Composition, additive for resins, and resin foam

Abstract

Provided is an additive for resins which includes a compound having a group represented by formula (1). [In formula (1), R1 and R2 each independently represent a hydrogen atom or an organic group, with the proviso that R1 and / or R2 includes an alkyl or alkylene group in which at least one hydrogen atom has been replaced with a halogen atom, and * indicates a bond.]

Description

Composition, resin additive, and resin foam

[0001] The present disclosure relates to a composition, an additive for a resin, and a resin foam.

[0002] Resin foams such as polyurethane foams are widely used as insulation materials for refrigerators, freezer warehouses, building materials, spray applications, etc., due to their excellent thermal insulation performance, dimensional stability, workability, etc. However, resin foams have the problem that their thermal conductivity increases over time, resulting in a decrease in their thermal insulation performance over time.

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

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

[0005] Synthetic Communications, 2005, 35 (11), 1441-1445 Journal of Polymer Science Part A: Polymer Chemistry, 1989, 27(4), 1415-1418

[0006] However, the method of Patent Document 1 requires complicated work steps and increases the manufacturing cost. Therefore, there is a need for a technology for manufacturing a resin foam that can maintain low thermal conductivity for a long period of time without including complicated steps in the manufacturing process.

[0007] Therefore, an object of one aspect of the present disclosure is to provide an additive that can suppress an increase in thermal conductivity of a resin foam over time. Also, some aspects of the present disclosure are to provide a composition and a resin foam containing the additive.

[0008] The inventors of the present disclosure discovered that a compound having a specific structure is effective in suppressing the increase in the thermal conductivity of a resin over time, particularly the increase in the thermal conductivity of a resin foam over time, and thus completed the invention of the present disclosure.

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

[10] .

[0010] [1] A composition comprising a resin or a resin raw material and a compound having a group represented by the following formula (1): [In formula (1), R １ and R ２ each independently represents a hydrogen atom or an organic group, and * represents a bond. １ and R ２ At least one of the groups contains an alkyl group or an alkylene group in which at least one hydrogen atom is substituted with a halogen atom.]

[0011] [2] The composition according to [1], wherein the halogen atom is a chlorine atom or a bromine atom.

[0012] [3] The R １ and the R ２ The composition according to [1] or [2], wherein at least one of the above is an alkyl group in which at least one hydrogen atom is substituted with a halogen atom.

[0013] [4] The R １ and the R ２ [4] The composition according to any one of [1] to [3], wherein at least one of the groups is a chloromethyl group or a bromomethyl group.

[0014] [5] The composition according to any one of [1] to [4], wherein the resin is a polyurethane resin, and a raw material of the resin is at least one of a polyol and a polyisocyanate.

[0015] [6] The composition according to [5], which is for use in polyurethane foam.

[0016] [7] A resin additive comprising a compound having a group represented by the following formula (1): [In formula (1), R １ and R ２ each independently represents a hydrogen atom or an organic group, and * represents a bond. １ and R ２ At least one of the groups contains an alkyl group or an alkylene group in which at least one hydrogen atom is substituted with a halogen atom.]

[0017] [8] The resin additive according to [7], which is a thermal conductivity modifier.

[0018] [9] A resin foam comprising a resin and a compound having a group represented by the following formula (1): [In formula (1), R １ and R ２ each independently represents a hydrogen atom or an organic group, and * represents a bond. １ and R ２ At least one of the groups contains an alkyl group or an alkylene group in which at least one hydrogen atom is substituted with a halogen atom.]

[0019]

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

[0020] According to the present disclosure, it is possible to provide an additive that can suppress an increase in thermal conductivity of a resin foam over time. Furthermore, according to the present disclosure, it is possible to provide a composition and a resin foam containing the additive.

[0021] 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 limit or lower limit of a numerical range in a certain stage may be replaced with the upper limit or lower limit of a numerical range in another stage. Furthermore, 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. Furthermore, the upper limit and lower limit values ​​described individually can be combined in any combination.

[0022] Hereinafter, embodiments of the present disclosure will be described, but the present disclosure is not limited to the following embodiments.

[0023] <Compound> One embodiment of the present disclosure is a compound (hereinafter referred to as "compound A") having a group represented by the following formula (1):

[0024] In formula (1), R １ and R ２each independently represents a hydrogen atom or an organic group, and * represents a bond. １ and R ２ At least one of the groups contains an alkyl group or an alkylene group in which at least one hydrogen atom is substituted with a halogen atom.

[0025] The compound A has the function of suppressing an increase in the thermal conductivity of the resin over time. That is, the compound A can suppress an increase in the thermal conductivity of the resin over time. This effect tends to be more pronounced when the compound A is added to a resin foam.

