阅读说明：本技术 二价膦腈盐和包含其的聚环氧烷组合物、以及包含该聚环氧烷组合物的聚氨酯形成性组合物 (Divalent phosphazenium salt, polyalkylene oxide composition containing the same, and polyurethane-forming composition containing the polyalkylene oxide composition ) 是由 井上善彰 山本敏秀 森胜朗 于 2019-03-05 设计创作，主要内容包括：本发明提供呈现中性且热稳定性和醛捕捉能力优异的二价膦腈盐及其制造方法。此外,提供挥发醛量得以降低、臭气和浑浊的发生得到抑制、且氨酯化反应性优异的聚环氧烷组合物、该聚环氧烷组合物的制造方法和包含该聚环氧烷组合物的聚氨酯形成性组合物。具有特定结构的二价膦腈盐。此外,包含具有特定结构的二价膦腈盐和聚环氧烷的聚环氧烷组合物、其制造方法、以及包含该聚环氧烷组合物的聚氨酯形成性组合物。(The present invention provides a divalent phosphazenium salt which exhibits neutrality and is excellent in thermal stability and aldehyde capturing ability, and a method for producing the same. Further, a polyalkylene oxide composition which is reduced in the amount of volatile aldehydes, suppressed in the generation of odor and turbidity, and excellent in urethane formation reactivity, a method for producing the polyalkylene oxide composition, and a polyurethane-forming composition containing the polyalkylene oxide composition are provided. A divalent phosphazenium salt having a specific structure. Also, a polyalkylene oxide composition comprising a divalent phosphazenium salt having a specific structure and a polyalkylene oxide, a method for producing the same, and a polyurethane-forming composition comprising the polyalkylene oxide composition.)

1. A divalent phosphazenium salt represented by the formula (1),

in the formula (1), the reaction mixture is,

R¹and R²Each independently represents:

a hydrogen atom,

A hydrocarbon group having 1 to 20 carbon atoms,

R¹And R²Ring structures bonded to each other, or

R¹Each other or R²Ring structures bonded to each other;

A^n-represents a deprotonated form of an organic sulfonic acid or organic disulfonic acid;

either one of n and m is 1, and the other is 2;

a is 2 when Y is a carbon atom and 3 when Y is a phosphorus atom.

2. A divalent phosphazenium salt represented by the formula (2),

in the formula (1), the reaction mixture is,

R¹and R²Each independently represents:

a hydrogen atom,

A hydrocarbon group having 1 to 20 carbon atoms,

R¹And R²Ring structures bonded to each other, or

R¹Each other or R²Ring structures bonded to each other;

A^-represents a deprotonated form of an organic sulfonic acid.

3. A divalent phosphazenium salt represented by the formula (3),

in the formula (3), the reaction mixture is,

R¹and R²Each independently represents:

a hydrogen atom,

A hydrocarbon group having 1 to 20 carbon atoms,

R¹And R²Ring structures bonded to each other;

A^n-represents a deprotonated form of an organic sulfonic acid or organic disulfonic acid;

either one of n and m is 1, and the other is 2.

4. The divalent phosphazenium salt according to any one of claims 1 to 3,

R¹and R²Is a methyl group, and the compound is,

A^n-or A^-Is a deprotonated form of dodecylbenzene sulphonic acid, linear alkyl benzene sulphonic acid (soft type) or branched alkyl benzene sulphonic acid (hard type).

5. The divalent phosphazenium salt according to any one of 1 to 4, wherein a 0.01mol/L aqueous solution of the divalent phosphazenium salt has a pH of 5 or more and 8 or less.

6. An aldehyde scavenger comprising the divalent phosphazenium salt according to any one of claims 1 to 5.

7. A method for producing a divalent phosphazene salt according to any one of claims 1 to 5, characterized in that 2 moles or more of an organic sulfonic acid is reacted with 1 mole of a phosphazene salt represented by formula (4),

in the formula (4), the reaction mixture is,

R¹and R²Each independently represents:

a hydrogen atom,

A hydrocarbon group having 1 to 20 carbon atoms,

R¹And R²Ring structures bonded to each other, or

R¹Each other or R²Ring structures bonded to each other;

X^-represents a hydroxyl anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxyl anion, an alkylcarboxy anion having 2 to 5 carbon atoms or a bicarbonate anion,

a is 2 when Y is a carbon atom and 3 when Y is a phosphorus atom.

8. A method for producing a divalent phosphazenium salt according to claim 2,

reacting 2 or more moles of an organic sulfonic acid with 1 mole of a phosphazene salt represented by the formula (5),

in the formula (5), the reaction mixture is,

R¹and R²Each independently represents:

a hydrogen atom,

A hydrocarbon group having 1 to 20 carbon atoms,

R¹And R²Ring structures bonded to each other, or

R¹Each other or R²Ring structures bonded to each other;

X^-represents a hydroxyl anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxyl anion, an alkylcarboxy anion having 2 to 5 carbon atoms or a bicarbonate anion.

9. A method for producing a divalent phosphazenium salt according to claim 3, characterized in that,

reacting 2 or more moles of an organic sulfonic acid with 1 mole of a phosphazene salt represented by formula (6),

in the formula (6), the reaction mixture is,

R¹and R²Each independently represents:

a hydrogen atom,

A hydrocarbon group having 1 to 20 carbon atoms,

R¹And R²Ring structures bonded to each other;

X^-represents a hydroxyl anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxyl anion, an alkylcarboxy anion having 2 to 5 carbon atoms or a bicarbonate anion.

10. A polyalkylene oxide composition comprising the divalent phosphazenium salt according to any one of claims 1 to 5 and a polyalkylene oxide.

11. The polyalkylene oxide composition according to claim 10, wherein when measured by the following measurement method,

the amount of volatilized aldehyde is less than 0.9ppm,

the amount of volatilized propanal is less than 3.0ppm,

the determination method comprises the following steps:

(I) the method comprises the following steps 10g of a sample was put into a container having an internal volume of 30 ml;

(II): after (I), nitrogen bubbling was performed at 65 ℃ for 2 hours under heating at 0.5L/min, and the volatilization amount was measured.

12. The polyalkylene oxide composition according to claim 10 or 11, wherein the pH of the polyalkylene oxide composition measured by the method described in JISK-1557-5 is 5 or more and 8 or less.

