JP2023010346A - Polyol-containing composition, foamable urethane resin composition, and polyurethane foam - Google Patents

Abstract

To provide a polyol-containing composition which prevents clogging in a filter inside a foaming machine while exhibiting good foamability, and enables formation of a polyurethane foam having high flame retardancy, in a process of reacting and foaming polyisocyanate by the foaming machine.SOLUTION: A polyol-containing composition contains polyol, a foaming agent, a catalyst, and a flame retardant, wherein the catalyst contains at least one metal catalyst selected from a bismuth compound and a tin compound, and the flame retardant contains a bromine-based flame retardant having a structure including at least two benzene rings per one molecule.SELECTED DRAWING: None

Description

The present invention relates to a polyol-containing composition, a foamable urethane resin composition, and a polyurethane foam.

Polyurethane foams have been put to practical use for heat insulation and dew condensation prevention of building members such as ceilings, roofs and walls of buildings such as condominiums and other collective housing, detached houses, commercial buildings, etc. there is A polyurethane foam is formed by spraying an expandable urethane resin composition containing a polyol compound and a polyisocyanate compound onto the surface of each structure, and then foaming and curing the composition.

Polyurethane foams are lightweight, but are combustible because they are organic. To remedy this, polyurethane foams with high flame retardancy are needed. As a means for increasing the flame retardancy of polyurethane foams, it is known to incorporate a brominated flame retardant in the polyol composition, as described in Patent Document 1, for example.

Japanese Patent Application Laid-Open No. 2020-172603

However, in such conventional polyol compositions, when a foaming machine is used to react and foam with polyisocyanate, the brominated flame retardant aggregates to form a large particle size. Clogging may occur. In such a case, a sufficient amount of the polyol composition for reacting and foaming with the polyisocyanate cannot be discharged, resulting in a problem such as a decrease in production efficiency of the polyurethane foam.
Accordingly, the present invention provides a highly flame-retardant polyurethane foam that exhibits good foamability in the step of reacting and foaming with polyisocyanate using a foaming machine, while preventing clogging of the filter inside the foaming machine. It is an object of the present invention to provide a formable polyol-containing composition.

Means for Solving the Problems As a result of intensive studies in order to solve the above problems, the present inventors have found that the above problems can be solved by a polyol-containing composition having the following constitution, and completed the present invention.

The gist of the present invention is the following [1] to [21].
[1] A polyol-containing composition containing a polyol, a blowing agent, a catalyst, and a flame retardant, wherein the catalyst comprises at least one metal catalyst selected from bismuth salts and tin salts, and the flame retardant comprises , a polyol-containing composition comprising a brominated flame retardant having a structure containing at least two benzene rings per molecule.
[2] The polyol-containing composition according to [1], wherein at least two of the benzene rings constituting the brominated flame retardant are chemically bonded via ethylene groups.
[3] The polyol-containing composition according to [1] or [2], wherein the brominated flame retardant contains at least one brominated benzene ring.
[4] The polyol-containing composition according to any one of [1] to [3], wherein the bromine content in the brominated flame retardant is 50% by mass or more based on the total amount of the brominated flame retardant.
[5] The polyol-containing composition according to any one of [1] to [4], wherein the brominated flame retardant is ethylenebis(pentabromophenyl).
[6] The polyol-containing composition according to any one of [1] to [5], wherein the flame retardant comprises a red phosphorus flame retardant.
[7] The polyol-containing composition according to [6], wherein the content of the red phosphorus-based flame retardant is 6 to 36% by mass based on the total amount of the polyol-containing composition.
[8] The polyol-containing composition according to any one of [1] to [7], wherein the foaming agent contains a hydrofluoroolefin.
[9] The polyol-containing composition according to any one of [1] to [8], wherein the catalyst contains an imidazole derivative.
[10] The polyol-containing composition according to any one of [1] to [9], wherein the catalyst comprises a trimerization catalyst.
[11] The polyol-containing composition according to [10], wherein the trimerization catalyst contains a quaternary ammonium salt.
[12] The polyol-containing composition according to any one of [1] to [11], wherein the polyol has a weighted average aromatic concentration of 10% by mass or more.
[13] The polyol-containing composition according to any one of [1] to [12], wherein the content of the flame retardant is 20 to 60% by mass based on the total amount of the polyol-containing composition.
[14] The polyol-containing composition according to any one of [1] to [13], wherein the content of the brominated flame retardant is 20% by mass or less based on the total amount of the polyol-containing composition.
[15] The polyol-containing composition according to any one of [1] to [14], which is used for spraying applications.
[16] A foamable urethane resin composition comprising the polyol-containing composition according to any one of [1] to [15] and a polyisocyanate.
[17] The expandable urethane resin composition according to [16], wherein the polyisocyanate is an aromatic polyisocyanate.
[18] The foamable urethane resin composition according to [16] or [17], which has an isocyanate index of 300 or more.
[19] The expandable urethane resin composition according to any one of [16] to [18], wherein the core density of the foam obtained by foaming the expandable urethane resin composition is 25 to 60 kg/m ³ . thing.
[20] The polyurethane foam obtained by foaming the expandable urethane resin composition was subjected to a cone calorimeter test in accordance with the test method of ISO-5660, and when heated at a radiant heat intensity of 50 kW / m ² for 20 minutes. The expandable urethane resin composition according to any one of [16] to [19], which has a total calorific value of less than 8 MJ/m ² .
[21] A polyurethane foam formed by reacting and foaming the expandable urethane resin composition according to any one of [16] to [20].

According to the present invention, in the step of reacting and foaming with polyisocyanate in a foaming machine, a polyurethane foam that exhibits good foamability, does not cause clogging in the filter inside the foaming machine, and has high flame resistance. It is possible to provide a polyol-containing composition capable of forming

The present invention will be described in detail below.
[Polyol-containing composition]
The polyol-containing composition of the present invention contains polyol, blowing agent, catalyst, and flame retardant. Polyol-containing compositions are used to react with polyisocyanates to obtain polyurethane foams. Also, the flame retardant includes at least a brominated flame retardant.

(Flame retardants)
<Brominated flame retardant>
The brominated flame retardant contained in the polyol-containing composition of the present invention has a structure containing at least two benzene rings per molecule. When the brominated flame retardant has such a structure, it is possible to prevent the brominated flame retardant from aggregating and increasing the particle size, and when reacting and foaming the polyol-containing composition and the polyisocyanate with a foaming machine, , it is possible to prevent clogging of the filter inside the foaming machine. Although the principle is not clear, the brominated flame retardant used in the present invention has a structure containing at least two benzene rings in the same molecule. Alternatively, it is thought to play a role in preventing bromine atoms from being attracted to each other due to interaction. As a result, it is thought that aggregation and increase in particle size of the brominated flame retardant can be prevented.
Specific examples of the brominated flame retardant having the above structure include polybrominated biphenyl, 1-benzyloxy-4-bromobenzene, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, ethylenebis(pentabromophenyl), and ethylene. bis(tetrabromophthalimide), tetrabromobisphenol A and the like.