[0026] R １ and R ２ The organic group represented by the formula (I) may be linear or branched. The organic group may have a ring. The ring may be an aliphatic ring or an aromatic ring, or an aliphatic heterocycle or an aromatic heterocycle. The number of carbon atoms in the organic group may be, for example, 1 to 18.

[0027] The organic group may be an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, or the like. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a 3-methylpentyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, and a nonyl group. Examples of the aryl group include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl group, a thienyl group, a furanyl group, a pyridyl group, and a quinolyl group. Examples of the alkylaryl group include a tolyl group, a xylyl group, and an ethylphenyl group. At least one hydrogen atom of these groups may be substituted with a halogen atom.

[0028] R １ and R ２ Examples of the halogen atom in the organic group represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of further suppressing an increase in the thermal conductivity of the resin over time, the halogen atom is preferably a chlorine atom or a bromine atom. From the same viewpoint, １ and R ２The number of halogen atoms in the organic group represented by R is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. １ and R ２ When both of the groups represent organic groups, the types and numbers of halogen atoms contained in both groups may be the same or different.

[0029] From the viewpoint of further suppressing the increase in the thermal conductivity of the resin over time, R １ and R ２ At least one of R is preferably an alkyl group in which at least one hydrogen atom is substituted with a halogen atom, and more preferably an alkyl group in which at least one hydrogen atom is substituted with a chlorine atom or a bromine atom. From the same viewpoint, the number of carbon atoms in the alkyl group is preferably 1 to 7, more preferably 1 to 4, even more preferably 1 to 2, and particularly preferably 1. From these viewpoints, R １ and R ２ It is particularly preferred that at least one of the groups is a chloromethyl group or a bromomethyl group.

[0030] From the viewpoint of further suppressing the increase in the thermal conductivity of the resin over time, R １ and R ２ is an organic group containing an alkyl group or an alkylene group in which at least one hydrogen atom is substituted with a halogen atom, and R １ and R ２ The other of R is preferably a hydrogen atom or an organic group containing an alkyl group or alkylene group in which at least one hydrogen atom is substituted with a halogen atom. １ and R ２ When the other of R is an organic group containing an alkyl group or an alkylene group in which at least one hydrogen atom is substituted with a halogen atom, the preferred examples of the organic group are the same as those described above. １ and R ２ at least one of R is a chloromethyl group or a bromomethyl group; １ and R ２ It is particularly preferred that the other of the groups is a hydrogen atom, a chloromethyl group, or a bromomethyl group.

[0031] Compound A may be a compound having one group represented by formula (1), or may be a compound having two or more groups represented by formula (1).

[0032] From the viewpoint of further suppressing an increase in the thermal conductivity of the resin over time, compound A preferably has two or more organic groups each containing an alkyl or alkylene group in which at least one hydrogen atom is substituted with a halogen atom, and more preferably has 2 to 3 such organic groups.

[0033] In one embodiment, compound A may be a compound represented by formula (I):

[0034] R in formula (I) １ and R ２ is R in formula (1). １ and R ２ and the preferred examples thereof are also the same. １ and R ２ At least one of the groups is an organic group containing an alkyl group or an alkylene group in which at least one hydrogen atom is substituted with a halogen atom, preferably an alkyl group in which at least one hydrogen atom is substituted with a halogen atom, more preferably an alkyl group in which at least one hydrogen atom is substituted with a chlorine atom or a bromine atom, and particularly preferably a chloromethyl group or a bromomethyl group.

[0035] R in formula (I) ３ and R ４ Each of the groups independently represents a hydrogen atom or an organic group. Examples of the organic group include R １ and R ２ The organic group is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

[0036] Specific examples of the compound represented by formula (I) include 4-(chloromethyl)-2,2-dimethyl-1,3-dioxolane, 4-(chloroethyl)-2,2-dimethyl-1,3-dioxolane, 4-(chloropropyl)-2,2-dimethyl-1,3-dioxolane, 4-(chlorobutyl)-2,2-dimethyl-1,3-dioxolane, 4,5-bis(chloromethyl)-2,2-dimethyl-1,3-dioxolane, 4,5-bis(chloromethyl)-2,2-diphenyl-1,3-dioxolane, 4-(chloromethyl)-2,2-diethyl-1,3-dioxolane, 4-(butyl)-2,2-dimethyl-1,3-dioxolane, 4-(bromomethyl)-2,2-dimethyl-1,3-dioxolane, 4-(bromoethyl)-2,2-dimethyl-1,3-dioxolane, 4-(bromopropyl)-2,2-dimethyl-1,3-dioxolane, 4-(bromobutyl)-2,2-dimethyl-1,3-dioxolane, 4,5-bis(bromomethyl)-2,2-diethyl-1,3-dioxolane, 4,5-bis(bromoethyl)-2,2-dimethyl-1,3-dioxolane, 2,2-diethyl-1,3-dioxolane, 4,4'-bis(chloromethyl)-2,2'-bi-1,3-dioxolane, and the like.

