JP2024050417A - Additive for resin, composition and resin foam - Google Patents

Abstract

［式（１）中、Ｒ^１は、少なくとも一つの水素原子が塩素原子で置換された、炭素数２～８のアルキレン基又は炭素数６～１８のアリーレン基を示し、＊は、他の構造単位との結合位置を示す。］
【選択図】なし The present invention provides an additive for resins that can suppress deterioration of the heat insulating performance of resins over time.
The present invention relates to a resin additive comprising a cyclic phosphazene compound having a structural unit represented by the following formula (1):

[In formula (1), R ¹ represents an alkylene group having 2 to 8 carbon atoms or an arylene group having 6 to 18 carbon atoms in which at least one hydrogen atom is substituted with a chlorine atom, and * represents the bonding position to other structural units.]
[Selection diagram] None

Description

This disclosure relates to resin additives, compositions, and resin foams.

Resin foams such as rigid polyurethane foams are widely used as insulation materials for refrigerators, freezer warehouses, building materials, etc., and as sprays, due to their excellent insulation performance, dimensional stability, and ease of application. However, resin foams have the problem that their thermal conductivity increases continuously (i.e., their insulation performance decreases over time).

In response to this, for example, Patent Document 1 discloses a method for suppressing deterioration of the insulating performance over time by adjusting the aspect ratio of the cell shape through the adjustment and control of the pressure applied to the front and back of the foamed resin insulation material when producing a foamed resin insulation material made of rigid polyurethane foam, thereby suppressing the change in the volume of the foam caused by the expansion of the outer and central layers.

JP 2007-332203 A

Z. Anorg. Allg. Chem., Vol. 425, No. 127, 1976

However, the method of Patent Document 1 is not practical because it complicates the work process and increases production costs. Therefore, it is desirable to develop a more practical method that can prevent the deterioration of the thermal insulation performance of the resin over time.

Therefore, one aspect of the present disclosure aims to provide an additive for resins that can suppress the deterioration of the insulating performance of resins over time.

The inventors of the present disclosure discovered that a cyclic phosphazene compound having a specific structure is effective in suppressing the deterioration of the insulating performance of a resin over time (particularly the deterioration of the insulating performance of a resin foam over time), and thus completed the present invention.

Some aspects of the present disclosure provide the following [1] to [9].

［式（１）中、Ｒ^１は、少なくとも一つの水素原子が塩素原子で置換された、炭素数２～８のアルキレン基又は炭素数６～１８のアリーレン基を示し、＊は、他の構造単位との結合位置を示す。］ [1]
A resin additive comprising a cyclic phosphazene compound having a structural unit represented by the following formula (1):

[In formula (1), R ¹ represents an alkylene group having 2 to 8 carbon atoms or an arylene group having 6 to 18 carbon atoms in which at least one hydrogen atom is substituted with a chlorine atom, and * represents the bonding position to other structural units.]

［式（４）中、Ｒ^１は、前記式（１）中のＲ^１と同義であり、複数のＲ^１は、互いに同一であっても異なっていてもよい。］ [2]
The resin additive according to [1], wherein the cyclic phosphazene compound is a compound represented by the following formula (4):

[In formula (4), R ¹ has the same meaning as R ¹ in formula (1), and multiple R ¹ may be the same or different.]

［式（ｃ－１）～（ｃ－６）中、＊は、酸素原子との結合位置を示す。］ [3]
The resin additive according to [1] or [2], wherein the cyclic phosphazene compound has, as the R ¹ , at least one group selected from groups represented by the following formulas (c-1) to (c-6):

[In formulas (c-1) to (c-6), * indicates the bonding position with the oxygen atom.]

[4]
The resin additive according to [3], wherein the cyclic phosphazene compound has, as the R ¹ , at least one group selected from the group represented by the formula (c-1) and the group represented by the formula (c-2).

［式（１）中、Ｒ^１は、少なくとも一つの水素原子が塩素原子で置換された、炭素数２～８のアルキレン基又は炭素数６～１８のアリーレン基を示し、＊は、他の構造単位との結合位置を示す。］ [5]
A composition comprising a resin or a raw material for a resin, and a cyclic phosphazene compound having a structural unit represented by the following formula (1):

[In formula (1), R ¹ represents an alkylene group having 2 to 8 carbon atoms or an arylene group having 6 to 18 carbon atoms in which at least one hydrogen atom is substituted with a chlorine atom, and * represents the bonding position to other structural units.]

[6]
The composition according to [5], wherein the resin is a polyurethane resin, and a raw material of the resin is at least one of a polyol and a polyisocyanate.

[7]
The composition according to [6], which is for forming a polyurethane foam.

［式（１）中、Ｒ^１は、少なくとも一つの水素原子が塩素原子で置換された、炭素数２～８のアルキレン基又は炭素数６～１８のアリーレン基を示し、＊は、他の構造単位との結合位置を示す。］ [8]
A resin foam comprising a resin and a cyclic phosphazene compound having a structural unit represented by the following formula (1):

[In formula (1), R ¹ represents an alkylene group having 2 to 8 carbon atoms or an arylene group having 6 to 18 carbon atoms in which at least one hydrogen atom is substituted with a chlorine atom, and * represents the bonding position to other structural units.]

[9]
The resin foam according to [8], which is a polyurethane foam.

According to one aspect of the present disclosure, it is possible to provide a resin additive that can suppress deterioration of the insulating performance of a resin over time.

In this specification, a numerical range indicated using "~" indicates a range that includes the numerical values before and after "~" as the minimum and maximum values, respectively. Furthermore, unless specifically stated otherwise, the units of the numerical values before and after "~" are the same. In the numerical ranges described in stages in this specification, the upper or lower limit of a numerical range of a certain stage may be replaced with the upper or lower limit of a numerical range of another stage. Furthermore, in the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in the examples. Furthermore, the upper and lower limits described individually can be combined in any combination.

Preferred embodiments of the present disclosure are described below. However, the present disclosure is not limited to the following embodiments.

