JP7670537B2 - Polyol-containing composition, foamable polyurethane composition, and polyurethane foam - Google Patents

Description

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

Due to its excellent heat 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. Polyurethane foam is obtained by mixing a polyol composition and a polyisocyanate, foaming the mixture, and spraying the mixture onto objects such as ceilings, walls, and roofs using a spray device. Since such polyurethane foam is used in buildings, it is required to be flame retardant in order to prevent the fire from spreading to the polyurethane foam and causing the fire to spread to the entire building in the event of a fire. For this reason, polyurethane foam may be blended with a solid flame retardant such as red phosphorus, which has a high flame retardant effect.

In recent years, as the range of applications for such polyurethane foams has expanded, they have come to be used in places that are visible to the public, and therefore the design of the surface has become important, and as a result, the demand for colored polyurethane foams is also increasing. One method for coloring polyurethane foams is, for example, to add a pigment to a composition for producing polyurethane foams that contains a polyol, as described in Patent Document 1.

Re-table 2018/225651 publication

However, when a pigment is used in this manner, the pigment does not disperse sufficiently in the composition for producing polyurethane foam, and the pigment precipitates, causing liquid separation of the composition, resulting in an uneven coloring of the polyurethane foam and a deterioration in the design.

The present invention aims to provide a polyol-containing composition that does not cause liquid separation and can produce polyurethane foam with excellent flame retardancy and design properties.

After extensive research, the inventors discovered that the above problems could be solved by a polyol-containing composition for reacting with a polyisocyanate to obtain a polyurethane foam, the polyol-containing composition containing a polyol, a blowing agent, a catalyst, a flame retardant, and a dye, and the flame retardant includes a solid flame retardant, and thus completed the present invention.

The present invention relates to the following items [1] to [13].
[1] A polyol-containing composition for reacting with a polyisocyanate to obtain a polyurethane foam, the polyol-containing composition comprising a polyol, a blowing agent, a catalyst, a flame retardant, and a dye, and the flame retardant comprises a solid flame retardant.
[2] The polyol-containing composition according to [1], wherein the solid flame retardant comprises a red phosphorus-based flame retardant.
[3] The polyol-containing composition according to [1] or [2], wherein the catalyst comprises a trimerization catalyst.
[4] The polyol-containing composition according to [3], wherein the trimerization catalyst comprises a quaternary ammonium salt.
[5] The polyol-containing composition according to any one of [1] to [4], wherein the catalyst comprises an imidazole derivative.
[6] The polyol-containing composition according to any one of [1] to [5], wherein the catalyst comprises at least one metal catalyst selected from bismuth and tin.
[7] The polyol-containing composition according to any one of [1] to [6], which does not undergo liquid separation when stored in an environment of 40° C. for 3 days.
[8] A foamable polyurethane composition comprising the polyol-containing composition according to any one of [1] to [7] and a polyisocyanate.
[9] A foamable polyurethane composition comprising a polyol, a polyisocyanate, a blowing agent, a catalyst, a flame retardant, and a dye, wherein the flame retardant comprises a solid flame retardant.
[10] The foamable polyurethane composition according to [8] or [9], having an isocyanate index of 200 or more.
[11] The foamable polyurethane composition according to any one of [8] to [10], which is used for spray applications.
[12] A polyurethane foam obtained by foaming the foamable polyurethane composition according to any one of [8] to [11].
[13] A method for producing a polyurethane foam, comprising: preparing a polyol-containing composition by blending at least a polyol, a blowing agent, a catalyst, and a flame retardant including a solid flame retardant; mixing the polyol-containing composition with a polyisocyanate; and foaming the composition to produce a polyurethane foam; wherein a dye is added to the polyol-containing composition or the polyisocyanate in advance, or is added when the polyol-containing composition and the polyisocyanate are mixed.

The present invention provides a polyol-containing composition that does not cause liquid separation and can produce polyurethane foam with excellent flame retardancy and design properties.

[Polyol-containing composition]
The polyol-containing composition of the present invention contains a polyol, a blowing agent, a catalyst, a flame retardant, and a dye.

<Dye>
The colorant contained in the polyol-containing composition of the present invention is a dye. Dyes are generally dissolved in the polyol-containing composition and are sufficiently dispersed in the polyol-containing composition. Therefore, by using a dye instead of a pigment, liquid separation of the polyol-containing composition can be prevented, and the polyurethane foam can be uniformly colored. The dye can be a solvent dye, a disperse dye, or the like.
The dye contained in the polyol-containing composition of the present invention is preferably at least one selected from the group consisting of black dyes and blue dyes. When the dye is a black dye, the color of the polyurethane foam becomes black or a gray color close to black, so that even if the polyurethane foam is colored red or pink by adding a flame retardant described later, the red color can be effectively masked to improve the design.
Furthermore, if the dye is a blue dye, the dye exerts a complementary color effect, and red colors are more effectively masked, so that the color of the polyurethane foam becomes gray or close to gray, thereby improving the design.
The term "blue dye" used in the present invention may refer not only to blue dyes but also to dyes of colors similar to blue, specifically purple dyes, light blue dyes, and the like.

