JP7583549B2 - Polyol composition, foamable polyurethane composition, and polyurethane foam - Google Patents

Description

The present invention relates to a polyol composition, a foamable polyurethane composition, and a polyurethane foam formed from the foamable polyurethane composition.

Due to its excellent insulating and adhesive properties, polyurethane foam is used as an insulating material for buildings such as apartment complexes, detached houses, various school facilities, and commercial buildings. Rigid polyurethane foam, which is flame-retardant against fire, is widely used as an insulating material, and flame retardants such as red phosphorus are used.

Polyurethane foam is obtained by mixing a polyol composition and a polyisocyanate and foaming the mixture, and the construction method is to mix the polyol composition and the polyisocyanate at the construction site, react them, foam them, and spray them, etc. Therefore, the polyol composition and the polyisocyanate are mixed immediately before construction (for example, see Patent Document 1).
In such on-site application, the initial reaction rate of the polyol composition and the polyisocyanate is important, and if the curing reaction rate during spraying is slow, there is a problem of dripping.

JP 2016-145360 A

As described above, the polyol composition and the polyisocyanate are mixed just before application, reacted, and foamed, so that the initial reaction rate is important. If the reaction rate is slow, dripping occurs, resulting in poor appearance, and if it takes too long to cure, the next work cannot be carried out.
On the other hand, flame retardants are added to polyurethane foams to impart flame retardancy, but because the flame retardant acts to slow down the initial reaction rate, the addition of the flame retardant may exacerbate the above problems.
Therefore, an object of the present invention is to provide a polyol composition which has flame retardancy and a fast initial reaction rate, and a foamable polyurethane composition which uses the polyol composition.

As a result of extensive research into solving the above problems, the inventors discovered that the above problems could be solved by including a polyol, a blowing agent, a catalyst, a solid phosphorus-containing compound, and an additive, with the additive including a boron-containing compound or a bromine-containing compound, and thus completed the present invention. In other words, the present invention provides the following [1] to [11].

[1] A polyol composition for producing a polyurethane foam by reacting with a polyisocyanate, comprising a polyol, a blowing agent, a catalyst, a solid phosphorus-containing compound, and an additive A, wherein the catalyst comprises at least one metal catalyst selected from a bismuth-containing compound and a tin-containing compound, and the additive A is at least one selected from a boron-containing compound and a bromine-containing compound.
[2] The polyol composition according to the above [1], wherein the solid phosphorus-containing compound contains at least one selected from red phosphorus and metal phosphinates.
[3] The polyol composition according to the above [1] or [2], wherein the catalyst comprises a trimerization catalyst.
[4] The polyol composition according to the above [3], wherein the trimerization catalyst contains a quaternary ammonium salt.
[5] The polyol composition according to any one of the above [1] to [4], wherein the catalyst comprises an imidazole derivative.
[6] The polyol composition according to any one of the above [1] to [5], wherein the catalyst comprises a metal catalyst comprising a bismuth-containing compound.
[7] The polyol composition according to any one of the above [1] to [6], wherein the solid phosphorus-containing compound is red phosphorus.
[8] The polyol composition according to any one of the above [1] to [7], wherein the blowing agent comprises a hydrofluoroolefin.
[9] A foamable polyurethane composition comprising the polyol composition according to any one of [1] to [8] above and a polyisocyanate.
[10] The foamable polyurethane composition according to the above [9], having an isocyanate index of 200 or more.
[11] A polyurethane foam obtained by reacting and foaming the foamable polyurethane composition according to [9] or [10] above.

The present invention provides a polyol composition that has a fast initial reaction rate and is flame retardant.

<Polyol Composition>
The polyol composition of the present invention contains a polyol, a blowing agent, a catalyst, a solid phosphorus-containing compound, and an additive, and is characterized in that the catalyst is a bismuth-containing compound or a tin-containing compound, and the additive is a boron-containing compound or a bromine-containing compound.
The present invention will be described in detail below.

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, polyether polyols, etc. Polyols are usually liquid at room temperature (23° C.) and normal pressure (1 atm).

Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol.
Examples of polycarbonate polyols include polyols obtained by dealcoholization reaction of hydroxyl group-containing compounds such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with ethylene carbonate, propylene carbonate, and the like.

Examples of aromatic polyols include bisphenol A, bisphenol F, phenol novolac, and cresol novolac.
Examples of alicyclic polyols include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol.
Aliphatic polyols include, for example, alkanediols such as ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.

Examples of polyester polyols include polymers obtained by dehydration condensation of polybasic acids and polyhydric alcohols, and condensates of hydroxycarboxylic acids and the above-mentioned polyhydric alcohols.
Examples of polybasic acids include adipic acid, azelaic acid, sebacic acid, isophthalic acid (m-phthalic acid), terephthalic acid (p-phthalic acid), and succinic acid, etc. Examples of polyhydric alcohols include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, and neopentyl glycol, etc.
Examples of hydroxycarboxylic acids include castor oil and reaction products of castor oil and ethylene glycol.