In the brominated flame retardant used in the present invention, it is preferable that at least two of the benzene rings constituting the flame retardant are chemically bonded via ethylene groups. By being chemically bonded via the ethylene group, the degree of freedom of rotation of the bond axis between the benzene rings increases, and it becomes easier to have a three-dimensional structure, so the brominated flame retardant aggregates and has a large particle size. It becomes easier to prevent erosion more effectively.
At least one of the benzene rings constituting the brominated flame retardant is preferably brominated. Here, the term "brominated" means that at least one of the hydrogen atoms other than the hydrogen atoms substituted by the ethylene group in the benzene ring is substituted with a bromine atom. Any one of the benzene rings constituting the brominated flame retardant may be brominated, or two or more benzene rings may be brominated. From the viewpoint of keeping the bromine content in the fuel within the desired range, it is more preferable that two or more benzene rings are brominated. In the brominated benzene ring, more preferably two or more hydrogen atoms are substituted with bromine atoms, and more preferably all hydrogen atoms are substituted with bromine atoms.

The content of bromine in the brominated flame retardant used in the present invention (hereinafter sometimes referred to as "bromine content") is determined from the viewpoint of increasing the flame retardancy of the polyurethane foam. It is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more. On the other hand, the upper limit of the bromine content is not particularly limited, but is, for example, less than 100% by mass, preferably 90% by mass or less.
Regarding the brominated flame retardant, from the above viewpoints, it is particularly preferable that the brominated flame retardant used in the present invention is ethylenebis(pentabromophenyl).

The content of the brominated flame retardant is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 17% by mass or less, based on the total amount of the polyol-containing composition. When the content of the brominated flame retardant is equal to or less than the above upper limit, it becomes easier to adjust the numerical value of the viscosity of the polyol-containing composition to an appropriate range, and the handleability and foamability are excellent. Although the content of the brominated flame retardant is not particularly limited, it is preferably 3% by mass or more, more preferably 6% by mass or more, and even more preferably 9% by mass or more from the viewpoint of flame retardancy.

The polyol-containing composition of the present invention preferably contains a solid flame retardant other than the brominated flame retardant in addition to the brominated flame retardant described above, from the viewpoint of more effectively increasing the flame retardancy of the polyurethane foam. A solid flame retardant is a flame retardant that becomes solid at 23° C. and 1 atm. Solid flame retardants include red phosphorus flame retardants, boron flame retardants, phosphate-containing flame retardants, chlorine-containing flame retardants, antimony-containing flame retardants, needle-like fillers, and metal hydroxides.

<Red phosphorus flame retardant>
The red phosphorus-based flame retardant may be composed of red phosphorus alone, or may be red phosphorus coated with resin, metal hydroxide, metal oxide, or the like, or may be red phosphorus coated with resin, metal hydroxide, metal A mixture of oxides or the like may also be used. Resins coated with red phosphorus or mixed with red phosphorus are not particularly limited, but include thermosetting resins such as phenol resins, epoxy resins, unsaturated polyester resins, melamine resins, urea resins, aniline resins, and silicone resins. be done. From the viewpoint of flame retardancy, metal hydroxides are preferable as the film or compound to be mixed. Metal hydroxides include, for example, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, hydroxide Tin or the like may be appropriately selected and used.

<Boron-based flame retardant>
Boron-based flame retardants include borax, boron oxide, boric acid, borates, and the like. Examples of boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide.
Examples of borates include borates of alkali metals, alkaline earth metals, elements of Groups 4, 12 and 13 of the periodic table, and ammonium. Specifically, alkali metal borate salts such as lithium borate, sodium borate, potassium borate and cesium borate; alkaline earth metal borate salts such as magnesium borate, calcium borate and barium borate; Zirconium borate, zinc borate, aluminum borate, ammonium borate and the like.
Boron-based flame retardants may be used singly or in combination of two or more.
The boron-based flame retardant used in the present invention is preferably a borate, more preferably zinc borate.

<Phosphate-containing flame retardant>
Specific examples of phosphate-containing flame retardants are selected from various phosphoric acids, metals of Groups IA to IVB of the periodic table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring. Phosphates comprising salts with at least one metal or compound are included.
Examples of phosphoric acid include, but are not particularly limited to, monophosphoric acid, pyrophosphoric acid, polyphosphoric acid, and the like.
Examples of metals of Groups IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum.
Examples of aliphatic amines include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine and the like. Examples of aromatic amines include aniline, o-triidine, 2,4,6-trimethylaniline, anisidine, 3-(trifluoromethyl)aniline and the like. Heterocyclic compounds containing nitrogen in the ring include pyridine, triazine, melamine and the like.

Specific examples of phosphate-containing flame retardants include monophosphates, pyrophosphates, polyphosphates, and the like. Here, the polyphosphate is not particularly limited, but examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate amide, and aluminum polyphosphate.
The phosphate-containing flame retardant may be used alone or in combination of two or more of the above.

<Chlorine-containing flame retardant>
Chlorine-containing flame retardants include those commonly used in polyurethane foams, for example, polychlorinated naphthalene, chlorendic acid, dodecachlorododecahydrodimethanodibenzocyclooctene sold under the trade name "Dechloran Plus", and the like. mentioned.

<Flame retardant containing antimony>
Antimony-containing flame retardants include, for example, antimony oxide, antimonate, pyroantimonate, and the like. Examples of antimony oxide include antimony trioxide and antimony pentoxide. Examples of antimonates include sodium antimonate and potassium antimonate. Examples of pyroantimonate include sodium pyroantimonate and potassium pyroantimonate.
Antimony-containing flame retardants may be used singly or in combination of two or more.
The antimony-containing flame retardant used in the present invention is preferably antimony oxide.

<Needle-shaped filler>
Needle-shaped fillers include, for example, potassium titanate whiskers, aluminum borate whiskers, silicon-containing whiskers, wollastonite, sepiolite, xonolite, elestadite, boehmite, asbestos fibers, carbon fibers, graphite fibers, slag fibers, silica fibers, and alumina. fibers, zirconia fibers, boron nitride fibers, stainless steel fibers and the like. The aspect ratio (length/diameter) of the needle-like filler is preferably in the range of 5-50, more preferably in the range of 10-40.

