Cyclic phosphazene compound, additive for resin, composition, and resin foam

Abstract

To provide a cyclic phosphazene compound usable as an additive for resin.SOLUTION: Specifically, there is presented, for example, a cyclic phosphazene compound (I) synthesized as follows.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a cyclic phosphazene compound, a resin additive, a composition, and a resin foam. [Background technology]

[0002] Resin foams such as rigid polyurethane foams are widely used as insulation materials for refrigerators, freezer warehouses, building materials, spray applications, etc., because of their excellent insulation performance, dimensional stability, workability, etc. However, resin foams have the problem that their thermal conductivity increases continuously (i.e., their insulation performance decreases over time).

[0003] In response to this, for example, Patent Document 1 discloses a method for suppressing deterioration of the insulating performance over time by adjusting and controlling 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 volume of the foam due to the expansion of the outer and central layers, thereby adjusting the aspect / width ratio of the cell shape. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2007-332203 A [Non-patent literature]

[0005] [Non-Patent Document 1] Z. Anorg. Allg. Chem., Vol. 425, No. 127, 1976 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the method of Patent Document 1 is not practical because of the problems of complicated work processes and the associated increase in production costs. Therefore, it is desirable to develop a more practical method that can suppress the deterioration of the thermal insulation performance of the resin over time.

[0007] In view of the above, an object of the present disclosure is to provide a resin additive capable of suppressing deterioration of the heat insulating performance of the resin over time. Other objects of the present disclosure are to provide a cyclic phosphazene compound usable as the resin additive as described above, and a composition and a resin foam containing the cyclic phosphazene compound. [Means for solving the problem]

[0008] The inventors of the present disclosure have 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 have thus completed the invention of the present disclosure.

[0009] Some aspects of the present disclosure provide the following [1] to

[10] .

[0010] [1] A cyclic phosphazene compound comprising a structural unit represented by the following formula (1): [ka] [In formula (1), R 1 represents any one of the groups represented by the following formulas (b-1) to (b-6), and * represents the bonding position to other structural units.] [ka] [In the formulas (b-1) to (b-6), * indicates the bonding position with the oxygen atom.]

[0011] [2] The cyclic phosphazene compound according to [1], which is a compound represented by the following formula (4): [ka] [In formula (4), R 1 is R in the formula (1). 1 Synonymous with R 1 may be the same or different.

[0012] [3] R 1 The cyclic phosphazene compound according to [1] or [2], wherein the cyclic phosphazene compound has at least one group selected from the groups represented by the formulae (b-1) and (b-5) as the ring unit.

[0013] [4] A resin additive comprising the cyclic phosphazene compound according to any one of [1] to [3].

[0014] [5] The resin additive according to [4], which is a thermal conductivity modifier.

[0015] [6] A composition comprising a resin or a raw material for a resin, and the cyclic phosphazene compound according to any one of [1] to [3].

[0016] [7] The composition according to [6], wherein the resin is a polyurethane resin, and a raw material of the resin is at least one of a polyol and a polyisocyanate.

[0017] [8] The composition according to [7], which is for forming a polyurethane foam.

[0018] [9] A resin foam comprising a resin and the cyclic phosphazene compound according to any one of [1] to [3].

[0019]

[10] The resin foam according to [9], which is a polyurethane foam. Effect of the Invention

[0020] According to one aspect of the present disclosure, it is possible to provide a resin additive capable of suppressing deterioration of the heat insulating performance of a resin over time. Also, according to other aspects of the present disclosure, it is possible to provide a cyclic phosphazene compound usable as the resin additive as described above, and a composition and a resin foam containing the cyclic phosphazene compound. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] In this specification, a numerical range indicated using "~" indicates a range including the numerical values ​​described before and after "~" as the minimum and maximum values, respectively. In addition, unless specifically stated otherwise, the units of the numerical values ​​described before and after "~" are the same. In the numerical ranges described in stages in this specification, the upper limit or lower limit of a certain numerical range may be replaced with the upper limit or lower limit of a numerical range of another stage. In addition, in the numerical ranges described in this specification, the upper limit or lower limit of the numerical range may be replaced with a value shown in the examples. In addition, the upper limit and lower limit values ​​described individually can be combined arbitrarily.

