Foamed resin-forming composition, polyurea resin foam, and method for producing polyurea resin foam

Abstract

A foamed resin-forming composition, a polyurea-based resin foam obtained by foam molding the foamed resin-forming composition, and a method for producing a polyurea-based resin foam including a step of foam molding the foamed resin-forming composition. The foamable resin-forming composition is used to obtain a polyurea resin foam, and contains (A) a reactant of a cyclic polyamine compound (a1) and carbon dioxide, (B) a polyisocyanate compound, and (C) an aromatic polyamine compound. Thus, the environmental burden can be reduced, and a polyurea resin foam having improved foamability can be obtained.

Description

Technical Field

[0001] The present invention relates to a foamable resin composition, a polyurea resin foam, and a method for producing the polyurea resin foam. Background Art

[0002] Polyurea resin is a resin compound having a urea bond generated by a chemical reaction between polyisocyanate and polyamine. It has excellent water resistance, chemical resistance, wear resistance, heat resistance, corrosion resistance, quick drying, and environmental safety, and is widely used in various fields such as synthetic leather, artificial leather, adhesives, and coatings.

[0003] In addition, studies have been conducted to impart functions such as heat insulation, sound insulation, and lightness to polyurea resins by foaming the polyurea resins.

[0004] As the technology related to the polyurea resin foam, the technology described in Patent Documents 1 and 2 can be cited, for example.

[0005] Patent document 1 states that a polyurea foam having an isocyanurate structure and an isocyanurate conversion rate of 25 to 50% has excellent flame retardancy and shape retention during combustion, can suppress time-dependent degradation in a hot and humid environment, has excellent adhesion to an adherend during coating, is unlikely to crack even when exposed to flames, and carbonization caused by exposure to flames is unlikely to advance from the surface to the depths.

[0006] Patent document 2 describes the following composition capable of producing polyurea foam with reduced formaldehyde emission, the composition comprising: an isocyanate component; an isocyanate-reactive component; a catalyst selected from a foaming catalyst and / or a gelling catalyst and comprising N-(3-dimethylaminopropyl)-N,N-diisopropanolamine; and a specific amine component, the total amount of which is 0.05% by weight to 0.50% by weight.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent No. 6925554

[0010] Patent Document 2: Japanese Patent Application Publication No. 2019-206712 Summary of the invention

[0011] Problem that the invention aims to solve

[0012] In the past, a foaming agent was required to obtain a foam, and in order to obtain higher foamability, a large amount of foam had to be used and discarded. On the other hand, polyamines used as raw materials for polyurea resins can absorb carbon dioxide and are therefore useful as materials for absorbing waste carbon dioxide.

[0013] The present invention provides a foaming resin forming composition capable of reducing environmental burden and obtaining a polyurea resin foam having improved foamability, a polyurea resin foam having improved foamability, and a method for producing the same.

[0014] Solutions for solving problems

[0015] The inventors of the present invention have repeatedly conducted in-depth research to solve the above-mentioned problems. As a result, it was found that by using the reactant of a cyclic amine compound and carbon dioxide and an aromatic amine as a raw material for obtaining a polyurea resin foam, the amount of the existing blowing agent with a large environmental burden can be reduced, and the environmental burden when manufacturing a polyurea resin foam can be reduced. It was also found that the foamability of the obtained polyurea resin foam can be further improved, thereby completing the present invention. In addition, the above-mentioned reactant can absorb carbon dioxide in the environment to be manufactured, so it also helps to reduce the environmental burden.

[0016] That is, according to the present invention, there are provided the foaming resin-forming composition, the polyurea resin foam, and the method for producing the polyurea resin foam described below.

[0017] [1] A foamable resin composition for obtaining a polyurea resin foam, the foamable resin composition comprising a reaction product (A) of a cyclic polyamine compound (a1) and carbon dioxide, a polyisocyanate compound (B), and an aromatic polyamine compound (C).

[0018] [2] The foamable resin forming composition according to the above [1], wherein the molar ratio ((A) / (C)) of the reaction product (A) of the cyclic polyamine compound (a1) and carbon dioxide to the aromatic polyamine compound (C) in the above foamable resin forming composition is 3 / 7 to 8 / 2.

