composition of the present invention may have a flame retardant other than the above-mentioned solid flame retardant. Examples of such a flame retardant include a flame retardant (liquid flame retardant) that is liquid at room temperature (23 ° C.) and normal pressure (1 atm), and specific examples thereof include a phosphoric acid ester. 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 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 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, a monophosphate ester is preferable from the viewpoint of facilitating the appropriate viscosity of the polyol composition and the viewpoint of improving the flame retardancy of the polyurethane foam, and a halogen-containing phosphoric acid ester such as tris (β-chloropropyl) phosphate is preferable. Is more preferable.
The content of the phosphoric acid ester in the polyol 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. The part is more preferable.

<Foam control agent>
The polyol 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 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 composition of the present invention is preferably 0.1 to 12 parts by mass, more preferably 1 to 10 parts by mass, and further preferably 2 to 8 parts by mass with respect to 100 parts by mass of the polyol. preferable. When the content of the defoaming agent is at least the above lower limit value, it becomes easy to foam the mixture of the polyol composition and the polyisocyanate, so that a homogeneous polyurethane foam can be obtained. Further, when the content of the defoaming agent is not more than the above upper limit value, the balance between the manufacturing cost and the obtained effect is optimized.

<Other ingredients>
The polyol composition may be a phenol-based, amine-based, sulfur-based or other antioxidant, heat stabilizer, metal damage inhibitor (metal inactivating agent), and antistatic 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 inhibitor, stabilizer, cross-linking agent, lubricant, softener, pigment, tackifier resin, and tackifier such as polybutene and petroleum resin.

[Viscosity of polyol composition]
In the present invention, the viscosity of the polyol composition at 25 ° C. is 300 to 2000 mPa · s. When the viscosity is less than 300 mPa · s, the stirring force by the stirring blade or the like described later cannot be sufficiently transmitted to the polyol composition, and it becomes difficult to uniformly disperse the filler in the polyol composition to be filled in the container. It also makes it difficult to add a sufficient amount of filler to the polyol composition. On the other hand, when it is higher than 2000 mPa · s, the stirring power is insufficient even if a stirring blade or the like described later is used, and it is difficult to uniformly disperse the filler in the polyol composition to be filled in the container. Further, in the polyol composition, if the filler is not uniformly dispersed, problems such as variation in the quality of the polyurethane foam occur.
From the viewpoint of more uniformly dispersing the filler at the construction site, the viscosity is preferably 300 to 1900 mPa · s, more preferably 350 to 1600 mPa · s, and even more preferably 400 to 1300 mPa · s.
The viscosity at 25 ° C. is a viscosity measured using a BM type viscometer under the conditions of a rotation speed of 60 rpm and a temperature of 25 ° C., and can be measured in more detail by the method described in Examples.

[container]
As the container filled with the polyol composition of the present invention, a known container filled with the polyol composition can be used, and a drum can is a typical example. A drum can is a container having a cylindrical body portion, a top surface portion that closes both openings of the body portion, and a bottom surface portion. In addition to the drum can, the container may be a bottle-shaped container or a square container. The square container has a square tubular body portion, a top surface portion that closes both openings of the body portion, and a bottom surface portion, and is known as an itto-kan or the like. In addition, a pail can or a top surface portion may be opened and closed.
It is preferable to use a drum can as the container. Drums are practical because they are versatile and have a relatively large capacity. Further, by having the cylindrical body portion, it is easy to uniformly stir the polyol composition filled in the container by the stirring blade described later.

The material of the container such as a drum can is not particularly limited, but may be metal or the like, or may be made of resin or the like. Further, the container may be a container in which a protective film or the like is formed on the inner peripheral surface by an internal coating.
In addition, each container such as a drum can has an opening for putting in and taking out the contents. The opening is provided on the top surface of a drum can or a square container, for example. Further, the drum can generally has a large opening on the top surface and a small opening having a diameter smaller than that of the large opening. When having a large opening and a small opening, the large opening is usually used to put in and take out the contents, and the small opening is a vent for putting in and out the contents.