[0037] The compound represented by formula (I) can be synthesized according to known methods, such as the method described in Non-Patent Document 1 (Synthetic Communications, 2005, 35(11), 1441-1445).

[0038] In one embodiment, compound A may be a compound represented by the following formula (II):

[0039] R in formula (II) １ａ and R ２ａ is R in formula (1). １ and R ２ and the preferred examples thereof are also the same. １ａ and R ２ａAt least one of the groups contains an alkyl group or alkylene group in which at least one hydrogen atom is substituted with a halogen atom, is preferably an alkyl group in which at least one hydrogen atom is substituted with a halogen atom, is more preferably an alkyl group in which at least one hydrogen atom is substituted with a chlorine atom or a bromine atom, and is particularly preferably a chloromethyl group or a bromomethyl group.

[0040] R in formula (II) １ｂ and R ２ｂ Each of the groups independently represents a hydrogen atom or an organic group. Examples of the organic group include R １ and R ２ The examples of the organic group represented by R are the same as those of the organic group represented by R １ｂ and R ２ｂ At least one of the groups preferably contains an alkyl group or alkylene group in which at least one hydrogen atom is substituted with a halogen atom, more preferably an alkyl group in which at least one hydrogen atom is substituted with a halogen atom, more preferably an alkyl group in which at least one hydrogen atom is substituted with a chlorine atom or a bromine atom, and particularly preferably a chloromethyl group or a bromomethyl group.

[0041] Specific examples of the compound represented by formula (II) include 2,7-bis(chloromethyl)-1,4,6,9-tetraoxaspiro[4.4]nonane, 2,7-bis(bromomethyl)-1,4,6,9-tetraoxaspiro[4.4]nonane, 2-(chloromethyl)-1,4,6,9-tetraoxaspiro[4.4]nonane, 2-(bromomethyl)-1,4,6,9-tetraoxaspiro[4.4]nonane, 2-(chloromethyl)-7-methyl-1,4,6,9-tetraoxaspiro[4.4]nonane, 2-(bromomethyl)-7-methyl-1,4,6,9-tetraoxaspiro[4.4]nonane, 2,3-bis(chloromethyl)-7-methyl-1,4,6,9-tetraoxaspiro[4.4]nonane, 2,3- Bis(bromomethyl)-7-methyl-1,4,6,9-tetraoxaspiro[4.4]nonane, 2,3-bis(chloromethyl)-1,4,6,9-tetraoxaspiro[4.4]nonane, 2,3,7-tris(chloromethyl)-1,4,6,9-tetraoxaspiro[4.4]nonane, 2,3,7,8-tetrakis(chloromethyl)-1,4,6,9-tetraoxaspiro[4.4]nonane, 2,3-bis(bromomethyl)-1,4,6,9-tetraoxaspiro[4.4]nonane, 2,3,7-tris(bromomethyl)-1,4,6,9-tetraoxaspiro[4.4]nonane, 2,3,7,8-tetrakis(bromomethyl)-1,4,6,9-tetraoxaspiro[4.4]nonane, and the like.

[0042] The compound represented by formula (II) can be synthesized according to known methods, such as the method described in Non-Patent Document 2 (Journal of Polymer Science Part A: Polymer Chemistry, 1989, 27(4), 1415-1418).

[0043] In one embodiment, compound A may be a compound represented by the following formula (III):

[0044] R in formula (III) １ｃ and R ２ｃ is R in formula (1). １ and R ２and the preferred examples thereof are also the same. １ｃ and R ２ｃ At least one of the groups contains an alkyl group or alkylene group in which at least one hydrogen atom is substituted with a halogen atom, is preferably an alkyl group in which at least one hydrogen atom is substituted with a halogen atom, is more preferably an alkyl group in which at least one hydrogen atom is substituted with a chlorine atom or a bromine atom, and is particularly preferably a chloromethyl group or a bromomethyl group.