[0019] [3] The foamable resin-forming composition according to [1] or [2], wherein the aromatic polyamine compound (C) has an amine value of 50 to 600 mgKOH / g.

[0020] [4] The foamable resin forming composition according to any one of [1] to [3] above, which is a foamable resin forming composition for obtaining a polyurea resin foam, wherein the polyurea resin foam comprises a polyurea having a repeating unit represented by the following general formula (I).

[0021] [Chemistry 1]

[0022]

[0023] (In formula (I), R 1is a divalent hydrocarbon group which may have a substituent and has a cyclic structure and a divalent organic group which may have a substituent and has an aromatic ring structure, R 2 It is a divalent hydrocarbon group optionally having a substituent. It should be noted that in the divalent organic group having an aromatic ring structure, the aromatic ring is bonded to the nitrogen atom.

[0024] [5] The foamable resin-forming composition according to any one of [1] to [4] above, wherein the polyisocyanate compound (B) contains a compound having two or more isocyanate groups.

[0025] [6] The foamable resin-forming composition according to any one of [1] to [5], wherein the cyclic polyamine compound (a1) has an amino group bonded to a primary carbon atom.

[0026] [7] The foamable resin-forming composition according to any one of [1] to [6] above, wherein the cyclic structure of the cyclic polyamine compound (a1) includes at least one selected from the group consisting of a five-membered ring and a six-membered ring.

[0027] [8] The foamable resin-forming composition according to any one of [1] to [7], wherein the number of amino groups in the cyclic polyamine compound (a1) is 2 or more and 6 or less.

[0028] [9] The foaming resin-forming composition according to any one of [1] to [8] above, wherein the cyclic polyamine compound (a1) contains at least one selected from the group consisting of xylylenediamine and its derivatives, bis(aminomethyl)cyclohexane and its derivatives, limonenediamine and its derivatives, and isophoronediamine and its derivatives.

[0029]

[10] The foamable resin-forming composition according to any one of [1] to [9] above, wherein the content of the foaming agent other than the reaction product (A) of the cyclic polyamine compound (a1) and carbon dioxide is 5% by mass or less.

[0030]

[11] A foamable resin forming composition according to any one of [1] to

[10] above, wherein the ratio of the total number of amino groups of the reactants (A) of the cyclic polyamine compound (a1) and carbon dioxide and the aromatic polyamine compound (C) in the foamable resin forming composition to the number of isocyanate groups of the polyisocyanate compound (B) (the aforementioned number of amino groups / the aforementioned number of isocyanate groups) is greater than 0.5 and less than 1.5.

[0031]

[12] The foamable resin-forming composition according to any one of [1] to

[11] above, wherein the aromatic polyamine compound (C) is a compound represented by the following formula (III).

[0032] [Chemistry 2]

[0033]

[0034] (In formula (III), X is a divalent organic group, and the divalent organic group is at least one selected from an alkylene group optionally having a substituent, a polyoxyalkylene group optionally having a substituent, an ether bond, an ester bond, an amide bond, and a single bond, or a combination thereof.)

[0035]

[13] The foamable resin-forming composition according to any one of [1] to

[12] above, wherein the aromatic polyamine compound (C) is a compound represented by the following formula (IIIa).

[0036] [Chemistry 3]

[0037]

[0038] (In formula (IIIa), n is preferably 1 to 20.)

[0039]

[14] A polyurea resin foam obtained by foaming the foam-forming composition according to any one of [1] to

[13] .

[0040]

[15] The polyurea resin foam according to

[14] above, comprising polyurea having a repeating unit represented by the following general formula (I).

[0041] [Chemistry 4]

[0042]

[0043] (In formula (I), R 1 is a divalent hydrocarbon group which may have a substituent and has a cyclic structure and a divalent organic group which may have a substituent and has an aromatic ring structure, R 2 It is a divalent hydrocarbon group optionally having a substituent. It should be noted that in the divalent organic group having an aromatic ring structure, the aromatic ring is bonded to the nitrogen atom.

[0044]

[16] The polyurea resin foam according to

[14] or

[15] , wherein the aromatic polyamine compound (C) has an amine value of 50 to 600 mgKOH / g.

[0045]

[17] A method for producing a polyurea resin foam, comprising the step of foaming the foam-forming composition according to any one of [1] to

[13] .