The black dye or blue dye used in the present invention may be one which expresses a black or blue color by using only one kind of compound, or may be one which expresses a black or blue color by using a combination of two or more kinds of compounds.
Below, some specific examples of black dyes and blue dyes are listed in more detail as dyes, but the dyes used in the present invention are not limited to these, and dyes other than those listed below may be used as long as they can suppress liquid separation of the composition when contained in a polyol-containing composition.

As the black dye, nigrosine dye, azo dye, azine dye, etc. can be used, and various solvent blacks, reactive blacks, and disperse blacks described in the Color Index can be used.
As the black dye, commercially available products may be used, such as Reactint Black X95AB, Reactint Black 1852, Reactint Black 2256, Reactint Black X77, and Reactint Black 454SS (all manufactured by Milken & Company).
When using a black dye in the present invention, one type may be used alone, or two or more types may be used in combination.

The blue dye may be a blue dye or a purple dye. The blue dye may be a light blue dye.
As the blue dye, various solvent blues, reactive blues, disperse blues, etc. described in the Color Index can be used.
As the purple dye, various solvent violets, reactive violets, disperse violets, etc. described in the Color Index can be used.
As the blue dye, commercially available products may be used, for example, blue dyes such as Reactint Blue X17AB and Reactint Blue X77 (both manufactured by Milken & Company). In addition, blue dyes may be cold dye navy blue (manufactured by Katsuraya Fine Goods Co., Ltd.) or light blue dyes such as cold dye sky blue (manufactured by Katsuraya Fine Goods Co., Ltd.).
Furthermore, an example of a purple dye is Reactint Violet X80LT (manufactured by Milken & Company).
When the black dye is used in the present invention, one type may be used alone or two or more types may be used in combination, similarly to the black dye.

In the present invention, a dye having a third color, such as red, yellow, or orange, other than the black dye or blue dye (hereinafter referred to as the third dye), may be used in combination with the black dye or blue dye, as long as the effect of the present invention is not impaired. The third dye may also be a commercially available dye. Examples of commercially available products include Reactint Red X64, Reactint Orange X94, Reactint Yellow X15, and Reactint Yellow X36 (all manufactured by Milken & Company).

The dye contained in the polyol-containing composition of the present invention is preferably a blue dye, and more preferably a blue dye. Blue dyes can suppress the red color of the flame retardant more effectively than black dyes, and the use of blue dyes can further improve the design of the polyurethane foam. In addition, the content can be reduced compared to when black dyes are used, so that an effect commensurate with the production cost can be obtained.

The dye content is not particularly limited, but is preferably 0.2 to 10 parts by mass per 100 parts by mass of polyol. When the dye content is 0.2 parts by mass or more, the effect of using the dye is obtained, and the colorability of the polyurethane foam is good. When the dye content is 10 parts by mass or less, an effect commensurate with the blending amount is obtained, and problems such as deterioration of the performance of the polyurethane foam due to blending of the dye are unlikely to occur.
From these viewpoints, the content of the dye is, for example, more preferably 2 to 10 parts by mass, and even more preferably 2 to 8 parts by mass, in the case of a black dye, and more preferably 0.1 to 8 parts by mass, and even more preferably 0.2 to 6 parts by mass, in the case of a blue dye.

<Liquid Separation>
The polyol-containing composition of the present invention preferably does not cause color separation of the liquid components even when stored at 40° C. for 3 days. The absence of color separation of the liquid components suppresses the variation in the shade of the colored polyurethane foam, and improves the design of the polyurethane foam. The absence of color separation of the liquid components means that there is no color separation of the liquid components and there is no color unevenness in appearance.

<Polyol>
The polyol is not particularly limited, but examples thereof include polyether polyol, polyester polyol, etc. From the viewpoint of improving the flame retardancy of the polyurethane foam, the polyol preferably includes polyester polyol. Also, from the viewpoint of improving the flame retardancy, it is preferable to use a halogen-containing polyol or a phosphorus-containing polyol.
From this viewpoint, for every 100 parts by mass of polyol, it is preferable that the polyester polyol is at least 20 parts by mass, more preferably at least 50 parts by mass, even more preferably at least 80 parts by mass, and particularly preferably at least 100 parts by mass.

The average hydroxyl value of the polyol used in the present invention is preferably 100 to 500 mgKOH/g, more preferably 150 to 450 mgKOH/g, and even more preferably 200 to 400 mgKOH/g, from the viewpoint of improving the flame retardancy of the polyurethane foam.