[0045] R in formula (III) １ｄ and R ２ｄ Each of the groups independently represents a hydrogen atom or an organic group. Examples of the organic group include R １ and R ２ The examples of the organic group represented by R are the same as those of the organic group represented by R １ｄ and R ２ｄ At least one of the groups preferably contains an alkyl group or alkylene group in which at least one hydrogen atom is substituted with a halogen atom, more preferably an alkyl group in which at least one hydrogen atom is substituted with a halogen atom, more preferably an alkyl group in which at least one hydrogen atom is substituted with a chlorine atom or a bromine atom, and particularly preferably a chloromethyl group or a bromomethyl group.

[0046] In formula (III), n represents 0, 1 or 2, and m represents 0 or 1, provided that n+m is 0 to 2.

[0047] Specific examples of the compound represented by formula (III) include 2,9-bis(chloromethyl)-1,4,8,11-tetraoxadispiro[4.1.4 ７ .1 ５ ] dodecane, 2,9-bis(chloromethyl)-1,4,8,11-tetraoxadispiro[4.1.4 ７ .2 ５ ]tridecane, 2,10-bis(chloromethyl)-1,4,9,12-tetraoxadispiro[4.2.4 ８ .2 ５ ]tetradecane, 2,9-bis(chloromethyl)-1,4,8,11-tetraoxadispiro[4.1.4 ７ .3 ５] tetradecane, etc.

[0048] From the viewpoint of being able to further suppress an increase in the thermal conductivity of the resin over time, compound A is preferably a compound represented by formula (I), formula (II), or formula (III), and more preferably a compound represented by formula (II).

[0049] <Resin Additive> One embodiment of the present disclosure is a resin additive (hereinafter also referred to as "additive A") containing compound A of the above embodiment. Additive A contains compound A, and therefore has the function of suppressing an increase in the thermal conductivity of a resin over time. In other words, additive A can suppress an increase in the thermal conductivity of a resin over time. This effect tends to be particularly pronounced when additive A is used in a resin foam. Therefore, additive A is suitably used as an additive for a resin foam.

[0050] Since Additive A has the function of suppressing the increase in the thermal conductivity of the resin over time, it can also be used as a thermal conductivity modifier for the resin or an agent for suppressing the increase in the thermal conductivity of the resin over time. However, Additive A may have effects other than the function of suppressing the increase in the thermal conductivity of the resin over time, so it does not necessarily have to be used for the purpose of suppressing the increase in the thermal conductivity of the resin over time.

[0051] Additive A may contain a component other than compound A, or may consist solely of compound A. Examples of components other than compound A include components that may be unavoidably mixed in during the production process of compound A. The content of compound A contained in additive A may be 90 to 100 mass % based on the total mass of additive A. The content of compound A contained in additive A may be 95 mass % or more, or 99 mass % or more, based on the total mass of additive A.

[0052] <Composition> One embodiment of the present disclosure is a composition containing a resin or a resin raw material and the compound A of the above embodiment. Compound A may be included in the composition as a resin additive (e.g., a thermal conductivity modifier). A composition containing a resin may be referred to as a resin composition. A composition containing a resin raw material may be referred to as a resin-forming composition or a resin-forming composition.

[0053] The composition is, for example, a composition for resin foam, preferably a composition for polyurethane foam, and more preferably a composition for thermal insulation. Here, the composition for resin foam refers to both a composition that constitutes a resin foam and a composition for forming a resin foam. Similarly, the composition for polyurethane foam refers to both a composition that constitutes a polyurethane foam and a composition for forming a polyurethane foam, and the composition for thermal insulation refers to both a composition that constitutes a thermal insulation and a composition for forming a thermal insulation. In the present disclosure, a resin foam containing a polyurethane resin as a constituent resin is referred to as a polyurethane foam. The above "composition for forming ~" can be rephrased as "~-forming composition" or "~-forming composition."

[0054] Examples of resins contained in the composition include polyurethane resin, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polyimide resin, phenol resin, etc. Examples of raw materials for the resin contained in the composition include raw materials for polyurethane resin such as polyol and polyisocyanate, and raw materials for phenol resin such as phenol and cresol.

[0055] The content of compound A may be, for example, 0.5 to 20% by mass based on the total mass of the composition.

[0056] The composition preferably contains at least one of a polyurethane resin, a polyol, and a polyisocyanate, and is preferably a polyurethane foam composition.

[0057] 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.

[0058] When the composition contains a polyurethane resin, the content of 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, there is a tendency for the increase in the thermal conductivity of the resin over time to be more effectively suppressed, and when the content is 15 parts by mass or less, there is a tendency for the increase in the thermal conductivity of the resin over time to be suppressed without impairing the mechanical properties of the resin. From the same viewpoint, the content of compound A may be 1 part by mass or more, or 3 parts by mass or more, 10 parts by mass or less, or 7 parts by mass or less, or may be 1 to 10 parts by mass, or 3 to 7 parts by mass relative to 100 parts by mass of the polyurethane resin.

