Composition for polyurethane foam, polyurethane foam-forming composition, and polyurethane foam

Abstract

A composition for polyurethane foam according to the present invention contains an aromatic polyester polyol and a chlorine-containing compound having a residue unit represented by formula (1). The chlorine-containing compound is a chlorine-containing polyol having a number average molecular weight of 500-3000, or a derivative thereof.　[In formula (1), R1 represents an m-valent hydroxy compound residue having a molecular weight of from 100 to 2500, m represents 2 or 3, the multiple n each independently represent an integer of from 0 to less than 25, and * represents a bond. However, at least one of the multiple n is 1 or more.]

Description

Composition for polyurethane foam, polyurethane foam-forming composition, and polyurethane foam

[0001] The present disclosure relates to a polyurethane foam composition, a polyurethane foam-forming composition, and a polyurethane foam.

[0002] Polyurethane foams are widely used as insulation materials for refrigerators, freezer warehouses, building materials, etc., due to their excellent thermal insulation performance, dimensional stability, workability, etc. On the other hand, polyurethane foams have a problem in that their thermal conductivity increases over time (i.e., their thermal insulation performance decreases over time).

[0003] In response to this, for example, Patent Document 1 discloses a method for suppressing deterioration over time of the thermal conductivity of polyurethane foam (particularly deterioration over time of thermal conductivity in the early stages when the change is large) by after-aging the molded polyurethane foam in amine or alcohol vapor.

[0004] Japanese Patent Application Laid-Open No. 2002-302528

[0005] However, the method of Patent Document 1 requires complicated manufacturing steps and increases the manufacturing cost. Therefore, a technology is desired that can obtain a polyurethane foam that can maintain low thermal conductivity for a long period of time without including complicated manufacturing steps.

[0006] Therefore, one aspect of the present disclosure aims to provide a composition for forming a polyurethane foam (a polyurethane foam composition) in which the increase in thermal conductivity over time is suppressed. Other aspects of the present disclosure aim to provide a polyurethane foam-forming composition comprising the above composition, and a polyurethane foam-forming composition containing the above composition as a polyol composition. Another aspect of the present disclosure aims to provide a polyurethane foam in which the increase in thermal conductivity over time is suppressed.

[0007] Some aspects of the present disclosure provide the following [1] to

[10] .

[0008] [1] A composition for polyurethane foam, comprising: an aromatic polyester polyol; and a chlorine-containing compound having a residue unit represented by the following formula (1), wherein the chlorine-containing compound is a chlorine-containing polyol having a number average molecular weight of 500 to 3,000 or a derivative thereof: [In formula (1), R １ represents an m-valent hydroxy compound residue having a molecular weight of 100 or more and 2500 or less, m represents 2 or 3, each of the multiple n's independently represents an integer of 0 or more and less than 25, and * represents a bond, provided that at least one of the multiple n's is 1 or more.

[0009] [2] The composition according to [1], wherein the content of the residue unit represented by the formula (1) is 0.1 to 11 parts by mass per 100 parts by mass of the aromatic polyester polyol.

[0010] [3] R in the formula (1) １ is a residue of a polyether polyol having a molecular weight of 200 or more and 1,000 or less, a polyester polyol having a molecular weight of 500 or more and 1,000 or less, or a polycarbonate polyol having a molecular weight of 500 or more and 1,000 or less.

[0011] [4] The composition according to any one of [1] to [3], wherein the chlorine-containing compound is at least one chlorine-containing compound selected from the group consisting of a chlorine-containing polyol represented by the following formula (2) and an NCO-terminated prepolymer obtained by modifying the chlorine-containing polyol with a modifying agent containing a polyisocyanate: [R in formula (2)] １ , n and m have the same meanings as defined above.]

[0012] [5] The composition according to any one of [1] to [4], further comprising at least one isocyanuration catalyst selected from the group consisting of carboxylic acid metal salts, quaternary ammonium salts, acetylacetone metal salts, and salicylaldehyde metal salts.

[0013] [6] The composition according to any one of [1] to [5], further comprising at least one isocyanuration catalyst selected from the group consisting of ammonium carboxylates and potassium carboxylates.

[0014] [7] The polyol composition for polyurethane foam according to claim 1, which does not contain a polyisocyanate, and contains, as the chlorine-containing compound, a chlorine-containing polyol represented by the following formula (2): [R in formula (2)] １ , n and m have the same meanings as defined above.]

[0015] [8] A polyurethane foam-forming composition comprising the composition according to [7] and a polyisocyanate.

[0016] [9] A polyurethane foam-forming composition containing a polyol and a polyisocyanate, wherein the chlorine-containing compound is an NCO-terminated prepolymer obtained by modifying a chlorine-containing polyol represented by the following formula (2) with a modifying agent containing a polyisocyanate. [R in formula (2)] １ , n and m have the same meanings as defined above.]

[0017]

[10] A polyurethane foam formed from the composition according to [8] or [9].

[0018] According to one aspect of the present disclosure, a composition for forming a polyurethane foam (a polyurethane foam composition) having a suppressed increase in thermal conductivity over time can be provided. Furthermore, according to some other aspects of the present disclosure, a polyurethane foam-forming composition comprising the above composition and a polyurethane foam-forming composition containing the above composition as a polyol composition can be provided. According to another aspect of the present disclosure, a polyurethane foam having a suppressed increase in thermal conductivity over time can be provided.

[0019] In this specification, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. Furthermore, unless specifically stated otherwise, the units of the numerical values ​​before and after "to" are the same. In the numerical ranges described in stages in this specification, the upper or lower limit of a certain numerical range 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 that numerical range may be replaced with a value shown in the examples. Furthermore, the upper and lower limits individually described can be arbitrarily combined. Furthermore, unless otherwise specified, the materials exemplified below may be used alone or in combination of two or more types. When multiple substances corresponding to each component are present in the composition, the content of each component in the composition means the total amount of those multiple substances present in the composition, unless otherwise specified.

[0020] Preferred embodiments of the present disclosure will be described below, but the present disclosure is not limited to the following embodiments.