Examples of polymer polyols include polymers obtained by graft-polymerizing ethylenically unsaturated compounds such as acrylonitrile, styrene, methyl acrylate, and methacrylate with aromatic polyols, alicyclic polyols, aliphatic polyols, and polyester polyols, polybutadiene polyols, and hydrogenated products thereof.

Examples of polyether polyols include polymers obtained by ring-opening polymerization of at least one alkylene oxide, such as ethylene oxide, propylene oxide, and tetrahydrofuran, in the presence of at least one low molecular weight active hydrogen compound having two or more active hydrogens. Examples of low molecular weight active hydrogen compounds having two or more active hydrogens include diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, and 1,6-hexanediol, triols such as glycerin and trimethylolpropane, tetrahydric to octahydric alcohols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, and dipentaerythritol, sucrose, glucose, mannose, fructose, methyl glucoside, and derivatives thereof, and amines such as ethylenediamine and butylenediamine.

The polyol used in the present invention is preferably at least one selected from the group consisting of polyester polyols and polyether polyols. From the viewpoint of foaming property and reactivity, polyester polyols are more preferable. Also, polyols having two hydroxyl groups are preferable. Among them, from the viewpoint of improving flame retardancy, aromatic polyester polyols, which are polyester polyols having aromatic rings, are preferable. As the aromatic polyester polyol, aromatic polyester polyols obtained by dehydration condensation of polybasic acids having aromatic rings such as isophthalic acid (m-phthalic acid) and terephthalic acid (p-phthalic acid) with dihydric alcohols such as bisphenol A, ethylene glycol, and 1,2-propylene glycol are more preferable. The use of aromatic polyester polyols makes it easier to improve flame retardancy.

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 equal to or less than the upper limit, the viscosity of the polyol composition is likely to decrease, which is preferable from the viewpoint of handleability, etc. On the other hand, when the hydroxyl value of the polyol is equal to or more than the lower limit, the crosslink density of the polyurethane foam increases, thereby increasing the strength.
The hydroxyl value of the polyol can be measured in accordance with JIS K 1557-1:2007.

The content of polyol in the polyol composition of the present invention is preferably 15 to 80% by mass, more preferably 20 to 70% by mass, and even more preferably 25 to 60% by mass. If the content of polyol is equal to or greater than the lower limit, it is preferable because it makes it easier for the polyol to react with the polyisocyanate. On the other hand, if the content of polyol is equal to or less than the upper limit, it is preferable from the viewpoint of ease of handling because the viscosity of the polyol composition does not become too high.

<Foaming Agent>
The foaming agent promotes foaming of the urethane resin. Examples of the foaming agent include organic physical foaming agents such as water, propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and other low-boiling point hydrocarbons, dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride, and other chlorinated aliphatic hydrocarbon compounds, hydrofluoroolefins (hereinafter sometimes referred to as "HFO"), ether compounds such as diisopropyl ether, and mixtures of these compounds, and inorganic physical foaming agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas.
Among these, it is preferable to use hydrofluoroolefins (HFOs), which have high stability as a blowing agent, are less likely to decrease in catalytic activity, and have a low environmental impact.

Examples of HFOs that are suitable blowing agents include fluoroalkenes having about 3 to 6 carbon atoms. In addition, 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 HFOs include trifluoropropene, tetrafluoropropenes such as HFO-1234, pentafluoropropenes such as HFO-1225, chlorodifluoropropenes, chlorotrifluoropropenes such as HFO-1233, and chlorotetrafluoropropene.
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, cis-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)), trans-1,2,3,3,3-pentafluoropropene (HFO-1234ze(Z)), Fluoropropene (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) and the like are included. Of these, HFO-1233zd(E) is preferred.

The amount of the blowing 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, per 100 parts by mass of polyol. When the amount of the blowing agent is equal to or greater than the lower limit, foaming is promoted, the foamability is improved, and the density of the resulting polyurethane foam can be reduced. On the other hand, when the amount of the blowing agent is equal to or less than the upper limit, excessive foaming can be prevented.

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

<Catalyst>
Metal catalyst (resinized metal catalyst)
The catalyst used in the polyol 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 can increase the initial reaction rate in particular. In addition, when a certain amount or more of a filler, which will be described later, is contained, the reactivity of the polyurethane foam is inhibited and the foamability is likely to decrease, but the inclusion of a metal catalyst makes it easier to maintain the foamability of the polyurethane foam well. It is more preferable that the metal catalyst contains bismuth from the viewpoint of foamability and the like.