[0046]

[18] A method for producing a polyurea resin foam according to the above-mentioned

[17] , which comprises: a step of contacting a cyclic polyamine compound (a1) with a gas containing carbon dioxide to obtain a reactant (A); and a step of mixing the obtained reactant (A) with a polyisocyanate compound (B) and an aromatic polyamine compound (C) to obtain a foaming resin forming composition.

[0047]

[19] The method for producing a polyurea resin foam according to

[17] or

[18] , wherein the aromatic polyamine compound (C) has an amine value of 50 to 600 mgKOH / g.

[0048] Effects of the Invention

[0049] According to the present invention, there are provided a foaming resin forming composition capable of reducing environmental load and obtaining a polyurea resin foam having improved foamability, a polyurea resin foam having improved foamability, and a method for producing the same. DETAILED DESCRIPTION

[0050] A method for implementing the present invention (hereinafter referred to as "this embodiment") is described in detail. The following embodiment is an example for illustrating the present invention and does not limit the content of the present invention. The present invention can be implemented with appropriate modifications within the scope of its main purpose. In this embodiment, the provisions considered to be preferred can be adopted arbitrarily, and it can be said that the combination of preferred provisions is more preferred. In this embodiment, the record of "XX to YY" means "above XX and below YY".

[0051] [Foamable resin forming composition]

[0052] The foamable resin composition of the present invention is a foamable resin composition for obtaining a polyurea resin foam, and contains a reaction product (A) of a cyclic polyamine compound (a1) and carbon dioxide, a polyisocyanate compound (B), and an aromatic polyamine compound (C).

[0053] The foamable resin-forming composition of the present invention has the above-mentioned structure, so that environmental burden can be reduced and a polyurea-based resin foam having improved foamability can be obtained.

[0054] The “foamable resin-forming composition” refers to a composition for obtaining a foamable resin or a foamed body formed of a foamable resin, and is a composition that serves as a raw material for the foamable resin or a foamed body formed of a foamable resin.

[0055] The foamable resin composition of the present invention is a foamable resin composition for obtaining a polyurea resin foam, preferably a foamable resin composition for obtaining a polyurea resin foam containing a polyurea having a repeating unit represented by the following general formula (I).

[0056] [Chemistry 5]

[0057]

[0058] (In formula (I), R 1 is a divalent hydrocarbon group which may have a substituent and has a cyclic structure and a divalent organic group which may have a substituent and has an aromatic ring structure, R 2 It is a divalent hydrocarbon group optionally having a substituent. It should be noted that in the divalent organic group having an aromatic ring structure, the aromatic ring is bonded to the nitrogen atom.

[0059] R 1 The divalent hydrocarbon group may be substituted and has a cyclic structure, and the divalent organic group may be substituted and has an aromatic ring structure. The divalent hydrocarbon group is derived from the cyclic polyamine compound (a1), and the preferred structure is the same as that of the cyclic polyamine compound (a1). The divalent organic group is derived from the aromatic polyamine compound (C), and the preferred structure is the same as that of the aromatic polyamine compound (C).

[0060] In polyurea, as R 1 , including both a divalent hydrocarbon group which may have a substituent and has a cyclic structure and a divalent organic group which may have a substituent and has an aromatic ring structure. 1 The divalent hydrocarbon group derived from the cyclic polyamine compound (a1) and the divalent organic group derived from the aromatic polyamine compound (C) are described in detail. In other words, the divalent hydrocarbon group having a cyclic structure and optionally having a substituent is a divalent hydrocarbon group derived from the cyclic polyamine compound (a1), and the divalent organic group having an aromatic ring structure and optionally having a substituent is a divalent organic group derived from the aromatic polyamine compound (C).

[0061] R 2 is a divalent hydrocarbon group which may have a substituent. 2 It is derived from the polyisocyanate compound (B), and preferably has the same structure as that of the polyisocyanate compound (B).

[0062] R 2 It is a divalent hydrocarbon group derived from the polyisocyanate compound (B). The divalent hydrocarbon group which may have a substituent is a divalent hydrocarbon group derived from the polyisocyanate compound (B).

[0063] According to the present invention, a polyurea resin foam having improved foamability can be obtained. The reason for this is not clear, but it is considered as follows.