<Resin additives>
The resin additive of one embodiment includes a cyclic phosphazene compound. Here, the cyclic phosphazene compound is a compound having a ring structure formed by alternately bonding phosphorus atoms (P) and nitrogen atoms (N). In other words, the cyclic phosphazene compound is a compound having a ring structure consisting of repetitions of [-P=N-] formed by bonding a plurality of structural units including [-P=N-]. The ring structure of the cyclic phosphazene compound can be represented by [-P=N-]x. That is, the number of ring members of the cyclic phosphazene compound (the total number of P and N forming the ring) is 2x. x is an integer of 3 or more, for example, 3 to 5.

The cyclic phosphazene compound contained in the resin additive contains a structural unit represented by the following formula (1): Hereinafter, the cyclic phosphazene compound containing the structural unit represented by the following formula (1) will be referred to as "cyclic phosphazene compound (A)".

In formula (1), R ¹ represents an alkylene group (alkanediyl group) having 2 to 8 carbon atoms or an arylene group (arenediyl group) having 6 to 18 carbon atoms, in which at least one hydrogen atom is substituted with a chlorine atom, and * represents a bonding position with another structural unit. The structural unit represented by formula (1) forms a ring structure (a ring structure consisting of repetitions of [-P=N-]) of a cyclic phosphazene compound (A) by bonding with another structural unit. In this specification, the term "arylene group" refers to a group derived by removing two hydrogen atoms bonded to a carbon atom of an arene, and the term "arylene group" includes not only a group derived by removing a hydrogen atom bonded to a ring carbon atom (a carbon atom constituting an aromatic ring), but also a group derived by removing a hydrogen atom bonded to a carbon atom constituting a side chain bonded to an aromatic ring.

The resin additive of this embodiment contains the cyclic phosphazene compound (A), and therefore has the function of suppressing the deterioration of the insulating performance of the resin over time. That is, the resin additive of this embodiment can suppress the deterioration of the insulating performance of the resin over time. This effect tends to be remarkable when the resin additive is used in a resin foam. Therefore, the resin additive of this embodiment is preferably used as an additive for a resin foam.

The alkylene group of ^R1 may be linear or branched. The number of carbon atoms in the alkylene group is 2 to 8, and preferably 2 to 4. Examples of the alkylene group include an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,2-diyl group, a butane-1,3-diyl group, and a butane-2,3-diyl group.

The arylene group of ^R1 may be monocyclic or polycyclic. The number of carbon atoms in the arylene group is 6 to 18, and preferably 6 to 10. Examples of the arylene group include a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, and an anthracenylene group.

The number of chlorine atoms contained in ^R1 (i.e., the number of chloro groups) is at least 1. The number of chlorine atoms is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.

R ¹ is preferably a group represented by the following formula (a) or a group represented by the following formula (b).

R ^a1 to R ^a4 in formula (a) and R ^b1 to R ^b6 in formula (b) each independently represent a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, or an alkyl group having 1 to 2 carbon atoms in which at least one hydrogen atom has been substituted with a chlorine atom, and * in formulas (a) and (b) indicates the bonding position to the oxygen atom. However, at least one of R ^a1 to R ^a4 and at least one of R ^b1 to R ^b6 is an alkyl group having 1 to 2 carbon atoms in which at least one hydrogen atom (preferably one hydrogen atom) has been substituted with a chlorine atom. Examples of R ^a1 to R ^a4 and R ^b1 to R ^b6 include a methyl group, an ethyl group, a chloromethyl group, and a 2-chloroethyl group.

The cyclic phosphazene compound (A) preferably has, as R ¹ , any one of the groups represented by the following formulae (c-1) to (c-6), more preferably has at least one group selected from the group represented by the following formula (c-1) (3-chloropropane-1,2-diyl group) and the group represented by the following formula (c-2) (1,4-dichlorobutane-2,3-diyl group), and further preferably has a group represented by the following formula (c-1). Among these, it is preferable that all of R ¹ in formula (1) are any one of the groups represented by the following formulae (c-1) to (c-6), it is more preferable that all of R ¹ in formula (1) are groups represented by the following formula (c-1) or the group represented by the following formula (c-2), and further preferably that all of R ¹ in formula (1) are groups represented by the following formula (c-1).

In formulas (c-1) to (c-6), * indicates the bonding position with the oxygen atom.

The number of the structural unit represented by formula (1) contained in the cyclic phosphazene compound (A) may be 1 to 5, or may be 3 to 5. When a plurality of structural units represented by formula (1) are present, the plurality of R ¹ 's may be the same or different from each other.

The cyclic phosphazene compound (A) may be composed only of a structural unit represented by formula (1), or may further contain a structural unit represented by the following formula (2) as a structural unit other than the structural unit represented by formula (1).

In formula (2), ^R2 represents a divalent hydrocarbon group (e.g., an alkylene group or an arylene group). In formula (2), * represents a bonding position to another structural unit.

Examples of the alkylene group and arylene group for ^R2 are the same as the examples of the alkylene group and arylene group for ^R1 , except that at least one hydrogen atom is not substituted with a chlorine atom.

The number of structural units represented by formula (2) may be 0 to 4, or may be 0 to 2.

The cyclic phosphazene compound (A) may be, for example, a compound represented by the following formula (3).

In formula (3), ^R1 has the same meaning as ^R1 in formula (1), and ^R2 has the same meaning as ^R2 in formula (2). When there are a plurality of ^R1s , the plurality of ^R1s may be the same or different from each other. Similarly, when there are a plurality of ^R2s , the plurality of ^R2s may be the same or different from each other.

m is an integer from 1 to 5, and n is an integer from 0 to 4. The sum of m and n (m+n) is, for example, 3 to 5. m/(m+n) is preferably 0.5 or more, and more preferably 1.

The cyclic phosphazene compound (A) may be, for example, a compound represented by the following formula (4).

In formula (4), R ¹ has the same meaning as R ¹ in formula (1). The multiple R ^1s may be the same or different from each other. Preferably, at least one of the multiple R ^1s is any of the groups represented by formulas (c-1) to (c-6), and more preferably, all of the multiple R ^1s are any of the groups represented by formulas (c-1) to (c-6).