The resinified metal catalyst is preferably a metal salt selected from bismuth and tin, 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. The carboxylic acid has 5 or more carbon atoms, and is stable to a blowing agent, particularly to hydrofluoroolefin. In addition, the carbon number of the carboxylic acid is preferably 18 or less, more preferably 12 or less, from the viewpoint of catalytic activity. 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 preferably has a branched structure.
Specific examples of the carboxylic acid include octylic acid, lauric acid, versatic acid, pentanoic acid, and acetic acid, and among these, octylic acid is preferred. 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 also have a branched structure. An example of an octylic acid having a branched structure is 2-ethylhexanoic acid.
As the metal salt of carboxylic acid, bismuth salt of carboxylic acid and tin salt of carboxylic acid are preferable, and among them, bismuth salt of octylic acid is preferable. In addition, the metal salt of carboxylic acid may be a carboxylate of an alkyl metal. For example, the tin salt of carboxylic acid may be a dialkyltin carboxylate, and preferably is a dioctyltin carboxylate.
Specific examples of metal salts of carboxylic acids include bismuth trioctate, dioctyltin versatate, dibutyltin dilaurate, dioctyltin dilaurate, tin dioctylate, etc., and are preferably bismuth trioctate or dioctyltin versatate, 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, even more preferably 1.5 to 6 parts by mass, and even more preferably 2 to 5 parts by mass, per 100 parts by mass of polyol. When the content of the metal catalyst is equal to or greater than the lower limit, the curing reaction speed of the foamable polyurethane composition is improved and the foamability is good. On the other hand, when the content of the metal catalyst is equal to or less than the upper limit, the reaction is easier to control.

<Imidazole derivatives>
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 hydrofluoroolefin, and enhances the stability of the polyol composition while facilitating the reaction between the polyol and the polyisocyanate. Therefore, by containing the imidazole derivative in addition to the above-mentioned metal catalyst, the polyol composition enhances the reactivity between the polyol and the isocyanate, and the foaming property is further improved.
The imidazole derivative is preferably an imidazole substituted at the 1- and 2-positions with an alkyl group having 8 or less carbon atoms, and the alkyl group preferably has 6 or less carbon atoms, more preferably has 4 or less carbon atoms. A specific example of a suitable imidazole derivative is represented by the following general formula (1).

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

In the general formula (1), ^R1 and ^R2 each independently represent an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms. The alkyl group and the alkenyl group may each be linear or have a branched structure.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a hexyl group, a heptyl group, and an octyl group.
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, and an octenyl group.
When the carbon numbers of the alkyl or alkenyl groups of ^R1 and ^R2 are equal to or greater than the lower limit, steric hindrance becomes large, and the resin is less susceptible to the effects of foaming agents such as hydrofluoroolefins, which is preferable. On the other hand, when the carbon numbers of the alkyl groups of ^R1 and ^R2 are equal to or less than the upper limit, the steric hindrance does not become extremely large, and the reaction between the polyol and the polyisocyanate can proceed quickly, and the foaming properties are also good.
From these viewpoints, R ¹ and R ² are each preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group.

Imidazole derivatives represented by general formula (1) include 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methylimidazole. Among these, 1,2-dimethylimidazole and 1-isobutyl-2-methylimidazole are preferred from the viewpoint of improving the activity of the catalyst in the presence of hydrofluoroolefin and from the viewpoint of rapidly progressing the reaction. Furthermore, 1,2-dimethylimidazole is even more preferred from the viewpoint of further increasing 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, even more preferably 2 to 15 parts by mass, and particularly preferably 3 to 10 parts by mass, relative to 100 parts by mass of polyol. If the content of the imidazole derivative is equal to or greater than the lower limit, urethane bonds are more likely to be formed, the reaction proceeds quickly, and foamability is good. On the other hand, if the content of the imidazole derivative is equal to or less than the upper limit, the reaction rate is easier to control, which is preferable.

<Trimerization catalyst>
The polyol composition of the present invention preferably further contains a trimerization catalyst. The trimerization catalyst is a catalyst that reacts the isocyanate groups contained in the polyisocyanate to trimerize them and promote the formation of isocyanurate rings. The inclusion of the trimerization catalyst has the advantage that a good foam can be obtained by completing the reaction of unreacted isocyanate groups. Examples of the trimerization catalyst include metal catalysts and ammonium salts.
The metal catalyst (trimerization metal catalyst) used as the trimerization catalyst includes potassium organic acids, and preferable examples thereof include potassium octylate such as potassium 2-ethylhexanoate, potassium acetate, potassium propionate, potassium butanoate, potassium benzoate, and other potassium carboxylates having 2 to 8 carbon atoms.
As the ammonium salt, tertiary ammonium salts such as triethylammonium salts and triphenylammonium salts, and quaternary ammonium salts such as tetramethylammonium salts, tetraethylammonium salts and tetraphenylammonium salts can be used, among which quaternary ammonium salts are preferred. The ammonium salt is, for example, an ammonium salt of a carboxylic acid. As the carboxylic acid in the ammonium salt, for example, a saturated fatty acid having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, can be mentioned. The saturated fatty acid may have a hydrocarbon group that is linear or branched, but preferably has a branched group. Specific examples of the carboxylic acid include 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid, among which 2,2-dimethylpropanoic acid is preferred. The trimerization catalyst may be used alone or in combination of two or more kinds. When using two or more kinds in combination, it is preferable to use a quaternary ammonium salt in combination with a metal catalyst.