When one type of polyol is used, the average hydroxyl value means the hydroxyl value of that polyol, and when two or more types of polyols are used, the weighted average value of the hydroxyl groups according to the blending ratio of the two or more types of polyol compounds is taken as the average hydroxyl value.
For example, when two types of polyols, polyol (d1) and polyol (d2), are used as the polyols, the average hydroxyl value is represented by the following formula, where the hydroxyl value of polyol (d1) is _X1 , the blending ratio is _m1 , _and the hydroxyl value of polyol (d2) is X2, and the blending ratio is _m2 . The blending ratio is based on mass.
Average hydroxyl value (mgKOH/g)= _X1 ×( _m1 /( _m1 + _m2 ))+ _X2 ×( _m2 /( _m1 + _m2 ))
The hydroxyl value is a value measured in accordance with JIS K1557-1:2007.

(Polyester polyol)
The polyester polyol may be a polyester polyol having an aromatic ring or an aliphatic polyester polyol, but in consideration of the flame retardancy of the resulting polyurethane foam, it is preferable to use a polyester polyol having an aromatic ring. The polyester polyol having an aromatic ring is preferably a condensate of an aromatic dicarboxylic acid such as o-phthalic acid (phthalic acid), m-phthalic acid (isophthalic acid), p-phthalic acid (terephthalic acid), or naphthalenedicarboxylic acid with a glycol. Among them, from the viewpoint of increasing the flame retardancy of the polyurethane foam, it is preferable that the polyol compound contains a phthalic acid-based polyester polyol which is a condensate of phthalic acid and a glycol, and it is more preferable that the polyol compound contains a p-phthalic acid-based polyester polyol which is a condensate of p-phthalic acid and a glycol.
The glycol is not particularly limited, but it is preferable to use low molecular weight aliphatic glycols known as components of polyester polyols, such as ethylene glycol, propylene glycol, and diethylene glycol.

The hydroxyl value of the polyester polyol is preferably 100 to 500 mgKOH/g, more preferably 150 to 450 mgKOH/g, and even more preferably 200 to 400 mgKOH/g.

(Polyether polyol)
Polyether polyol is a polyoxyalkylene polyol obtained by ring-opening addition polymerization of an alkylene oxide to an initiator having two or more active hydrogen atoms. Specific examples of the initiator include aliphatic polyhydric alcohols (e.g., glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexylene glycol, and cyclohexanedimethanol, triols such as trimethylolpropane and glycerin, tetrafunctional alcohols such as pentaerythritol, and highly functional alcohols such as sucrose and sorbitol), aliphatic amines (e.g., alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, and neopentyldiamine, and alkanolamines such as monoethanolamine and diethanolamine), and aromatic amines (e.g., aniline, tolylenediamine, xylylenediamine, diphenylmethanediamine, and Mannich condensation products).
Polyether polyol preferably has aromatic ring.Among the above, the polyether polyol produced by using an initiator having aromatic ring is the polyether polyol having aromatic ring, for example, the polyether polyol produced by using aromatic amine as initiator is the polyether polyol having aromatic ring.Among the polyether polyols having aromatic ring, tolylenediamine-based polyether polyol, Mannich-based polyether polyol, etc. can be preferably used.

The tolylenediamine-based polyether polyol is a tolylenediamine-based polyether polyol produced using tolylenediamine as an initiator.
The Mannich polyether polyol is a polyether polyol obtained by utilizing the Mannich reaction, which is a Mannich condensation product having two or more hydroxyl groups in the molecule, or an alkylene oxide added to such a Mannich condensation product. More specifically, it is a Mannich condensation product obtained by the Mannich reaction of at least one of phenol and its alkyl-substituted derivatives, formaldehyde and alkanolamine, or a polyether polyol obtained by ring-opening addition polymerization of at least one of ethylene oxide and propylene oxide to this compound.

The hydroxyl value of the polyether polyol is preferably 200 to 2000 mg KOH/g, and more preferably 300 to 1000 mg KOH/g.

<Catalyst>
(Metal catalyst (resinized metal catalyst))
The polyol-containing composition of the present invention contains a catalyst. The catalyst may contain, for example, one or both of a resinification catalyst and a trimerization catalyst, and preferably contains both.
The resinification catalyst preferably contains a metal catalyst. This metal catalyst is generally called a resinification metal catalyst. In the present invention, by containing the resinification metal catalyst, the reaction between the polyol and the polyisocyanate is promoted, and the initial reaction rate can be increased in particular. In addition, when a certain amount or more of a filler such as a red phosphorus-based flame retardant described later is contained, the reactivity of the polyurethane foam is inhibited and the foamability is likely to decrease, but by containing the resinification metal catalyst, the foamability of the polyurethane foam can be easily maintained well. From the viewpoint of foamability, the metal catalyst preferably contains bismuth or tin, and more preferably contains bismuth.