[0059] When the composition contains a polyol, the content of compound A may be, for example, 1 to 50 parts by mass relative to 100 parts by mass of the polyol. When the content is 1 part by mass or more, there is a tendency that the increase in the thermal conductivity of the resin over time can be further suppressed, and when the content is 50 parts by mass or less, there is a tendency that the increase in the thermal conductivity of the resin over time can be suppressed without impairing the mechanical properties of the resin. From the same viewpoint, the content of compound A may be 3 parts by mass or more or 10 parts by mass or more, 30 parts by mass or less or 20 parts by mass or less, or may be 3 to 30 parts by mass or 10 to 20 parts by mass relative to 100 parts by mass of the polyol.

[0060] The composition may further contain other components in addition to the resin, resin raw materials, and compound A. The other components may be known components contained in resin foams or known components used in forming resin foams. Specific examples of the other components include catalysts, flame retardants, blowing agents, foam stabilizers, plasticizers, and colorants.

[0061] <Resin Foam> One embodiment of the present disclosure is a resin foam containing compound A. Compound A may be contained in the resin foam as a resin additive (e.g., a thermal conductivity modifier). The content of compound A may be, for example, 0.3 to 15 mass % based on the total mass of the resin foam.

[0062] The resin foam may be a foam formed from the composition of the above embodiment. That is, the resin foam may contain components that can be contained in the composition of the above embodiment (e.g., a resin, a catalyst, a flame retardant, a blowing agent, a foam stabilizer, a plasticizer, a colorant, etc.). The resin foam is suitably used, for example, as a thermal insulating material or a material for forming a thermal insulating material.

[0063] The resin contained in the resin foam is preferably a polyurethane resin, from the viewpoint of more significantly suppressing the increase in thermal conductivity over time due to compound A. In other words, the resin foam is preferably a polyurethane foam.

[0064] <Polyurethane Foam> One embodiment of the present disclosure is a polyurethane foam containing a polyurethane resin and the compound A of the above embodiment. The polyurethane foam may be a flexible polyurethane foam or a rigid polyurethane foam, but is preferably 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.

[0065] 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.

[0066] Polyurethane foam can be obtained, for example, from a polyurethane foam-forming composition. The polyurethane foam-forming composition is a composition containing at least one of a polyol and a polyisocyanate, and compound A. In the present disclosure, a composition containing a polyol but not a polyisocyanate may be referred to as a polyol composition, and a composition containing a polyisocyanate but not a polyol may be referred to as a polyisocyanate composition.

[0067] When the polyurethane foam-forming composition is a composition containing a polyol and a polyisocyanate, a polyurethane foam is formed by reacting the polyurethane foam-forming composition, i.e., by foaming and curing the polyurethane foam-forming composition. When the polyurethane foam-forming composition is a polyol composition, a polyurethane foam is formed by mixing the polyurethane foam-forming composition with a polyisocyanate or a polyisocyanate composition and reacting (foaming and curing). When the polyurethane foam-forming composition is a polyisocyanate composition, a polyurethane foam is formed by mixing the polyurethane foam-forming composition with a polyol or a polyol composition and reacting (foaming and curing).

[0068] The polyurethane foam-forming composition containing a polyol and a polyisocyanate 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 containing a polyol (e.g., a polyol composition) and a second component containing a polyisocyanate (e.g., a polyisocyanate composition), each of which is independently composed of a first component containing a polyol and a second component containing a polyisocyanate. In this case, the first component containing a polyol and the second component containing a polyisocyanate are mixed and reacted (foamed and cured) to form a polyurethane foam. Compound A may be contained in at least one of the first component and the second component, or in a component different from the first component and the second component. That is, the multi-component composition may also comprise a third component containing compound A, separate from the first component and the second component.

[0069] Among the above examples, when 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 compound A, compound A tends to be easily dispersed uniformly in the polyurethane foam-forming composition.

[0070] The mixed solution containing polyol, polyisocyanate, and compound A to be reacted by the above method may be prepared so as to have an isocyanate index of 100 to 400, for example. That is, the isocyanate index of the polyurethane foam-forming composition may be 100 to 400. Here, the isocyanate index refers to the percentage of the number of moles of all isocyanate groups (NCO groups) in the isocyanate group-containing compounds relative to the number of moles of all active hydrogen groups in the active hydrogen group-containing compounds contained in the mixed solution (NCO groups / active hydrogen groups × 100). The active hydrogen group-containing compounds include not only polyols but also water. The isocyanate index may be 150 to 300 or 180 to 250.