The content of the trimerization catalyst in the polyol composition is preferably 0.4 to 30 parts by mass, more preferably 1 to 25 parts by mass, even more preferably 2 to 20 parts by mass, and even more preferably 4 to 18 parts by mass, relative to 100 parts by mass of polyol. When the content of the trimerization catalyst is equal to or greater than the lower limit, there is no significant difference in activity between resinification and trimerization, and foaming can be prevented from occurring in two stages, resulting in good foamability. On the other hand, when the content of the trimerization catalyst is equal to or less than the upper limit, the resinification reaction proceeds actively, and the activity of trimerization can be promoted by the heat of the resinification reaction, resulting in good foamability and allowing the formation of a good foam.

<Solid phosphorus-containing compound>
The polyol composition of the present invention contains a solid phosphorus-containing compound as a flame retardant. The phosphorus-containing compound is not particularly limited as long as it is solid at room temperature (23° C.) and normal pressure (1 atm). For example, , red phosphorus, metal phosphinates, and other phosphates. Among these, red phosphorus-based flame retardants containing red phosphorus and metal phosphinates are preferred from the viewpoint of the effect as a flame retardant. In particular, red phosphorus-based flame retardants are preferred.

(Red phosphorus)
The red phosphorus used as the 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-based flame retardant in which red phosphorus is mixed with a resin, a metal hydroxide, a metal oxide, or the like. The resin that coats the red phosphorus or is mixed with the red phosphorus is not particularly limited, but examples thereof include thermosetting resins such as phenol resins, epoxy resins, unsaturated polyester resins, melamine resins, urea resins, aniline resins, and silicone resins. As the compound to be coated or mixed, a metal hydroxide is preferred from the viewpoint of flame retardancy. The metal hydroxide may be appropriately selected from those described below and used.

(Metal Phosphinate)
The metal phosphinate is, for example, a compound represented by the following general formula (2).

In the formula, R ¹ and R ² each independently represent a linear or branched alkyl group or aryl group having 1 to 6 carbon atoms, and M is a metal. Examples of the metal include alkali metals such as Li, Na, and K, alkaline earth metals such as Mg, Ca, Sr, and Ba, group 4 elements such as Ti and Zr, group 7 elements such as Mn, group 8 elements such as Fe, group 12 elements such as Zn, group 13 elements such as Al, group 14 elements such as Sn, and group 15 elements such as Sb and Bi. Among the above metals, phosphinic acid metal salts in which the metal is aluminum are preferred in terms of high flame retardancy. n is an integer of 1 to 4.
Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group, and ^R1 and ^R2 may be the same or different. Examples of the aryl group include a phenyl group, a tolyl group, and a benzyl group.
These metal phosphinates may be used alone or in combination of two or more.

Specific examples of the metal phosphinate include aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, and zinc bisdiphenylphosphinate. Of these, aluminum trisdiethylphosphinate and aluminum trismethylethylphosphinate are particularly preferred because of their high flame retardancy.
The red phosphorus may be used in combination with a metal phosphinate.

(Other phosphorus-containing compounds)
The polyol composition of the present invention may contain a phosphorus-containing compound other than the above-mentioned red phosphorus and metal phosphinate, so long as the effect of the present application is not impaired. For example, phosphates made of a salt of a phosphoric acid other than phosphinic acid and a metal salt of Groups 1 to 4, various phosphoric acids and at least one metal or compound selected from ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring, may be mentioned. The term "various phosphoric acids" is a concept that includes not only phosphoric acid but also phosphorous acid and the like.
Examples of aliphatic amines include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine, etc. Examples of aromatic amines include aniline, o-triidine, 2,4,6-trimethylaniline, anisidine, 3-(trifluoromethyl)aniline, etc. Examples of heterocyclic compounds containing nitrogen in the ring include pyridine, triazine, melamine, etc.