The compound represented by formula (4) includes all of the various possible stereoisomers. For example, when all of the three R ¹ in formula (4) are groups represented by formula (a), that is, when the cyclic phosphazene compound (A) is a compound represented by the following formula (5), the 5-membered ring composed of the group represented by formula (a) and the oxygen atom and phosphorus atom to which the group is bonded has a rigid structure and forms a spiro structure perpendicular to the phosphazene ring, so that the compound represented by formula (5) may have stereoisomers represented by the following formulas (5-1) to (5-6). In this specification, for convenience, it is described as formula (5), but the compound represented by formula (5) includes all of the stereoisomers represented by the following formulas (5-1) to (5-6). The compound represented by formula (5) includes at least one of the stereoisomers represented by formulas (5-1) to (5-6), and may include all of the stereoisomers represented by formulas (5-1) to (5-6).

R ^a1 , R ^a2 , R ^a3 and R ^a4 in formula (5) and formulas (5-1) to (5-6) have the same meanings as R ^a1 , R ^a2 , R ^a3 and R ^a4 in formula (a). In each formula, multiple R ^a1 may be the same or different from each other, multiple R ^a2 may be the same or different from each other, multiple R ^a3 may be the same or different from each other, and multiple R ^a4 may be the same or different from each other.

The cyclic phosphazene compound (A) can be synthesized by a known method (e.g., the method described in Non-Patent Document 1) of reacting a cyclic phosphazene compound represented by (PX ₂ N)q (each X is independently a halogen atom such as Cl or Br, and q is an integer of 3 or more (e.g., 3 to 5)) with an alcohol compound or a method shown in a synthesis example. Specifically, the cyclic phosphazene compound (A) can be obtained by using a compound represented by R ¹ (OH) ₂ (R ¹ has the same meaning as R ¹ in formula (1)) as the alcohol compound.

As the alcohol compound, a compound represented by ^R2 (OH) ₂ ( ^R2 has the same meaning as ^R2 in formula (2)) can also be used. When such a compound is used, a cyclic phosphazene compound (A) further containing a structural unit represented by formula (2) can be obtained.

The resin additive of this embodiment may contain components other than the cyclic phosphazene compound (A) (for example, components that may be inevitably mixed in during the manufacturing process of the cyclic phosphazene compound (A)), or may consist only of the cyclic phosphazene compound (A).

The resin additive of this embodiment described above has the function of suppressing the deterioration of the insulating performance of the resin over time, and therefore can be called a thermal conductivity modifier for resin (or an agent for suppressing the deterioration of the insulating performance of the resin over time). However, since the resin additive of this embodiment can have an effect other than suppressing the deterioration of the insulating performance of the resin over time, it does not necessarily have to be used for the purpose of suppressing the deterioration of the insulating performance of the resin over time.

<Composition>
The composition of one embodiment is a resin composition or a resin-forming composition, and includes a resin or a raw material for a resin, and a cyclic phosphazene compound (A). The cyclic phosphazene compound (A) may be included in the composition as a resin additive (e.g., a thermal conductivity modifier).

Examples of resins contained in the composition include polyurethane resin, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polyimide resin, and phenol resin. Examples of raw materials for the resins contained in the composition include raw materials for polyurethane resins such as polyol and polyisocyanate, and raw materials for phenol resins such as phenol and cresol.

The content of the cyclic phosphazene compound (A) may be, for example, 0.5 to 20% by mass based on the total mass of the composition.

The composition preferably contains at least one of a polyurethane resin, or a polyol and a polyisocyanate. These compositions are preferably compositions that constitute polyurethane foams, which will be described later, or compositions for forming polyurethane foams (polyurethane foam-forming compositions).

When the composition contains a polyurethane resin, the content of the cyclic phosphazene compound (A) may be, for example, 0.5 to 15 parts by mass per 100 parts by mass of the polyurethane resin. When the content is 0.5 parts by mass or more, there is a tendency that the deterioration of the heat insulating performance of the resin over time can be more suppressed, and when the content is 15 parts by mass or less, there is a tendency that the deterioration of the heat insulating performance of the resin over time can be suppressed without impairing the mechanical properties of the resin. From the same viewpoint, the content of the cyclic phosphazene compound (A) may be 1 part by mass or more or 3 parts by mass or more, or 10 parts by mass or less or 7 parts by mass or less per 100 parts by mass of the polyurethane resin.

When the composition contains a polyol, the content of the cyclic phosphazene compound (A) may be, for example, 1 to 50 parts by mass per 100 parts by mass of the polyol. When the content is 1 part by mass or more, there is a tendency that the deterioration of the heat insulating performance of the resin over time can be more suppressed, and when the content is 50 parts by mass or less, there is a tendency that the deterioration of the heat insulating performance of the resin over time can be suppressed without impairing the mechanical properties of the resin. From the same viewpoint, the content of the cyclic phosphazene compound (A) may be 3 parts by mass or more or 10 parts by mass or more, or 30 parts by mass or less or 20 parts by mass or less per 100 parts by mass of the polyol.

The composition may further contain other components other than the above resin, the resin raw material, and the cyclic phosphazene compound (A). The other components may be known components used in resin foams or materials for forming resin foams. In other words, the composition may be a resin foam or a material for forming resin foams. Specific examples of other components include catalysts, flame retardants, blowing agents, foam stabilizers, plasticizers, colorants, etc.

The composition is suitable for use as an insulating material or as a material for forming insulating materials.

<Resin foam>
The resin foam of one embodiment contains a cyclic phosphazene compound (A). The cyclic phosphazene compound (A) may be contained in the resin foam as a resin additive (e.g., a thermal conductivity modifier). The content of the cyclic phosphazene compound (A) may be, for example, 0.3 to 15 mass% based on the total mass of the resin foam.

The resin foam may be a foam formed from the composition of the above embodiment. That is, the resin foam may contain components that may be contained in the composition of the above embodiment (resin, catalyst, flame retardant, foaming agent, foam stabilizer, plasticizer, colorant, etc.). The resin foam is preferably used, for example, as a heat insulating material or a material for forming a heat insulating material.

The resin contained in the resin foam is preferably a polyurethane resin, from the viewpoint of obtaining a more significant effect of suppressing the deterioration of the heat insulating performance over time by the cyclic phosphazene compound (A). Hereinafter, a resin foam containing a polyurethane resin as a constituent resin will be referred to as a polyurethane foam.