[0071] The reaction (foaming and curing) may be carried out by a conventionally known method, for example, by heating in a mold.

[0072] Next, a description will be given of components that may be contained in the polyurethane foam-forming composition other than compound A. The components described below may be contained in the polyurethane foam.

[0073] [Polyol] Polyol is a compound having two or more hydroxyl groups. Examples of polyols include polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, etc. One type of polyol may be used alone, or multiple types may be used in combination.

[0074] As the polyol, an aromatic polyester polyol is preferably used from the viewpoint of being able to easily obtain higher heat insulating performance and to further suppress deterioration of heat insulating performance over time. Here, the aromatic polyester polyol is a polyester polyol having an aromatic ring in the molecule. Examples of the aromatic polyester polyol include polyester polyols obtained by a condensation polymerization reaction between a polyfunctional alcohol and an acid component containing at least one selected from the group consisting of phthalic acid, isophthalic acid, terephthalic acid, and anhydrides thereof.

[0075] The polyfunctional alcohol is preferably 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.

[0076] As the aromatic polyester polyol, a condensation polymerization reaction product of an acid component containing at least one of phthalic acid, isophthalic acid, terephthalic acid, or anhydrides thereof, and a polyfunctional alcohol containing at least one selected from the group consisting of ethylene glycol and diethylene glycol is preferably used, from the viewpoints of making it easier to obtain higher heat insulating performance and further suppressing deterioration of heat insulating performance over time.

[0077] From the viewpoint of making it easier to obtain higher heat insulating performance and further suppressing deterioration of heat insulating performance over time, 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 using gel permeation chromatography (GPC).

[0078] The hydroxyl value of the polyol may be 70 to 800 mgKOH / g, 100 to 650 mgKOH / g, or 150 to 450 mgKOH / g, from the viewpoint of making it easier to obtain higher heat insulating performance and further suppressing deterioration of heat insulating performance over time. The hydroxyl value is a value measured in accordance with JIS K1557-1.

[0079] [Polyisocyanate] Polyisocyanate is a compound having a plurality of isocyanate groups. Examples of polyisocyanates include diphenylmethane diisocyanate (MDI), polyphenylene polymethylene polyisocyanate (P-MDI), and various modified products of MDI or P-MDI (urethane modified product, urea modified product, allophanate modified product, nurate modified product, biuret modified product, etc.). One type of polyisocyanate may be used alone, or multiple types may be used in combination.

[0080] [Other Components] 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.

[0081] As the catalyst, various urethanization catalysts, isocyanuration catalysts, etc. known in the art can be used. A urethanization catalyst and an isocyanuration catalyst may be used in combination.

[0082] 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, N,N-dimethyl Examples of the urethane-forming catalyst include amine compounds such as N,N-dimethylaminoethanol, N,N,N'-trimethylaminoethylethanolamine, 2-(2-dimethylaminoethoxy)ethanol, N,N,N'-trimethyl-N'-hydroxyethylbisaminoethyl ether, alkanolamines such as N-(3-dimethylaminopropyl)-N,N-diisopropanolamine, N-(2-hydroxyethyl)-N'-methylpiperazine, N,N-dimethylaminohexanol, and 5-dimethylamino-3-methyl-1-pentanol, and imidazoles such as 1,2-dimethylimidazole and 1-isobutyl-2-methylimidazole. These urethane-forming catalysts may be used alone or in combination of two or more.

[0083] Examples of isocyanuration catalysts (hereinafter also referred to as "trimerization catalysts") include quaternary ammonium salts, alkali metal salts of carboxylic acids having 2 to 12 carbon atoms, alkali metal salts of acetylacetone, salicylaldehyde, etc., Lewis acid complex salts of amines, metal catalysts, etc. These isocyanuration catalysts may be used alone or in combination of two or more.

[0084] The amount (content) of the catalyst may be 0.1 to 20 parts by mass based on 100 parts by mass of the total amount of the polyol and polyisocyanate.

[0085] Known flame retardants can be used as the flame retardant, and specific examples of the flame retardant include phosphate esters such as tris(chloropropyl)phosphate, and organophosphazenes such as methoxyphenoxycyclophosphazene.

[0086] 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.

[0087] 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. Conventional 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. From the viewpoints of easily reducing the global warming potential of the blowing agent itself, easily achieving higher thermal insulation performance, and more effectively suppressing deterioration of thermal insulation performance over time, it is particularly preferable to use at least one selected from the group consisting of HFOs and HCFOs in combination with water.

[0088] The amount of the chemical foaming agent may be 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the polyol and polyisocyanate, 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 polyisocyanate.