Specific examples of other phosphates include monophosphates, polyphosphates, etc. Examples of monophosphates include, but are not limited to, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate; sodium salts of monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, and disodium phosphite; potassium salts such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, and dipotassium phosphite; lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, and dilithium phosphite; barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, and tribarium phosphate; magnesium salts such as magnesium monohydrogen phosphate, magnesium hydrogen phosphate, and trimagnesium phosphate; calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, and tricalcium phosphate; and zinc salts such as zinc phosphate and zinc phosphite.
Here, the polyphosphate is not particularly limited, but examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, and aluminum polyphosphate.
The other phosphates may be used alone or in combination of two or more of the above-mentioned ones.

The content of the solid phosphorus-containing compound is preferably 1 to 100 parts by mass, more preferably 10 to 70 parts by mass, even more preferably 15 to 50 parts by mass, and most preferably 20 to 40 parts by mass, per 100 parts by mass of polyol.

<Additive A>
In the polyol composition of the present invention, the additive A added as an essential component is a boron-containing compound or a bromine-containing compound, which may be used alone or in combination. The additive A functions as a flame retardant auxiliary exhibiting high flame retardancy in combination with the solid phosphorus-containing compound.

(Boron-containing compounds)
Specific examples of boron-containing compounds include borax, boron oxide, boric acid, and borates.
Specific examples of boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide.
Specific examples of borates include borates of alkali metals, alkaline earth metals, elements of Groups 4, 12, and 13 of the periodic table, and ammonium. Specific examples include alkali metal borates such as lithium borate, sodium borate, potassium borate, and cesium borate, alkaline earth metal borates such as magnesium borate, calcium borate, and barium borate, zirconium borate, aluminum borate, zinc borate, and ammonium borate. A preferred boron-containing compound is a borate, particularly zinc borate.
The boron-containing compounds may be used alone or in combination of two or more kinds.

Bromine-containing compounds
The bromine-containing compound is not particularly limited as long as it contains bromine in its molecular structure. Specific examples of the bromine-containing compound include aromatic brominated compounds.
Specific examples of aromatic brominated compounds include monomeric organic bromine compounds such as hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylene bis(pentabromophenyl), ethylene bis(tetrabromophthalimide), and tetrabromobisphenol A.
The brominated aromatic ring-containing aromatic compound may be a bromine compound polymer.Specific examples of the brominated aromatic ring-containing aromatic compound include brominated polycarbonates such as polycarbonate oligomers produced from brominated bisphenol A as a raw material, copolymers of the polycarbonate oligomers and bisphenol A, and diepoxy compounds produced by the reaction of brominated bisphenol A and epichlorohydrin.Further examples include brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols with epichlorohydrin, poly(brominated benzyl acrylate), brominated phenol condensates of brominated polyphenylene ether, brominated bisphenol A, and cyanuric chloride, brominated (polystyrene), poly(brominated styrene), brominated polystyrenes such as crosslinked brominated polystyrene, crosslinked or non-crosslinked brominated poly(-methylstyrene), and the like.
In addition, compounds other than brominated aromatic ring-containing aromatic compounds such as hexabromocyclododecane may be used.
From the viewpoint of controlling the amount of heat generated in the early stage of combustion, monomeric organic bromine compounds are preferred, and among them, decabromodiphenylethane and hexabromobenzene are more preferred. The bromine-containing flame retardants may be used alone or in combination of two or more.
The content of additive A is preferably in the range of 1 to 100 parts by mass, more preferably in the range of 5 to 50 parts by mass, even more preferably in the range of 10 to 40 parts by mass, and most preferably in the range of 20 to 30 parts by mass, relative to 100 parts by mass of the polyol compound.

<Filler>
The polyol composition of the present invention preferably contains a filler other than the solid phosphorus-containing compound and additive A. The filler is contained as a solid component in the polyol composition, and is generally a component present in the form of particles or powder in the polyol composition. In the present invention, by containing the filler, various physical properties such as flame retardancy and mechanical properties of the obtained polyurethane foam can be easily improved.

The filler may be any component that is solid at room temperature (23° C.) and normal pressure (1 atm) and does not dissolve in the polyol composition. From the viewpoint of reducing the water absorption rate of the polyurethane foam, the filler is preferably one that does not have hygroscopicity or deliquescent properties.
As the filler, a solid flame retardant other than the above-mentioned flame retardants that is solid at room temperature (23° C.) and normal pressure (1 atm) may be used. Specific examples include antimony-containing flame retardants, chlorine-containing flame retardants, and metal hydroxides. These fillers may be used alone or in combination of two or more.

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

<Chlorine-containing flame retardants>
Chlorine-containing flame retardants include those commonly used in polyurethane foams, such as polychlorinated naphthalenes, chlorendic acid, and dodecachlorododecahydrodimethanodibenzocyclooctene, sold under the trade name "Dechlorane Plus."