[0021] <Composition for Polyurethane Foam> One embodiment of the present disclosure is a composition for polyurethane foam, containing an aromatic polyester polyol and a chlorine-containing compound having a residue unit represented by the following formula (1) (hereinafter referred to as "chlorine-containing compound A").

[0022] In formula (1), R １ represents an m-valent hydroxy compound residue having a molecular weight of 100 or more and 2500 or less, m represents 2 or 3, multiple n's each independently represent an integer of 0 or more and less than 25, and * represents a bond, provided that at least one of the multiple n's is 1 or more.

[0023] In the above composition, the chlorine-containing compound A is a chlorine-containing polyol having a number-average molecular weight of 500 to 3,000, or a derivative thereof. Here, the number-average molecular weight described in this specification is a polystyrene-equivalent number-average molecular weight measured using gel permeation chromatography (GPC). The derivative is a compound derived from a chlorine-containing polyol having a number-average molecular weight of 500 to 3,000. An example of the derivative is an NCO-terminated prepolymer obtained by modifying a chlorine-containing polyol having a number-average molecular weight of 500 to 3,000 with a modifier containing polyisocyanate.

[0024] The composition can form a polyurethane foam whose thermal conductivity is inhibited from increasing over time, and is therefore suitable for use as a material for insulation (polyurethane foam for insulation).

[0025] The composition may be a polyol composition for forming a polyurethane foam, or may be a polyurethane foam-forming composition. That is, one embodiment of the present disclosure (hereinafter referred to as the "first embodiment") is a polyol composition for polyurethane foams containing an aromatic polyester polyol and a chlorine-containing compound A, and another embodiment of the present disclosure (hereinafter referred to as the "second embodiment") is a polyurethane foam-forming composition containing an aromatic polyester polyol and a chlorine-containing compound A. Here, the polyol composition is a composition containing a polyol but not a polyisocyanate, and is used in combination with a polyisocyanate. On the other hand, the polyurethane foam-forming composition is a composition capable of forming a polyurethane foam by itself, and contains at least a polyol and a polyisocyanate. The polyol composition can be combined with a polyisocyanate to form a polyurethane foam-forming composition.

[0026] The composition can be used to form both flexible polyurethane foams (e.g., polyurethane foams having a 10% deformation compressive stress of less than 20 kPa as measured in accordance with JIS K7220) and rigid polyurethane foams (e.g., polyurethane foams having a 10% deformation compressive stress of 20 kPa or more as measured in accordance with JIS K7220), but is particularly suitable for use in forming rigid polyurethane foams.

[0027] First Embodiment A composition of a first embodiment (hereinafter referred to as "composition A") is a composition (polyol composition) that contains at least an aromatic polyester polyol and a chlorine-containing compound A, but does not contain a polyisocyanate.

[0028] (Aromatic polyester polyol) Aromatic polyester polyol is a polyester polyol having an aromatic ring in the molecule. Aromatic polyester polyol can be obtained by, for example, esterifying at least one acid component selected from the group consisting of aromatic polybasic acids, acid anhydrides of aromatic polybasic acids, and methyl esters of aromatic polybasic acids with polyfunctional alcohols by a known method (condensation polymerization reaction). Note that aromatic polyester polyol is a compound different from the chlorine-containing compound A in that it does not have the residue unit represented by formula (1).

[0029] Examples of aromatic polybasic acids include phthalic acid (orthophthalic acid), isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid.

[0030] The polyfunctional alcohol is, for example, a low molecular weight polyol having a molecular weight of not more than 500. 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, an ethylene oxide or propylene oxide adduct of bisphenol A, bis(β-hydroxyethyl)benzene, xylylene glycol, glycerin, trimethylolpropane, and pentaerythritol.

[0031] The aromatic polyester polyol may be a polyester polyol (hereinafter referred to as a "phthalic acid polyol") having a structure derived from phthalic acid (phthalic acid, isophthalic acid, and / or terephthalic acid), from the viewpoint of facilitating the production of a polyurethane foam with higher thermal insulation performance (initial and long-term thermal insulation properties). The phthalic acid polyester polyol may be, for example, a condensation polymerization reaction product of an acid component containing at least one selected from the group consisting of phthalic acid, isophthalic acid, terephthalic acid, and anhydrides thereof, with the above-mentioned polyfunctional alcohol. In particular, when the polyfunctional alcohol contains at least one selected from the group consisting of ethylene glycol and diethylene glycol (i.e., when the aromatic polyester polyol is a condensation polymerization reaction product of an acid component containing at least one selected from the group consisting of phthalic acid, isophthalic acid, terephthalic acid, and anhydrides thereof, with a polyfunctional alcohol containing at least one selected from the group consisting of ethylene glycol and diethylene glycol), a polyurethane foam with higher thermal insulation performance (initial and long-term thermal insulation properties) is more likely to be produced.

[0032] The number average molecular weight of the aromatic polyester polyol may be 300 to 1500, 350 to 1000, or 400 to 700, from the viewpoint that a polyurethane foam having higher thermal insulation performance (initial and long-term thermal insulation properties) can be easily obtained.

[0033] The average hydroxyl value of the aromatic polyester 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 a polyurethane foam having higher thermal insulation performance (initial and long-term thermal insulation). The hydroxyl value described in this specification is a value measured in accordance with JIS K1557-1.

[0034] The content of the aromatic polyester polyol may be 30 to 80 mass%, 35 to 70 mass%, or 40 to 60 mass%, based on the total mass of composition A, from the viewpoint of making it easier to obtain a polyurethane foam having higher thermal insulation performance (initial and long-term thermal insulation properties).

[0035] (Chlorine-containing Compound A) The chlorine-containing compound A has a residue unit represented by the above formula (1).

[0036] R in formula (1) １ is an m-valent hydroxy compound residue having a molecular weight of 100 or more and 2500 or less. Here, since m is 2 or 3, the hydroxy compound residue is a diol acid group or a triol residue. The molecular weight of the hydroxy compound residue may be 200 or more or 300 or more from the viewpoint of improving the moldability of the polyurethane foam, and may be 2000 or less, 1000 or less, or 700 or less from the viewpoint of improving the hardness of the polyurethane foam. From these viewpoints, the molecular weight of the hydroxy compound residue may be 200 or more and 2000 or less, 300 or more and 1000 or less, or 300 or more and 700 or less.