13. A polyalkylene oxide composition comprising the divalent phosphazenium salt of claim 2 and a polyalkylene oxide.

14. A polyurethane-forming composition comprising (a) the polyalkylene oxide composition according to any one of claims 10 to 13 and (B) an isocyanate compound.

15. A method for producing the polyalkylene oxide composition according to claim 13,

in the presence of a phosphazene salt represented by formula (5) and an active hydrogen-containing compound, an alkylene oxide polymerization reaction is carried out to produce a polyalkylene oxide,

then, 2 or more moles of an organic sulfonic acid are added to 1 mole of the phosphazene salt,

in the formula (5), the reaction mixture is,

R¹and R²Each independently represents:

a hydrogen atom,

A hydrocarbon group having 1 to 20 carbon atoms,

R¹And R²Ring structures bonded to each other, or

R¹Each other or R²Ring structures bonded to each other;

X^-represents a hydroxyl anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxyl anion, an alkylcarboxy anion having 2 to 5 carbon atoms or a bicarbonate anion.

Technical Field

The present disclosure relates to divalent phosphazenium salts and methods of making the same. Also disclosed are a polyalkylene oxide composition containing such a divalent phosphazenium salt, a method for producing such a polyalkylene oxide composition, and a polyurethane-forming composition containing such a polyalkylene oxide composition.

Background

Monovalent phosphazenium salts are known as useful organic bases.

For example, patent document 1 discloses a method for producing a polyoxyalkyleneoxide, in which a monovalent phosphazenium salt having a specific structure represented by formula (I) is used to perform a polymerization reaction of an alkylene oxide.

Patent document 2 discloses a method for producing a polyoxyalkylene polyol, which comprises producing a crude polyoxyalkylene polyol by addition polymerization of an active hydrogen compound with a compound having a P ═ N bond as a catalyst, and then bringing the crude polyoxyalkylene polyol into contact with a specific solid acid to control the residual amount of the catalyst in the polyoxyalkylene polyol to 150ppm or less. Patent document 2 discloses a monovalent phosphazenium salt as the compound having a P ═ N bond.

Further, polyalkylene oxide compositions containing a phosphazene salt and a polyalkylene oxide are known.

Patent document 1 discloses a method for producing a polyalkylene oxide, in which a monovalent phosphazenium salt having a specific structure is used as a catalyst to produce a polyalkylene oxide, and the phosphazenium salt is removed by an adsorbent. The polyalkylene oxide described in patent document 1 is a polyalkylene oxide having a pH in a specific range and excellent urethane formation reactivity.

Patent document 2 discloses a method for producing a polyoxyalkylene polyol, which is characterized in that a crude polyoxyalkylene polyol is produced by addition polymerization of an active hydrogen compound using a compound having a P ═ N bond as a catalyst, and then the crude polyoxyalkylene polyol is brought into contact with a specific solid acid, thereby controlling the residual amount of the catalyst in the polyoxyalkylene polyol to 150ppm or less, and a polyoxyalkylene polyol obtained by the production method.

Disclosure of Invention

Problems to be solved by the invention

However, the monovalent phosphazenium salts described in patent documents 1 and 2 are removed from the produced polyalkylene oxide because the monovalent phosphazenium salts exhibit strong basicity. Therefore, a neutral phosphazenium salt which does not need to be removed is sought.

However, polyalkylene oxides are useful as a raw material for resins such as polyurethane and polyester, and their uses include articles for use indoors and in vehicles. Polyalkylene oxides and resins using the same are strongly required to reduce aldehydes generated in living spaces such as indoor spaces and vehicle interiors.

In addition, in a production process of a product using these resins, the resin is sometimes exposed to high temperature, and therefore, excellent thermal stability is desired.

Accordingly, an object of one embodiment of the present invention is to provide a divalent phosphazenium salt which exhibits neutrality and is excellent in thermal stability and aldehyde capturing ability, and a method for producing the same.

Further, as a result of further studies on the polyalkylene oxide described in patent document 1 or 2, the inventors of the present invention found that: the polyalkylene oxide still has room for further improvement in terms of reduction in the amount of volatile aldehydes. Reduction of aldehydes generated in living spaces such as indoors and in vehicles is strongly desired.

Furthermore, polyalkylene oxides are useful as a raw material for urethane and the like, and their applications include products used indoors and in vehicles, and therefore, it is desired to suppress the occurrence of odor and turbidity.

Accordingly, an object of one embodiment of the present invention is to provide a polyalkylene oxide composition which has a reduced amount of volatile aldehydes, is suppressed in the generation of odor and turbidity, and is excellent in urethane formation reactivity. Another embodiment of the present invention is directed to a method for producing the polyalkylene oxide composition. It is still another object of the present invention to provide a polyurethane-forming composition which contributes to the formation of a polyurethane with suppressed generation of odor and turbidity.

Means for solving the problems

The divalent phosphazene salt according to one embodiment of the present invention is as follows:

[1] a divalent phosphazenium salt represented by the formula (1),

in the formula (1), the reaction mixture is,

R¹and R²Each independently represents:

a hydrogen atom,

A hydrocarbon group having 1 to 20 carbon atoms,

R¹And R²Ring structures bonded to each other, or

R¹Each other or R²Ring structures bonded to each other;

A^n-represents a deprotonated form of an organic sulfonic acid or organic disulfonic acid.

Either one of n and m is 1, and the other is 2.

a is 2 when Y is a carbon atom and 3 when Y is a phosphorus atom.

[2] A divalent phosphazenium salt represented by the formula (2),

in the formula (2), the reaction mixture is,

R¹and R²Each independently represents:

a hydrogen atom,

A hydrocarbon group having 1 to 20 carbon atoms,

R¹And R²Ring structures bonded to each other, or

R¹Each other or R²Ring structures bonded to each other;

A^-represents a deprotonated form of an organic sulfonic acid.

[3] A divalent phosphazenium salt represented by the formula (3),

in the formula (3), the reaction mixture is,

R¹and R²Each independently represents:

a hydrogen atom,

A hydrocarbon group having 1 to 20 carbon atoms,

R¹And R²Ring structures bonded to each other;

A^n-represents a deprotonated form of an organic sulfonic acid or organic disulfonic acid;

either one of n and m is 1, and the other is 2.