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

(Inorganic filler)
The polyol composition of the present invention may contain an inorganic filler. The inorganic filler is not particularly limited, but a needle-shaped filler is preferably used.
Examples of needle-like fillers include potassium titanate whiskers, aluminum borate whiskers, magnesium-containing whiskers, silicon-containing whiskers, wollastonite, sepiolite, zonolite, elestadite, boehmite, rod-shaped hydroxyapatite, glass fibers, carbon fibers, graphite fibers, metal fibers, slag fibers, gypsum fibers, silica fibers, alumina fibers, silica alumina fibers, zirconia fibers, boron nitride fibers, boron fibers, and stainless steel fibers.
These needle-like fillers can be used alone or in combination of two or more.
The aspect ratio (length/diameter) of the needle-like 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 determined by observing the needle-like filler with a scanning electron microscope and measuring its length and width.

In addition, inorganic fillers other than the needle-shaped filler may be used, and examples of such inorganic fillers include alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, talc, mica, montmorillonite, bentonite, activated 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, etc. 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 kinds.

The content of the filler other than the solid phosphorus-containing compound and additive A in the polyol composition is preferably in the range of 1 to 100 parts by mass, more preferably in the range of 5 to 50 parts by mass, and even more preferably in the range of 10 to 40 parts by mass, per 100 parts by mass of polyol. By making the content of the filler equal to or greater than the lower limit, it becomes easier to impart various properties such as flame retardancy to the polyurethane foam. Furthermore, by making the content of the filler equal to or less than these upper limits, it becomes easier to obtain good foaming properties without reducing reactivity.

<Phosphate ester>
The polyol composition of the present invention may contain a flame retardant other than the solid flame retardant described above. Such flame retardants include flame retardants that are liquid at room temperature (23°C) and normal pressure (1 atm), specifically, phosphate esters. By using phosphate esters, it is easy to improve the flame retardancy of urethane foam without reducing the fluidity of the polyol composition.

As the phosphate ester, monophosphate ester, condensed phosphate ester, etc. can be used. A monophosphate ester is a phosphate ester having one phosphorus atom in the molecule. Examples of 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, trialkoxy phosphates such as tributoxyethyl phosphate, aromatic ring-containing phosphate esters such as tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl)phosphate, cresyl diphenyl phosphate, and diphenyl(2-ethylhexyl)phosphate, and acidic phosphate esters such as monoisodecyl phosphate and diisodecyl phosphate.

Examples of the condensed phosphate ester include aromatic condensed phosphate esters such as trialkyl polyphosphate, resorcinol polyphenyl phosphate, bisphenol A polycresyl phosphate, and bisphenol A polyphenyl phosphate.
Commercially available condensed phosphate esters include, for example, "CR-733S", "CR-741", and "CR747" manufactured by Daihachi Chemical Industry Co., Ltd., and "ADEKA STAB PFR" and "FP-600" manufactured by ADEKA Corporation.

The phosphoric acid ester may be used alone or in combination of two or more of the above-mentioned phosphoric acid esters. Among these, from the viewpoint of easily adjusting the viscosity of the polyol composition to an appropriate value and from the viewpoint of improving the flame retardancy of the polyurethane foam, monophosphate esters are preferred, and halogen-containing phosphoric acid esters such as tris(β-chloropropyl)phosphate are more preferred.
The content of the phosphate ester in the polyol composition is preferably 5 to 100 parts by mass, more preferably 12 to 90 parts by mass, even more preferably 20 to 75 parts by mass, and even more preferably 30 to 60 parts by mass, relative to 100 parts by mass of the polyol.

<Foam stabilizer>
The polyol composition of the present invention may contain a foam stabilizer. By containing a foam stabilizer, the foamability of the polyurethane foam can be improved, and for example, foaming can be promoted when reacting with a polyisocyanate during spraying.
The foam stabilizer may be specifically a surfactant, more specifically a nonionic surfactant, a cationic surfactant, an anionic surfactant, etc. Specific examples of the nonionic surfactant include polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ethers, silicone foam stabilizers such as organopolysiloxanes, etc. The foam stabilizer used in the present invention is not particularly limited, but silicone foam stabilizers are preferred from the viewpoint of foaming properties. The foam stabilizer may be used alone or in combination of two or more kinds.

The content of the foam stabilizer 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 even more preferably 2 to 8 parts by mass, per 100 parts by mass of polyol. When the content of the foam stabilizer is equal to or greater than the lower limit, the mixture of the polyol composition and the polyisocyanate is easily foamed, making it possible to obtain a homogeneous polyurethane foam. When the content of the foam stabilizer is equal to or less than the upper limit, the balance between the production cost and the obtained effect is optimal.

<Other ingredients>
The polyol composition may contain, as necessary, one or more selected from additives such as phenol-based, amine-based, and sulfur-based antioxidants, heat stabilizers, metal damage inhibitors (metal deactivators), antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, plasticizers, pigments, and tackifier resins, tackifiers such as polybutene and petroleum resins, etc., within the scope of the present invention.