[0037] Examples of hydroxy compound residues (diol residues and triol residues) include residues of polyether polyols (polyether diols and polyether triols), polyester polyols (polyester diols and polyester triols), polycarbonate polyols (polycarbonate diols and polycarbonate triols), alkane polyols (alkane diols and alkane triols), arene polyols (arene diols and arene triols), and dialkylene glycols.

[0038] Examples of polyether polyols include polypropylene glycol, polyethylene glycol, polytetramethylene glycol, propylene oxide-ethylene oxide copolymers, etc. The polypropylene glycol may be tripropylene glycol.

[0039] Examples of polyester polyols include polycondensation products of at least one acid component selected from the group consisting of aromatic polybasic acids, aliphatic polybasic acids, and their acid anhydrides and methyl esters, with a polyfunctional alcohol (diol or triol) having two or three hydroxyl groups. These may be produced by esterifying the acid component and the diol using a known method (polycondensation reaction). Furthermore, polyester polyols may be produced by ring-opening polymerization of ε-caprolactone using a polyfunctional alcohol (diol or triol) as an initiator. Examples of aromatic polybasic acids and polyfunctional alcohols are the same as the examples of aromatic polybasic acids and diols and triols in the aromatic polyester polyols. Examples of aliphatic polybasic acids include adipic acid and sebacic acid.

[0040] Examples of polycarbonate polyols include reaction products of alkanediols such as 1,6-hexanediol, 1,5-pentanediol, and 3-methyl-1,5-pentanediol with carbonic acid diesters such as dimethyl carbonate and diethyl carbonate. These may be produced by reacting raw materials containing an alkanediol and a carbonic acid diester by a known method.

[0041] Examples of alkane polyols include 1,6-hexanediol, 1,9-nonanediol, 2,5-hexanediol, 1,3-cyclohexanediol, 3-methylpentane-1,5-diol, 2,5-dimethyl-2,5-hexanediol, and hexanetriol.

[0042] Examples of arene polyols include bisphenols.

[0043] Examples of dialkylene glycols include dipropylene glycol.

[0044] R in formula (1) １ From the viewpoint of enabling efficient production of chlorine-containing polyol and improving moldability of polyurethane foam, R may be a residue of polyether polyol having a molecular weight of 200 or more and 1,000 or less, polyester polyol having a molecular weight of 500 or more and 1,000 or less, or polycarbonate polyol having a molecular weight of 500 or more and 1,000 or less. １ is a residue of a polyether polyol having a molecular weight of 200 or more and 1000 or less, the moldability of the polyurethane foam tends to be better, １ However, when the polyether polyol is a polyester polyol having a molecular weight of 500 or more and 1000 or less, the flame retardancy of the polyurethane foam tends to be good. The polyether polyol may be a polyalkylene glycol from the viewpoint of easily achieving the above-mentioned effect, or may be a polypropylene glycol from the viewpoint of more easily achieving the above-mentioned effect. The polyester polyol may be an aromatic polyester polyol from the viewpoint of easily achieving the above-mentioned effect, or may be a phthalic acid-based polyester polyol from the viewpoint of more easily achieving the above-mentioned effect.

[0045] Since m in formula (1) is 2 or 3, there are multiple n's (two or three n's) in formula (1), and the multiple n's are each independently an integer of 0 or more and less than 25. At least one of the multiple n's is 1 or more, and preferably all of the multiple n's are 1 or more. The total of the multiple n's is preferably 1 or more and 25 or less.

[0046] The chlorine-containing compound A is, for example, a chlorine-containing polyol having a number average molecular weight of 500 to 3000. Examples of the chlorine-containing polyol include a chlorine-containing polyol represented by the following formula (2) (hereinafter referred to as "chlorine-containing polyol A").

[0047] R in formula (2) １ , n and m have the same meanings as defined above.

[0048] 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 chlorine-containing polyol may be 600 or more, 700 or more, or 800 or more, and may be 2000 or less, 1500 or less, or 1000 or less, or may be 600 to 2000, 700 to 1500, or 800 to 1000. The number average molecular weight of the chlorine-containing compound A may be within the above range.

[0049] The average hydroxyl value of the chlorine-containing polyol A 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 heat insulating performance (initial and long-term heat insulating properties).

[0050] The specific gravity of the chlorine-containing compound A may be 1.40 or less, or may be 1.30 or less, from the viewpoint of improving the ease of mixing with the aromatic polyester polyol. From the above viewpoint, the specific gravity of the chlorine-containing compound A may be 1.10 to 1.40 or 1.10 to 1.30. The specific gravity of the chlorine-containing polyol may be within the above range, and the specific gravity of the chlorine-containing polyol A may be within the above range. The specific gravity described in this specification is a value measured by a method using a pycnometer specified in JIS K0061.

[0051] Chlorine-containing compound A can be obtained, for example, by ring-opening polymerization of epichlorohydrin using the hydroxy compound as an initiator in the presence of a composition containing an onium salt, a Lewis acid, and the hydroxy compound.The terminal hydroxyl group of the chlorine-containing compound (chlorine-containing polyol) thus obtained can be modified (modified) to obtain chlorine-containing compound A (a derivative of chlorine-containing polyol).Examples of Lewis acids include aluminum compounds such as triisopropoxyaluminum, zinc compounds, boron compounds, etc.Examples of onium salts include ammonium salts such as tetrabutylammonium bromide, phosphazenium salts, phosphonium salts, etc.

[0052] The content of the chlorine-containing compound A may be such that the content of the residue unit represented by formula (1) is 0.1 to 11 parts by mass relative to 100 parts by mass of the aromatic polyester polyol. In this case, the moldability of the polyurethane foam tends to be better. The content of the residue unit represented by formula (1) may be 0.5 parts by mass or more or 1 part by mass or more relative to 100 parts by mass of the aromatic polyester polyol, from the viewpoint of easily obtaining a polyurethane foam having high thermal insulation performance (initial and long-term thermal insulation). The content of the residue unit represented by formula (1) may be 7 parts by mass or less or 5 parts by mass or less relative to 100 parts by mass of the aromatic polyester polyol, from the viewpoint of easily obtaining a polyurethane foam having even higher thermal insulation performance (initial and long-term thermal insulation). From these viewpoints, the content of the residue unit represented by formula (1) may be 0.5 to 7 parts by mass or 1 to 5 parts by mass relative to 100 parts by mass of the aromatic polyester polyol.