[4] The divalent phosphazenium salt according to any one of the above [1] to [3], which is characterized in that,

R¹and R²Is a methyl group, and the compound is,

A^n-or A^-Is a deprotonated form of dodecylbenzene sulphonic acid, linear alkyl benzene sulphonic acid (soft type) or branched alkyl benzene sulphonic acid (hard type).

[5] The divalent phosphazenium salt according to any one of the above [1] to [4], which is characterized in that,

the pH of a 0.01mol/L aqueous solution of the divalent phosphazenium salt is 5 or more and 8 or less.

[6] An aldehyde scavenger comprising the divalent phosphazenium salt according to any one of the above [1] to [5 ].

[7] A method for producing the divalent phosphazenium salt according to any one of the above [1] to [5], which is characterized in that,

reacting 2 or more moles of an organic sulfonic acid with 1 mole of a phosphazene salt represented by the formula (4),

in the formula (4), the reaction mixture is,

R¹and R²Each independently represents:

a hydrogen atom,

A hydrocarbon group having 1 to 20 carbon atoms,

R¹And R²Ring structures bonded to each other, or

R¹Each other or R²Ring structures bonded to each other;

X^-represents a hydroxyl anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxyl anion, an alkylcarboxy anion having 2 to 5 carbon atoms or a bicarbonate anion.

a is 2 when Y is a carbon atom and 3 when Y is a phosphorus atom.

[8] A process for producing the divalent phosphazenium salt according to [2], which is characterized in that,

reacting 2 or more moles of an organic sulfonic acid with 1 mole of a phosphazene salt represented by the formula (5),

in the formula (5), the reaction mixture is,

R¹and R²Each independently represents:

a hydrogen atom,

A hydrocarbon group having 1 to 20 carbon atoms,

R¹And R²Ring structures bonded to each other, or

R¹Each other or R²Ring structures bonded to each other;

X^-represents a hydroxyl anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxyl anion, an alkylcarboxy anion having 2 to 5 carbon atoms or a bicarbonate anion.

[9] A process for producing the divalent phosphazenium salt according to [3], which is characterized in that,

reacting 2 or more moles of an organic sulfonic acid with 1 mole of a phosphazene salt represented by formula (6),

in the formula (6), the reaction mixture is,

R¹and R²Each independently represents:

a hydrogen atom,

A hydrocarbon group having 1 to 20 carbon atoms,

R¹And R²Ring structures bonded to each other;

X^-represents a hydroxyl anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxyl anion, an alkylcarboxy anion having 2 to 5 carbon atoms or a bicarbonate anion.

[10] A polyalkylene oxide composition comprising the divalent phosphazenium salt according to any one of the above [1] to [5] and a polyalkylene oxide.

[11] The polyalkylene oxide composition according to the above [10], which is characterized in that when measured by the following measurement method,

the amount of volatilized aldehyde is less than 0.9ppm,

the amount of the volatilized propanal is 3.0ppm or less.

[ measurement method ]

(I) The method comprises the following steps A container having an internal volume of 30ml was charged with 10g of the sample.

(II): after (I), nitrogen bubbling was performed at 65 ℃ for 2 hours under heating at 0.5L/min, and the volatilization amount was measured.

[12] The polyalkylene oxide composition according to [10] or [11], wherein the pH of the polyalkylene oxide composition is 5 or more and 8 or less as measured by a method described in JIS K-1557-5.

[13] A polyalkylene oxide composition comprising the divalent phosphazenium salt according to [2] and a polyalkylene oxide.

[14] A polyurethane-forming composition comprising (A) the polyalkylene oxide composition according to any one of [10] to [13] above and (B) an isocyanate compound.

[15] A method for producing the polyalkylene oxide composition according to [13], which is characterized in that,

in the presence of a phosphazene salt represented by formula (5) and an active hydrogen-containing compound, an alkylene oxide polymerization reaction is carried out to produce a polyalkylene oxide,

then, 2 or more moles of an organic sulfonic acid are added to 1 mole of the phosphazene salt,

in the formula (5), the reaction mixture is,

R¹and R²Each independently represents:

a hydrogen atom,

A hydrocarbon group having 1 to 20 carbon atoms,

R¹And R²Ring structures bonded to each other, or

R¹Each other or R²Ring structures bonded to each other;

X^-represents a hydroxyl anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxyl anion, an alkylcarboxy anion having 2 to 5 carbon atoms or a bicarbonate anion.

ADVANTAGEOUS EFFECTS OF INVENTION

One embodiment of the present invention can provide a divalent phosphazenium salt which exhibits neutrality and is excellent in thermal stability and aldehyde capturing ability, and a method for producing the same.

Further, an embodiment of the present invention can provide a polyalkylene oxide composition which is reduced in the amount of volatile aldehydes, suppressed in the generation of odor and turbidity, and excellent in urethane formation reactivity. Another embodiment of the present invention can provide a method for producing the polyalkylene oxide composition. Still another embodiment of the present invention can provide a polyurethane-forming composition that contributes to the formation of a polyurethane in which the occurrence of odor and turbidity is suppressed.

Drawings

FIG. 1 is a schematic view showing a phosphazene salt-A obtained in Synthesis example 1¹Graph of H-NMR.

FIG. 2 is a graph showing the change in pH in the neutralization titration of the phosphazene salt-A obtained in Synthesis example 1.

FIG. 3 is a view showing a phosphazene salt-B obtained in example 1¹Graph of H-NMR.

FIG. 4 is a view showing phosphazenium salt-C obtained in comparative example 1¹Graph of H-NMR.

Detailed Description

Exemplary embodiments for carrying out the present invention are described in detail below.

< divalent Phosphinenitrile salt >

The divalent phosphazene salt according to one embodiment of the present invention is a divalent phosphazene salt represented by formulas (1) to (3):

in the formula (1), the reaction mixture is,

R¹and R²Each independently represents:

a hydrogen atom,

A hydrocarbon group having 1 to 20 carbon atoms,

R¹And R²Ring structures bonded to each other, or

R¹Each other or R²Ring structures bonded to each other;

A^n-represents a deprotonated form of an organic sulfonic acid or organic disulfonic acid.