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

[Foamable Polyurethane Composition and Polyurethane Foam]
The foamable polyurethane composition of the present invention contains the above-mentioned polyol composition and a polyisocyanate, and is obtained by mixing them. The polyurethane foam of the present invention is a reaction product obtained by reacting and foaming the foamable polyurethane composition.

<Polyisocyanate>
Examples of the polyisocyanate include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.
Examples of aromatic polyisocyanates include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate (polymeric MDI).

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

Examples of aliphatic polyisocyanates include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

Among these, from the viewpoints of ease of use and availability, aromatic polyisocyanates are preferred, and diphenylmethane diisocyanate, polymeric MDI, or a mixture thereof are more preferred. The polyisocyanates may be used alone or in combination of two or more.
Furthermore, the polyisocyanate may be appropriately mixed with known additives that are mixed with polyisocyanates before being mixed with the polyol composition.

It is preferable that the polyol composition and the polyisocyanate mixed into the polyol composition have substantially the same volume. 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.

<Isocyanate Index>
The isocyanate index in the foamable polyurethane composition of the present invention is not particularly limited, but is preferably 200 or more. If the isocyanate index is equal to or more than the lower limit, the amount of polyisocyanate relative to the polyol becomes excessive, and isocyanurate bonds due to the trimerization of the polyisocyanate are easily generated, resulting in improved flame retardancy of the polyurethane foam. In addition, it is also possible to impart non-flammability. Furthermore, if the isocyanate index is equal to or more than the lower limit, it is easy to produce a polyurethane foam having sufficient isocyanurate bonds, that is, a polyurethane foam having both flame retardancy and heat insulation at a high level, in combination with the use of the various catalysts described above. From these viewpoints, the isocyanate index is more preferably 250 or more, more preferably 300 or more, even more preferably 350 or more, and particularly preferably 400 or more.
The isocyanate index is preferably not more than 1,000, more preferably not more than 800, and even more preferably not more than 600. When the isocyanate index is not more than the upper limit, flame retardancy that is sufficiently commensurate with the production cost can be obtained.

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

<Method of manufacturing polyurethane foam>
The method for producing the polyurethane foam is not particularly limited, but it is preferable to produce the polyurethane foam by mixing the polyol composition with the polyisocyanate in a foaming machine or the like, and reacting and foaming the resulting mixed liquid (foamable polyurethane composition). As the foaming machine, it is preferable to use a spray device having a spray gun or the like.
The polyol composition is preferably fed to a foaming machine and mixed by collision inside the foaming machine with a polyisocyanate fed from another container, etc. Then, the mixed liquid (foamable polyurethane composition) is preferably discharged from a discharge port of a spray gun, etc., and a polyurethane foam is formed from the discharged foamable polyurethane composition.

The present manufacturing method can be applied to, for example, spraying applications. Therefore, the mixed liquid discharged from the foaming machine is sprayed onto a target surface at a certain discharge pressure, and foamed to form a polyurethane foam on the target surface.
In the present invention, the polyurethane foam may be obtained by mixing the polyisocyanate and the polyol composition, pouring the mixture into a container such as a mold or a frame, and curing the mixture.

<Applications of polyurethane foam>
The uses of the polyurethane foam of the present invention are not particularly limited, but since it has excellent flame retardancy and heat insulation, it can be suitably used for the walls, ceilings, roofs, floors, etc. of buildings, and it is advisable to mold the polyurethane foam onto the target surfaces such as walls, ceilings, roofs, floors, etc. It can also be suitably used as a member for filling any openings that occur in buildings, including joints and holes that occur between structural materials of buildings.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these.
[Materials used]
<Polyol Composition>
[Polyol]
p-Phthalic acid polyester polyol (manufactured by Kawasaki Chemical Industries, Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mg KOH/g)

〔catalyst〕
Resinized amine catalyst, 1,2-dimethylimidazole (manufactured by Tosoh Corporation, product name: TOYOCAT (registered trademark)-DM70) concentration 65 to 75% by mass
Resinized metal catalyst, bismuth trioctate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-600) concentration 55 to 58% by mass
Resinized metal catalyst, dioctyltin versatate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-830), concentration approximately 99% by mass
Ammonium salt (trimerization catalyst), tetramethylammonium salt of 2,2-dimethylpropanoic acid (Air Products, product name: DABCO (registered trademark) TMR7) concentration 45 to 55 mass%
Metal catalyst (trimerization catalyst), potassium 2-ethylhexanoate (manufactured by Air Products, product name: DABCO (registered trademark) K-15) concentration 70 to 80% by mass

[Foaming Agent]
Hydrofluoroolefin (HFO), trans-1-chloro-3,3,3-trifluoropropene (manufactured by Honeywell Japan, product name: Soltis LBA)
·water