<Polyurethane foam>
The polyurethane foam of one embodiment includes a polyurethane resin and a cyclic phosphazene compound (A). The polyurethane foam is, for example, a rigid polyurethane foam. The foam density of the polyurethane foam may be, for example, 25 to 60 kg/ ^m3 . When the polyurethane foam has a core and a skin layer, the core density of the polyurethane foam may be, for example, 20 to 55 kg/ ^m3 .

Polyurethane foam is suitable for use as an insulating material for, for example, roofs and walls of buildings, underground structures, bridge decks, water tanks, tanks, and the inside of housings such as refrigerators.

The polyurethane foam can be obtained, for example, by using a polyurethane foam-forming composition as a material. The polyurethane foam-forming composition is a composition containing at least one of a polyol and a polyisocyanate, and a cyclic phosphazene compound (A). When the polyurethane foam-forming composition is a composition containing a polyol and a polyisocyanate, the polyurethane foam is formed by reacting (foaming and curing) the polyurethane foam-forming composition. When the polyurethane foam-forming composition is a composition containing a polyol and not containing a polyisocyanate (polyol composition), the polyurethane foam is formed by mixing the polyurethane foam-forming composition (polyol composition) with a polyisocyanate or a composition containing a polyisocyanate (polyisocyanate composition) and reacting (foaming and curing). When the polyurethane foam-forming composition is a composition containing a polyisocyanate and not containing a polyol (polyisocyanate composition), the polyurethane foam is formed by mixing the polyurethane foam-forming composition (polyisocyanate composition) with a polyol or a composition containing a polyol (polyol composition) and reacting (foaming and curing).

The polyurethane foam-forming composition containing a polyol and a polyisocyanate may be a one-liquid composition or a multi-liquid composition consisting of two or more liquids. The multi-liquid composition may be, for example, a two-liquid composition that independently comprises a first liquid (e.g., a polyol composition) containing a polyol and a second liquid (e.g., a polyisocyanate composition) containing a polyisocyanate. In this case, the first liquid containing a polyol and the second liquid containing a polyisocyanate are mixed and reacted (foamed and cured) to form a polyurethane foam. The cyclic phosphazene compound (A) may be contained in at least one of the first liquid and the second liquid, or may be contained in a liquid different from the first liquid and the second liquid. That is, the multi-liquid composition may comprise a third liquid containing a cyclic phosphazene compound (A) in addition to the first liquid and the second liquid.

Among the above examples, when the cyclic phosphazene compound (A) is contained in the polyol composition, i.e., when the polyurethane foam-forming composition is a polyol composition or a two-liquid composition including a polyol composition containing the cyclic phosphazene compound (A), the cyclic phosphazene compound (A) tends to be easily dispersed uniformly in the polyurethane foam-forming composition.

The mixed solution (mixed solution containing polyol, polyisocyanate, and cyclic phosphazene compound (A)) to be reacted by the above method may be prepared so that the isocyanate index is, for example, 100 to 400. Here, the isocyanate index (NCO index) means the percentage of the number of moles of all isocyanate groups (NCO groups) in the isocyanate group-containing compound relative to the number of moles of all active hydrogen groups in the active hydrogen group-containing compound contained in the mixed solution (NCO groups/active hydrogen groups x 100). The active hydrogen group-containing compound includes not only polyol but also water. The isocyanate index (NCO index) may be 150 to 300 or 180 to 250.

The reaction (foaming and curing) may be carried out by a conventional method, for example, by heating in a mold.

Next, components other than the cyclic phosphazene compound (A) that may be contained in the polyurethane foam-forming composition will be described. The components described below may be contained in the polyurethane foam.

[Polyol]
The polyol is a compound having two or more hydroxyl groups. Examples of the polyol include polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, etc. The polyol may be used alone or in combination of two or more kinds.

As the polyol, aromatic polyester polyol is preferably used from the viewpoint of obtaining higher heat insulating performance (initial and long-term heat insulating properties). Here, aromatic polyester polyol is a polyester polyol having an aromatic ring in the molecule, for example, a polyester polyol obtained by a condensation polymerization reaction between an acid component containing at least one selected from the group consisting of phthalic acid, isophthalic acid, terephthalic acid, and anhydrides thereof, and a polyfunctional alcohol.

The polyfunctional alcohol is preferably a low molecular weight polyol having a molecular weight of 500 or less. Examples of polyfunctional alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer diol, ethylene oxide or propylene oxide adduct of bisphenol A, bis(β-hydroxyethyl)benzene, xylylene glycol, glycerin, trimethylolpropane, and pentaerythritol.

As the aromatic polyester polyol, a condensation polymerization reaction product of an acid component containing at least one of phthalic acid, isophthalic acid, terephthalic acid, or anhydrides thereof, and a polyfunctional alcohol containing at least one selected from the group consisting of ethylene glycol and diethylene glycol is preferably used, from the viewpoint of making it easier to obtain higher heat insulating performance (initial and long-term heat insulating properties).

The number average molecular weight of the polyol may be 300 to 1500, 350 to 1000, or 400 to 700, from the viewpoint of making it easier to obtain higher insulation performance (initial and long-term insulation). The number average molecular weight of the polyol is a polystyrene-equivalent number average molecular weight measured using gel permeation chromatography (GPC).

The hydroxyl value of the polyol may be 70 to 800 mgKOH/g, 100 to 650 mgKOH/g, or 150 to 450 mgKOH/g, from the viewpoint of making it easier to obtain higher insulation performance (initial and long-term insulation). The hydroxyl value is a value measured in accordance with JIS K1557-1.

[Polyisocyanate]
The polyisocyanate is a compound having a plurality of isocyanate groups, and examples thereof include diphenylmethane diisocyanate (MDI), polyphenylene polymethylene polyisocyanate (P-MDI), various modified products of MDI or P-MDI (urethane modified product, urea modified product, allophanate modified product, nurate modified product, biuret modified product, etc.), etc. One type of polyisocyanate may be used alone, or multiple types may be used in combination.