Either one of n and m is 1, and the other is 2.

a is 2 when Y is a carbon atom and 3 when Y is a phosphorus atom.

In the formula (2), the reaction mixture is,

R¹and R²Each independently represents:

a hydrogen atom,

A hydrocarbon group having 1 to 20 carbon atoms,

R¹And R²Ring structures bonded to each other, or

R¹Each other or R²Ring structures bonded to each other;

A^-represents a deprotonated form of an organic sulfonic acid.

In the formula (3), the reaction mixture is,

R¹and R²Each independently represents:

a hydrogen atom,

A hydrocarbon group having 1 to 20 carbon atoms,

R¹And R²Ring structures bonded to each other;

A^n-represents a deprotonated form of an organic sulfonic acid or organic disulfonic acid;

either one of n and m is 1, and the other is 2.

The divalent phosphazene salt according to the present embodiment may be any salt as long as it falls within the scope of the salts represented by the above formulas (1) to (3).

<<<R¹、R²>>>

In the formulae (1) to (3), R¹And R²Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, R¹And R²Ring structures bonded to each other, or R¹Each other or R²Ring structures bonded to each other.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, vinyl, n-propyl, isopropyl, cyclopropyl, allyl, n-butyl, isobutyl, tert-butyl, cyclobutyl, n-pentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl, phenyl, heptyl, cycloheptyl, octyl, cyclooctyl, nonyl, cyclononyl, decyl, cyclodecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, and nonadecyl.

As R¹And R²Examples of the ring structures bonded to each other include a pyrrolidinyl group, a pyrrolyl group, a piperidinyl group, an indolyl group, and an isoindolyl group.

In the formulae (1) and (2), R is¹Each other or R²Examples of the ring structure in which the two R groups are bonded to each other¹Or two R²Each independently forms a ring structure in which 1 group selected from alkylene groups such as methylene, ethylene, propylene, and butylene is bonded to each other.

Among these, R is a guanidine compound which is easily obtained as a raw material¹And R²Methyl, ethyl and isopropyl are each independently preferred. R¹And R²More preferably methyl.

Specific examples of the cation species in the formulae (1) and (2) include tetrakis (1,1,3, 3-tetramethylguanidino) phosphonium (hydrogen) dication, tetrakis (1,1,3, 3-tetraethylguanidino) phosphonium (hydrogen) dication, tetrakis (1,1,3, 3-tetra (n-propyl) guanidino) phosphonium (hydrogen) dication, tetrakis (1,1,3, 3-tetraisopropylguanidino) phosphonium (hydrogen) dication, tetrakis (1,1,3, 3-tetra (n-butyl) guanidino) phosphonium (hydrogen) dication, tetrakis (1,1,3, 3-tetraphenylguanidino) phosphonium (hydrogen) dication, tetrakis (1,1,3, 3-tetrabenzylphosphonium) guanidino (hydrogen) dication, tetrakis (1, 3-dimethylbenzyl-2-imino) imidazolium (hydrogen) dication, tetrakis (1, 3-diethylimidazolidin-2-imino) phosphonium (hydr) dication. Of these, tetrakis (1,1,3, 3-tetramethylguanidino) phosphonium (hydrogen) dications are preferred.

Specific examples of the cation species in the formulae (1) and (3) include tetrakis [ tris (dimethylamino) phosphoranylideneamino ] phosphonium (hydrogen) dication, tetrakis [ tris (diethylamino) phosphoranylideneamino ] phosphonium (hydrogen) dication, tetrakis [ tris (di-n-propylamino) phosphoranylideneamino ] phosphonium (hydrogen) dication, tetrakis [ tris (diisopropylamino) phosphoranylideneamino ] phosphonium (hydrogen) dication, tetrakis [ tris (di-n-butylamino) phosphoranylideneamino ] phosphonium (hydrogen) dication, tetrakis [ tris (diphenylamino) phosphoranylideneamino ] phosphonium (hydro) dication, tetrakis [ tris (dibenzylamino) phosphoranylideneamino ] phosphonium (hydro) dication, tetrakis [ tris (dipyrrolidinylamino) phosphoranylideneamino ] phosphonium (hydro) dication, tetrakis [ tris (dipyrrolylamino) phosphoranylideneamino ] phosphonium (hydro) dication. Among these, tetrakis [ tris (dimethylamino) phosphoranylideneamino ] phosphonium (hydrogen) dication is preferable.

<<A^-And A^n->>

In the formulae (1) to (3), A^-Represents a deprotonated form of an organic sulfonic acid. A. the^n-Represents a deprotonated form of an organic sulfonic acid or organic disulfonic acid. Using inorganic acids such as hydrochloric acid, perchloric acid, sulfuric acid, sulfurous acid, nitric acid, etc.; when an organic carboxylic acid such as acetic acid, adipic acid, benzoic acid or oxalic acid is used in place of the organic sulfonic acid, the phosphazene salt precipitates from the polyalkylene oxide, and this is not preferable because the polyalkylene oxide composition is turbid or odor derived from the acid is generated.

The organic sulfonic acid and the organic disulfonic acid may be any sulfonic acid or disulfonic acid as long as they fall within the category of commonly known organic sulfonic acids and organic disulfonic acids.

Examples of the organic sulfonic acid include alkanesulfonic acid, α -olefinsulfonic acid, higher alcohol sulfuric acid, and polyoxyethylene alkyl ether sulfuric acid.

Examples of the organic disulfonic acid include alkanedisulfonic acid, α -olefinedisulfonic acid, higher alcohol disulfuric acid, and polyoxyethylene alkyl ether disulfuric acid.

Specific examples of the organic sulfonic acid and the organic disulfonic acid include p-toluenesulfonic acid, xylenesulfonic acid, isopropylbenzenesulfonic acid, methoxybenzenesulfonic acid, dodecylbenzenesulfonic acid, linear alkylbenzenesulfonic acid (soft type), branched alkylbenzenesulfonic acid (hard type), alkyldiphenylether disulfonic acid, linear alkylnaphthalenesulfonic acid, branched alkylnaphthalenesulfonic acid, β -naphthalenesulfonic acid-formaldehyde condensate, p-phenylaminosulfonic acid, and o-phenylaminosulfonic acid. Among these, dodecylbenzenesulfonic acid, linear alkylbenzenesulfonic acid (soft type), and branched alkylbenzenesulfonic acid (hard type) are preferable from the viewpoint of easy industrial availability and excellent stability of phosphazene salt and aldehyde capturing effect.