[0022] Preferred embodiments of the present disclosure will be described below, however, the present disclosure is not limited to the following embodiments.

[0023] <Cyclic phosphazene compounds> The cyclic phosphazene compound of one embodiment 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)". [ka]

[0024] In formula (1), R 1 represents any one of the groups represented by the following formulas (b-1) to (b-6), and * represents the bonding position to other structural units. [ka]

[0025] In the formulae (b-1) to (b-6), * indicates the bonding position with the oxygen atom.

[0026] 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 containing [-P=N-]. The ring structure of the cyclic phosphazene compound can be expressed as [-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.

[0027] In this embodiment, the structural unit represented by formula (1) is bonded to other structural units to form a ring structure of a cyclic phosphazene compound (A) (a ring structure consisting of repetitions of [-P=N-]).

[0028] The cyclic phosphazene compound (A) has a function of suppressing the deterioration of the heat insulating performance of the resin over time. That is, the cyclic phosphazene compound (A) can suppress the deterioration of the heat insulating performance of the resin over time. This effect tends to be remarkable when the cyclic phosphazene compound (A) is added to a resin foam.

[0029] The cyclic phosphazene compound (A) is R 1 As R in formula (1), it is preferable that R has at least one group selected from the group represented by formula (b-1) (3-bromopropane-1,2-diyl group) and the group represented by formula (b-5) (4-bromobenzene-1,2-diyl group), and it is more preferable that R has a group represented by formula (b-1). 1 are preferably a group represented by formula (b-1) or a group represented by formula (b-5), and R 1 It is more preferable that all of the above are groups represented by formula (b-1).

[0030] The number of structural units 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, a plurality of R 1 may be the same or different from each other.

[0031] The cyclic phosphazene compound (A) may be composed only of the 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). [ka]

[0032] R in Equation (2) 2 indicates a divalent hydrocarbon group, and * indicates a bonding position with another structural unit. The divalent hydrocarbon group may be an alkylene group (alkanediyl group) or an arylene group (arenediyl group). 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.

[0033] R 2 The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is, for example, 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.

[0034] R 2The arylene group may be monocyclic or polycyclic. The number of carbon atoms in the arylene group is, for example, 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.

[0035] The number of structural units represented by formula (2) may be 0-4, or may be 0-2.

[0036] The cyclic phosphazene compound (A) may be, for example, a compound represented by the following formula (3). [ka]

[0037] In formula (3), R 1 is R in formula (1). 1 is synonymous with R 2 is R in Eq. (2). 2 Synonymous with R. 1 If there are multiple R 1 may be the same or different. Similarly, R 2 If there are multiple R 2 may be the same or different from each other.

[0038] m represents an integer of 1 to 5, and n represents an integer of 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.

[0039] The cyclic phosphazene compound (A) may be, for example, a compound represented by the following formula (4). [ka]

[0040] In formula (4), R 1 is R in formula (1). 1 Synonyms: Multiple R 1may be the same or different from each other.

[0041] The compound represented by formula (4) includes all of the various possible stereoisomers. For example, when the cyclic phosphazene compound (A) is a compound represented by the following formula (5), a 5-membered ring consisting of two oxygen atoms, a group bonded thereto, and a phosphorus atom 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). [ka] [ka]

[0042] R in formula (5) and formulas (5-1) to (5-6) a1 , R a2 , R a3 and R a4 represents, for example, a hydrogen atom or a bromomethyl group. 1 In the case where all of R a1 , R a2 and R a3 is a hydrogen atom, and R a4 is a bromomethyl group.

[0043] 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 (PXN)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, when R 1 (OH)2(R 1 is R in formula (1). 1 The cyclic phosphazene compound (A) can be obtained by using the compound represented by the formula (I) below.