[0053] From the same viewpoint as above, the content of the chlorine-containing polyol may be in the same range as above. For example, the content of the chlorine-containing polyol A may be 0.1 to 11 parts by mass, 0.5 to 7 parts by mass, or 1 to 5 parts by mass per 100 parts by mass of the aromatic polyester polyol.

[0054] The content of the residue unit represented by formula (1) may be 0.1 to 9 parts by mass, 0.5 to 5 parts by mass, or 1.0 to 4 parts by mass, based on the total mass of composition A.

[0055] (Others) Composition A may further contain, as other optional components, components other than the aromatic polyester polyol and the chlorine-containing compound A. The other optional components may be polyurethane foams and known components used for forming the same. Examples of the other optional components include polyol components other than the aromatic polyester polyol and the chlorine-containing compound A (chlorine-containing polyol), catalysts, flame retardants, blowing agents, foam stabilizers, plasticizers, colorants, etc.

[0056] [Other Polyol Components] Examples of other polyol components include polyester polyols, polyether polyols, polycaprolactone polyols, and polycarbonate polyols.

[0057] The content of the other polyol component may be 10% by mass or less, 5% by mass or less, or 1% by mass or less, based on the total mass of the polyol components contained in composition A.

[0058] When composition A contains other polyol components, the content of the residue unit represented by formula (1) per 100 parts by mass of the aromatic polyester polyol may be interpreted as the content of the residue unit represented by formula (1) per 100 parts by mass of all polyol components in composition A. That is, the content of the residue unit represented by formula (1) may be 0.1 to 11 parts by mass, 0.5 to 7 parts by mass, or 1 to 5 parts by mass per 100 parts by mass of all polyol components in composition A.

[0059] [Catalyst] As the catalyst, various urethanization catalysts, isocyanuration catalysts, etc. known in the art can be used. A urethanization catalyst and an isocyanuration catalyst (trimerization catalyst) may be used in combination.

[0060] Examples of urethanization 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, 1,2-dimethylimidazole, 1-isobutyl-2-methylpropanol ... and alkanolamines such as N-(3-dimethylaminopropyl)-N,N-diisopropanolamine, N-(2-hydroxyethyl)-N'-methylpiperazine, N,N-dimethylaminohexanol, and 5-dimethylamino-3-methyl-1-pentanol. These urethane-forming catalysts may be used singly or in combination.

[0061] The amount (content) of the urethanization catalyst may be 0.1 to 8.0 parts by mass relative to 100 parts by mass of the total amount of all polyol components in composition A.

[0062] Examples of the isocyanurate catalyst include metal carboxylates, quaternary ammonium salts, metal acetylacetone salts, metal salicylaldehyde salts, and Lewis acid complex salts of amines. These isocyanurate catalysts may be used alone or in combination. The quaternary ammonium salt may be an ammonium carboxylate salt. The carboxylate ion (RCOO) in the metal carboxylate salt and the ammonium carboxylate salt may be used. －The carbon number of the carboxylic acid metal salt, the acetylacetone metal salt, and the salicylaldehyde metal salt may be an alkali metal salt. The alkali metal ion in the alkali metal salt may be a potassium ion.

[0063] As the isocyanurate catalyst, from the viewpoint of easily obtaining higher heat insulating performance (initial and long-term heat insulating properties), it is preferable to use at least one selected from the group consisting of metal carboxylates, quaternary ammonium salts, metal acetylacetone salts, and metal salicylaldehyde salts, it is preferable to use at least one selected from the group consisting of quaternary ammonium salts and potassium carboxylate salts, and it is more preferable to use a combination of a quaternary ammonium salt and a potassium carboxylate salt. Among these, it is preferable to use at least one selected from the group consisting of ammonium carboxylates and potassium carboxylate salts, and it is more preferable to use a combination of an ammonium carboxylate and a potassium carboxylate salt.

[0064] The amount (content) of the isocyanurate catalyst may be 0.1 to 8.0 parts by mass relative to 100 parts by mass of the total amount of all polyol components in composition A.

[0065] The total amount (content) of the catalyst may be 0.2 to 16 parts by mass relative to 100 parts by mass of the total amount of all polyol components in composition A.

[0066] [Foam stabilizer] As the foam stabilizer, a foam stabilizer known in the art (for example, 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.

[0067] Commercially available foam stabilizers 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 Co., Ltd.

[0068] The amount of the foam stabilizer may be 0.1 to 5.0 parts by mass per 100 parts by mass of the total amount of all polyol components in composition A.

[0069] [Blowing Agent] The blowing agent is, for example, water. Water reacts with isocyanate groups to generate carbon dioxide gas, which causes foaming. In addition to water, which is a chemical blowing agent, a physical blowing agent can also be used as the blowing agent. Conventionally known physical blowing agents such as hydrocarbon compounds, HFCs, HFOs, and HCFOs can be used as the blowing agent. These physical blowing agents may be used alone or in combination of two or more. From the viewpoint of easily reducing the global warming potential of the blowing agent itself and easily obtaining high thermal insulation performance (initial and long-term thermal insulation), it is particularly preferable to use at least one selected from the group consisting of HFOs and HCFOs in combination with water.

[0070] 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 all polyol components in composition A. 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 all polyol components in composition A.

[0071] [Flame Retardant] Known flame retardants can be used as the flame retardant. Specific examples of the flame retardant include phosphate esters such as tris(chloropropyl)phosphate, and organophosphazenes such as methoxyphenoxycyclophosphazene.

[0072] The blending amount (content) of the flame retardant may be 0 to 50 parts by mass relative to 100 parts by mass of the total amount of all polyol components in composition A.