[Other ingredients]
The polyurethane foam-forming composition may further contain a catalyst, a flame retardant, a blowing agent, a foam stabilizer, a plasticizer, a colorant, and the like.

As the catalyst, various urethane catalysts, isocyanurate catalysts, etc., known in the art can be used. A urethane catalyst and an isocyanurate catalyst may be used in combination.

Examples of urethane catalysts include triethylenediamine, N,N-dimethylcyclohexylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'',N''-pentamethyldiethylenetriamine, N,N,N',N'',N''',N''-hexamethyltriethylenetetramine, bis(dimethylaminoethyl)ether, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, 2,4,6-tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, N-dimethylaminoethyl-N'-methylpiperazine, N,N,N',N'-tetramethylhexamethylenediamine, 1, Examples of the urethane catalyst include amine compounds such as 2-dimethylimidazole, 1-isobutyl-2-methylimidazole, N,N-dimethylaminopropylamine, and bis(dimethylaminopropyl)amine, and alkanolamines such as N,N-dimethylaminoethanol, N,N,N'-trimethylaminoethylethanolamine, 2-(2-dimethylaminoethoxy)ethanol, N,N,N'-trimethyl-N'-hydroxyethylbisaminoethylether, N-(3-dimethylaminopropyl)-N,N-diisopropanolamine, N-(2-hydroxyethyl)-N'-methylpiperazine, N,N-dimethylaminohexanol, and 5-dimethylamino-3-methyl-1-pentanol. These urethane catalysts may be used alone or in combination.

Examples of isocyanurate catalysts include quaternary ammonium salts, alkali metal salts of carboxylic acids having 2 to 12 carbon atoms, alkali metal salts of acetylacetone, salicylaldehyde, etc., Lewis acid complex salts of amines, metal catalysts, etc. These isocyanurate catalysts may be used alone or in combination.

The amount (content) of the catalyst may be 0.1 to 20 parts by mass based on 100 parts by mass of the total amount of polyol and polyisocyanate.

As the flame retardant, a known flame retardant can be used. Specific examples of flame retardants include phosphate esters such as tris(chloropropyl)phosphate, and organophosphazenes such as methoxyphenoxycyclophosphazene.

The amount (content) of the flame retardant may be 0 to 100 parts by mass based on 100 parts by mass of the total amount of polyol and polyisocyanate.

The foaming agent is, for example, water. Water generates carbon dioxide gas by reacting with isocyanate groups, which causes foaming. In addition to water, which is a chemical foaming agent, a physical foaming agent can also be used. As the physical foaming agent, conventionally known ones such as hydrocarbon compounds, HFCs, HFOs, and HCFOs can be used. These physical foaming agents may be used alone or in combination. From the viewpoint that the global warming potential of the foaming agent itself is likely to be low, and that high insulation performance (initial and long-term insulation properties) is likely to be obtained, it is particularly preferable to use at least one selected from the group consisting of HFOs and HCFOs in combination with water.

The amount of the chemical foaming agent may be 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the polyol and polyisocyanate. The amount of the physical foaming agent may be 1 to 80 parts by mass based on 100 parts by mass of the total amount of the polyol and polyisocyanate.

As the foam stabilizer, a foam stabilizer known in the art (e.g., a foam stabilizer for forming rigid polyurethane foam) can be used. The foam stabilizer is, for example, a surfactant, and may be a nonionic surfactant such as an organic silicone surfactant. One type of foam stabilizer may be used alone, or multiple types may be used in combination.

Commercially available products can also be used as foam stabilizers. Examples of commercially available products include L5420, L5340, L6188, L6877, L6889, L6900, L6866, L6643, and L6978 manufactured by Momentive Corporation; B8040, B8155, B8239, B8244, B8330, B8443, B8450, B8460, B8462, B8465, B8466, B8467, B8481, B8484, B8485, B8486, B8496, B8870, and B8871 manufactured by Evonik; SZ-1328, SZ-1642, SZ-1677, and SH-193 manufactured by Dow-Toray; and DC-193 and DC5598 manufactured by Air Products.

The amount of foam stabilizer may be 0.1 to 5.0 parts by mass based on 100 parts by mass of the total amount of polyol and polyisocyanate.

The contents of this disclosure will be explained in more detail below using examples and comparative examples, but this disclosure is not limited to the following examples.

[ ¹ H and ³¹ P ( ¹ H)-NMR Measurements]
For the measurements of ¹ H and ³¹ P ( ¹ H)-NMR, AVANCE III HD 400 (400 MHz; manufactured by BRUKER) and AVANCE III 400 (400 MHz; manufactured by BRUKER) were used. For ¹ H and ³¹ P ( ¹ H)-NMR, deuterated chloroform (CDCl ₃ ) was used as the measurement solvent, for ¹ H-NMR, tetramethylsilane (TMS) was used as the internal standard, and for ³¹ P ( ¹ H)-NMR, 85% phosphoric acid was used as the external standard. Commercially available reagents were used.

[TG/DTA Measurement]
The thermal decomposition temperature was measured by thermogravimetric analysis in a dry air atmosphere using a thermogravimetric analyzer (Hitachi High-Technologies, TG/DTA-6200). The powdered compound (approximately 5 mg) was used as a sample, and the measurement was performed in the temperature range from 30°C to 1000°C at a heating rate of 10°C min ^-1 .