The size of the opening of the container is not particularly limited, but may be sufficiently smaller than the diameter of the top surface, and the diameter of the opening is typically about 1/100 to 1/2 of the diameter of the top surface. It is about 1/50 to 1/5. The specific dimensions are about 1 to 10 cm, and more typically 1.5 to 8 cm. When a plurality of openings (for example, the above-mentioned large opening and the above-mentioned small opening) are provided as in a drum can, the diameter of each opening may be within the above range.
The capacity of the container is not particularly limited, but is, for example, about 15 to 400 L, preferably about 50 to 300 L, and more preferably about 150 to 250 L. When the capacity of the container is within the above range, the container is versatile, and the manufacturing method described later can be carried out on a relatively large scale, and it becomes easy to put it into practical use. In addition, the stirring blade described later makes it easier to make the filler to be blended uniform.

A container filled with the polyol composition (polypoly composition-filled container) may be prepared by filling the above-mentioned container with the components constituting the polyol composition. The method for preparing the polyol composition is not particularly limited, but each component may be added and the components may be mixed and prepared by stirring or the like. Each component may be added directly to the container and each component may be mixed in the container to prepare a polyol composition, or each component may be mixed in advance in a container other than a container such as a mixing device to obtain a polyol composition. It may be prepared and the prepared polyol composition may be filled in a container.

[Manufacturing method of polyurethane foam]
Next, a method for producing a polyurethane foam using the above polyol composition will be described in detail. In the present production method, first, a container filled with the polyol composition (polypoly composition-filled container) is prepared as described above. Next, the polyol composition filled in the container is stirred. Then, the stirred polyol composition is mixed with polyisocyanate, and the obtained mixture is foamed to obtain a polyurethane foam.
As described above, the polyol composition of the present invention is a pre-stirring polyol composition that is stirred before being mixed with isocyanate.

In the present production method, the polyol composition filled in the container may be appropriately stored and then stirred. Storage is usually carried out at a temperature near room temperature (for example, about 0 to 30 ° C.). The storage time is not particularly limited, and is, for example, within about 1 year, more typically within about 6 months, and more preferably within 3 months.

As a method for stirring the polyol composition, it is sufficient that the filler can be uniformly dispersed in the polyol composition, but it is preferable to use stirring blades. The stirring blades are placed in the polyol composition and rotated to stir the polyol composition.
For stirring the polyol composition, for example, a stirrer equipped with a stirring blade may be used. More specifically, the stirrer includes a shaft portion, a stirrer blade attached to the shaft portion, and a stirrer that rotates around the shaft portion.
In such a stirrer, the stirring blade can be arranged in the polyol composition by inserting the shaft portion into the container through the opening of the container such as a drum can. Further, the stirring blade may be of a type in which the stirring blade is opened by the centrifugal force and resistance acted by being put in the polyol composition. As the stirrer, for example, a commercially available mixer for drums may be used.
A stirrer equipped with a stirrer blade such as a mixer for drums can be carried around and can be practically used even when polyurethane foam is manufactured by in-situ foaming.

The opening of the container is generally closed by a stopper, but as described above, when stirring using a stirring blade, it is preferable to stir after opening the container. Further, in a drum can or the like, the opening of the container may be provided with a large opening and a small opening as described above. At this time, the stirring blade may be inserted into the container from either the large opening or the small opening, but it is preferably inserted from the small opening. In the present invention, even if the stirring blade has a size that allows it to be inserted through a small opening, the filler can be uniformly dispersed by setting the viscosity of the polyol composition within the above-mentioned predetermined range.

The temperature at the time of stirring the polyol composition filled in the container is not particularly limited, but is preferably, for example, 5 to 35 ° C, preferably 10 to 30 ° C. The stirring time is, for example, about 1 to 120 minutes, preferably about 10 to 60 minutes.