[0044] As an alcohol compound, R 2 (OH)2(R 2 is R in Eq. (2). 2 It is also possible to use a compound represented by the formula (1). When these compounds are used, a cyclic phosphazene compound (A) further containing a structural unit represented by the formula (2) is obtained.

[0045] <Resin additives> The resin additive of one embodiment includes a cyclic phosphazene compound (A). The resin additive of this embodiment has a function of suppressing the deterioration of the heat insulating performance of the resin over time, so it can be called a thermal conductivity modifier for resin (or an agent for suppressing the deterioration of the heat 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 heat insulating performance of the resin over time, it is not necessarily used for the purpose of suppressing the deterioration of the heat insulating performance of the resin over time.

[0046] The resin additive may contain components other than the cyclic phosphazene compound (A) (for example, components that may be inevitably mixed in during the production process of the cyclic phosphazene compound (A)), or may consist only of the cyclic phosphazene compound (A).

[0047] <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).

[0048] Examples of the resin contained in the composition include polyurethane resin, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polyimide resin, phenol resin, etc. Examples of the raw material of the resin contained in the composition include raw materials of polyurethane resin such as polyol and polyisocyanate, raw materials of phenol resin such as phenol and cresol, etc.

[0049] 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.

[0050] The composition preferably contains at least one of a polyurethane resin, or a polyol and a polyisocyanate. These compositions are preferably compositions constituting polyurethane foams described below, or compositions for forming polyurethane foams (polyurethane foam-forming compositions).

[0051] 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 relative to 100 parts by mass of the polyurethane resin. When the content is 0.5 parts by mass or more, the deterioration of the heat insulating performance of the resin over time tends to be suppressed, and when the content is 15 parts by mass or less, the deterioration of the heat insulating performance of the resin over time tends to 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 relative to 100 parts by mass of the polyurethane resin.

[0052] When the composition contains polyol, the content of the cyclic phosphazene compound (A) may be, for example, 1 to 50 parts by mass relative to 100 parts by mass of polyol. When the content is 1 part by mass or more, the deterioration of the heat insulating performance of the resin over time tends to be suppressed, and when the content is 50 parts by mass or less, the deterioration of the heat insulating performance of the resin over time tends to 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, and may be 30 parts by mass or less or 20 parts by mass or less relative to 100 parts by mass of polyol.

[0053] The composition may further contain other components other than the above resin, the raw material of the resin, and the cyclic phosphazene compound (A). The other components may be known components used in resin foams or materials for forming resin foams. That is, the composition may be a resin foam or a material for forming resin foams. Specific examples of the other components include catalysts, flame retardants, foaming agents, foam stabilizers, plasticizers, colorants, etc.

[0054] The composition is suitable for use as a thermal insulation material or as a material for forming a thermal insulation material.

[0055] <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.

[0056] 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 suitably used, for example, as a heat insulating material or a material for forming a heat insulating material.

[0057] 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 due to the cyclic phosphazene compound (A). Hereinafter, a resin foam containing a polyurethane resin as a constituent resin is referred to as a polyurethane foam.

[0058] <Polyurethane foam> The polyurethane foam of one embodiment contains 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 is, for example, 25 to 60 kg / m 3 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 / m 3 It may be.

[0059] Polyurethane foams are suitably used as insulating materials for, for example, roofs and walls of buildings, underground structures, bridge decks, water tanks, tanks, the inside of housings such as refrigerators, and the like.

[0060] 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 (polyol composition) containing a polyol and not containing a polyisocyanate, the polyurethane foam is formed by mixing the polyurethane foam-forming composition (polyol composition) with a polyisocyanate or a composition (polyisocyanate composition) containing a polyisocyanate and reacting (foaming and curing). When the polyurethane foam-forming composition is a composition (polyisocyanate composition) containing a polyisocyanate and not containing a polyol, the polyurethane foam is formed by mixing the polyurethane foam-forming composition (polyisocyanate composition) with a polyol or a composition (polyol composition) containing a polyol and reacting (foaming and curing).