[0064] By heating the resin during molding, the reactant (A) of the cyclic polyamine compound (a1) and carbon dioxide is generated into a cyclic polyamine compound (a1) and carbon dioxide. The cyclic polyamine compound (a1) has a high ability to retain carbon dioxide and low water absorption. Therefore, it can be considered that a sufficient amount of carbon dioxide can contribute to foaming, and a polyurea resin foam with improved foamability can be obtained. Furthermore, it can be considered that at the same time as the foaming resin forming composition begins to foam, the aromatic polyamine compound (C) directly bonded to the aromatic ring with an amino group begins to react, and therefore, the foamability is further improved. In addition, since the cyclic polyamine compound (a1) has a high ability to retain carbon dioxide, it can not only absorb carbon dioxide in the environment, but also reduce the use of other foaming agents, and can also reduce the environmental burden.

[0065] <Reaction product (A) of cyclic polyamine compound (a1) and carbon dioxide>

[0066] The reaction product (A) of the cyclic polyamine compound (a1) and carbon dioxide contained in the foamable resin forming composition of the present invention functions as a foaming agent in the foamable resin forming composition.

[0067] In other words, by using the reaction product (A) of the cyclic polyamine compound (a1) and carbon dioxide as a blowing agent for molding a polyurea resin foam, environmental load can be reduced and a polyurea resin foam having improved foamability can be obtained.

[0068] From the viewpoint of further improving the reactivity with carbon dioxide and the foaming property, the cyclic polyamine compound (a1) preferably has an amino group bonded to a primary carbon atom. It is considered that such an amino group has little steric hindrance and easily absorbs carbon dioxide.

[0069] The cyclic polyamine compound (a1) is a polyamine compound having a cyclic structure. Examples of the cyclic structure of the cyclic polyamine compound (a1) include an alicyclic hydrocarbon structure, an aromatic hydrocarbon structure, and a heterocyclic structure containing a heteroatom in the ring. From the viewpoint of further improving the reactivity with carbon dioxide and the foaming property, it is preferred that the cyclic polyamine compound (a1) contain at least one structure selected from an alicyclic hydrocarbon structure and an aromatic hydrocarbon structure, and more preferably contain an aromatic hydrocarbon structure.

[0070] Here, in the present embodiment, the alicyclic hydrocarbon structure refers to a cyclic structure formed of saturated carbon or unsaturated carbon and hydrogen without aromaticity, excluding a heterocyclic structure containing a heteroatom in the ring. In addition, a heterocyclic structure refers to a ring structure containing a heteroatom in the atoms constituting the ring.

[0071] The cyclic polyamine compound (a1) may be any of a cis isomer, a trans isomer, and a mixture of a cis isomer and a trans isomer.

[0072] From the viewpoint of further improving the reactivity with carbon dioxide and the foaming property, the cyclic structure of the cyclic polyamine compound (a1) preferably contains at least one selected from the group consisting of a five-membered ring and a six-membered ring, and more preferably contains a six-membered ring.

[0073] In addition, from the viewpoint of further improving the reactivity with carbon dioxide and the foaming property, the cyclic polyamine compound (a1) preferably has one cyclic structure. That is, the cyclic polyamine compound (a1) is preferably a monocyclic compound.

[0074] Examples of the alicyclic hydrocarbon structure of the cyclic polyamine compound (a1) include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, etc. Among the above ring structures, cyclopentane ring and cyclohexane ring are preferred, cyclohexane ring is more preferred, and 1,3-substituted cyclohexane ring is further preferred.

[0075] The cyclic polyamine compound (a1) preferably has 2 or more amino groups, and preferably 6 or less, more preferably 4 or less, further preferably 3 or less, and further preferably 2, from the viewpoint of further improving the reactivity with carbon dioxide, curability, and foaming properties.

[0076] In addition, the amino group is preferably an amino group having a nitrogen-hydrogen bond, more preferably at least one amino group selected from the group consisting of a primary amino group and a secondary amino group, and still more preferably a primary amino group, from the viewpoint of improving reactivity with carbon dioxide, curability, and foamability.

[0077] The cyclic polyamine compound (a1) is preferably at least one selected from o-xylylenediamine and its derivatives, m-xylylenediamine and its derivatives, p-xylylenediamine and its derivatives, and a compound represented by the following formula (II).