<Metal hydroxide>
Examples of metal hydroxides include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, water Tin oxide etc. are mentioned. A metal hydroxide may be used individually by 1 type, and may be used in combination of 2 or more types.

The content of solid flame retardants other than brominated flame retardants is preferably 7 to 51% by mass, more preferably 9 to 40% by mass, and still more preferably 12 to 22% by mass, based on the total amount of the polyol-containing composition. When the content of the solid flame retardant other than the brominated flame retardant is at least the above lower limit, the flame retardancy of the polyurethane foam can be enhanced. On the other hand, if the content of the solid flame retardant other than the brominated flame retardant is equal to or less than the above upper limit, it becomes easier to adjust the viscosity value of the polyol-containing composition to an appropriate range, and the content of the foaming agent is large. It becomes easy to prevent it becoming too much, and it is excellent in handleability and foamability.

As the solid flame retardant other than the brominated flame retardant, it is preferable to contain at least the red phosphorus flame retardant among the above-described ones from the viewpoint of more effectively increasing the flame retardancy.
The content of the red phosphorus flame retardant is preferably 6 to 36% by mass, more preferably 8 to 30% by mass, and even more preferably 10 to 15% by mass, based on the total amount of the polyol-containing composition. When the content of the red phosphorus-based flame retardant is at least the above lower limit, the flame retardancy of the polyurethane foam can be enhanced. On the other hand, when the content of the red phosphorus-based flame retardant is equal to or less than the above upper limit value, it becomes easier to adjust the viscosity value of the polyol-containing composition to an appropriate range, and it is possible to prevent the content from becoming too large relative to the foaming agent. It becomes easy to prevent it, and it is excellent in handleability and foamability.

Moreover, as a solid flame retardant, the aspect which uses together solid flame retardants other than a red phosphorus flame retardant, such as a boric-acid flame retardant, is also preferable with a red phosphorus flame retardant. The content of the boron-based flame retardant is preferably 1 to 15% by mass, more preferably 1.5 to 10% by mass, and even more preferably 2 to 7% by mass, based on the total amount of the polyol-containing composition. When the content of the boron-based flame retardant is at least the above lower limit, the flame retardancy of the polyurethane foam can be enhanced. On the other hand, when the content of the boron-based flame retardant is equal to or less than the above upper limit, it becomes easier to adjust the viscosity value of the polyol-containing composition to an appropriate range, and the content of the foaming agent is prevented from becoming too large. It becomes easy to do, and it is excellent in handleability and foamability.

<Phosphate Ester Flame Retardant>
The polyol-containing composition of the present invention may further contain a liquid flame retardant. A liquid flame retardant is a flame retardant that becomes liquid at 23° C. and 1 atmospheric pressure. As the liquid flame retardant, it is preferable to contain a phosphate ester flame retardant. The use of the phosphate ester facilitates increasing the flame retardancy of the polyurethane foam without reducing the fluidity of the polyol-containing composition.

Monophosphates, condensed phosphates, and the like can be used as phosphate ester-based flame retardants. A monophosphate is a phosphate having one phosphorus atom in the molecule. Examples of monophosphates include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate and tri(2-ethylhexyl) phosphate, halogen-containing phosphates such as tris(β-chloropropyl) phosphate, and tributoxyethyl phosphate. Aromatic ring-containing phosphates such as trialkoxy phosphate, tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl) phosphate, cresyldiphenyl phosphate, diphenyl(2-ethylhexyl) phosphate, monoisodecyl phosphate, diisodecyl Acidic phosphoric acid esters such as phosphate and the like are included.

Examples of condensed phosphates include aromatic condensed phosphates 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. etc.

The phosphate ester flame retardant may be used singly or in combination of two or more of the above. Among these, monophosphates are preferable from the viewpoint of making it easier to adjust the viscosity of the polyol-containing composition and improving the flame retardancy of the polyurethane foam, and halogen-containing phosphorus such as tris(β-chloropropyl) phosphate. Acid esters are more preferred.
The content of the phosphate ester flame retardant in the polyol-containing composition is preferably 1 to 15% by mass, more preferably 1.5 to 10% by mass, and 2 to 7% by mass, based on the total amount of the polyol-containing composition. % is more preferred. When the content of the phosphate ester-based flame retardant is at least the above lower limit, the flame retardancy of the polyurethane foam can be effectively enhanced. On the other hand, when the content of the phosphate ester-based flame retardant is equal to or less than the above upper limit, the viscosity of the polyol-containing composition can be maintained at a certain level or higher, resulting in excellent handleability.

The content (total content) of the flame retardant in the polyol-containing composition of the present invention is preferably 20 to 60% by mass, more preferably 30 to 55% by mass, and 35 to 50% by mass, based on the total amount of the polyol-containing composition. is more preferred. When the content of the flame retardant is at least the above lower limit, the flame retardancy of the polyol-containing composition can be effectively enhanced. In addition, when the content of the flame retardant is equal to or less than the above upper limit, it becomes easier to adjust the viscosity value of the polyol-containing composition to an appropriate range, and it is easier to prevent the content of the foaming agent from becoming too large. It is excellent in handleability and foamability.

(catalyst)
<Urethane catalyst>
The polyol-containing composition of the present invention contains at least one metal catalyst selected from bismuth salts and tin salts as a urethanization catalyst. By containing these metal catalysts, the initial activity of the urethane resin composition is improved, and accordingly, the foamability of the composition is also improved. Therefore, dripping after foaming is less likely to occur, and flame retardancy of the polyurethane foam is improved. In addition, even if the polyol-containing composition is stored for a long period of time, it becomes difficult to deactivate.
The catalyst is preferably a metal salt of an organic acid, 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, the stability against the foaming agent, especially hydrofluoroolefin, is improved. Moreover, the number of carbon atoms in 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 have a branched structure, but preferably has a branched structure.
Specific examples of carboxylic acids include octylic acid, lauric acid, versatic acid, pentanoic acid and acetic acid, among which 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 have a branched structure. 2-Ethylhexanoic acid can be mentioned as the octylic acid having a branched structure.
As the metal salt of carboxylic acid, bismuth salt of carboxylic acid and tin salt of carboxylic acid are preferable, and bismuth salt of octylic acid is particularly preferable. Also, the metal salt of carboxylic acid may be an alkyl metal carboxylate. For example, the tin carboxylate may be a dialkyltin carboxylate or the like, preferably a dioctyltin carboxylate or the like.
Specific examples of metal salts of carboxylic acids include bismuth trioctate, dioctyltin versatate, dibutyltin dilaurate, dioctyltin dilaurate, and tin dioctate. Bismuth trioctate and dioctyltin versatate are preferred, and bismuth trioctate and dioctyltin versatate are more preferred. is bismuth trioctate.