ピリジン（５００ｍＬ）に窒化塩化リン三量体（４５．０ｇ，０．１３ｍｏｌ）を溶解させ、０℃に冷却した。同温にて、この溶液に３－クロロプロパン－１，２－ジオール（８６．０ｇ，０．７８ｍｏｌ）を加えた。得られた溶液を室温で２４時間攪拌した後、反応溶液中の低沸分を減圧留去し、得られた残渣に１Ｍの塩酸を加えた。この溶液からクロロホルムを用いて有機層を抽出した。有機層から溶媒を留去した後、ヘキサンを加え、生じた粘稠固体を真空乾燥することにより、無色固体として、上記式（Ｉ）で表される環状ホスファゼン化合物（Ｉ）を得た。収量は４８．７ｇであり、収率は８１％であった。^１Ｈ及び^３１Ｐ（^１Ｈ）－ＮＭＲ、並びに、５％重量減少温度（Ｔｄ５）を以下に示す。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ３．６６（ｍ，３Ｈ），３．７７（ｍ，３Ｈ），４．２８（ｍ，３Ｈ），４．５０（ｍ，３Ｈ），４．７４（ｍ，３Ｈ）．
^３１Ｐ（^１Ｈ）－ＮＭＲ（ＣＤＣｌ_３）：δ３６．１．
Ｔｄ５＝２８０℃ <Synthesis Example 1>

Phosphorus nitrile chloride trimer (45.0 g, 0.13 mol) was dissolved in pyridine (500 mL) and cooled to 0° C. At the same temperature, 3-chloropropane-1,2-diol (86.0 g, 0.78 mol) was added to this solution. The resulting solution was stirred at room temperature for 24 hours, and then low boiling points in the reaction solution were distilled off under reduced pressure, and 1M hydrochloric acid was added to the resulting residue. An organic layer was extracted from this solution using chloroform. After the solvent was distilled off from the organic layer, hexane was added, and the resulting viscous solid was dried in vacuum to obtain a cyclic phosphazene compound (I) represented by the above formula (I) as a colorless solid. The yield was 48.7 g, and the yield was 81%. ¹ H and ³¹ P ( ¹ H)-NMR and the 5% weight loss temperature (Td5) are shown below.
¹ H-NMR (CDCl ₃ ): δ 3.66 (m, 3H), 3.77 (m, 3H), 4.28 (m, 3H), 4.50 (m, 3H), 4.74 (m, 3H).
^31P ( ¹ H)-NMR(CDCl ₃ ): δ 36.1.
Td5=280° C.

窒化塩化リン三量体の使用量を６０．０ｇ（０．１７ｍｏｌ）に変更し、ピリジンの使用量を４００ｍＬに変更したこと、及び、３－クロロプロパン－１，２－ジオールに代えて１，２－プロパンジオール（５９．０ｇ，０．７７ｍｏｌ）を使用したこと以外は合成例１と同様の操作を行い、結晶質の固体として、上記式（ＩＩ）で表される環状ホスファゼン化合物（ＩＩ）を得た。収量は５６．６ｇであり、収率は９２％であった。^１Ｈ及び^３１Ｐ（^１Ｈ）－ＮＭＲ、並びに、５％重量減少温度（Ｔｄ５）を以下に示す。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ１．４３（ｂｒｄ，Ｊ＝６．２Ｈｚ，９Ｈ），３．９５（ｍ，３Ｈ），４．３８（ｍ，３Ｈ），４．７６（ｍ，３Ｈ）
^３１Ｐ－ＮＭＲ（ＣＤＣｌ_３）：δ３５．２．
Ｔｄ５＝２４０℃ <Synthesis Example 2>

The same procedure as in Synthesis Example 1 was carried out except that the amount of phosphorus nitrile chloride trimer was changed to 60.0 g (0.17 mol), the amount of pyridine was changed to 400 mL, and 1,2-propanediol (59.0 g, 0.77 mol) was used instead of 3-chloropropane-1,2-diol, to obtain a cyclic phosphazene compound (II) represented by the above formula (II) as a crystalline solid. The yield was 56.6 g, which was 92%. ^{The 1} H and ³¹ P( ¹ H)-NMR spectra and the 5% weight loss temperature (Td5) are shown below.
^1H -NMR ( _CDCl3 ): δ 1.43 (brd, J = 6.2 Hz, 9H), 3.95 (m, 3H), 4.38 (m, 3H), 4.76 (m, 3H)
^31P -NMR( _CDCl3 ): δ 35.2.
Td5=240° C.

窒化塩化リン三量体の使用量を３２．０ｇ（０．０９２ｍｏｌ）に変更し、ピリジンの使用量を４００ｍｌに変更したこと、３－クロロプロパン－１，２－ジオールに代えてＤＬ－１，４－ジクロロ－２，３－ブタンジオール（５１ｇ，０．３２ｍｏｌ）を使用したこと、及び撹拌時間を７２時間に変更したこと以外は合成例１と同様の操作を行い、非晶質な無色固体として、上記式（ＩＩＩ）で表される環状ホスファゼン化合物（ＩＩＩ）を得た。収量は４９ｇであり、収率は８７％であった。^１Ｈ及び^３１Ｐ（^１Ｈ）－ＮＭＲ、並びに、５％重量減少温度（Ｔｄ５）を以下に示す。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ３．７７（ｍ，１２Ｈ），４．６３（ｍ，６Ｈ）．
^３１Ｐ（^１Ｈ）－ＮＭＲ（ＣＤＣｌ_３）：δ３４．９．
Ｔｄ５＝２６０℃ <Synthesis Example 3>

The same operations as in Synthesis Example 1 were carried out except that the amount of phosphorus nitrile chloride trimer was changed to 32.0 g (0.092 mol), the amount of pyridine was changed to 400 ml, DL-1,4-dichloro-2,3-butanediol (51 g, 0.32 mol) was used instead of 3-chloropropane-1,2-diol, and the stirring time was changed to 72 hours, to obtain a cyclic phosphazene compound (III) represented by the above formula (III) as an amorphous colorless solid. The yield was 49 g, and the yield was 87%. ¹ H and ³¹ P( ¹ H)-NMR and the 5% weight loss temperature (Td5) are shown below.
¹ H-NMR (CDCl ₃ ): δ 3.77 (m, 12H), 4.63 (m, 6H).
^31P ( ¹ H)-NMR(CDCl ₃ ): δ 34.9.
Td5=260° C.