[0078] [Chemistry 6]

[0079]

[0080] In the above formula (1), R 3 ~R 6 Each independently represents a hydrogen atom, or a hydrocarbon group having 1 to 10 carbon atoms which may have at least one substituent selected from an amino group, a cyano group, a phenyl group, a hydroxyl group, and a carboxyl group, 7 ~R 12 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, x and y each independently represent an integer from 0 to 6, x+y is from 1 to 6, p and q each independently represent an integer from 0 to 4, and at least one of p and q is 1 or more.

[0081] R 3 ~R 6Each is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have at least one substituent selected from an amino group, a cyano group, a phenyl group, a hydroxyl group and a carboxyl group, preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have at least one substituent selected from an amino group, a cyano group and a phenyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have at least one substituent selected from an amino group, a cyano group and a phenyl group, further preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have at least one substituent selected from an amino group and a cyano group, further preferably a hydrogen atom or an alkyl group having 2 to 4 carbon atoms which may have at least one substituent selected from an amino group and a cyano group, and further preferably a hydrogen atom.

[0082] R 3 ~R 6 The number of carbon atoms of the hydrocarbon groups is independently 1 or more, preferably 2 or more, and 10 or less, preferably 5 or less, more preferably 4 or less, and further preferably 3 or less.

[0083] R 7 ~R 12 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, further preferably a hydrogen atom or a methyl group, further preferably a hydrogen atom.

[0084] R 7 ~R 12 The number of carbon atoms of the hydrocarbon groups is independently 1 or more and 4 or less, preferably 1 or 2, and more preferably 1.

[0085] p and q are each independently 0 or more, preferably 1 or more, and 4 or less, preferably 2 or less, and more preferably 1. However, at least one of p and q is 1 or more.

[0086] x and y each independently represent an integer of 0 to 6, and x+y is 1 to 6. From the viewpoint of further improving the carbon dioxide absorption and foaming properties, x+y is preferably 2 or more, more preferably 3 or more, and more preferably 4 or more. From the viewpoint of further improving the carbon dioxide absorption and foaming properties, it is preferably 5 or less, and more preferably 4. That is, the alicyclic hydrocarbon structure is preferably a five-membered ring or a six-membered ring, and more preferably a six-membered ring. When x+y is 4, it is preferred that x is 1 and y is 3.

[0087] From the viewpoint of improving the reactivity with carbon dioxide, the curing property and the foaming property, the cyclic polyamine compound (a1) preferably contains at least one selected from the group consisting of xylylenediamine and its derivatives, bis(aminomethyl)cyclohexane and its derivatives, limonenediamine and its derivatives, isophoronediamine and its derivatives, 2,5-bis(aminomethyl)furan and its derivatives, and 2,5-bis(aminomethyl)tetrahydrofuran and its derivatives. It is more preferred that the cyclic polyamine compound (a1) contains at least one selected from the group consisting of xylylenediamine and its derivatives, bis(aminomethyl)cyclohexane and its derivatives, limonenediamine and its derivatives, and isophoronediamine and its derivatives. It is further preferred that the cyclic polyamine compound (a1) contains at least one selected from the group consisting of xylylenediamine and its derivatives, bis(aminomethyl)cyclohexane and its derivatives, and isophoronediamine and its derivatives. It is further preferred that the cyclic polyamine compound (a1) contains at least one selected from the group consisting of xylylenediamine and its derivatives, and bis(aminomethyl)cyclohexane ... xylylenediamine and its derivatives, and bis(aminomethyl)cyclohexane and its derivatives.

[0088] The cyclic polyamine compound (a1) is preferably at least one selected from the group consisting of xylylenediamine and its derivatives, bis(aminomethyl)cyclohexane and its derivatives, limonenediamine and its derivatives, isophoronediamine and its derivatives, 2,5-bis(aminomethyl)furan and its derivatives, and 2,5-bis(aminomethyl)tetrahydrofuran and its derivatives, from the viewpoint of improving the reactivity with carbon dioxide, curability and foaming property. It is more preferably at least one selected from the group consisting of xylylenediamine and its derivatives, bis(aminomethyl)cyclohexane and its derivatives, limonenediamine and its derivatives, and isophoronediamine and its derivatives. It is further preferably at least one selected from the group consisting of xylylenediamine and its derivatives, bis(aminomethyl)cyclohexane and its derivatives, and isophoronediamine and its derivatives. It is still more preferably at least one selected from the group consisting of xylylenediamine and its derivatives, bis(aminomethyl)cyclohexane and its derivatives, and isophoronediamine and its derivatives. It is still more preferably at least one selected from the group consisting of xylylenediamine and its derivatives, and bis(aminomethyl)cyclohexane and its derivatives. It is still more preferably xylylenediamine and its derivatives.