The resinified metal catalyst is preferably a metal salt selected from bismuth salts and tin salts, 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 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 resinified metal catalyst in the polyol-containing composition is not particularly limited, but is preferably 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, even more preferably 1.5 to 8 parts by mass, and even more preferably 2 to 5 parts by mass, relative to 100 parts by mass of polyol.

(Imidazole Derivatives)
The catalyst used in the polyol-containing composition of the present invention preferably contains a resinified amine catalyst as a resinification catalyst, and more preferably contains an imidazole derivative as the resinification amine catalyst.
The imidazole derivative is less susceptible to the influence of hydrofluoroolefin, and makes it easier to react the polyol with the polyisocyanate while increasing the stability of the polyol-containing composition. Therefore, by containing the imidazole derivative in addition to the above-mentioned metal catalyst, the polyol-containing composition has increased reactivity between the polyol and the polyisocyanate, and has further improved foamability.
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 independently preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group.

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-containing 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-containing 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 polyurethane 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. One type may be used alone, or two or more types may be used in combination.
The trimerization catalyst preferably contains at least a quaternary ammonium salt, and more preferably uses a quaternary ammonium salt in combination with a metal catalyst.

The content of the trimerization catalyst in the polyol-containing composition is preferably 0.5 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 5 to 15 parts by mass, per 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 polyurethane foam.

From the above viewpoints, for example, when an ammonium salt is contained as the trimerization catalyst, the content of the ammonium salt is preferably 0.3 to 23 parts by mass, more preferably 0.7 to 19 parts by mass, even more preferably 1.5 to 15 parts by mass, and even more preferably 3 to 11 parts by mass, relative to 100 parts by mass of polyol. Furthermore, when a metal catalyst is contained as the trimerization catalyst, the content of the metal catalyst is preferably 0.2 to 7 parts by mass, more preferably 0.3 to 6 parts by mass, even more preferably 0.5 to 5 parts by mass, and even more preferably 2 to 4 parts by mass, relative to 100 parts by mass of polyol.

<Solid flame retardants>
The polyol-containing composition of the present invention contains a solid flame retardant as a filler. Here, the solid flame retardant is a flame retardant that is solid at room temperature (23°C) and normal pressure (1 atm), and is generally a component that exists as a granule or powder in a polyol-containing composition. The polyol-containing composition of the present invention can improve the flame retardancy of a polyurethane foam by containing the solid flame retardant.

The solid flame retardant may be a component that is solid at room temperature (23°C) and normal pressure (1 atm) and does not dissolve in the polyol-containing composition. From the viewpoint of reducing the water absorption rate of the polyurethane foam, the solid flame retardant is preferably one that does not have hygroscopicity and deliquescence. The above-mentioned catalysts are not included in the solid flame retardant.
Specific examples of the solid flame retardant in the present invention include red phosphorus-based flame retardants, metal phosphinates, phosphate-containing flame retardants, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, chlorine-containing flame retardants, metal hydroxides, etc. These solid flame retardants may be used alone or in combination of two or more.

(Red phosphorus flame retardant)
The red phosphorus-based flame retardant may be made of red phosphorus alone, may be red phosphorus coated with a resin, a metal hydroxide, a metal oxide, or the like, or may be red phosphorus 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 to be used may be appropriately selected from those described below.

(Metal Phosphinate)
The metal phosphinate is a metal salt of an organic phosphinic acid. Specific examples of the metal phosphinate include aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, titanyl bisdiethylphosphinate, titanium tetrakisdiethylphosphinate, titanyl bismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanyl bisdiphenylphosphinate, titanium tetrakisdiphenylphosphinate, and the like.

(Phosphate-containing flame retardants)
Examples of phosphate-containing flame retardants include phosphates consisting of salts of various phosphoric acids and at least one metal or compound selected from metals in Groups IA to IVB of the periodic table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring. The term "various phosphoric acids" is a concept that includes not only phosphoric acid, but also phosphorous acid, hypophosphorous acid, and the like.
Examples of metals in 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, 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 the phosphate-containing flame retardant include monophosphates, polyphosphates, etc. Examples of the monophosphates include, but are not limited to, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate; sodium salts such as monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, disodium phosphite, and sodium hypophosphite; potassium salts such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, and potassium hypophosphite; lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, and lithium hypophosphite; barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, tribarium phosphate, and barium hypophosphite; magnesium salts such as monohydrogen magnesium phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, and magnesium hypophosphite; calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, and calcium hypophosphite; and zinc salts such as zinc phosphate, zinc phosphite, and zinc hypophosphite.
Here, the polyphosphate is not particularly limited, but examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, and aluminum polyphosphate.
The phosphate-containing flame retardants may be used alone or in combination of two or more of the above-mentioned compounds.

(Bromine-containing flame retardants)
The bromine-containing flame retardant is not particularly limited as long as it contains bromine in its molecular structure and is a solid at room temperature (23° C.) and normal pressure (1 atm), and examples thereof include brominated aromatic ring-containing aromatic compounds.
Examples of the brominated aromatic ring-containing aromatic compound 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.