[0073] Composition A described above can be used to form a polyurethane foam whose thermal conductivity is inhibited from increasing over time. Specifically, for example, composition A can be reacted with a polyisocyanate, followed by foaming and curing, to form a polyurethane foam whose thermal conductivity is inhibited from increasing over time. The reaction (foaming and curing) can be carried out by a conventional method, for example, by heating in a mold.

[0074] Composition A may be used in combination with a polyisocyanate 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 (NCO groups / active hydrogen groups x 100). The active hydrogen group-containing compound includes not only polyols but also water. The isocyanate index (NCO index) may be 150 to 300 or 180 to 250.

[0075] Second Embodiment A composition according to a second embodiment (hereinafter referred to as "composition B") is a composition (polyurethane foam-forming composition) that contains at least an aromatic polyester polyol and a chlorine-containing compound A and has the property of being able to form a polyurethane foam by itself. Composition B may also be a composition that contains composition A and a polyisocyanate.

[0076] (Aromatic polyester polyol) As the aromatic polyester polyol, the same aromatic polyester polyol as in the first embodiment can be used from the same viewpoint as in the first embodiment. The number average molecular weight and average hydroxyl value of the aromatic polyester polyol may also be in the same range as in the first embodiment from the same viewpoint as in the first embodiment.

[0077] The content of the aromatic polyester polyol may be 10 to 50 mass %, 15 to 45 mass %, or 20 to 40 mass %, based on the total mass of the polyurethane foam-forming composition, from the viewpoint of making it easier to obtain a polyurethane foam having higher thermal insulation performance (initial and long-term thermal insulation properties).

[0078] (Chlorine-containing compound A) From the same viewpoint as in the first embodiment, the same chlorine-containing compound A as in the first embodiment can be used as the chlorine-containing compound A. Furthermore, as the chlorine-containing compound A, a chlorine-containing polyisocyanate having a residue unit represented by formula (1) and a plurality of isocyanate groups can also be used.

[0079] Examples of the chlorine-containing compound A include an NCO-terminated prepolymer obtained by modifying a chlorine-containing polyol having a number average molecular weight of 500 to 3000 (for example, chlorine-containing polyol A) with a modifier containing polyisocyanate. Hereinafter, the NCO-terminated prepolymer obtained by modifying the chlorine-containing polyol A with a modifier containing polyisocyanate will be referred to as "NCO-terminated prepolymer A."

[0080] The modifier may contain other polyol components in addition to polyisocyanate. That is, the NCO-terminated prepolymer (e.g., NCO-terminated prepolymer A) may be a reaction product of a chlorine-containing polyol (e.g., chlorine-containing polyol A) and a polyisocyanate, or may be a reaction product of a chlorine-containing polyol (e.g., chlorine-containing polyol A), a polyisocyanate, and another polyol component. Examples of polyisocyanates that can be used include diphenylmethane diisocyanate (MDI), polyphenylene polymethylene polyisocyanate, and various modified products of MDI or polyphenylene polymethylene polyisocyanate (urethane modified product, urea modified product, allophanate modified product, nurate modified product, biuret modified product, etc.). Examples of other polyol components that can be used include polyol components (e.g., aromatic polyester polyol) other than the chlorine-containing polyol A exemplified in the first embodiment.

[0081] The chlorine-containing compound A may contain both the chlorine-containing polyol and the NCO-terminated prepolymer. For example, the chlorine-containing compound A may contain both the chlorine-containing polyol A and the NCO-terminated prepolymer A.

[0082] The number average molecular weights and specific gravities of the chlorine-containing compound A, the chlorine-containing polyol and the chlorine-containing polyol A may be in the same ranges as in the first embodiment, from the same viewpoint as in the first embodiment.

[0083] When the chlorine-containing compound A contains a chlorine-containing polyisocyanate, the NCO content of the chlorine-containing polyisocyanate may be 15 to 33 mass%, 18 to 31 mass%, or 20 to 30 mass%, from the viewpoint of easily obtaining higher heat insulating performance (initial and long-term heat insulating properties). The NCO content of the NCO-terminated prepolymer A may be within the above range. The NCO content is determined by Method A in accordance with JIS K 1603-1.

[0084] The contents of the chlorine-containing compound A, the chlorine-containing polyol, and the chlorine-containing polyol A may be in the same ranges as in the first embodiment, from the same viewpoint as in the first embodiment. For example, the content of the chlorine-containing compound A may be an amount such that the content of the residue unit represented by formula (1) is 0.1 to 11 parts by mass, 0.5 to 7 parts by mass, or 1 to 5 parts by mass per 100 parts by mass of the aromatic polyester polyol. The same applies to the chlorine-containing polyisocyanate and the NCO-terminated prepolymer A.

[0085] The content of the residue unit represented by formula (1) may be 0.1 to 9 parts by mass, 0.5 to 5 parts by mass, or 1.0 to 4 parts by mass, based on the total mass of composition B.

[0086] (Polyisocyanate) Composition B contains a polyisocyanate. The polyisocyanate contained in composition B may be the above-mentioned chlorine-containing polyisocyanate, or may be a polyisocyanate other than the above-mentioned chlorine-containing polyisocyanate. The polyisocyanate may contain both of these. When the chlorine-containing compound A is not a polyisocyanate, composition B contains a polyisocyanate in addition to the aromatic polyester polyol and the chlorine-containing compound A.

[0087] The polyisocyanate may be any compound having a plurality of isocyanate groups, such as diphenylmethane diisocyanate (MDI), polyphenylene polymethylene polyisocyanate, various modified products of MDI or polyphenylene polymethylene polyisocyanate (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.

[0088] The NCO content of the entire polyisocyanate contained in composition B may be 15 to 33 mass%, 18 to 31 mass%, or 20 to 30 mass%, from the viewpoint of making it easier to obtain higher heat insulating performance (initial and long-term heat insulating properties).

[0089] (Others) Composition B may contain, as other optional components, the other optional components exemplified in the first embodiment (other polyol components, catalysts, flame retardants, foaming agents, foam stabilizers, plasticizers, colorants, etc.).

[0090] The content of the other polyol component may be 10% by mass or less, 5% by mass or less, or 1% by mass or less, based on the total mass of the polyol components contained in composition B.