In the formulae (1) and (3), one of n and m is 1 and the other is 2. That is, when n is 1, m is 2; when n is 2, m is 1.

As R¹And R²And A^n-Or A^-From the viewpoint of easy availability of guanidines as a raw material and excellent stability of phosphazene salt and aldehyde capturing effect, the combination of (b) is preferably: r¹And R²Is methyl, A^n-Or A^-Is a deprotonated form of dodecylbenzene sulphonic acid, linear alkyl benzene sulphonic acid (soft type) or branched alkyl benzene sulphonic acid (hard type).

The divalent phosphazenium salt according to the present embodiment preferably exhibits neutrality. When the divalent phosphazenium salt is added to, for example, a resin or the like, a change in pH of the resin or the like is suppressed. The pH of a 0.01mol/L aqueous solution of the divalent phosphazenium salt is preferably 5 or more and 9 or less, more preferably 5 or more and 8 or less. The pH can be measured, for example, by attaching a 0.01mol/L aqueous solution of a divalent phosphazenium salt to a pH test paper.

The phosphazene salt according to the present embodiment is excellent in thermal stability. The divalent phosphazene salt generates no or hardly any odor when heat-treated at 120 ℃ for 8 hours, and has no or hardly any change in purity as measured by an NMR (nuclear magnetic resonance) apparatus.

The divalent phosphazene salt according to the present embodiment can be used as an aldehyde scavenger. For example, the amount of aldehyde volatilized from the polyalkylene oxide can be reduced by adding the phosphazene salt represented by the above formulas (1) to (3) to the polyalkylene oxide.

< Process for producing a divalent Phosphinenitrile salt >

A method for producing a divalent phosphazene salt according to one embodiment of the invention is a method for producing a divalent phosphazene salt according to one of the above formulas (1) to (3),

reacting 2 or more moles of an organic sulfonic acid with 1 mole of a phosphazene salt represented by the formula (4),

in the formula (4), the reaction mixture is,

R¹and R²Each independently represents:

a hydrogen atom,

A hydrocarbon group having 1 to 20 carbon atoms,

R¹And R²Ring structures bonded to each other, or

R¹Each other or R²Ring structures bonded to each other;

X^-represents a hydroxyl anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxyl anion, an alkylcarboxy anion having 2 to 5 carbon atoms or a bicarbonate anion.

a is 2 when Y is a carbon atom and 3 when Y is a phosphorus atom.

A method for producing a divalent phosphazene salt according to one embodiment of the invention is a method for producing a divalent phosphazene salt according to formula (2) above, characterized in that,

reacting 2 or more moles of an organic sulfonic acid with 1 mole of a phosphazene salt represented by the formula (5),

in the formula (5), the reaction mixture is,

R¹and R²Each independently represents:

a hydrogen atom,

A hydrocarbon group having 1 to 20 carbon atoms,

R¹And R²Ring structures bonded to each other, or

R¹Each other or R²Ring structures bonded to each other;

X^-represents a hydroxyl anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxyl anion, an alkylcarboxy anion having 2 to 5 carbon atoms or a bicarbonate anion.

The method for producing a divalent phosphazene salt according to one embodiment of the invention is a method for producing a divalent phosphazene salt according to formula (3) above, and is characterized in that,

reacting 2 or more moles of an organic sulfonic acid with 1 mole of a phosphazene salt represented by formula (6),

in the formula (6), the reaction mixture is,

R¹and R²Each independently represents:

a hydrogen atom,

A hydrocarbon group having 1 to 20 carbon atoms,

R¹And R²Ring structures bonded to each other;

X^-represents a hydroxyl anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxyl anion, an alkylcarboxy anion having 2 to 5 carbon atoms or a bicarbonate anion.

<<<R¹、R²>>>

In the formulae (4) to (6), R¹And R²Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, R¹And R²Ring structures bonded to each other, or R¹Each other or R²Ring structures bonded to each other. Specific examples thereof includeR in the above formulae (1) to (3)¹And R²The same groups. And as R, in the same manner as in the above formulas (1) to (3), from the viewpoint of easy availability of guanidines as a raw material¹And R²Methyl, ethyl and isopropyl are preferred.

Specific examples of the monovalent phosphazenium salts represented by the formulae (4) and (5) include tetrakis (1,1,3, 3-tetramethylguanidino) phosphonium hydroxide, tetrakis (1,1,3, 3-tetraethylguanidino) phosphonium hydroxide, tetrakis (1,1,3, 3-tetrakis (n-propyl) guanidino) phosphonium hydroxide, tetrakis (1,1,3, 3-tetraisopropylguanidino) phosphonium hydroxide, tetrakis (1,1,3, 3-tetrakis (n-butyl) guanidino) phosphonium hydroxide, tetrakis (1,1,3, 3-tetraphenylguanidino) phosphonium hydroxide, tetrakis (1,1,3, 3-tetrabenzylguanidino) phosphonium hydroxide, tetrakis (1, 3-dimethylimidazolidin-2-imino) phosphonium hydroxide, tetrakis (1, 3-diethylimidazolidin-2-imino) phosphonium hydroxide; tetrakis (1,1,3, 3-tetramethylguanidino) phosphonium bicarbonate, tetrakis (1,1,3, 3-tetraethylguanidino) phosphonium bicarbonate, tetrakis (1,1,3, 3-tetrakis (n-propyl) guanidino) phosphonium bicarbonate, tetrakis (1,1,3, 3-tetraisopropylguanidino) phosphonium bicarbonate, tetrakis (1,1,3, 3-tetrakis (n-butyl) guanidino) phosphonium bicarbonate, tetrakis (1,1,3, 3-tetraphenylguanidino) phosphonium bicarbonate, tetrakis (1,1,3, 3-tetrabenzylguanidino) phosphonium bicarbonate, tetrakis (1, 3-dimethylimidazolidin-2-imino) phosphonium bicarbonate, tetrakis (1, 3-diethylimidazolidin-2-imino) phosphonium bicarbonate, and the like. Among these, tetrakis (1,1,3, 3-tetramethylguanidino) phosphonium hydroxide is preferable from the viewpoint of easy availability of guanidines as a raw material.