The content of the metal catalyst is preferably 0.1 to 2.5% by mass, more preferably 0.2 to 2% by mass, and 0.5 to 1.5% by mass, based on the total amount of the polyol-containing composition. is more preferred. When the content of the metal catalyst is at least the above lower limit value, the initial activity of the foamable urethane resin composition is improved, and accordingly the foamability of the composition is also improved. On the other hand, when the content of the metal catalyst is equal to or less than the above upper limit, the foamable urethane resin composition can be reacted and foamed at an appropriate rate.

The urethanization catalyst used in the polyol-containing composition of the present invention preferably contains an amine catalyst in addition to the metal catalyst, and more preferably contains an imidazole derivative as the urethanization amine catalyst.
The imidazole derivative is less susceptible to hydrofluoroolefins and facilitates the reaction between the polyol and the polyisocyanate while enhancing the stability of the polyol-containing composition. Therefore, the polyol-containing composition contains an imidazole derivative in addition to the metal catalyst described above, so that the reactivity between the polyol and the polyisocyanate is enhanced and the foamability is further improved.
The imidazole derivative is preferably imidazole in which the 1- and 2-positions are each independently substituted with an alkyl group having 8 or less carbon atoms, and the alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less carbon atoms. A preferred 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 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.)

R ¹ and R ² in general formula (1) each independently represent an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms. Each of the alkyl group and alkenyl group may be linear or may have a branched structure.
Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, neopentyl, isopentyl, sec-pentyl, hexyl and heptyl groups. group, octyl group, and the like.
Specific examples of alkenyl groups include vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, pentenyl, hexenyl, heptenyl and octenyl groups.
It is preferable that the number of carbon atoms in the alkyl or alkenyl groups of R ¹ and R ² is at least the above lower limit, because steric hindrance is increased and the influence of foaming agents such as hydrofluoroolefins is reduced. On the other hand, when the number of carbon atoms in the alkyl groups of R ¹ and R ² is equal to or less than the above upper limit, the steric hindrance does not become extremely large, so the reaction between the polyol and the polyisocyanate can be rapidly progressed, resulting in foamability. is also 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 even more preferably a methyl group.

Examples of 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 and the like, among them, from the viewpoint of improving the activity of the catalyst in the presence of hydrofluoroolefin and from the viewpoint of rapidly advancing the reaction, 1,2-dimethylimidazole, 1-isobutyl-2-methyl Imidazole is preferred. Further, 1,2-dimethylimidazole is more preferable from the viewpoint of further enhancing stability.

The content of the imidazole derivative in the polyol-containing composition is preferably 0.5 to 8% by mass, more preferably 1 to 5% by mass, and even more preferably 1.5 to 3% by mass, based on the total amount of the polyol-containing composition. . When the content of the imidazole derivative is at least the above lower limit, urethane bonds are likely to be formed, the reaction proceeds rapidly, and foamability is improved. On the other hand, when the content of the imidazole derivative is equal to or less than the upper limit, the reaction rate is easily controlled, which is preferable.

<Trimerization catalyst>
The polyol-containing composition of the present invention preferably contains a trimerization catalyst in addition to the urethanization catalyst. The trimerization catalyst is a catalyst that promotes trimerization to form an isocyanurate bond, and promotes trimerization in the polyol-containing composition, thereby improving the flame retardancy and flame spread resistance of the polyurethane foam. .
Trimerization catalysts include aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine, acetic acid Potassium, sodium acetate, potassium 2-ethylhexanoate, sodium 2-ethylhexanoate, potassium formate, potassium octylate, alkali metal salts such as sodium octylate, aziridines such as 2-ethylaziridine, lead naphthenate, octylic acid lead compounds such as lead; alcoholate compounds such as sodium methoxide; phenolate compounds such as potassium phenoxide; Quaternary ammonium salts such as tetraphenylammonium salts and the like can be used. Among these, quaternary ammonium salts are preferred. When a quaternary ammonium salt is used, even if a hydrofluoroolefin compound such as hydrochlorofluoroolefin is used as a blowing agent, the catalyst activity is maintained satisfactorily, so the trimerization proceeds appropriately and flame retardancy is improved. improves.
The trimerization catalyst may be used alone or in combination of two or more. From the viewpoint of sufficiently enhancing the flame retardancy of the polyurethane foam, two or more of them are used in combination. preferably. When two or more are used in combination, it is preferable to use an alkali metal salt and a quaternary ammonium salt, and it is more preferable to use potassium 2-ethylhexanoate and a tetramethylammonium salt.

When a quaternary ammonium salt is contained as a trimerization catalyst, the content of the quaternary ammonium salt is not particularly limited, but is preferably 0.5 to 10% by mass, preferably 1 to 5% by mass, based on the total amount of the polyol-containing composition. is more preferred, and 1.5 to 3% by mass is even more preferred. By setting the content of the trimerization catalyst within the above range, isocyanurate bonds are appropriately formed, and flame retardancy is improved.

In addition, when an alkali metal salt is contained as a trimerization catalyst, the content of the alkali metal salt is not particularly limited, but is preferably 0.1 to 3% by mass, based on the total amount of the polyol-containing composition. 5 to 2.5% by mass is more preferable, and 0.8 to 2% by mass is even more preferable. By setting the content of the trimerization catalyst within the above range, isocyanurate bonds are appropriately formed, and flame retardancy is improved.

The content of the trimerization catalyst is not particularly limited, but is preferably 0.6 to 13% by mass, more preferably 1.5 to 7.5% by mass, and 2.3 to 5% by mass, based on the total amount of the polyol-containing composition. is more preferred. By setting the content of the trimerization catalyst within the above range, isocyanurate bonds are appropriately formed, and flame retardancy is improved.

(polyol)
Examples of polyols used in the present invention include polylactone polyols, polycarbonate polyols, polyester polyols, polymer polyols, and polyether polyols.

Polylactone polyols include, for example, polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol.
Examples of polycarbonate polyols include polyols obtained by dealcoholization 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. etc.

Polyester polyols include, for example, polymers obtained by dehydration condensation of polybasic acids and polyhydric alcohols, and condensates of hydroxycarboxylic acids and the polyhydric alcohols.
Examples of polybasic acids include adipic acid, azelaic acid, sebacic acid, isophthalic acid (m-phthalic acid), terephthalic acid (p-phthalic acid), o-phthalic acid (phthalic acid), naphthalenedicarboxylic 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.
Examples of hydroxycarboxylic acids include castor oil, reaction products of castor oil and ethylene glycol, and the like.