[0089] As the foam stabilizer, a foam stabilizer known in the art (e.g., a foam stabilizer for forming rigid polyurethane foam) can be used. The foam stabilizer is, for example, a surfactant, and may be a nonionic surfactant such as an organic silicone surfactant. One type of foam stabilizer may be used alone, or multiple types may be used in combination.

[0090] 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 DC-5598 manufactured by Air Products Co., Ltd.

[0091] The 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.

[0092] 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.

[0093] [ １ H-NMR measurement] １ For H-NMR measurements, an AVANCE III HD 400 (400 MHz; manufactured by BRUKER) was used. １ H-NMR was performed in deuterated chloroform (CDCl ３ The measurement was carried out using tetramethylsilane (TMS) as the internal standard. Commercially available reagents were used.

[0094] [Materials] Details of the materials used in this example are shown below. Polyol a: Maximol RFK-505 (manufactured by Air Water Performance Chemicals, Inc., phthalic acid-based polyester polyol, hydroxyl value 250 mg KOH / g) Polyol b: Maximol RFK-556 (manufactured by Air Water Performance Chemicals, Inc., phthalic acid-based polyester polyol, hydroxyl value 250 mg KOH / g) Additive A-1: ​​Compound synthesized in Synthesis Example 1 below Additive A-2: Compound synthesized in Synthesis Example 2 below Foam stabilizer: VORASURF SH-193fluid (manufactured by Dow Toray Industries, Inc.) Urethane catalyst: DM70 (manufactured by Tosoh Corporation, imidazole-based catalyst) Trimerization catalyst: TOYOCAT TRX (manufactured by Tosoh Corporation, quaternary ammonium salt)

[0095] <Synthesis Example 1> Under an argon atmosphere, 3-chloro-1,2-propanediol (71.9 g, 0.65 mol), tetraethoxymethane (50.0 g, 0.26 mol), and paratoluenesulfonic acid monohydrate (0.49 g, 2.6 mmol) were dissolved in dehydrated xylene (800 mL). The resulting solution was stirred at 130°C for 1 hour, then heated to 160°C and stirred for 2 hours. After stirring, the solution was allowed to cool to room temperature, and triethylamine (8.0 mL) was added and stirred for 13 hours. Next, a saturated aqueous solution of sodium bicarbonate was added, and the organic layer was extracted with diethyl ether. The resulting organic layer was dried over sodium sulfate, and low-boiling components were then distilled off. The resulting liquid was then distilled to obtain Additive A-1, a colorless liquid consisting of the compound represented by formula (IIa) above (2,7-bis(chloromethyl)-1,4,6,9-tetraoxaspiro[4.4]nonane). The amount of additive A-1 obtained was 48.5 g, and the yield was 81%. １ The H-NMR is shown below. １ H-NMR (400MHz, CDCl ３ ): δ4.49 (m, 2H), 4.23 (m, 2H), 4.03 (m, 2H), 3.66 (m, 2H), 3.56 (m, 2H).

[0096] <Synthesis Example 2> Under an argon atmosphere, 3-bromo-1,2-propanediol (52.5 g, 0.34 mol), tetraethoxymethane (21.7 g, 0.11 mol), and paratoluenesulfonic acid monohydrate (0.22 g, 1.1 mmol) were dissolved in dehydrated xylene (350 mL). The resulting solution was stirred at 130°C for 1 hour, then heated to 160°C and stirred for 2 hours. After the stirred solution was allowed to cool to room temperature, triethylamine (3.5 mL) was added and the mixture was stirred for 13 hours. Next, a 1.0 M aqueous solution of sodium hydroxide was added, and the organic layer was extracted with diethyl ether. The resulting organic layer was dried over sodium sulfate, and low-boiling components were then distilled off. The resulting liquid was then purified by silica gel column chromatography (hexane:ethyl acetate=10:1) to obtain Additive A-2 in the form of white crystals comprising the compound represented by formula (IIb) above (2,7-bis(bromomethyl)-1,4,6,9-tetraoxaspiro[4.4]nonane). The yield of Additive A-2 was 25.3 g, and the yield was 71%. １ The H-NMR is shown below. １ H-NMR (400MHz, CDCl ３ ): δ4.53 (m, 2H), 4.25 (m, 2H), 4.02 (m, 2H), 3.50 (m, 2H), 3.40 (m, 2H).

[0097] Preparation Example 1 Polyol a, polyol b, a foam stabilizer, a urethanization catalyst, a trimerization catalyst, water, and additive A-1 were added to a 300 mL separable flask and stirred at 300 rpm for 5 minutes while maintaining the liquid temperature at 25°C to 35°C. This yielded polyol composition (1). The blending amounts of each component are as shown in Table 1.