Specific examples of the monovalent phosphazenium salt represented by the formulae (4) and (6) include tetrakis [ tris (dimethylamino) phosphoranylideneamino ] phosphonium hydroxide, tetrakis [ tris (diethylamino) phosphoranylideneamino ] phosphonium hydroxide, tetrakis [ tris (di-n-propylamino) phosphoranylideneamino ] phosphonium hydroxide, tetrakis [ tris (diisopropylamino) phosphoranylideneamino ] phosphonium hydroxide, tetrakis [ tris (di-n-butylamino) phosphoranylideneamino ] phosphonium hydroxide, tetrakis [ tris (diphenylamino) phosphoranylideneamino ] phosphonium hydroxide, tetrakis [ tris (dibenzylamino) phosphoranylideneamino ] phosphonium hydroxide, tetrakis [ tris (dipyrrolidinylamino) phosphoranylideneamino ] phosphonium hydroxide; tetrakis [ tris (dimethylamino) phosphoranylideneamino ] phosphonium hydrogencarbonate, tetrakis [ tris (diethylamino) phosphoranylideneamino ] phosphonium hydrogencarbonate, tetrakis [ tris (di-n-propylamino) phosphoranylideneamino ] phosphonium hydrogencarbonate, tetrakis [ tris (diisopropylamino) phosphoranylideneamino ] phosphonium hydrogencarbonate, tetrakis [ tris (di-n-butylamino) phosphoranylideneamino ] phosphonium hydrogencarbonate, tetrakis [ tris (diphenylamino) phosphoranylideneamino ] phosphonium hydrogencarbonate, tetrakis [ tris (dibenzylamino) phosphoranylideneamino ] phosphonium hydrogencarbonate, tetrakis [ tris (dipyrrolidinylamino) phosphoranylideneamino ] phosphonium hydrogencarbonate and the like. Among these, tetrakis [ tris (dimethylamino) phosphoranylideneamino ] phosphonium hydroxide and tetrakis [ tris (dimethylamino) phosphoranylideneamino ] phosphonium hydrogencarbonate are preferable from the viewpoint of easy availability of raw materials.

The amount of the organic sulfonic acid is 2 moles or more, preferably 2.1 moles or more and 10 moles or less, and more preferably 2.2 moles or more and 5 moles or less, based on 1 mole of the monovalent phosphazenium salt represented by the formulae (4) to (6). When the amount of the organic sulfonic acid is less than 2 moles based on 1 mole of the monovalent phosphazene salt, the resulting phosphazene salt may be unstable and the purity may be lowered, which is not preferable.

The reaction of the monovalent phosphazenium salt represented by the formulae (4) to (6) with the organic sulfonic acid may be carried out in a solvent. Examples of the solvent include water; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-pentanol, neopentyl alcohol, n-hexanol, n-heptanol, n-octanol, n-nonanol, and n-decanol; polyhydric alcohols such as diethylene glycol, triethylene glycol, propylene glycol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, and glycerin; polyhydric alcohol derivatives such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobenzyl ether, and ethylene glycol monophenyl ether; fatty acids such as formic acid and acetic acid; and nitrogen-containing compounds such as ethylenediamine, aniline, and acetonitrile. The solvent may be only 1 kind, or may be a mixed solvent of 2 or more kinds.

The phosphazene salt according to one embodiment of the present invention is neutral and has excellent thermal stability, and further has an aldehyde trapping effect. Therefore, when the divalent phosphazene salt is added to, for example, a polyalkylene oxide, it is possible to trap an aldehyde in the polyalkylene oxide while maintaining the polyalkylene oxide in a neutral state.

< polyalkylene oxide composition >

The polyalkylene oxide composition according to one embodiment of the present invention contains a divalent phosphazene salt according to the above formulas (1) to (3) and a polyalkylene oxide.

< polyalkylene oxide > <

The polyalkylene oxide may be any polyalkylene oxide as long as it falls within a category generally known as polyalkylene oxides, and examples thereof include polyethylene oxide, polypropylene oxide, poly (1, 2-butylene oxide), poly (2, 3-butylene oxide), polyisobutylene oxide, polybutadiene oxide, polypentalene oxide, polycyclohexane oxide, and polyethylene oxide. Further, block copolymers and random copolymers containing these as a copolymerization component can be mentioned. Among these, polyethylene oxide, polypropylene oxide, and polypropylene oxide-polyethylene oxide block copolymers are preferable.

The content of the divalent phosphazene salt in the polyalkylene oxide composition is not particularly limited, and is preferably 50ppm or more and 10000ppm or less, more preferably 100ppm or more and 5000ppm or less, and further preferably 200ppm or more and 3000ppm or less, from the viewpoint of forming a polyalkylene oxide composition in which odor and turbidity are suppressed and the amount of volatile aldehyde is small.

The polyalkylene oxide composition may contain an antioxidant. Examples of the antioxidant include phenol antioxidants such as 2, 6-di-t-butyl-4-methylphenol, 2-t-butyl-4-methoxyphenol, 2, 6-di-t-butylphenol, 6-t-butyl-2, 4-methylphenol, pentaerythrityl tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl propionate ] (e.g., Irganox1010 manufactured by BASF corporation), octadecyl 3, 5-di-t-butyl-4-hydroxyphenyl propionate (e.g., Irganox1076 manufactured by BASF corporation), isooctyl 3, 5-di-t-butyl-4-hydroxyphenyl propionate (e.g., Irganox1135 manufactured by BASF corporation), amine antioxidants such as n-butyl-p-aminophenol, 4-dimethyldiamine, and 4, 4-dioctyldiphenylamine, and the like antioxidants can be used alone, a mixture of 2 or more thereof may be used.

The polyalkylene oxide composition according to the present embodiment suppresses generation of odor. Regarding the polyalkylene oxide composition, 10g of the polyalkylene oxide composition was put into a 20ml sample tube, and after standing for 12 hours in a closed state, there was no or almost no odor at the time of unsealing.

The polyalkylene oxide composition according to the present embodiment suppresses the occurrence of turbidity. As for the polyalkylene oxide composition, 10g of the polyalkylene oxide composition was put into a 20ml sample tube, and there was little or no turbidity when visually observed.