[0061] The polyurethane foam-forming composition containing a polyol and a polyisocyanate may be a one-liquid composition or a multi-liquid composition composed of two or more liquids. The multi-liquid composition may be, for example, a two-liquid composition independently comprising 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.

[0062] Among the above examples, when the cyclic phosphazene compound (A) is contained in a polyol composition, i.e., when the polyurethane foam-forming composition is a polyol composition or a two-component composition comprising 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.

[0063] 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 group / active hydrogen group 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.

[0064] The reaction (foaming and curing) may be carried out by a conventionally known method, for example, by heating in a mold.

[0065] 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.

[0066] [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.

[0067] 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, the 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.

[0068] The polyfunctional alcohol is preferably a low molecular weight polyol having a molecular weight of 500 or less. Examples of the polyfunctional alcohol 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.

[0069] As the aromatic polyester polyol, from the viewpoint of easily obtaining higher heat insulating performance (initial and long-term heat insulating properties), 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.

[0070] From the viewpoint of easily obtaining 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. The number average molecular weight of the polyol is a polystyrene-equivalent number average molecular weight measured by gel permeation chromatography (GPC).

[0071] 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 easily obtaining higher heat insulating performance (initial and long-term heat insulating properties). The hydroxyl value is a value measured in accordance with JIS K1557-1.

[0072] [Polyisocyanate] Polyisocyanates are compounds 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.

[0073] [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.

[0074] As the catalyst, various urethanization catalysts, isocyanurate catalysts, etc. known in the art can be used. The urethanization catalyst and the isocyanurate catalyst may be used in combination.

[0075] Examples of the urethanization catalyst 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.

[0076] Examples of the isocyanurate catalyst 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 of two or more kinds.

[0077] The amount (content) of the catalyst may be 0.1 to 20 parts by mass based on 100 parts by mass, which is the total amount of the polyol and the polyisocyanate.

[0078] As the flame retardant, a known flame retardant can be used, and specific examples of the flame retardant include phosphoric esters such as tris(chloropropyl)phosphate, and organophosphazenes such as methoxyphenoxycyclophosphazene.

[0079] The blending amount (content) of the flame retardant may be 0 to 100 parts by mass based on 100 parts by mass, which is the total amount of the polyol and the polyisocyanate.

[0080] 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, a conventionally known one such as a hydrocarbon compound, HFCs, HFOs, or HCFOs can be used. These physical foaming agents may be used alone or in combination of two or more. From the viewpoint of easily reducing the global warming potential of the foaming agent itself and easily obtaining high heat insulating performance (initial and long-term heat insulating properties), it is particularly preferable to use at least one selected from the group consisting of HFOs and HCFOs in combination with water.

[0081] 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 the polyisocyanate, and 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 the polyisocyanate.

[0082] As the foam stabilizer, a foam stabilizer known in the art (e.g., a foam stabilizer for forming a 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. The foam stabilizer may be used alone or in combination of two or more kinds.

[0083] As the foam stabilizer, a commercially available product can also be used. 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.

[0084] The blending amount of the foam stabilizer may be 0.1 to 5.0 parts by mass based on 100 parts by mass of the total amount of the polyol and the polyisocyanate. EXAMPLES

[0085] The contents of the present disclosure will be described in more detail below using examples and comparative examples, but the present disclosure is not limited to the following examples.

[0086] [ 1 H and 31 P( 1 H)-NMR measurement] 1 H and 31 P( 1 H-NMR measurements were performed using AVANCE III HD 400 (400 MHz; manufactured by BRUKER) and AVANCE III 400 (400 MHz; manufactured by BRUKER). 1 H and 31 P( 1 H-NMR was performed using deuterated chloroform (CDCl3) as the measurement solvent. 1 H-NMR was performed using tetramethylsilane (TMS) as an internal standard. 31 P( 1 H-NMR was measured using 85% phosphoric acid as an external standard. Commercially available reagents were used.

[0087] [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 sample was a powdered compound (approximately 5 mg), and the temperature range was 30°C to 1000°C, with a heating rate of 10°C min -1 Measurements were performed.