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

As the polyether polyol, for example, an alkylene oxide having 2 to 6 carbon atoms, specifically ethylene oxide, is dissolved in the presence of at least one low-molecular-weight active hydrogen compound having two or more active hydrogens such as a polyhydric alcohol. , propylene oxide, tetrahydrofuran, and the like. Alkylene oxide includes at least one of ethylene oxide and propylene oxide.
Low molecular weight active hydrogen compounds having two or more active hydrogens include, for example, bisphenol A, ethylene glycol, propylene glycol, butylene glycol, diols such as 1,6-hexanediol, triols such as glycerin and trimethylolpropane, Pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, sucrose, glucose, mannose, fructose, methylglucoside and derivatives thereof, and other tetravalent to octahydric alcohols, phloroglucinol, cresol, pyrogallol, catechol , hydroquinone, bisphenol A, bisphenol F, bisphenol S, polyols such as 1,3,6,8-tetrahydroxynaphthalene, and 1,4,5,8-tetrahydroxyanthracene, castor oil polyol, hydroxyalkyl (meth)acrylate Polyfunctional (for example, 2 to 100 functional groups) polyols such as (co)polymers and polyvinyl alcohol, condensates of phenol and formaldehyde (novolak), amines such as ethylenediamine and butylenediamine, and the like.

Polyester polyols and polyether polyols are preferred as the polyols used in the present invention. Moreover, a polyol compound having two hydroxyl groups is preferable. Among them, aromatic polyester polyols, which are polyester polyols having an aromatic ring, are preferred from the viewpoint of enhancing flame retardancy of polyurethane foam. In that case, the weighted average aromatic concentration of the polyol is preferably 10% by mass or more, more preferably 12% by mass or more.
Here, the aromatic concentration is obtained by the total mass% of the carbon atoms and hydrogen atoms constituting the aromatic ring in the polyol, and the weighted average aromatic concentration is the carbon atoms and hydrogen atoms of the aromatic ring. It is the concentration of aromatics obtained by weighted average from each content of atoms.
Aromatic polyester polyol is a condensate of aromatic dicarboxylic acid such as o-phthalic acid (phthalic acid), m-phthalic acid (isophthalic acid), p-phthalic acid (terephthalic acid), naphthalene dicarboxylic acid and glycol. is preferred. Among them, the aromatic polyester polyol more preferably contains a phthalic acid-based polyester polyol, which is a condensate of phthalic acid and glycol, from the viewpoint of improving the flame retardancy of the polyurethane foam, particularly the performance of preventing the spread of flames. Contains at least one selected from p-phthalic acid-based polyester polyol, which is a condensate of p-phthalic acid and glycol, and o-phthalic acid-based polyester polyol, which is a condensate of o-phthalic acid and glycol is more preferred.

When the polyol contains an aromatic polyester polyol, the content is not particularly limited, but it is preferably 50 parts by mass or more, and 70 parts by mass or more with respect to 100 parts by mass of the polyol compound in the polyol-containing composition. is more preferable, and 100 parts by mass is even more preferable.

The weighted average hydroxyl value of the polyol is preferably 20 to 350 mgKOH/g, more preferably 30 to 300 mgKOH/g, even more preferably 50 to 250 mgKOH/g. When the hydroxyl value of the polyol is equal to or less than the above upper limit, the viscosity of the polyol-containing composition tends to decrease, which is preferable from the viewpoint of handleability and the like. On the other hand, when the hydroxyl value of the polyol is at least the above lower limit, the crosslink density of the polyurethane foam increases, resulting in increased strength and improved workability during spraying.
The hydroxyl value of polyol can be measured according to JIS K 1557-1:2007.

Here, the weighted average hydroxyl value of a polyol is obtained by summing up the product of the hydroxyl value of each polyol constituting the polyol and the mass fraction of each polyol in the polyol. For example, when two types of polyol (d1) and polyol (d2) are used as the polyol compound, the hydroxyl value of polyol (d1) is X ₁ , the blending amount is m ₁ , the hydroxyl value of polyol (d2) is X ₂ , Assuming that the blending amount is _m2 , the weighted average hydroxyl value is expressed by the following formula. The blending amounts m1 and _m2 are the _number of parts by mass in 100 parts by mass of the polyol compound.
Weighted average hydroxyl value (mgKOH/g)=X ₁ ×(m ₁ /(m ₁ +m ₂ ))+X ₂ ×(m ₂ /(m ₁ +m ₂ ))

(foaming agent)
Specific examples of foaming agents include water, low-boiling hydrocarbons, chlorinated aliphatic hydrocarbon compounds, fluorine compounds, hydrochlorofluorocarbon compounds, hydrofluorocarbons, ether compounds, and hydrofluoroolefins. Furthermore, examples of foaming agents include organic physical foaming agents such as mixtures of these compounds, and inorganic physical foaming agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas.
Examples of the low boiling point hydrocarbons include propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane.
Examples of the chlorinated aliphatic hydrocarbon compounds include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride and isopentyl chloride.
Examples of the fluorine compound include CHF ₃ , CH ₂ F ₂ , CH ₃ F and the like.
Examples of the hydrochlorofluorocarbon compounds include trichloromonofluoromethane, trichlorotrifluoroethane, dichloromonofluoroethane (e.g., HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b ( 1-chloro-1,1-difluoroethane)) and the like.
Examples of the hydrofluorocarbon include HFC-245fa (1,1,1,3,3-pentafluoropropane) and HFC-365mfc (1,1,1,3,3-pentafluorobutane).
Examples of the ether compound include diisopropyl ether and the like.
Examples of the hydrofluoroolefins include HFO-1233zd(E) (trans-1-chloro-3,3,3-trifluoropropene), HFO-1234yf (2,3,3,3-tetrafluoro-1- propene), HFO-1336mzz(Z) (cis-1,1,1,4,4,4-hexafluorobut-2-ene), HFO-1224yd(Z) and the like.

Among the above-mentioned foaming agents, it is preferable to contain hydrofluoroolefin, and it is more preferable to use hydrofluoroolefin and water in combination.
The content of the foaming agent is preferably 5 to 26% by mass, more preferably 8 to 20% by mass, more preferably 10 to 15% by mass, based on the total amount of the polyol-containing composition, from the viewpoint of adjusting the core density of the foam to a desired range. % by mass is more preferred.