The polyalkylene oxide composition according to the present embodiment is excellent in urethane formation reactivity. The pH of the polyalkylene oxide composition is preferably 5 or more and 8 or less as measured by the method described in JIS K-1557-5. When the pH is 5 or more and 8 or less, the reactivity when the polyalkylene oxide composition and the isocyanate compound are mixed to synthesize the polyurethane-forming composition is more favorable, and therefore, this is preferable.

The polyalkylene oxide composition of the present embodiment has a small amount of volatile aldehydes. As an index of the above, the amount of acetaldehyde volatilized by bubbling nitrogen gas (flow rate: 0.5L/min) under heating under a certain condition (65 ℃ C., 2 hours) is preferably 0.9ppm or less, more preferably 0.8ppm or less. The amount of propionaldehyde volatilized under the above conditions is preferably 3.0ppm or less, and more preferably 2.5ppm or less.

The polyalkylene oxide composition of the present embodiment has a small amount of volatile aldehydes. As the index of this embodiment, when the measurement is carried out by the following measurement method,

the amount of acetaldehyde volatilized is preferably 0.9ppm or less,

The amount of propionaldehyde volatilized is preferably 3.0ppm or less.

[ measurement method ]

(I) The method comprises the following steps A container having an internal volume of 30ml was charged with 10g of the sample.

(II): after (I), nitrogen bubbling was performed at 65 ℃ for 2 hours under heating at 0.5L/min, and the volatilization amount was measured.

More specifically, the amount of acetaldehyde volatilized is preferably 0.9ppm or less, more preferably 0.8ppm or less, when measured in the order of the following (i) to (iv). When the amount of propionaldehyde volatilized is measured in the order of the following (i) to (iv), the amount of propionaldehyde volatilized is preferably 3.0ppm or less, more preferably 2.5ppm or less.

(i) The polyalkylene oxide composition was charged into an impact absorption tube (Impinger) having an internal volume of 30ml, and was bubbled with nitrogen gas (flow rate: 0.5L/min) at 65 ℃ through a hydrocarbon trap under heating under certain conditions (65 ℃ C., 2 hours),

(ii) the volatilized gas was trapped in a 2, 4-Dinitrophenylhydrazine (DNPH) cartridge (cartridge),

(iii) eluting the adsorbed components with 5ml of eluent,

(iv) high Performance Liquid Chromatography (HPLC) was performed.

< method for producing polyalkylene oxide composition >

The method for producing a polyalkylene oxide composition comprising a phosphazene salt represented by the formula (1) or (3) and a polyalkylene oxide may be any method as long as it can produce a polyalkylene oxide composition comprising a divalent phosphazene salt represented by the formula (1) or (3) and a polyalkylene oxide. For example, a method of mixing a divalent phosphazenium salt represented by the above formula (1) or (3) with a polyalkylene oxide is exemplified. The temperature at which the phosphazene salt and the polyalkylene oxide are mixed may be any temperature, and for example, the temperature is in the range of 40 to 130 ℃.

The method for producing a polyalkylene oxide composition containing a divalent phosphazenium salt represented by the formula (2) and a polyalkylene oxide may be any method as long as it can produce a polyalkylene oxide composition containing a divalent phosphazenium salt represented by the formula (2) and a polyalkylene oxide. For example, a method of mixing a divalent phosphazenium salt represented by the above formula (2) with a polyalkylene oxide is exemplified. Further, the following methods can be exemplified: in the presence of a monovalent phosphazene salt represented by the above formula (5) and an active hydrogen-containing compound, ring-opening polymerization of an alkylene oxide is carried out to produce a polyalkylene oxide, and then 2 moles or more of an organic sulfonic acid is added to 1 mole of the phosphazene salt.

A method for producing a polyalkylene oxide composition according to one embodiment of the present invention is the method for producing a polyalkylene oxide composition described above,

in the presence of a phosphazene salt represented by formula (5) and an active hydrogen-containing compound, an alkylene oxide polymerization reaction is carried out to produce a polyalkylene oxide,

then, 2 moles or more of an organic sulfonic acid is added to 1 mole of the phosphazene salt,

in the formula (5), the reaction mixture is,

R¹and R²Each independently represents:

a hydrogen atom,

A hydrocarbon group having 1 to 20 carbon atoms,

R¹And R²Ring structures bonded to each other, or

R¹Each other or R²Ring structures bonded to each other;

X^-represents a hydroxyl anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxyl anion, an alkylcarboxy anion having 2 to 5 carbon atoms or a bicarbonate anion.

Examples of the alkylene oxide include alkylene oxides having 2 to 20 carbon atoms. Specific examples thereof include ethylene oxide, propylene oxide, 1, 2-butylene oxide, 2, 3-butylene oxide, isobutylene oxide, butadiene monoxide, cyclopentane oxide, styrene oxide, and cyclohexane oxide. Among these, ethylene oxide and propylene oxide are preferable because they are easily available and the obtained polyalkylene oxide has a high industrial value. The alkylene oxides may be used alone or in combination of 2 or more. When 2 or more kinds are used in combination, for example, the first alkylene oxide may be reacted and then the second alkylene oxide may be reacted, or two or more kinds of alkylene oxides may be reacted simultaneously.

Examples of the active hydrogen-containing compound include a hydroxyl compound, an amine compound, a carboxylic acid compound, a thiol compound, and a polyether polyol having a hydroxyl group.

Examples of the hydroxyl compound include water, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 6-hexanediol, glycerin, trimethylolpropane, hexanetriol, pentaerythritol, diglycerin, sorbitol, sucrose, glucose, 2-naphthol, and bisphenol.

Examples of the amine compound include ethylenediamine, N' -dimethylethylenediamine, piperidine, and piperazine.

Examples of the carboxylic acid compound include benzoic acid and adipic acid.

Examples of the thiol compound include ethanedithiol and butanedithiol.

Examples of the polyether polyol having a hydroxyl group include polyether polyols having a hydroxyl group such as polyether polyols having a molecular weight of 200 to 3000.

These active hydrogen-containing compounds may be used alone or in combination of two or more.

Examples of the organic sulfonic acid include the same organic sulfonic acids as those exemplified in the above formula (2).