[0098] Preparation Example 2 A polyol composition (2) was obtained in the same manner as in Preparation Example 1, except that additive A-2, which had been previously heated and melted in a constant temperature bath at 60°C, was used instead of additive A-1.

[0099] Preparation Example 3 A polyol composition (3) was obtained in the same manner as in Preparation Example 1, except that additive A-1 was not added and the blending amounts of each component were changed as shown in Table 1.

[0100]

[0101] 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 (1) obtained in Preparation Example 1 and the physical foaming agent HFO-1233zd (Solstice LBA, manufactured by Honeywell) were mixed in the mass ratio shown in Table 2. Next, the resulting mixture was temperature-controlled to 20°C and poured into a 500 mL polypropylene cup. To this was added polyisocyanate (Millionate MR-200, Polymeric MDI manufactured by Tosoh Corporation, NCO content 31% by mass) separately temperature-controlled to 20°C, and the mixture was mixed at 6000 rpm for 3 seconds 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 additive A-1 based on the total amount of the blended components was 5.0% by mass. Next, approximately 133 g (133 ± 2 g) of the resulting mixture (polyurethane foam-forming composition) was poured into the mold, immediately covered, 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 immediately removed from the mold after the reaction was completed and used for density and core density measurements and thermal conductivity evaluation.

[0102] 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.

[0103] Example 2 and Comparative Example 1 Polyurethane foams of Example 2 and Comparative Example 1 were obtained in the same manner as in Example 1, except that polyol compositions (2) and (3) were used instead of polyol composition (1) and the blending ratios of the respective components were as shown in Table 2. The content of Additive A-2 in the polyurethane foam-forming composition of Example 2 was 5.0 mass % based on the total amount of the blended components.

[0104] <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 and 2 and Comparative Example 1 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 the heat flow meter method specified in JIS A1412 using an Auto HC-074 / 314 manufactured by Eiko Seiki Co., Ltd. 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 28 days.

[0105] This test is an accelerated test based on the concept of scaling coefficients as defined in JIS A 1486, and the aging of the 14 mm thick core panel for 28 days corresponds to the aging of a 50 mm thick core panel for approximately half a year. The results are shown in Table 2.

[0106]

[0107] Content C in Table 2 Ａ is the content of additive A (additive A-1 or additive A-2) in the polyurethane foam relative to 100 parts by mass of polyurethane resin. The amount of polyurethane resin in the polyurethane foam was determined by subtracting the "mass of carbon dioxide gas generated during the reaction between water and polyisocyanate" from the total blend mass of polyol (polyol a and polyol b), polyisocyanate, and water.

[0108] In Examples 1 and 2 in which Additive A was used, it was confirmed that the increase in thermal conductivity of the polyurethane foam over time was suppressed.

Claims

1. A composition comprising a resin or a resin raw material and a compound having a group represented by the following formula (1): [In formula (1), R １ and R ２ each independently represents a hydrogen atom or an organic group, and * represents a bond. １ and R ２ At least one of the groups contains an alkyl group or an alkylene group in which at least one hydrogen atom is substituted with a halogen atom.] 2. The composition of claim 1, wherein the halogen atom is a chlorine atom or a bromine atom.

3. The above R １ and the R ２ 3. The composition according to claim 1, wherein at least one of the groups is an alkyl group in which at least one hydrogen atom is substituted with a halogen atom.

4. The above R １ and the R ２ The composition according to any one of claims 1 to 3, wherein at least one of the groups is a chloromethyl group or a bromomethyl group.

5. The composition according to any one of claims 1 to 4, wherein the resin is a polyurethane resin, and the raw material of the resin is at least one of a polyol and a polyisocyanate.

6. The composition according to claim 5, which is for use in polyurethane foam.

7. A resin additive comprising a compound having a group represented by the following formula (1): [In formula (1), R １ and R ２ each independently represents a hydrogen atom or an organic group, and * represents a bond. １ and R ２ At least one of the groups contains an alkyl group or an alkylene group in which at least one hydrogen atom is substituted with a halogen atom.] 8. The resin additive according to claim 7, which is a thermal conductivity modifier.

9. A resin foam comprising a resin and a compound having a group represented by the following formula (1): [In formula (1), R １ and R ２ each independently represents a hydrogen atom or an organic group, and * represents a bond. １ and R ２ At least one of the groups contains an alkyl group or an alkylene group in which at least one hydrogen atom is substituted with a halogen atom.] 10. The resin foam according to claim 9, which is a polyurethane foam.

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