The content of the hydrofluoroolefin used as a foaming agent is preferably 5 to 25% by mass, preferably 8 to 20% by mass, based on the total amount of the polyol-containing composition, from the viewpoint of setting the core density of the polyurethane foam within the desired range. More preferably, 10 to 15% by mass is even more preferable.

As the water used as the foaming agent, for example, ion-exchanged water, distilled water, or the like can be used as appropriate. Among these, it is preferable to use ion-exchanged water. The water content is preferably 0.05 to 1% by mass, more preferably 0.1 to 0.5% by mass, and even more preferably 0.2 to 0.3% by mass, based on the total amount of the polyol-containing composition. By setting the water content within the above range, a good balance between flame retardancy and foamability can be obtained.

(foam stabilizer)
The polyol-containing 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 foaming can be promoted, for example, when reacting with polyisocyanate in spraying.
Specific examples of foam stabilizers include surfactants, and more specifically nonionic surfactants, cationic surfactants, anionic surfactants, and the like. Specific examples of nonionic surfactants include polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ethers, silicone foam stabilizers such as organopolysiloxane, and the like. Although the foam stabilizer used in the present invention is not particularly limited, silicone foam stabilizers are preferred from the viewpoint of foamability. A foam stabilizer may be used individually by 1 type, and may be used in combination of 2 or more types.

The content of the foam stabilizer in the polyol-containing composition of the present invention is preferably 0.3 to 2% by mass, more preferably 0.5 to 1.5% by mass, based on the total amount of the polyol-containing composition. 7 to 1.2% by mass is more preferable. When the content of the foam stabilizer is at least the above lower limit, the mixture of the polyol-containing composition and the polyisocyanate can be easily foamed, making it possible to obtain a homogeneous polyurethane foam. Further, when the content of the foam stabilizer is equal to or less than the above upper limit, the balance between the production cost and the effect obtained is optimal.

(Other ingredients)
The polyol-containing composition may optionally contain antioxidants such as phenolic, amine, and sulfur antioxidants, heat stabilizers, light stabilizers, metal damage inhibitors, and antistatic agents, as long as the objects of the present invention are not compromised. , stabilizers, cross-linking agents, lubricants, softeners, pigments, dyes, fillers other than solid flame retardants, and the like.

(Production method)
The method for producing the polyol-containing composition of the present invention is not particularly limited. For example, it can be produced by stirring each component at about room temperature using a homodisper or the like for about 30 seconds to 20 minutes. The polyol-containing composition of the present invention contains a brominated flame retardant having a predetermined structure in the composition, thereby preventing aggregation of the brominated flame retardant even during production of the composition. Therefore, it is easy to handle during production.

[Expandable urethane resin composition and polyurethane foam]
The foamable urethane resin composition of the present invention contains the above polyol-containing composition and polyisocyanate. A foamable urethane resin composition is obtained by mixing the polyol-containing composition and polyisocyanate.

(polyisocyanate)
In the present invention, examples of polyisocyanates 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). be done.

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

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

Among these, from the viewpoint of ease of use and availability, aromatic polyisocyanates are preferred, diphenylmethane diisocyanate, polymeric MDI, or mixtures thereof are more preferred, and diphenylmethane diisocyanate is more preferred. 4'-diphenylmethane diisocyanate is preferred. One type of polyisocyanate may be used alone, or two or more types may be mixed and used.
Moreover, before mixing the polyisocyanate with the polyol-containing composition, known additives that are blended with polyisocyanate may be appropriately blended.

The polyol-containing composition and the polyisocyanate mixed with the polyol-containing composition preferably have substantially the same volume. Specifically, the volume ratio of the polyisocyanate to the polyol-containing composition is preferably 0.8 to 1.2, more preferably 0.9 to 1.1, even more preferably 0.95 to 1.05.

(isocyanate index)
Although the isocyanate index in the foamable urethane resin composition of the present invention is not particularly limited, it is preferably 300 or more. When the isocyanate index is equal to or higher than the lower limit, the amount of polyisocyanate is excessive relative to the polyol, and the trimerization of polyisocyanate tends to form isocyanurate bonds, resulting in improved flame retardancy of the polyurethane foam. It also becomes possible to impart flame retardancy. Furthermore, if the above lower limit is exceeded, combined with the use of the various catalysts described above, a polyurethane foam having sufficient isocyanurate bonds, that is, a polyurethane foam that has both flame retardancy and heat insulation at a high level. Easy to manufacture body. From these points of view, the isocyanate index is more preferably 350 or more, and even more preferably 400 or more.
Also, 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 equal to or less than the above upper limit, flame retardancy sufficiently matching the production cost can be obtained.

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

(Total calorific value)
The polyurethane foam made of the expandable urethane resin composition of the present invention preferably has a total calorific value of less than 8 MJ/m ² when subjected to a cone calorimeter test according to the test method of ISO-5660. With a total calorific value of less than 8 MJ/m ² , the polyurethane foam made of the expandable urethane resin composition of the present invention has a predetermined flame retardancy.
From the viewpoint of further improving the flame retardancy of the foam, the total calorific value is more preferably less than 7.8 MJ/m ² and even more preferably less than 7.5 MJ/m ² . The lower the total calorific value, the better, ideally 0 MJ/m ² , but usually 1 MJ/m ² or more.
The total calorific value can be easily adjusted to the above-described desired value by adjusting the composition of the expandable urethane resin composition, generally by adjusting the content of the flame retardant.
The cone calorimeter test is performed by heating for 20 minutes at a radiant heat intensity of 50 kW/m ² . A polyurethane foam for the cone calorimeter test is formed from an expandable urethane resin composition by the method described in the Examples.

(core density)
The core density of the polyurethane foam comprising the expandable urethane resin composition of the present invention is not particularly limited, but is preferably in the range of 25-60 kg/m ³ . By setting the density to 60 kg/m ³ or less, the weight of the polyurethane foam is reduced, and the workability to the structure is enhanced. Further, by making it 25 kg/m ³ or more, desired flame retardancy is likely to be exhibited. From these points of view, the core density of the polyurethane foam is more preferably in the range of 25-55 kg/m ^{3 , still more preferably in the range of 30-50 kg/m 3 .} The core density can be determined by forming a foam from the foamable urethane resin composition by the method described in Examples and measuring the core density of the foam.

There are no particular restrictions on the method for producing a polyurethane foam, but a polyol-containing composition is mixed with a polyisocyanate in a foaming machine or the like, and the resulting mixture (expandable urethane resin composition) is reacted and foamed. , to produce a polyurethane foam.