[0091] When composition B contains another polyol component, the content of the residue unit represented by formula (1) per 100 parts by mass of the aromatic polyester polyol may be interpreted as the content of the residue unit represented by formula (1) per 100 parts by mass of all polyol components in composition B. That is, the content of the residue unit represented by formula (1) may be 0.1 to 11 parts by mass, 0.5 to 7 parts by mass, or 1 to 5 parts by mass per 100 parts by mass of all polyol components in composition B.

[0092] The amount (content) of the catalyst may be 0.2 to 16 parts by mass based on 100 parts by mass of the total amount of the polyol and polyisocyanate. The amount (content) of the urethanization catalyst may be 0.1 to 4 parts by mass based on 100 parts by mass of the total amount of the polyol and polyisocyanate. The amount (content) of the isocyanuration catalyst may be 0.1 to 8 parts by mass based on 100 parts by mass of the polyisocyanate.

[0093] 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 polyisocyanate. The blending 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 blending 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.

[0094] The blending 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 the polyol and polyisocyanate.

[0095] Composition B may be a one-component composition or a multi-component composition consisting of two or more components. The multi-component composition may be, for example, a two-component composition comprising a first component (e.g., a polyol composition) containing a polyol and a second component (e.g., a polyisocyanate composition) containing a polyisocyanate. The specific polyol (aromatic polyester polyol and chlorine-containing polyol) may be contained in the first component. That is, composition B may be a multi-component composition comprising composition A as the first component. Composition B may also be a multi-component composition comprising a first component (polyol composition) containing an aromatic polyester polyol and a second component (polyisocyanate composition) containing a chlorine-containing polyisocyanate or an NCO-terminated prepolymer A. Composition B may also comprise a third component, separate from the first and second components.

[0096] The isocyanate index of composition B may be 100-400, 150-300, or 180-250.

[0097] Composition B described above can be used to form a polyurethane foam in which the increase in thermal conductivity over time is suppressed. Specifically, for example, a polyurethane foam can be formed by reacting a polyol and a polyisocyanate in composition B, and then foaming and curing composition B. When composition B is a multi-component composition, a polyurethane foam can be formed by mixing the liquids that make up composition B (e.g., a first liquid containing a polyol and a second liquid containing a polyisocyanate) and reacting (foaming and curing). The reaction (foaming and curing) can be carried out by a conventionally known method, for example, by heating in a mold.

[0098] <Polyurethane Foam> Another embodiment of the present disclosure is a polyurethane foam (hereinafter referred to as "polyurethane foam A") formed from composition B above.

[0099] Polyurethane foam A can also be said to be a polyurethane foam that contains a polyurethane resin that is a reaction product of the above-mentioned polyol and polyisocyanate, and that may also contain other components that may be contained in composition B (catalyst, flame retardant, blowing agent, foam stabilizer, plasticizer, colorant, etc.).

[0100] Polyurethane foams are suitably used as heat 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.

[0101] 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.

[0102] Details of the materials used in this example are shown below. Polyester polyol a: Maximol RFK-505 (manufactured by Air Water Performance Chemicals, phthalic acid-based polyester polyol, number average molecular weight: 449, average hydroxyl value: 250 mgKOH / g) Polyester polyol b: Maximol RFK-556 (manufactured by Air Water Performance Chemicals, phthalic acid-based polyester polyol, number average molecular weight: 449, average hydroxyl value: 250 mgKOH / g) Polyester polyol c: ISOEXTER 4566 (manufactured by COIM, phthalic acid-based polyester polyol, number average molecular weight: 450, average hydroxyl value: 250 mgKOH / g) Chlorine-containing polyol a: chlorine-containing polyol synthesized in Synthesis Example 1 below (average hydroxyl value: 173 mgKOH / g, number average molecular weight: 649, specific gravity: 1.12) Chlorine-containing polyol b: a chlorine-containing polyol (average hydroxyl value 112 mg KOH / g, number average molecular weight 1002, specific gravity 1.20) synthesized in Synthesis Example 2 below. Chlorine-containing polyol c: a chlorine-containing polyol (average hydroxyl value 112 mg KOH / g, number average molecular weight 1004, specific gravity 1.25) synthesized in Synthesis Example 3 below. Polyether polyol a: Sannix PP-1000 (manufactured by Sanyo Chemical Industries, Ltd., polypropylene glycol, number average molecular weight: 1000). Polyisocyanate I: Millionate MR-200, Polymeric MDI manufactured by Tosoh Corporation, NCO content 31% by mass, dinuclear content 41%. Polyisocyanate II: an isocyanate-terminated prepolymer synthesized in Synthesis Example 4 below. Flame retardant a: TMCPP (manufactured by Daihachi Chemical Industry Co., Ltd., trischloropropyl phosphate). Foam stabilizer a: NIAX L-6978 (manufactured by Momentive) Foam stabilizer b: NIAX L-6643 (manufactured by Momentive) Foam stabilizer c: SH-193 (manufactured by Dow-Toray) Urethane catalyst a: DM70 (manufactured by Tosoh Corporation, imidazole catalyst) Urethane catalyst b: Kao-Rizer No. 10 (manufactured by Kao Corporation, tertiary amine catalyst) Trimerization catalyst a: TOYOCAT TRX (manufactured by Tosoh Corporation, tetramethylammonium acetate) Trimerization catalyst b: POLYCAT 46 (manufactured by Evonik, potassium acetate) Physical blowing agent: Solstice LBA (manufactured by Honeywell Japan, HCFO-1233zd)