窒化塩化リン三量体の使用量を５０ｇ(０．１４ｍｏｌ）に変更し、ピリジンの使用量を４００ｍｌに変更したこと、３－クロロプロパン－１，２－ジオールに代えて１，２－ヘキサンジオール（７６ｇ，０．６５ｍｏｌ）を使用したこと、及び撹拌時間を１６時間に変更したこと以外は合成例１と同様の操作を行い、無色粘性液体として、上記式（ＩＶ）で表される環状ホスファゼン化合物（ＩＶ）を得た。収量は６２ｇであり、収率は８９％であった。^１Ｈ及び^３１Ｐ（^１Ｈ）－ＮＭＲ、並びに、５％重量減少温度（Ｔｄ５）を以下に示す。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ０．９０（ｂｒｄ，９Ｈ），１．２５－１．４９（ｍ，１２Ｈ），１．５９（ｂｒｄ，３Ｈ），１．８１（ｂｒｄ，３Ｈ），３．９６（ｍ，３Ｈ），４．３６（ｍ，３Ｈ），４．５９（ｍ，３Ｈ）．
^３１Ｐ（^１Ｈ）－ＮＭＲ（ＣＤＣｌ_３）：δ３５．３．
Ｔｄ５＝１４０℃ <Synthesis Example 4>

The same operations as in Synthesis Example 1 were carried out except that the amount of phosphorus nitrile chloride trimer was changed to 50 g (0.14 mol), the amount of pyridine was changed to 400 ml, 1,2-hexanediol (76 g, 0.65 mol) was used instead of 3-chloropropane-1,2-diol, and the stirring time was changed to 16 hours, to obtain a cyclic phosphazene compound (IV) represented by the above formula (IV) as a colorless viscous liquid. The yield was 62 g, and the yield was 89%. ^{The 1} H and ³¹ P( ¹ H)-NMR and the 5% weight loss temperature (Td5) are shown below.
^1H -NMR ( _CDCl3 ): δ 0.90 (brd, 9H), 1.25-1.49 (m, 12H), 1.59 (brd, 3H), 1.81 (brd, 3H), 3.96 (m, 3H), 4.36 (m, 3H), 4.59 (m, 3H).
^31P ( ¹ H)-NMR(CDCl ₃ ): δ 35.3.
Td5=140° C.

窒化塩化リン三量体の使用量を０．７ｇ(２．０ｍｍｏｌ）に変更し、ピリジンの使用量を５ｍｌに変更したこと、３－クロロプロパン－１，２－ジオールに代えて２－クロロエタノール（１．１ｇ，１４．１ｍｍｏｌ）を使用したこと、及び撹拌時間を１６時間に変更したこと以外は合成例１と同様の操作を行い、無色粘性液体として、上記式（Ｖ）で表される環状ホスファゼン化合物（Ｖ）を得た。収量は１．１ｇであり、収率は９０％であった。^１Ｈ及び^３１Ｐ（^１Ｈ）－ＮＭＲを以下に示す。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ３．７４（ｍ，１２Ｈ），４．２３（ｍ，６Ｈ），４．３７（ｍ，６Ｈ）．
^３１Ｐ（^１Ｈ）－ＮＭＲ（ＣＤＣｌ_３）：δ１７．３． <Synthesis Example 5>

The same operations as in Synthesis Example 1 were carried out except that the amount of phosphorus nitrile chloride trimer was changed to 0.7 g (2.0 mmol), the amount of pyridine was changed to 5 ml, 2-chloroethanol (1.1 g, 14.1 mmol) was used instead of 3-chloropropane-1,2-diol, and the stirring time was changed to 16 hours, to obtain a cyclic phosphazene compound (V) represented by the above formula (V) as a colorless viscous liquid. The yield was 1.1 g, and the yield was 90%. ¹ H and ³¹ P( ¹ H)-NMR are shown below.
¹ H-NMR (CDCl ₃ ): δ 3.74 (m, 12H), 4.23 (m, 6H), 4.37 (m, 6H).
^31P ( ¹ H)-NMR(CDCl ₃ ): δ 17.3.

<Preparation Example 1>
In a 300 mL separable flask, polyol a and polyol b were added, and then the cyclic phosphazene compound (I) synthesized in the above Synthesis Example 1 was added, and the mixture was stirred at 300 rpm for 30 minutes while adjusting the temperature in the system to 70° C. As a result, a mixed liquid in which the cyclic phosphazene compound (I) was dissolved in the polyol (mixture of polyol a and polyol b) was obtained. Next, the liquid temperature of the obtained mixed liquid was cooled to 30° C. or less, and then a foam stabilizer, a urethane catalyst, a trimerization catalyst, and water were added to the mixed liquid, and the mixture was stirred at 300 rpm for 5 minutes while maintaining the liquid temperature at 15° C. to 30° C. As a result, a polyol composition (1) was obtained. The blending amounts of each component are as shown in Table 1, and the details of the polyol a, polyol b, foam stabilizer, and catalyst used are as follows. The blending amounts shown in Table 1 are parts by mass.
Polyol a: Maximol RFK-505 (manufactured by Air Water Performance Chemicals, phthalic acid-based polyester polyol, hydroxyl value 250 mg KOH/g)
Polyol b: Maximol RFK-556 (manufactured by Air Water Performance Chemicals, phthalic acid-based polyester polyol, hydroxyl value 250 mg KOH/g)
Foam stabilizer: VORASURF SH-193 fluid (manufactured by Dow Toray Industries, Inc.)
Urethane catalyst: DM70 (manufactured by Tosoh Corporation, imidazole catalyst)
Trimerization catalyst: TOYOCAT TRX (manufactured by Tosoh Corporation, quaternary ammonium salt)

<Preparation Example 2>
A polyol composition (2) was obtained in the same manner as in Preparation Example 1, except that the amounts of each component were changed as shown in Table 1.

<Preparation Example 3>
Polyol a, polyol b, a foam stabilizer, a urethanization catalyst, a trimerization catalyst, and water were added to a 300 mL separable flask, and the mixture was stirred at 300 rpm for 5 minutes while maintaining the liquid temperature at 15° C. to 30° C. Thus, polyol composition (3) was obtained. The blending amounts of each component are as shown in Table 1, and the details of polyol a, polyol b, foam stabilizer, and catalyst used are the same as those in Preparation Example 1.

<Preparation Example 4>
A polyol composition (4) was obtained in the same manner as in Preparation Example 1, except that the cyclic phosphazene compound (II) was used instead of the cyclic phosphazene compound (I). The cyclic phosphazene compound (II) was not dissolved in the polyol, and the polyol composition (4) was obtained as a suspension in which the cyclic phosphazene compound (II) was dispersed.