The foaming machine may be provided with a filter for removing dust contained in the polyol-containing composition. The filter may be a mesh filter or the like, which allows the solid flame retardant and the like contained in the polyol-containing composition to pass through but removes dust and the like. The filter is preferably installed at a position prior to mixing with the polyisocyanate.
The polyol-containing composition is preferably fed to the foaming machine and mixed with the polyisocyanate fed from another container or the like by collision mixing inside the foaming machine. At this time, since the brominated flame retardant contained in the polyol-containing composition has a predetermined structure, aggregation of the brominated flame retardant does not occur, and clogging of the filter inside the foaming machine is prevented. can do.

The polyol-containing composition and the expandable urethane resin composition are preferably used for spray applications. Therefore, it is preferable to use a spray device having a spray gun as the foaming machine. When using a spray device, a mixed solution (expandable urethane resin composition) obtained by collision-mixing the polyol-containing composition and polyisocyanate is discharged from an outlet such as a spray gun, and the discharged expandable urethane resin The composition may be molded into a polyurethane foam.
The mixed liquid discharged from the spray device is preferably sprayed onto the surface to be applied at a constant discharge pressure to cause foaming, thereby forming a polyurethane foam on the surface to be applied. Polyurethane foam is preferably molded using a wall, ceiling, roof, floor, or the like as the surface to be sprayed. In addition, since the isocyanate in the foaming stock solution and the polyol-containing composition are uniformly reacted and sprayed, the volume ratio of the foaming stock solution is 1.0 for isocyanate and 0.8 to 0.8 for the polyol-containing composition. It can be made to react in the range of 1.2.
As a more specific method, spraying can be carried out using a spraying device (eg, GRACO: A-25) and a spray gun (eg, Gasmer: D gun). Spraying can be carried out by adjusting the temperature of the polyol-containing composition for spraying and the polyisocyanate in a separate container in a spraying device, mixing the two by collision with the tip of the spray gun, and making the mixture mist by air pressure. .
In addition, as described above, the spraying device and the spray gun are known ones, and commercially available products can be used. In addition, the temperature setting, pressure, etc. of the stock solution can be applied to general polyurethane foam spraying conditions.

The present invention will be described in more detail with reference to examples, but the present invention is not limited by these examples.

The details of each component used in each example and comparative example are as follows.
(polyisocyanate)
・Polyisocyanate (MDI, manufactured by Sumika Covestro Urethane Co., Ltd., trade name: Sumidule 44V20)

(polyol)
Aromatic polyester polyol p-phthalic acid-based polyester polyol (manufactured by Kawasaki Chemical Industries, Ltd., product name “Maximol RLK-087”, aromatic concentration 8% by mass, hydroxyl value = 200 mgKOH / g)
Aromatic polyester polyol p-phthalic acid-based polyester polyol (manufactured by Kawasaki Chemical Industries, Ltd., product name “Maximol RFK-509”, aromatic concentration 24%, hydroxyl value = 200 mgKOH / g)

(foam stabilizer)
・Silicone-based foam stabilizer (manufactured by Dow Toray Industries, product name “SH-193”)

(catalyst)
(1) Trimerization catalyst/alkali metal salt: Potassium 2-ethylhexanoate (manufactured by Evonik, product name “DABCO K-15”) concentration 70 to 80 mass%
・ Quaternary ammonium salt: 2,2-dimethylpropanoic acid tetramethylammonium salt (manufactured by Evonik, product name “DABCO TMR7”) concentration 45 to 55% by mass
(2) Urethane catalyst/amine catalyst 1: 1,2-dimethylimidazole (manufactured by Tosoh Corporation, product name: TOYOCAT (registered trademark)-DM70) concentration 65 to 75 mass%
・Metal catalyst: bismuth trioctate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-600) concentration 55 to 58% by mass
(3) Foaming catalyst/amine catalyst 2: Bis(2-dimethylaminoethyl) ether (manufactured by Momentive Performance Materials Japan, product name “NIAX CATALYST A-1”) concentration of about 70% by mass

(Flame retardants)
・Red phosphorus flame retardant (manufactured by Rin Kagaku Kogyo Co., Ltd., product name: Nova Excel 140)
・ Phosphate flame retardant: tris (β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP)
・Boron-based flame retardant: Zinc borate (manufactured by Hayakawa Shoji Co., Ltd., product name: Firebrake ZB)
- Brominated flame retardant 1: ethylene bis (pentabromophenyl) (manufactured by Albemarle, product name: SAYTEX 8010, bromine content 82% by mass)
・Brominated flame retardant 2: Hexabromobenzene (manufactured by Nippo Chemical Co., Ltd., product name: FR-B, bromine content 87% by mass)
Brominated flame retardant 3: Tetrabromobisphenol A bis (2,3-dibromo 2-methylpropyl) ether (manufactured by Daiichi Pharmaceutical Co., Ltd., product name: Pyroguard SR-130, bromine content 65% by mass)
- Brominated flame retardant 4: Tetrabromobisphenol A (manufactured by Tosoh Corporation, product name: Flamecut 120G, bromine content 59% by mass)

[Examples 1 to 7, Comparative Examples 1 to 3]
A spray device was charged with the polyol-containing composition and the polyisocyanate, respectively. Foam obtained by adjusting the temperature of the filled polyol-containing composition and polyisocyanate in the spraying device, and using a spray gun to impingement-mix the polyol-containing composition and polyisocyanate according to the formulation shown in Table 1. A polyurethane foam was obtained by spraying the urethane resin composition on a gypsum board in the form of a mist to foam it. Commercial products were used for both the blowing machine and the spray gun.

The methods for measuring each physical property of the polyurethane foam and evaluating each property of the polyol-containing composition are as follows.
[Total calorific value]
The total calorific value of the polyurethane foam produced in each example and comparative example was evaluated by the following method.
(1) In order to obtain a test piece for measuring the total calorific value, the expandable urethane resin composition obtained in each example and comparative example was applied to a gypsum board having a thickness of 12.5 mm using the above-described spraying machine. A first layer of polyurethane foam was obtained by spraying to a thickness of 10 mm.
(2) A foamable urethane resin composition was sprayed onto the first-layer polyurethane foam to a thickness of 20 mm to obtain a second-layer polyurethane foam. Therefore, at this point, the total thickness of the polyurethane foam from the first layer to the second layer is 30 mm.
Polyurethane foam specimens obtained by the above methods (1) and (2) were prepared as cone calorimeter test samples. The sample was heated for 20 minutes at a radiant heat intensity of 50 kW/m ² by a cone calorimeter test according to the ISO-5660 test method, and the total calorific value was measured.