In addition, the brominated aromatic ring-containing aromatic compound may be a bromine compound polymer.Specific examples thereof include brominated polycarbonates such as polycarbonate oligomers produced from brominated bisphenol A as a raw material, copolymers of this polycarbonate oligomer and bisphenol A, and diepoxy compounds produced by the reaction of brominated bisphenol A and epichlorohydrin.Furthermore, examples thereof include brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols and epichlorohydrin, brominated phenol condensates of brominated polyphenylene ether, brominated bisphenol A and cyanuric chloride, and uncrosslinked or crosslinked brominated polystyrene.
In addition, compounds other than brominated aromatic ring-containing aromatic compounds such as hexabromocyclododecane may also be used.
These bromine-containing flame retardants may be used alone or in combination of two or more.

(Boron-containing flame retardants)
The boron-containing flame retardant used in the present invention includes borax, boron oxide, boric acid, borate, etc. 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. 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, zinc borate, aluminum borate, and ammonium borate.
The boron-containing flame retardants may be used alone or in combination of two or more kinds.
The boron-containing flame retardant used in the present invention is preferably a borate, more preferably zinc borate.

(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.

From the viewpoint of imparting good flame retardancy to the polyurethane foam, the solid flame retardant contained in the polyol-containing composition of the present invention is preferably at least one selected from the group consisting of red phosphorus-based flame retardants and metal phosphinates, and more preferably contains at least a red phosphorus-based flame retardant.

The content of the solid flame retardant in the polyol-containing composition is preferably 20 to 150 parts by mass, more preferably 25 to 130 parts by mass, and even more preferably 30 to 120 parts by mass, based on 100 parts by mass of the polyol.
When a red phosphorus-based flame retardant is contained as the solid flame retardant, the content of the red phosphorus-based flame retardant is preferably 10 to 60 parts by mass, more preferably 15 to 50 parts by mass, and even more preferably 20 to 40 parts by mass, relative to 100 parts by mass of the polyol. When a metal phosphinate is contained as the solid flame retardant, the content of the metal phosphinate is preferably 35 to 120 parts by mass, more preferably 50 to 100 parts by mass, and even more preferably 60 to 90 parts by mass.
When the content of the solid flame retardant is equal to or more than the lower limit, the polyurethane foam can be provided with good flame retardancy and good mechanical properties, whereas when the content of the solid flame retardant is equal to or less than the upper limit, the polyol-containing composition is easy to handle when mixed with a polyisocyanate and has good foaming properties.

<Liquid flame retardant>
The polyol-containing composition of the present invention may contain a liquid flame retardant that is liquid at room temperature (23° C.) and normal pressure (1 atm). Specific examples of liquid flame retardants include phosphoric esters. By using phosphoric esters, the fluidity of the polyol-containing composition can be maintained, making it easier to form a polyurethane foam.

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-containing 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-containing 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.

<Inorganic filler>
The filler contained in the polyol-containing composition of the present invention may be an inorganic filler other than the solid flame retardant described above. As such inorganic fillers, needle-shaped fillers, 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. may be appropriately used. These inorganic fillers may be used alone or in combination of two or more. The inorganic fillers used in the present invention are not particularly limited, but from the viewpoint of imparting good mechanical properties to polyurethane foam, it is preferable to contain a needle-shaped filler among the above-mentioned ones. Further, the polyol-containing composition more preferably contains at least one selected from the group consisting of a red phosphorus-based flame retardant and a metal phosphinate, and a needle-like filler.

(Needle filler)
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.

The content of the inorganic filler in the polyol-containing composition is not particularly limited, but is preferably 20 to 120 parts by mass, more preferably 30 to 100 parts by mass, and even more preferably 40 to 80 parts by mass, relative to 100 parts by mass of the polyol. When the content of the inorganic filler is equal to or greater than the lower limit, it is possible to impart good mechanical properties to the polyurethane foam. On the other hand, when the content of the inorganic filler is equal to or less than the upper limit, the polyol-containing composition is easy to handle when mixed with the polyisocyanate composition, and has good foaming properties.
When a needle-like filler is used as the inorganic filler, the content of the needle-like filler is preferably 20 to 100 parts by mass, more preferably 25 to 95 parts by mass, and even more preferably 30 to 90 parts by mass, per 100 parts by mass of the polyol.

<Foaming Agent>
The foaming agent promotes foaming of the foamable polyurethane composition described below. 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 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.

The content of HFO is not particularly limited, and is preferably 19 to 75 parts by mass, more preferably 29 to 67 parts by mass, and even more preferably 34 to 58 parts by mass, per 100 parts by mass of polyol. When the content of the blowing agent is equal to or greater than the lower limit, foaming is promoted, the foaming properties are improved, and the density of the polyurethane foam can be reduced. On the other hand, when the content of the blowing agent is equal to or less than the upper limit, excessive foaming can be suppressed.