[0088] <Synthesis Example 1> [ka] Phosphorus nitrile chloride trimer (35 g, 0.10 mol) was dissolved in pyridine (300 mL) and cooled to 0°C. 3-Bromopropane-1,2-diol (70 g, 0.45 mol) was added to this solution at the same temperature. The resulting solution was stirred at room temperature for 12 hours, and then low boiling points in the reaction solution were distilled off under reduced pressure, and 1 M hydrochloric acid was added to the resulting residue. An organic layer was extracted from this solution using chloroform. The solvent was distilled off from the organic layer, and the layer was dried in vacuum to obtain a cyclic phosphazene compound (I) represented by the above formula (I) as an amorphous colorless solid. The yield was 43 g, which was 72%. 1 H and 31 P( 1 The H-NMR and 5% weight loss temperature (Td5) are shown below. 1 H-NMR (CDCl3): δ3.48(m,3H),3.61(m,3H),4.25(m,3H),4.52(m,3H),4.77(m,3H). 31 P( 1 H)-NMR(CDCl3): δ 36.2. Td5=260℃

[0089] <Synthesis Example 2> [ka] Phosphorus nitrile chloride trimer (0.52 g, 1.50 mmol) and 4-bromocatechol (0.88 g, 4.65 mmol) were dissolved in tetrahydrofuran (10 mL) and cooled to 0°C. At the same temperature, 1,8-diazabicyclo[5.4.0]undec-7-ene (1.4 g, 9.29 mmol) was added dropwise to this solution. The resulting solution was stirred at room temperature for 16 hours, and the resulting precipitate was filtered off. Then, 1M ammonium chloride aqueous solution was added to the resulting filtrate. The organic layer was extracted from this solution using chloroform, the solvent was distilled off, and the residue was dried in vacuum to obtain a cyclic phosphazene compound (II) represented by the above formula (II) as an amorphous colorless solid. The yield was 0.86 g, which was 82%. 1 H and 31 P( 1 The H-NMR and 5% weight loss temperature (Td5) are shown below. 1 H-NMR (CDCl3): δ7.00(d,J=8.6Hz,3H),7.20(d,J=8.6Hz,3H),7.27(s,3H). 31 P( 1 H)-NMR(CDCl3): δ 33.6. Td5=300℃

[0090] <Synthesis Example 3> [ka] The same operation 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, 1,2-propanediol (59.0 g, 0.77 mol) was used instead of 3-bromopropane-1,2-diol, and the stirring time was changed to 24 hours, and a cyclic phosphazene compound (III) represented by the above formula (III) was obtained as a crystalline solid. The yield was 56.6 g, and the yield was 92%. 1 H and 31 P( 1 The H-NMR and 5% weight loss temperature (Td5) are shown below. 1H-NMR (CDCl3): δ1.43(brd,J=6.2Hz,9H),3.95(m,3H),4.38(m,3H),4.76(m,3H). 31 P-NMR(CDCl3): δ 35.2. Td5=240℃

[0091] <Synthesis Example 4> [ka] 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-bromopropane-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%. 1 H and 31 P( 1 The H-NMR and 5% weight loss temperature (Td5) are shown below. 1 H-NMR (CDCl3): 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). 31 P( 1 H)-NMR(CDCl3): δ 35.3. Td5=140℃

[0092] <Preparation Example 1> After polyol a and polyol b were put into a 300 mL separable flask, the cyclic phosphazene compound (I) synthesized in the above Synthesis Example 1 was put in, 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 amount of each component is as shown in Table 1, and the details of the polyol a, polyol b, foam stabilizer, and catalyst used are as follows. The unit of blending amount shown in Table 1 is parts by mass. Polyol a: Maximol RFK-505 (Air Water Performance Chemicals, phthalate-based polyester polyol, hydroxyl value 250 mg KOH / g) Polyol b: Maximol RFK-556 (Air Water Performance Chemicals, phthalate-based polyester polyol, hydroxyl value 250 mg KOH / g) Foam stabilizer: VORASURF SH-193 fluid (manufactured by Dow Toray Industries, Inc.) Urethane catalyst: DM70 (Tosoh Corporation, imidazole catalyst) ·Trimerization catalyst: TOYOCAT TRX (Tosoh Corporation, quaternary ammonium salt)

[0093] <Preparation Example 2> In a 300 mL separable flask, polyol a, polyol b, a foam stabilizer, a urethane catalyst, a trimerization catalyst, and water were added, and the mixture was stirred at 300 rpm for 5 minutes while maintaining the liquid temperature at 15°C to 30°C. This resulted in a polyol composition (2). 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.