The polyol composition stirred by the stirring blade or the like as described above is then 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.
More specifically, the polyol composition is sent to the foaming machine in a state where the composition such as the filler is uniformly dispersed by stirring, and the polyisocyanate sent from another container or the like and the inside of the foaming machine. It is good to mix them by collision. The polyol composition may be agitated during feeding, but usually does not need to be agitated. The mixed liquid (foamable polyurethane composition) obtained by mixing may be discharged from a discharge port of a spray gun or the like, and a polyurethane foam may be formed from the discharged foamable polyurethane composition.

This manufacturing method is preferably applied to, for example, spraying construction. Therefore, it is preferable that the mixed liquid discharged from the foaming machine is sprayed on the construction target surface at a constant discharge pressure and foamed to form a polyurethane foam on the construction target surface.
Further, in the present invention, a polyurethane foam may be obtained by mixing a polyisocyanate and a polyol composition, and then injecting the polyisocyanate into a container such as a mold or a frame material and curing the mixture.

[Effervescent polyurethane composition and polyurethane foam]
The effervescent polyurethane composition according to the present invention contains the above-mentioned polyol composition and polyisocyanate. The polyol composition and the polyisocyanate may be separate liquids, and these may be mixed and used. The polyurethane foam of the present invention is a reaction product obtained by reacting and foaming a mixture (foamable polyurethane composition) of a polyol composition and a polyisocyanate.

<Polyisocyanate>
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 polyisocyanates are preferable from the viewpoint of ease of use and availability, and diphenylmethane diisocyanate, polypeptide MDI, or a mixture thereof is more preferable. 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 other components such as known additives to be blended with the polyisocyanate before being mixed with the polyol composition.

It is preferable that the volume of the polyol composition and the polyisocyanate mixed in the polyol composition are substantially the same. Specifically, the volume ratio of the polyisocyanate to the polyol composition is preferably 0.8 to 1.2, more preferably 0.9 to 1.1, and even more preferably 0.95 to 1.05. The volume of the polyisocyanate is, when a component other than the polyisocyanate is added, the volume of the polyisocyanate after the addition of the component.

<Isocyanate index>
The isocyanate index of the effervescent polyurethane composition 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, further preferably 300 or more, further preferably 350 or more, and particularly preferably 400 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.

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.

The content of the filler in the polyurethane foam (that is, the foamable polyurethane composition) is, for example, 4 parts by mass or more, preferably 6 parts by mass or more, and 8 parts by mass or more with respect to 100 parts by mass of the urethane resin. It is more preferable that the amount is 10 parts by mass or more. By setting the content of the filler in the foamable polyurethane composition to the above lower limit value or more, the proportion of the filler in the polyurethane foam becomes sufficient, the water absorption rate of the polyurethane foam can be reduced, and hydrolysis is satisfactorily suppressed. be able to. The filler content is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, based on 100 parts by mass of the urethane resin. By setting the value to the upper limit or less, it becomes easy to obtain a polyurethane foam having good foamability. The total amount of the polyol and the polyisocyanate blended in the foamable polyurethane composition can be regarded as the amount of the urethane resin in the polyurethane foam or the foamable polyurethane composition.

<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 formed with the roof, floor, etc. as the surface to be sprayed. Further, it can be suitably used as a member for filling an arbitrary opening generated in a building, including joints and holes generated between structural materials of the building.

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

The components used in Examples and Comparative Examples were as follows.
<Polyform composition>
[Polyol]
-P-Phthalic acid polyester polyol (manufactured by Kawasaki Kasei Chemicals, product name: Maximol RLK-087, hydroxyl value = 200 mgKOH / g)
〔catalyst〕
・ 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
-Resinylated amine catalyst, 1,2-dimethylimidazole (manufactured by Tosoh Corporation, product name: TOYOCAT (registered trademark) -DM70) concentration 65-75% 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
-Quaternary ammonium salt (triquantization catalyst), tetramethylammonium 2,2-dimethylpropanoate salt (Air Products, Chemicals, product name: DABCO (registered trademark) TMR7) concentration 45-55% by mass
[Effervescent agent]
-Hydrofluoroolefin (HFO, manufactured by Honeywell Japan Co., Ltd., product name: Solstice LBA, trans-1-chloro-3,3,3-trifluoropropene)
・ Water [Liquid flame retardant]
-Tris (β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP)
[Filler]
(Solid flame retardant)
・ Wollastonite (SiO ₂・ CaO) (manufactured by Kinsei Matek Co., Ltd., product name: SH-1250)
(Thickener)
・ Humed Alumina (manufactured by Aerosil Japan, product name: AEROXIDE AluC805)
<Polyisocyanate>
・ 4,4'-Diphenylmethane diisocyanate (4,4'-MDI) (manufactured by Manka Chemical Japan Co., Ltd., product name: PM200)