The water content is not particularly limited, and is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, and even more preferably 0.5 to 2 parts by mass, per 100 parts by mass of polyol. When the foaming agent content is equal to or greater than the lower limit, foaming is promoted, the foaming properties are good, and the density of the polyurethane foam can be reduced. On the other hand, when the foaming agent content is equal to or less than the upper limit, excessive foaming can be suppressed.

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

[Fabric-forming polyurethane composition and polyurethane foam]
The present invention also provides a foamable polyurethane composition. The foamable polyurethane composition of the present invention contains a polyisocyanate in addition to a polyol, a blowing agent, a catalyst, a flame retardant, and a dye.
The foamable polyurethane composition may also contain a filler other than the flame retardant, a liquid flame retardant such as a phosphoric ester, a foam stabilizer, and other components.
The details of each component contained in the foamable polyurethane composition are as described above, and therefore description thereof will be omitted.

The foamable polyurethane composition of the present invention preferably contains the above-mentioned polyol-containing composition and a polyisocyanate, and is obtained by mixing them. The polyol-containing composition and the polyisocyanate are preferably stored in separate containers before being mixed.
As described later, the foamable polyurethane composition may contain a polyol-containing composition that does not contain a dye and a polyisocyanate that contains a dye, or may be obtained by mixing these.
The foamable polyurethane composition may also be one obtained by separately preparing a dye-free polyol-containing composition, a dye-free polyisocyanate, and a dye, and mixing these together immediately before use.

<Polyisocyanate>
Examples of the polyisocyanate in the present invention 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, diphenylmethane diisocyanate, polymeric MDI, or a mixture thereof is more preferred, and among these, diphenylmethane diisocyanate is even more preferred, and 4,4'-diphenylmethane diisocyanate is particularly preferred. The polyisocyanates may be used alone or in combination of two or more kinds.
Furthermore, the polyisocyanate may be appropriately mixed with known additives that are mixed with polyisocyanates before being mixed with the polyol-containing composition.

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

<Isocyanate Index>
The isocyanate index in the 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, which makes it easier to generate isocyanurate bonds due to the trimerization of the polyisocyanate, and as a result, the flame retardancy of the polyurethane foam is improved. It is also possible to impart flame retardancy. 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, and even more preferably 300 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.

<Total heat generation>
The polyurethane foam made from the foamable polyurethane composition of the present invention preferably has a total heat release amount of 8 MJ/ ^m2 or less when heated for 10 minutes at a radiant heat intensity of 50 kW/ ^m2 in accordance with the test method of ISO-5660. By having a total heat release amount of 8 MJ/m2 or ^less , the polyurethane foam made from the foamable polyurethane 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 7.5 MJ/ ^m2 or less, and further preferably 7 MJ/ ^m2 or less.
Furthermore, it is even more preferable that the polyurethane foam made from the foamable polyurethane composition of the present invention has a total heat generation amount of 8 MJ/ ^m2 or less, and particularly preferably 7.5 MJ/ ^m2 or less, when heated for 20 minutes in the same manner as above.

In the foamable polyurethane composition of the present invention, the color difference ΔE between polyurethane foam A obtained by mixing the above-mentioned polyol-containing composition with a polyisocyanate and polyurethane foam B obtained by mixing a colorant-free polyol-containing composition with a polyisocyanate is preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more. When the color difference ΔE is equal to or more than the lower limit, it can be said that the polyurethane foam is well colored.
The colorant-free polyol-containing composition means a polyol-containing composition having the same composition as the polyol-containing composition except that a colorant such as a dye is not blended.
The color difference ΔE can be determined by producing polyurethane foams A and B by the method described in the examples using the polyol-containing composition and polyisocyanate that constitute the foamable polyurethane composition, and using a colorant-free polyol-containing composition and polyisocyanate, and then measuring the color difference between the polyurethane foams A and B.

<Applications>
The foamable polyurethane composition of the present invention can be preferably used for spraying. Therefore, the foamable polyurethane composition of the present invention and the polyurethane foam can be preferably used for buildings such as walls, ceilings, roofs, and floors of buildings, due to their excellent flame retardancy and heat insulation properties, and the polyurethane foam can be molded by spraying the walls, ceilings, roofs, floors, etc.

<Method of manufacturing polyurethane foam>
The method for producing a polyurethane foam of the present invention involves blending at least a polyol, a blowing agent, a catalyst, and a flame retardant including a solid flame retardant to prepare a polyol-containing composition, and then mixing the polyol-containing composition with a polyisocyanate and foaming the mixture to produce a polyurethane foam.
In the method for producing a polyurethane foam, the dye may be added in advance to either the polyol-containing composition or the polyisocyanate, or may be added when the polyol-containing composition and the polyisocyanate are mixed.