<Preparation Examples 5 to 7>
Polyol compositions (5), (6), and (7) were obtained in the same manner as in Preparation Example 1, except that the cyclic phosphazene compound (III), (IV), or (V) was used instead of the cyclic phosphazene compound (I), respectively.

Example 1
(Formation of Rigid Polyurethane Foam)
First, an aluminum mold (mold inner dimensions: height 250 mm, width 250 mm, thickness 50 mm) equipped with a lid was adjusted in a 60 ° C. thermostatic chamber. Next, the polyol composition (1) obtained in Preparation Example 1 and HFO-1233zd (Solstice LBA, manufactured by Honeywell) as a physical foaming agent were mixed in the mass ratio shown in Table 2. Next, the resulting mixed liquid was adjusted to 20 ° C. and poured into a 500 mL polypropylene cup, and a polyisocyanate (Millionate MR-200, Polymeric MDI manufactured by Tosoh Corporation, NCO content 31 mass%) separately adjusted to 20 ° C. was poured therein and mixed for 3 seconds at 6000 rpm using a laboratory mixer. At this time, the amount of polyisocyanate added was adjusted so that the isocyanate index was 200, and the content of the cyclic phosphazene compound (I) based on the total amount of the blended components was 5.0 mass%. Next, about 133 g (133±2 g) of the resulting mixture was poured into the mold, immediately covered, and heated in a 60° C. thermostatic chamber for 20 minutes to react, foam, and harden. This resulted in a rectangular rigid polyurethane foam. The resulting rigid polyurethane foam was removed from the mold immediately after the reaction was completed, and used for density and core density measurements, as well as thermal conductivity evaluation.

The mass and dimensions of the rigid polyurethane foam were measured immediately after demolding, and the foam density of the rigid polyurethane foam was calculated according to JIS A9521. Next, the skin layers on all six sides were immediately cut off to cut out a core panel from the center of the rigid polyurethane foam, and the mass and dimensions of the core panel were measured to calculate the core density. The results are shown in Table 2. The dimensions of the core panel were 200 mm x 200 mm x 14 mm.

<Examples 2 to 3 and Comparative Examples 1 to 4>
Except for using polyol composition (2), (3), (4), (5), (6) or (7) instead of polyol composition (1), polyurethane foams of Examples 2 to 3 and Comparative Examples 1 to 4 were obtained in the same manner as in Example 1. The content of cyclic phosphazene compound (I) based on the total amount of blended components in Example 2 was 3.0 mass%, and the content of cyclic phosphazene compounds (II) to (V) based on the total amount of blended components in Example 3 and Comparative Examples 2 to 4 was 5.0 mass%.

<Evaluation>
The amount of change in heat insulating performance over time was evaluated by measuring the thermal conductivity of the polyurethane foams obtained in Examples 1 to 3 and Comparative Examples 1 to 4 over time. Specifically, the thermal conductivity λ (initial value) of the core panel immediately after cutting and the thermal conductivity λ of the core panel after the storage test were measured at an average temperature of 23°C using an Auto λHC-074/314 manufactured by Eiko Seiki Co., Ltd., according to the heat flow meter method specified in JIS A1412. The storage test was performed by storing the core panel after the initial value measurement in a constant temperature and humidity room at 23°C/50% R.H. for 60 days. However, the polyurethane foam obtained in Comparative Example 2 showed a significant increase in thermal conductivity immediately after the storage test, so the test was terminated 12 days after the start of the storage test.

This test is an accelerated test based on the idea of scaling coefficients shown in JIS A1486, and the aging of the 14 mm thick core panel over 60 days corresponds to the aging of a 50 mm thick core panel over approximately 2 years. The results are shown in Table 2.

The content C _A in Table 2 is the content of the cyclic phosphazene compound (A) (cyclic phosphazene compound containing a structural unit represented by formula (1)) in the rigid polyurethane foam relative to 100 parts by mass of the polyurethane resin. The amount of the polyurethane resin in the rigid polyurethane foam was calculated by subtracting the "mass of carbon dioxide gas generated during the reaction of water and polyisocyanate" from the "total blended mass of polyol (polyol a and polyol b), polyisocyanate, and water."

Claims (9)

A resin additive comprising a cyclic phosphazene compound having a structural unit represented by the following formula (1):

[In formula (1), R ¹ represents an alkylene group having 2 to 8 carbon atoms or an arylene group having 6 to 18 carbon atoms in which at least one hydrogen atom is substituted with a chlorine atom, and * represents the bonding position to other structural units.] The resin additive according to claim 1 , wherein the cyclic phosphazene compound is a compound represented by the following formula (4):

[In formula (4), R ¹ has the same meaning as R ¹ in formula (1), and multiple R ¹ may be the same or different.] The resin additive according to claim 1 or 2, wherein the cyclic phosphazene compound has, as the R ¹ , at least one group selected from groups represented by the following formulas (c-1) to (c-6):

[In formulas (c-1) to (c-6), * indicates the bonding position with the oxygen atom.] The resin additive according to claim 3, wherein the cyclic phosphazene compound has, as the R ¹ , at least one group selected from the group represented by the formula (c-1) and the group represented by the formula (c-2). A composition comprising a resin or a raw material for a resin, and a cyclic phosphazene compound having a structural unit represented by the following formula (1):

[In formula (1), R ¹ represents an alkylene group having 2 to 8 carbon atoms or an arylene group having 6 to 18 carbon atoms in which at least one hydrogen atom is substituted with a chlorine atom, and * represents the bonding position to other structural units.] The composition according to claim 5, wherein the resin is a polyurethane resin, and the raw material of the resin is at least one of a polyol and a polyisocyanate. The composition according to claim 6, which is for forming a polyurethane foam. A resin foam comprising a resin and a cyclic phosphazene compound having a structural unit represented by the following formula (1):

[In formula (1), R ¹ represents an alkylene group having 2 to 8 carbon atoms or an arylene group having 6 to 18 carbon atoms in which at least one hydrogen atom is substituted with a chlorine atom, and * represents the bonding position to other structural units.] The resin foam according to claim 8, which is a polyurethane foam.