Examples 1-9, Comparative Example 1
Each component was mixed according to the formulation shown in Table 1 to prepare a polyol composition. The polyol composition was filled in a 200 L drum having a small opening (3/4 inch (1.9 cm) in diameter) and a large opening (2 inches (5.1 cm) in diameter) on the top surface.
The polyol composition filled in the drum can was stored at room temperature (25 ° C.) for 24 hours. After that, the small opening of the drum can was opened, and a mixer for drums (“Air-driven agitator for drums, with 3-stage wings, product number: NUE035B-1” manufactured by Nippon Urethane Engineering Co., Ltd.) was set. Next, the large opening of the drum can was opened, and the mixture was stirred at 25 ° C. for 30 minutes with a drum mixer. Immediately after the completion of stirring, the contents were visually observed from the large opening, and the uniformity was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1.
Further, after stirring, the polyol composition was mixed with polyisocyanate from a spray device according to the description in Table 1, and spray foaming was performed from a spray gun. .. On the other hand, in the comparative example, since the components of the entire drum were non-uniform, the components differed between the beginning and the end of use when the drum was used, resulting in variations in quality.

(Uniformity)
A: The transparency of the entire liquid was lost and there was no transparent portion, and the filler was uniformly dispersed.
B: Although the transparent portion was mottled, the transparency of the entire liquid was generally lost and the filler was dispersed almost uniformly.
C: In the upper part of the drum can located far from the stirring blade, the polyol composition remained transparent and the filler was not uniformly dispersed.

(Viscosity of polyol composition)
The viscosity of the polyol composition was measured using a BM type viscometer (Viscometer / TV-22, manufactured by Toki Sangyo Co., Ltd.) under the conditions of spindle BM3, rotation speed 60 rpm, and temperature 25 ° C. Table 1 shows the viscosities of the polyol compositions of each Example and Comparative Example.

As described above, in Examples 1 to 9 in which the viscosity at 25 ° C. is within a predetermined range, the polyol composition filled in the container is stirred by a stirrer that can be used at the construction site to obtain the polyol composition. The contained filler could be uniformly dispersed. On the other hand, in Comparative Example 1, the viscosity at 25 ° C. was too high, and even if the polyol composition was stirred with a stirrer, the contained filler could not be uniformly dispersed.

Claims (11)

A polyol composition for reacting with polyisocyanate to obtain polyurethane foam.
A polyol composition that is filled in a container, contains a polyol, a foaming agent, a catalyst, and a filler, and has a viscosity at 25 ° C. of 300 to 2000 mPa · s. The polyol composition according to claim 1, wherein the catalyst comprises a trimerization catalyst. The polyol composition according to claim 2, wherein the trimerization catalyst contains a quaternary ammonium salt. The polyol composition according to any one of claims 1 to 3, wherein the catalyst contains a metal catalyst containing at least one selected from the group consisting of bismuth and tin. The polyol composition according to any one of claims 1 to 4, wherein the catalyst contains an imidazole derivative. The polyol composition according to any one of claims 1 to 5, wherein the foaming agent contains a hydrofluoroolefin. The polyol composition according to any one of claims 1 to 6, wherein the filler contains a thickener. The polyol composition according to any one of claims 1 to 7, which is for spraying construction. A foamable polyurethane composition comprising the polyol composition according to any one of claims 1 to 8 and a polyisocyanate. 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.