First, a method in which the dye is added in advance to the polyol-containing composition will be described below as a first embodiment.
In the method for producing a polyurethane foam according to the first embodiment of the present invention, first, a polyol-containing composition is prepared by blending at least a polyol, a blowing agent, a catalyst, a flame retardant including a solid flame retardant, and a dye. Here, there is no particular limitation on the method for preparing the polyol-containing composition, and for example, the polyol-containing composition can be obtained by stirring each component at about 20 to 40°C for about 30 seconds to 20 minutes using a homodisper or the like. The polyol-containing composition prepared by this method contains a dye, and the details thereof are as described above.
The polyol-containing composition thus prepared and a polyisocyanate are then brought to a construction site and mixed on site to obtain a foamable polyurethane composition, which is then reacted and foamed to produce a polyurethane foam.

Next, a method in which a dye is added to a polyisocyanate in advance will be described as a second embodiment.
In the method for producing a polyurethane foam according to the second embodiment of the present invention, first, a polyol-containing composition is prepared by blending at least a polyol, a blowing agent, a catalyst, and a flame retardant including a solid flame retardant. Here, the method for preparing the polyol-containing composition is as described above. The polyol-containing composition prepared by this method is the same as the polyol-containing composition described above, except that it does not contain a dye.
The polyol-containing composition thus prepared and the polyisocyanate to which the dye has been added are then brought to a construction site and mixed on site to obtain a foamable polyurethane composition, which is then reacted and foamed to produce a polyurethane foam.

Furthermore, a method of adding a dye when mixing a polyol-containing composition with a polyisocyanate will be described as a third embodiment.
That is, in the third embodiment, a polyol-containing composition is prepared by blending at least a polyol, a blowing agent, a catalyst, and a flame retardant including a solid flame retardant. At this time, the polyol-containing composition does not need to contain a dye. Therefore, the polyol-containing composition prepared by this method is the same as the polyol-containing composition described above, except that it does not contain a dye.
The polyol-containing composition, the polyisocyanate, and the dye are then brought to a construction site, and the dye is added (also called post-addition) when the polyol-containing composition and the polyisocyanate are mixed at the construction site. By post-adding the dye, it is possible to adjust the color tone to a desired tone at the construction site.
In addition, the phrase "when mixing the polyol-containing composition and the polyisocyanate" does not necessarily mean that the dye is added at the same time as the polyol-containing composition and the polyisocyanate are mixed, and includes the embodiment in which the dye is added to the polyol-containing composition or the polyisocyanate just before mixing that has been brought to the construction site. In addition, "just before mixing" refers to, for example, within about one week before mixing, preferably within about three days, and more preferably within about one day. In addition, the polyol-containing composition or the polyisocyanate to which the dye has been added once can be used by re-stirring when reused, regardless of the storage period.

Therefore, the dye may be added to a polyol-containing composition at the construction site, and the polyol-containing composition to which the dye has been added may then be mixed with a polyisocyanate.
The dye may be added to the polyisocyanate at the construction site, and the polyisocyanate to which the dye has been added may be mixed with the polyol-containing composition. Furthermore, the dye, the polyol-containing composition, and the polyisocyanate may be mixed simultaneously at the construction site.
Among these, it is preferred that the dye is added to the polyol-containing composition at the construction site, and the polyol-containing composition to which the dye has been added is then mixed with the polyisocyanate.

The polyurethane foam is preferably produced using, for example, a foaming machine. For example, the polyol-containing composition is mixed with a polyisocyanate in a foaming machine or the like, and the resulting mixed liquid (foamable polyurethane composition) is foamed. As the foaming machine, a spray device having a spray gun or the like is preferably used.
In this case, as described above, the dye may be blended in either the polyol-containing composition or the polyisocyanate, but it is preferable that the dye is blended in the polyol-containing composition.
The polyol-containing 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.

This manufacturing method is preferably applicable to spray applications. Therefore, the mixed liquid discharged from the foaming machine is sprayed onto the surface to be treated at a constant discharge pressure, and foamed to form a polyurethane foam on the surface to be treated.

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

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

<Polyol-containing 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)
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
Resinized amine catalyst, 1,2-dimethylimidazole (manufactured by Tosoh Corporation, product name: TOYOCAT 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, dioctyl (2-ethylhexyl) tin versatate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-830), concentration approximately 99% by mass

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

(Liquid flame retardant)
Phosphate ester plasticizer: Tris(β-chloropropyl)phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., product name: TMCPP)

(Solid flame retardant)
・Red phosphorus-based flame retardant (manufactured by Rinkagaku Kogyo Co., Ltd., product name: Nova Excel 140)
Phosphinic acid metal salt (Clariant, product name: EXOLIT OP930)

(Inorganic filler)
Wollastonite (SiO2.CaO) (Kinsei Matec Co., Ltd., product name: SH-1250)