[0103] Synthesis Example 1 To a 2-liter four-neck flask equipped with a stirring blade, 906.24 g of polypropylene glycol having a molecular weight of 400 (manufactured by Sanyo Chemical Industries, Ltd., trade name: Sannix PK-400) and 10.96 g of tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added. After creating a nitrogen atmosphere inside the flask, the internal temperature was increased to 100°C, and dehydration treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours. Thereafter, 20.83 g of triisopropoxyaluminum (manufactured by Kawaken Fine Chemicals Co., Ltd., PADM) was added, the internal temperature was increased to 100°C, and decompression treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours, thereby obtaining an initiator composition. The obtained initiator composition was heated to 98°C, and 480 mL of epichlorohydrin (ECH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was continuously fed over 4 hours. After the epichlorohydrin was added, the mixture was aged for 2 hours at an internal temperature of 90 to 100°C, and then the residual epichlorohydrin was removed at 100°C and a reduced pressure of 0.5 kPa to obtain crude chlorine-containing polyol a. 78.08 g of water (ion-exchanged water) was added to the obtained crude chlorine-containing polyol a, and the mixture was stirred at 80°C for 2 hours. Thereafter, dehydration was initiated while increasing the temperature and reducing the pressure, and finally, a reduced-pressure dehydration operation was carried out for 3 hours under conditions of 100°C and 0.2 kPa. 2.50 g of diatomaceous earth (Radiolite #3000, manufactured by Showa Chemical Industry Co., Ltd.) was added to the crude chlorine-containing polyol a and stirred for 1 minute, followed by pressure filtration at 90°C and 0.3 MPa using a stainless steel holder with a tank KST-142 manufactured by Advantec Toyo Co., Ltd. (filter material: stainless steel mesh, 120 mesh). This resulted in a pale yellow chlorine-containing polyol a having the structure represented by the above formula (2). In the chlorine-containing polyol a, R in formula (2) １ is a polypropylene glycol residue having a molecular weight of 400, and m is 2.

[0104] Synthesis Example 2 566.40 g of polypropylene glycol having a molecular weight of 400 (manufactured by Sanyo Chemical Industries, Ltd., trade name: Sannix PK-400) and 6.85 g of tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 2-liter four-neck flask equipped with a stirring blade. After creating a nitrogen atmosphere in the flask, the internal temperature was increased to 100°C, and dehydration treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours. Thereafter, 13.02 g of triisopropoxyaluminum (manufactured by Kawaken Fine Chemicals Co., Ltd., PADM) was added, the internal temperature was increased to 100°C, and decompression treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours, thereby obtaining an initiator composition. The obtained initiator composition was heated to 98°C, and 720 mL of epichlorohydrin (ECH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was continuously fed thereto over 4 hours. After the epichlorohydrin was added, the mixture was aged for 2 hours at an internal temperature in the range of 90 to 100°C, and then the residual epichlorohydrin was removed at 100°C and a reduced pressure of 0.5 kPa to obtain crude chlorine-containing polyol b. 74.89 g of water (ion-exchanged water) was added to the obtained crude chlorine-containing polyol b, and the mixture was stirred at 80°C for 2 hours. Thereafter, dehydration was initiated while increasing the temperature and reducing the pressure, and finally, a reduced-pressure dehydration operation was carried out for 3 hours under conditions of 100°C and 0.2 kPa. 2.40 g of diatomaceous earth (Radiolite #3000, manufactured by Showa Chemical Industry Co., Ltd.) was added to the crude chlorine-containing polyol b, and the mixture was stirred for 1 minute. The mixture was then subjected to pressure filtration at 90°C and 0.3 MPa using a stainless steel holder with a tank KST-142 manufactured by Advantec Toyo Co., Ltd. (filter material: stainless steel mesh, 120 mesh). This resulted in a pale yellow chlorine-containing polyol b having the structure represented by the above formula (2). In the chlorine-containing polyol b, R in formula (2) １ is a polypropylene glycol residue having a molecular weight of 400, and m is 2.

[0105] Synthesis Example 3 Into a 2-liter four-neck flask equipped with a stirring blade, 720.87 g of polyester polyol having a molecular weight of 560 (manufactured by Air Water Performance Chemicals Inc., trade name: Maximol RLK-087, number of hydroxyl groups: 2) and 10.37 g of tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added. After creating a nitrogen atmosphere in the flask, the internal temperature was raised to 100 ° C., and dehydration treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours. Thereafter, 19.72 g of triisopropoxyaluminum (manufactured by Kawaken Fine Chemicals Co., Ltd., PADM) was added, the internal temperature was raised to 100 ° C., and decompression treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours to obtain an initiator composition. The obtained initiator composition was heated to 98 ° C., and 480 mL of epichlorohydrin (ECH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was continuously fed over 4 hours. After the epichlorohydrin was added, the mixture was aged for 2 hours at an internal temperature of 90 to 100 ° C., and then the residual epichlorohydrin was removed at 100 ° C. and a reduced pressure of 0.5 kPa to obtain crude chlorine-containing polyol c. 68.30 g of water (ion-exchanged water) was added to the obtained crude chlorine-containing polyol c, and the mixture was stirred at 80 ° C. for 2 hours. Thereafter, dehydration was initiated while increasing the temperature and reducing the pressure, and finally, a reduced-pressure dehydration operation was carried out for 3 hours under conditions of 100 ° C. and 0.2 kPa. 13.66 g of diatomaceous earth (Radiolite #3000, manufactured by Showa Chemical Industry Co., Ltd.) was added to the crude chlorine-containing polyol c, and the mixture was stirred for 1 minute. The mixture was then subjected to pressure filtration at 90 ° C. and 0.3 MPa using a stainless steel holder with a tank KST-142 manufactured by Advantec Toyo Co., Ltd. (filter material: stainless steel mesh, 120 mesh). This resulted in a pale yellow chlorine-containing polyol c having the structure represented by the above formula (2). In the chlorine-containing polyol c, R in formula (2) １ is a polyester polyol residue having a molecular weight of 560, and m is 2.

[0106] Synthesis Example 4 After a reactor equipped with a stirrer, a nitrogen inlet tube, a thermometer, and a temperature controller was purged with nitrogen, 60.5 parts by mass of MR-200, 10.8 parts by mass of ISOEXTER 4566, and 2.7 parts by mass of the chlorine-containing polyol b synthesized in Synthesis Example 2 were charged and reacted with stirring at 75°C for 3 hours. Next, 26.0 parts by mass of Millionate NM (manufactured by Tosoh Corporation, MDI, NCO content 33.5%) was charged and stirred at 70°C for 30 minutes to obtain polyisocyanate (II) as a polyisocyanate composition containing an isocyanate group-terminated prepolymer. The NCO content of polyisocyanate (II) was 25.2%.