[Phosphate ester]
Tris(β-chloropropyl)phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., product name: TMCPP)

[Flame retardant]
Red phosphorus (manufactured by Rinkagaku Kogyo Co., Ltd., product name: Nova Excel 140)
Phosphinic acid metal salts (manufactured by Clariant, product name: EXOLIT OP930), aluminum tris-diethylphosphinate; Phosphinic acid metal salts (manufactured by Clariant, product name: EXOLIT OP935), aluminum tris-diethylphosphinate

[Additives]
Zinc borate, product name: Firebrake ZB (manufactured by Hayakawa Shoji Co., Ltd.)
Hexabromobenzene, product name: HBB-b (manufactured by Manac Corporation)
Ethylene-bis(pentabromophenyl), product name: SAYTEX 8010 (manufactured by Albemarle Corporation)

[Inorganic filler]
Wollastonite ( _SiO2.CaO ) (Kinsei Matec Co., Ltd., product name: SH-1250)

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

[Evaluation method]
1. Non-flammability A polyol composition was prepared by mixing the components according to the formulation shown in Table 1. Using the polyol composition and an isocyanate, a urethane foam was produced under the following conditions.
<Production conditions>
・Spraying machine: Graco H-25 spraying machine
・Settings (Heater settings)
Isocyanate heater: 38℃
Premix heater (for heating polyol composition): 38°C
Hose heater (for heating the isocyanate and polyol composition before mixing): 38°C
Pressure: Adjust so that the mist is a wide circular shape. Base material: RC (concrete).
・Base material temperature: 0℃±1℃
<Evaluation of non-flammability>
Cone calorimeter test samples of 10 cm x 10 cm x 5 cm were cut out from the urethane foams produced in each Example and Comparative Example, and the total heat generation was measured when heated for 10 minutes and 20 minutes at a radiant heat intensity of 50 kW/ ^m2 in accordance with ISO-5660. The evaluation criteria were as follows.
◎: 8 MJ or less at 20 minutes 〇: 8 MJ or less at 10 minutes, more than 8 MJ at 20 minutes ×: 8 MJ or more at 10 minutes

2. Initial reactivity The polyol composition and polyisocyanate produced in each Example and Comparative Example were sprayed onto a substrate and visually observed. The time (cream time) from when the mixed solution started to react and when the color of the solution started to change was measured. The measurement conditions were the same as the above-mentioned production conditions, and the evaluation criteria were as follows.
<Evaluation criteria>
◎: 3 seconds or less 〇: More than 3 seconds but less than 5 seconds ×: 5 seconds or more

Examples 1 to 11, Comparative Examples 1 and 2
A polyol composition was prepared by mixing the components according to the formulation shown in Table 1. Using the polyol composition and the polyisocyanate, evaluations were carried out according to the above-mentioned evaluation methods 1 and 2. The results are shown in Table 1.

As is clear from the results of the above examples and comparative examples, the foamable polyurethane composition using the polyol composition of the present invention is excellent in non-flammability evaluation results and initial reactivity. On the other hand, the foamable polyurethane composition of Comparative Example 1 does not contain a solid phosphorus-containing compound, so the non-flammability is insufficient, and the foamable polyurethane composition of Comparative Example 2 does not use a metal catalyst having a bismuth-containing compound or a tin-containing compound, so the initial reactivity is poor.

Claims (8)

A polyol composition for spraying, which is used to react with a polyisocyanate using a spray gun to obtain a polyurethane foam, comprises a polyol, a blowing agent, a catalyst, a solid phosphorus-containing compound, and additive A, wherein the catalyst comprises at least one metal catalyst selected from a bismuth-containing compound and a tin-containing compound, 1,2-dimethylimidazole, and tetramethylammonium salt of 2,2-dimethylpropanoate, the additive A being at least one selected from a boron-containing compound and a bromine-containing compound, and the catalyst comprises a metal catalyst consisting of a bismuth-containing compound . The spray polyol composition according to claim 1, wherein the solid phosphorus-containing compound contains at least one selected from red phosphorus and metal phosphinate. The polyol composition for spraying according to claim 1 or 2, wherein the catalyst further contains a potassium organic acid. The spray polyol composition according to any one of claims 1 to 3, wherein the solid phosphorus-containing compound is red phosphorus. The spray polyol composition according to any one of claims 1 to 4, wherein the blowing agent comprises a hydrofluoroolefin. A foamable polyurethane composition comprising the spray polyol composition according to any one of claims 1 to 5 and a polyisocyanate. The foamable polyurethane composition according to claim 6, having an isocyanate index of 200 or more. A polyurethane foam obtained by reacting and foaming the foamable polyurethane composition according to claim 6 or 7.