Using inorganic acids such as hydrochloric acid, perchloric acid, sulfuric acid, sulfurous acid, nitric acid, etc.; when an organic carboxylic acid such as acetic acid, adipic acid, benzoic acid or oxalic acid is used in place of the organic sulfonic acid, the phosphazene salt precipitates from the polyalkylene oxide composition, and the polyalkylene oxide composition is cloudy or an odor derived from the acid is generated, which is not preferable.

The amount of the organic sulfonic acid added is 2 moles or more, preferably 2 moles or more and 10 moles or less, more preferably 2.1 moles or more and 8 moles or less, and further preferably 2.2 moles or more and 5.0 moles or less, based on 1 mole of the phosphazene salt represented by the formula (5). If the amount is less than 2 moles, unreacted monovalent phosphazenium salt remains, and the polyalkylene oxide composition generates an odor, which is not preferable. On the other hand, 10 mol or less is preferable because the polyalkylene oxide composition exhibits good liquid properties (pH) and is excellent in urethane reactivity.

< polyurethane-Forming composition >

A polyurethane-forming composition according to an embodiment of the present invention includes:

(A) a polyalkylene oxide composition comprising a divalent phosphazenium salt represented by the above formulas (1) to (3) and a polyalkylene oxide; and

(B) an isocyanate compound.

The isocyanate compound (B) may be any compound as long as it belongs to a category generally known as isocyanate compounds, and examples thereof include aromatic isocyanate compounds, aliphatic isocyanate compounds, alicyclic isocyanate compounds, and polyisocyanate derivatives thereof.

Examples of the aromatic isocyanate compound include tolylene diisocyanate (2, 4-or 2, 6-tolylene diisocyanate or a mixture Thereof) (TDI), phenylene diisocyanate (m-phenylene diisocyanate, p-phenylene diisocyanate or a mixture thereof), 4 '-diphenyl diisocyanate, diphenylmethane diisocyanate (4, 4' -, 2,4 '-or 2, 2' -diphenylmethane diisocyanate or a mixture thereof) (MDI), 4 '-toluidine diisocyanate (TODI), 4' -diphenyl ether diisocyanate, xylylene diisocyanate (1, 3-or 1, 4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethylxylylene diisocyanate (1, 3-or 1, 4-tetramethylxylylene diisocyanate or a mixture Thereof) (TMXDI), ω ' -diisocyanate-1, 4-diethylbenzene, naphthalene diisocyanate (1,5-, 1, 4-or 1, 8-naphthalene diisocyanate or a mixture thereof) (NDI), triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4, 4 ' -diisocyanate, 3 ' -dimethyldiphenylmethane-4, 4 ' -diisocyanate, 4 ' -diphenylpropane diisocyanate, 3 ' -dimethoxydiphenyl-4, 4 ' -diisocyanate and the like.

Examples of the aliphatic isocyanate compound include trimethylene diisocyanate, 1, 2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1, 2-butylene diisocyanate, 2, 3-butylene diisocyanate, 1, 3-butylene diisocyanate), hexamethylene diisocyanate, pentamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, 2, 6-diisocyanatomethylheptanoate, lysine diisocyanate, lysine ester triisocyanate, 1,6, 11-undecane triisocyanate, 1,3, 6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, decamethylene diisocyanate, etc.

Examples of the alicyclic isocyanate compound include 1, 3-cyclopentane diisocyanate, 1, 3-cyclopentene diisocyanate, cyclohexane diisocyanate (1, 4-cyclohexane diisocyanate, 1, 3-cyclohexane diisocyanate), 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylenebis (cyclohexyl isocyanate (4,4 ' -, 2,4 ' -or 2,2 ' -methylenebis (cyclohexyl isocyanate or a mixture thereof) (hydrogenated MDI), methylcyclohexane diisocyanate (methyl-2, 4-cyclohexane diisocyanate, methyl-2, 6-cyclohexane diisocyanate, bis (isocyanatomethyl) cyclohexane (1, monocyclic alicyclic isocyanate compounds such as 3-or 1, 4-bis (isocyanatomethyl) cyclohexane or a mixture thereof) (hydrogenated XDI), dimer acid diisocyanate, trans-cyclohexane 1, 4-diisocyanate, hydrogenated toluene diisocyanate (hydrogenated TDI), hydrogenated tetramethylxylylene diisocyanate (hydrogenated TMXDI), and the like; bridged alicyclic isocyanate compounds such as norbornene diisocyanate, norbornane diisocyanate methyl ester, bicycloheptane triisocyanate, isocyanatomethylbicycloheptane, bis (diisocyanatomethyl) tricyclodecane and the like.

Examples of the derivative of the polyisocyanate include polymers (dimer, trimer, pentamer, heptamer, uretdione (uretonimine), isocyanurate-modified product, polycarbodiimide and the like) of the above-mentioned isocyanate compound, urethane-modified product (for example, urethane-modified product obtained by modifying or reacting a part of the isocyanate groups in the above-mentioned isocyanate compound or polymer with a monohydric alcohol or a polyhydric alcohol), biuret-modified product (for example, biuret-modified product obtained by reacting the above-mentioned isocyanate compound with water), allophanate-modified product (for example, allophanate-modified product obtained by reacting the above-mentioned isocyanate compound with a monohydric alcohol or a polyhydric alcohol component), urea-modified product (for example, urea-modified product obtained by reacting the above-mentioned isocyanate compound with a diamine and the like), and the like, And oxadiazinetrione (for example, oxadiazinetrione produced by the reaction of the isocyanate compound with carbon dioxide or the like).

The isocyanate compound or a derivative thereof may be used alone, or 2 or more kinds thereof may be used.

The polyurethane-forming composition may contain various additives. The effect of the additive in the polyurethane-forming composition containing the additive can be expected.

Examples of the additives include catalysts, foam regulators, crosslinking agents, linking agents, foaming agents, dyes, organic pigments, inorganic reinforcing materials, plasticizers, processing aids, ultraviolet absorbing materials, light stabilizers, lubricants, waxes, crystal nucleating agents, mold release agents, hydrolysis preventing agents, antifogging agents, dust inhibitors, rust inhibitors, ion trapping agents, flame retardants, flame retardant aids, inorganic fillers, and organic fillers.