[Core density]
A polyurethane foam test specimen was prepared in the same manner as when the total calorific value was measured. From the second layer of the test body, a rectangular parallelepiped test body of approximately 100 mm long x 50 mm wide x 10 mm high was cut out so as not to include the skin layer, and the mass and volume of the cut test body were measured. Core density was determined from mass and volume.

[Filter clogging]
Two types of foaming machine filters (40 micron mesh and 80 micron mesh) with different meshes (roughness of mesh) were prepared. Each filter is loaded on the path through which the polyol-containing composition passes in the foaming machine, and about 10 L of the expandable urethane resin composition obtained by mixing the polyol-containing composition and polyisocyanate is discharged from the foaming machine. The presence or absence of clogging was visually confirmed. Criteria for evaluating filter clogging are as follows.
O: A 40 micron mesh filter was loaded, and clogging did not occur.
Δ: Clogging occurred when a 40-micron mesh filter was loaded, but no clogging occurred when an 80-micron mesh filter was loaded.
x: A filter of 80 micron mesh was loaded, and clogging occurred.

[liquid drip]
The polyol-containing composition and polyisocyanate were mixed according to the formulation shown in Table 1, and the thickness of the polyurethane foam was 30 mm against the substrate (gypsum board) with a spraying machine under the above-described polyurethane foam production conditions. The liquid was sprayed so as to scatter in the following manner, and the presence or absence of dripping was visually confirmed. Evaluation criteria for dripping are as follows.
O: No dripping occurred.
Δ: Partial dripping occurred.
x: Dripping occurred on the whole.

[Flame retardance]
The flame retardancy of the polyurethane foam was evaluated based on the total calorific value measured by the above method. The evaluation criteria for flame retardancy are as follows.
○: Less than 8 MJ/m ² △: 8 MJ/m ² or more and less than 10 MJ/m ² ×: 10 MJ/m ² or more

[Deactivation]
A polyol-containing composition and a polyisocyanate were mixed according to the formulation shown in Table 1 to obtain an expandable urethane resin composition. Thereafter, under the above-described polyurethane foam production conditions, the composition is sprayed onto the base material (gypsum board) using a sprayer so that the thickness of the polyurethane foam becomes 5 mm or less, and the composition is scattered. A tack-free time (TFT), which is the surface hardening time after spraying, was measured.
At this time, the polyol-containing composition was subjected to an accelerated deterioration test at 60° C. for one week. Before and after the accelerated deterioration test, the spraying operation and measurement of the TFT were carried out. Deactivation of the foamable urethane resin composition was evaluated based on the difference between the TFT before the accelerated deterioration test and the TFT after the accelerated deterioration test. Evaluation criteria for deactivation are as follows.
○: The rate of increase in TFTs due to the accelerated deterioration test is less than 30% ×: The rate of increase in TFTs due to the accelerated deterioration test is 30% or more

Each of the above evaluations was carried out using the obtained polyurethane foam. Table 1 shows the evaluation results for each item.

Parts by mass of each catalyst are parts by mass of the product.

As described above, all of the polyol-containing compositions prepared in each example had good foamability and could prevent clogging of the filter inside the foaming machine. Polyurethane foams formed by reacting and foaming the composition with polyisocyanate were all excellent in flame retardancy.
On the other hand, since the polyol-containing composition prepared in Comparative Example 1 did not contain a brominated flame retardant having a predetermined structure, clogging of the filter inside the foaming machine occurred, and a sufficient amount of polyol was contained. The composition could not be ejected. In addition, the polyol-containing compositions prepared in Comparative Examples 2 and 3 were able to prevent clogging of the filter inside the foaming machine, but the foamability of the composition and the polyurethane formed from the composition At least one of the flame retardant properties of the foam was compromised.

Claims (21)

A polyol-containing composition comprising a polyol, a blowing agent, a catalyst, and a flame retardant,
the catalyst comprises at least one metal catalyst selected from bismuth salts and tin salts;
A polyol-containing composition, wherein the flame retardant comprises a brominated flame retardant having a structure containing at least two benzene rings per molecule. 2. The polyol-containing composition according to claim 1, wherein at least two of the benzene rings constituting the brominated flame retardant are chemically bonded via ethylene groups. 3. A polyol-containing composition according to claim 1 or 2, wherein the brominated flame retardant comprises at least one brominated benzene ring. The polyol-containing composition according to any one of claims 1 to 3, wherein the bromine content in the brominated flame retardant is 50% by mass or more based on the total amount of the brominated flame retardant. A polyol-containing composition according to any preceding claim, wherein the brominated flame retardant is ethylenebis(pentabromophenyl). The polyol-containing composition according to any one of claims 1-5, wherein the flame retardant comprises a red phosphorus flame retardant. 7. The polyol-containing composition according to claim 6, wherein the content of said red phosphorus-based flame retardant is 6 to 36% by mass based on the total amount of the polyol-containing composition. A polyol-containing composition according to any preceding claim, wherein said blowing agent comprises a hydrofluoroolefin. A polyol-containing composition according to any one of claims 1-8, wherein the catalyst comprises an imidazole derivative. A polyol-containing composition according to any one of claims 1-9, wherein the catalyst comprises a trimerization catalyst. 11. The polyol-containing composition of claim 10, wherein said trimerization catalyst comprises a quaternary ammonium salt. The polyol-containing composition according to any one of claims 1 to 11, wherein the polyol has a weighted average aromatic concentration of 10% by weight or more. The polyol-containing composition according to any one of claims 1 to 12, wherein the content of the flame retardant is 20 to 60 mass% based on the total amount of the polyol-containing composition. The polyol-containing composition according to any one of claims 1 to 13, wherein the content of the brominated flame retardant is 20% by mass or less based on the total amount of the polyol-containing composition. A polyol-containing composition according to any one of claims 1 to 14 for use in spray applications. A foamable urethane resin composition comprising the polyol-containing composition according to any one of claims 1 to 15 and a polyisocyanate. 17. The foamable urethane resin composition according to claim 16, wherein said polyisocyanate is an aromatic polyisocyanate. The foamable urethane resin composition according to claim 16 or 17, which has an isocyanate index of 300 or more. The expandable urethane resin composition according to any one of claims 16 to 18, wherein a core density of a foam obtained by foaming the expandable urethane resin composition is 25 to 60 kg/m ³ . A polyurethane foam obtained by foaming the expandable urethane resin composition was subjected to a cone calorimeter test in accordance with the test method of ISO-5660, and the total calorific value when heated at a radiant heat intensity of 50 kW/m ² for 20 minutes. is less than 8 MJ/m ² , the expandable urethane resin composition according to any one of claims 16 to 19. A polyurethane foam formed by reacting and foaming the foamable urethane resin composition according to any one of claims 16 to 20.