(Coloring Agent)
Black colorant: black dye (manufactured by Milliken & Company, product name: REACTINT BLACK X95AB), black pigment (manufactured by Milliken & Company, product name: DispersiTech Black 2140)
Blue colorant: blue pigment (manufactured by Milken & Company, product name: DispersiTech Blue 2402)

[Production of polyurethane foam]
A polyol-containing composition was prepared by mixing the components according to the formulation shown in Table 1. Using the polyol-containing composition and a polyisocyanate, a polyurethane 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-containing compositions): 38°C
Hose heater (for heating polyisocyanate- and polyol-containing compositions before mixing): 38°C
Pressure: Adjust appropriately so that the mist becomes a wide circular shape. Substrate temperature (temperature of the surface to be sprayed): 20°C ± 1°C

[Evaluation methods for each physical property]
1. Liquid Separation The polyol-containing composition was stored in a mayonnaise bottle at 40° C. for 3 days, and the state of liquid separation of the composition was visually confirmed. The evaluation criteria for liquid separation are as follows:
◯: No liquid separation ×: Liquid separation

2. Flame retardancy The polyurethane foam produced under the above manufacturing conditions was cut into a test piece measuring 10 cm x 10 cm x 5 cm. The test piece was heated for 10 to 20 minutes at a radiant heat intensity of 50 kW/ ^m2 in accordance with ISO 5660, and the total heat generation was measured. The evaluation criteria for flame retardancy are as follows:
◯: 8 MJ/m2 or ^less 20 minutes after the start of heating △: 8 MJ/m2 or ^less 10 minutes after the start of heating ×: More than 8 MJ/ ^m2 10 minutes after the start of heating

3. Colorability A polyurethane foam A formed by reacting a dye-containing polyol-containing composition with a polyisocyanate, and a polyurethane foam B formed by reacting a colorant-free polyol-containing composition with a polyisocyanate were prepared. A colorimeter (KONICA MINOLTA, product name: SPECTROPHOTOMETER CM-5) was applied to the surfaces of each of the polyurethane foams A and B to obtain the color difference ΔE between the two polyurethane foams, and the colorability of the surfaces was evaluated based on the color difference ΔE. The evaluation criteria for colorability are as follows:
◯: ΔE=3 or more, coloring present ×: ΔE=less than 3, coloring absent

[Examples 1 to 12, Comparative Examples 1 to 6]
A polyol-containing composition was prepared by mixing the components according to the formulation shown in Table 1. A polyurethane foam was produced using the polyol-containing composition and polyisocyanate, and evaluated based on the above-mentioned evaluation methods 1 to 3. The results are shown in Table 1. The mixing ratio of the polyol-containing composition to the polyisocyanate was 1:1 by volume.

The catalyst contents are the contents in the product.

As is clear from the results of the above examples and comparative examples, the polyol-containing composition of the present invention does not suffer from liquid separation, and the polyurethane foam formed from the composition has both good flame retardancy and colorability.
In contrast, the polyol-containing compositions of Comparative Examples 1 to 5 contained a pigment as a colorant, and thus liquid separation occurred. The polyol-containing composition of Comparative Example 5 not only caused liquid separation, but also impaired the flame retardancy of the polyurethane foam because it did not contain a solid flame retardant. Moreover, the polyol-containing composition of Comparative Example 6 did not contain any colorant, and thus was unable to color the polyurethane foam.

Claims (10)

1. A polyol-containing composition for reacting with a polyisocyanate to obtain a polyurethane foam, comprising:
the polyol-containing composition comprises a polyol, a blowing agent, a catalyst, a flame retardant, and a dye, and the flame retardant comprises a solid flame retardant;
The solid flame retardant comprises a red phosphorus-based flame retardant,
The dye includes a black dye and/or a blue dye,
The polyol-containing composition, wherein the catalyst comprises a resinification catalyst . The polyol-containing composition of claim 1 , wherein the catalyst comprises a trimerization catalyst. The polyol-containing composition of claim 2 , wherein the trimerization catalyst comprises a quaternary ammonium salt. The polyol-containing composition according to any one of claims 1 to 3 , wherein the catalyst comprises an imidazole derivative. The polyol-containing composition according to any one of claims 1 to 4 , wherein the catalyst comprises at least one metal catalyst selected from bismuth and tin. The polyol-containing composition according to any one of claims 1 to 5 , which does not undergo liquid separation when stored in an environment at 40°C for 3 days. A foamable polyurethane composition comprising the polyol-containing composition according to any one of claims 1 to 6 and a polyisocyanate. 8. The foamable polyurethane composition of claim 7 , having an isocyanate index of 200 or greater. 9. The foamable polyurethane composition according to claim 7 or 8, which is used for spray applications. A polyurethane foam obtained by foaming the foamable polyurethane composition according to any one of claims 7 to 9 .