[0107] Preparation Example 1 Polyol components (polyester polyol, chlorine-containing polyol, polyether polyol), flame retardant, foam stabilizer, urethanization catalyst, 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 a liquid temperature of 15°C to 30°C. This yielded polyol composition (P1). The blending amounts of each component are as shown in Table 1. The blending amounts shown in Table 1 are in parts by mass.

[0108] Preparation Examples 2 to 8 Polyol compositions (P2) to (P8) were obtained in the same manner as in Preparation Example 1, except that the blending amounts of each component were changed as shown in Table 1.

[0109]

[0110] Example 1 First, an aluminum mold equipped with a lid (mold inner dimensions: height 250 mm, width 250 mm, thickness 50 mm) was temperature-controlled in a 60°C thermostatic chamber. Next, the polyol composition (P1) obtained in Preparation Example 1 and a physical blowing agent were mixed in the mass ratio shown in Table 2. The resulting mixture was then temperature-controlled to 20°C and poured into a 500 mL polypropylene cup. Polyisocyanate I, separately temperature-controlled to 20°C, was added and mixed for 3 seconds at 6000 rpm using a laboratory mixer. The amount of polyisocyanate I added was adjusted so that the isocyanate index was 200. Approximately 133 g (133±2 g) of the resulting mixture (polyurethane foam-forming composition) was then poured into the mold, and the mold was immediately covered with a lid and heated in a 60°C thermostatic chamber for 20 minutes to react, foam, and cure. This resulted in a rectangular parallelepiped polyurethane foam (rigid polyurethane foam). The resulting polyurethane foam was removed from the mold immediately after the reaction was completed, and used for measuring the density and core density, and for evaluating the thermal conductivity.

[0111] The mass and dimensions of the polyurethane foam immediately after demolding were measured, and the foam density of the polyurethane foam was calculated in accordance with JIS A9521. Next, all six skin layers were immediately cut off to cut out a core panel from the center of the 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.

[0112] Examples 2 to 5, Comparative Examples 1 and 2 Polyurethane foams of Examples 2 to 5 and Comparative Examples 1 and 2 were obtained in the same manner as in Example 1, except that polyol compositions (P2) to (P6) or (P8) were used in place of polyol composition (P1) in the blending ratios shown in Table 2. The content of chlorine-containing polyol in each Example, based on the total amount of the blended components in the polyurethane foam-forming composition, is as shown in Table 2.

[0113] Example 6 A polyurethane foam of Example 6 was obtained in the same manner as in Example 1, except that the polyol composition (P7) was used instead of the polyol composition (P1), the polyisocyanate (II) was used instead of the polyisocyanate (I), and the amount of polyisocyanate added was adjusted so that the isocyanate index was 220, resulting in the blending ratio shown in Table 2.

[0114] <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 6 and Comparative Examples 1 and 2 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 a 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 initial value measurement in a constant temperature and humidity chamber at 23°C / 50% RH for 14 days.

[0115] This test is an accelerated test based on the concept of scaling coefficients as specified in JIS A 1486, and the aging of the 14 mm thick core panel for 14 days corresponds to the aging of a 50 mm thick core panel for approximately 3 months. The results are shown in Table 2.

[0116]

[0117] In Examples 1 to 5, in which an aromatic polyester polyol and a chlorine-containing polyol were contained in the polyol composition, and in Example 6, in which polyisocyanate II containing a chlorine-containing polyol and an aromatic polyol was used as a modifier, it was confirmed that the increase in thermal conductivity of the polyurethane foam over time was suppressed.

Claims

1. A polyurethane foam composition comprising an aromatic polyester polyol and a chlorine-containing compound having a residue unit represented by the following formula (1), wherein the chlorine-containing compound is a chlorine-containing polyol having a number average molecular weight of 500 to 3,000 or a derivative thereof: [In formula (1), R １ represents an m-valent hydroxy compound residue having a molecular weight of 100 or more and 2500 or less, m represents 2 or 3, each of the multiple n's independently represents an integer of 0 or more and less than 25, and * represents a bond, provided that at least one of the multiple n's is 1 or more.

2. The composition according to claim 1, wherein the content of the residue unit represented by formula (1) is 0.1 to 11 parts by mass per 100 parts by mass of the aromatic polyester polyol.

3. R in the formula (1) １ is a residue of a polyether polyol having a molecular weight of 200 or more and 1000 or less, a polyester polyol having a molecular weight of 500 or more and 1000 or less, or a polycarbonate polyol having a molecular weight of 500 or more and 1000 or less.

4. The composition according to claim 1, wherein the chlorine-containing compound comprises at least one chlorine-containing compound selected from the group consisting of chlorine-containing polyols represented by the following formula (2) and NCO-terminated prepolymers obtained by modifying the chlorine-containing polyols with a modifying agent containing polyisocyanate: [R in formula (2)] １ , n and m have the same meanings as defined above.] 5. The composition according to claim 1, further comprising at least one isocyanuration catalyst selected from the group consisting of metal salts of carboxylic acids, quaternary ammonium salts, metal salts of acetylacetone, and metal salts of salicylaldehyde.

6. The composition according to claim 1, further comprising at least one isocyanuration catalyst selected from the group consisting of ammonium carboxylates and potassium carboxylates.

7. The polyol composition for polyurethane foam according to claim 1, which does not contain polyisocyanate and contains, as the chlorine-containing compound, a chlorine-containing polyol represented by the following formula (2): [R in formula (2)] １ , n and m have the same meanings as defined above.] 8. A polyurethane foam-forming composition comprising the composition of claim 7 and a polyisocyanate.

9. A polyurethane foam-forming composition comprising a polyol and a polyisocyanate, wherein the chlorine-containing compound is an NCO-terminated prepolymer obtained by modifying a chlorine-containing polyol represented by the following formula (2) with a modifying agent containing a polyisocyanate, as described in claim 1: [R in formula (2)] １ , n and m have the same meanings as defined above.] 10. A polyurethane foam formed from the composition of claim 8 or 9.

Images