[0094] <Preparation Example 3> A polyol composition (3) was obtained in the same manner as in Preparation Example 1, except that a cyclic phosphazene compound (III) was used instead of the cyclic phosphazene compound (I). The cyclic phosphazene compound (III) did not dissolve in the polyol, and the polyol composition (3) was obtained as a suspension in which the cyclic phosphazene compound (III) was dispersed.

[0095] <Preparation Example 4> A polyol composition (4) was obtained in the same manner as in Preparation Example 1, except that the cyclic phosphazene compound (I) was replaced with the cyclic phosphazene compound (IV).

[0096] [Table 1]

[0097] <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 mixture was adjusted to 20°C and poured into a 500mL polypropylene cup, and a polyisocyanate (Millionate MR-200, Polymeric MDI manufactured by Tosoh Corporation, NCO content 31% by mass) separately adjusted to 20°C was poured therein and mixed for 3 seconds at 6000 rpm using a lab 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% by 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 for thermal conductivity evaluation.

[0098] The mass and dimensions of the rigid polyurethane foam immediately after demolding were measured, 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.

[0099] <Comparative Examples 1 to 3> Except for using polyol composition (2), (3) or (4) instead of polyol composition (1), polyurethane foams of Comparative Examples 1 to 3 were obtained in the same manner as in Example 1. The contents of cyclic phosphazene compounds (III) to (IV) in Comparative Examples 2 to 3 were 5.0 mass% based on the total amount of the blended components.

[0100] <Evaluation> The amount of change in heat insulating performance over time was evaluated by measuring the thermal conductivity of the polyurethane foams obtained in Example 1 and Comparative Examples 1 to 3 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%RH for 60 days. However, since the thermal conductivity of the polyurethane foam obtained in Comparative Example 2 increased significantly immediately after the storage test, the test was terminated 12 days after the start of the storage test.

[0101] This test is an accelerated test based on the idea of ​​scaling coefficients shown in JISA1486, and the aging of the 14mm thick core panel for 60 days corresponds to the aging of a 50mm thick core panel for about 2 years. The results are shown in Table 2.

[0102] [Table 2] Content C in Table 2 A 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

1. A cyclic phosphazene compound comprising a structural unit represented by the following formula (1): 【Chemistry 1】 [In formula (1), R １ represents any one of the groups represented by the following formulas (b-1) to (b-6), and * represents the bonding position to other structural units. 【Chemistry 2】 [In formulas (b-1) to (b-6), * indicates the bonding position with the oxygen atom.]

2. The cyclic phosphazene compound according to claim 1, which is a compound represented by the following formula (4): 【Chemistry 3】 [In formula (4), R １ is R in the formula (1). １ and R １ may be the same or different.

3. The R １ 2. The cyclic phosphazene compound according to claim 1, having at least one group selected from the groups represented by the formulae (b-1) and (b-5) as the cyclic phosphazene compound.

4. A resin additive comprising the cyclic phosphazene compound according to any one of claims 1 to 3.

5. 5. The resin additive of claim 4 which is a thermal conductivity modifier.

6. A composition comprising a resin or a raw material for a resin and the cyclic phosphazene compound according to any one of claims 1 to 3.

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

8. The composition according to claim 7 for forming a polyurethane foam.

9. A resin foam comprising a resin and the cyclic phosphazene compound according to any one of claims 1 to 3.

10. The resin foam according to claim 9, which is a polyurethane foam.

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