[0089] Examples of xylylenediamine and its derivatives include at least one selected from the group consisting of o-xylylenediamine and its derivatives, m-xylylenediamine and its derivatives, and p-xylylenediamine and its derivatives. Preferably, it is at least one selected from the group consisting of m-xylylenediamine and its derivatives, and p-xylylenediamine and its derivatives. More preferably, it is m-xylylenediamine and its derivatives.

[0090] Examples of bis(aminomethyl)cyclohexane and derivatives thereof include at least one selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane and derivatives thereof, 1,4-bis(aminomethyl)cyclohexane and derivatives thereof, and trans-1,4-bis(aminomethyl)cyclohexane and derivatives thereof, and 1,3-bis(aminomethyl)cyclohexane and derivatives thereof are preferred.

[0091] Among these, from the viewpoint of improving the reactivity with carbon dioxide and the foaming property, the cyclic polyamine compound (a1) is preferably at least one selected from the group consisting of meta-xylylenediamine and its derivatives, and 1,3-bis(aminomethyl)cyclohexane and its derivatives, and more preferably meta-xylylenediamine and its derivatives.

[0092] Here, examples of the derivatives of the various amines include compounds in which at least one of the hydrogen atoms of an amino group is substituted with a hydrocarbon group having 1 to 10 carbon atoms and optionally having at least one substituent selected from the group consisting of an amino group, a cyano group, and a phenyl group; preferably, a compound substituted with an alkyl group having 1 to 4 carbon atoms and optionally having at least one substituent selected from the group consisting of an amino group, a cyano group, and a phenyl group; more preferably, a compound substituted with an alkyl group having 1 to 4 carbon atoms and optionally having at least one substituent selected from the group consisting of an amino group and a cyano group; and further preferably, a compound substituted with an alkyl group having 2 to 4 carbon atoms and optionally having at least one substituent selected from the group consisting of an amino group and a cyano group.

[0093] In addition, examples of derivatives of the above-mentioned various amines include compounds in which at least a part of the hydrogen atoms in the ring structure are substituted with a hydrocarbon group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0094] As described above, the cyclic polyamine compound (a1) is preferably an amine (primary amine). That is, from the viewpoint of improving the reactivity with carbon dioxide and the foaming property, the cyclic polyamine compound (a1) is preferably at least one selected from the group consisting of xylylenediamine and bis(aminomethyl)cyclohexane.

[0095] Examples of the xylylenediamine include at least one selected from the group consisting of o-xylylenediamine, m-xylylenediamine, and p-xylylenediamine, preferably at least one selected from the group consisting of m-xylylenediamine and p-xylylenediamine, and more preferably m-xylylenediamine.

[0096] Examples of the bis(aminomethyl)cyclohexane include at least one selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, and trans-1,4-bis(aminomethyl)cyclohexane, and 1,3-bis(aminomethyl)cyclohexane is preferred.

[0097] Among these, from the viewpoint of improving the reactivity with carbon dioxide and the foaming property, the cyclic polyamine compound (a1) is preferably at least one selected from the group consisting of meta-xylylenediamine and 1,3-bis(aminomethyl)cyclohexane, and more preferably meta-xylylenediamine.

[0098] These cyclic polyamine compounds (a1) can be used alone or in combination of two or more.

[0099] From the viewpoint of improving the dissociation property of carbon dioxide and improving the foaming property, the maximum dissociation temperature of carbon dioxide of the cyclic polyamine compound (a1) measured by the following method is preferably 200° C. or less, more preferably 180° C. or less, further preferably 160° C. or less, further preferably 150° C. or less, further preferably 140° C. or less, further preferably 135° C. or less, further preferably 130° C. or less. The lower limit of the maximum dissociation temperature of carbon dioxide is not particularly limited, and is, for example, 40° C. or more.

[0100] (method)

[0101] The cyclic polyamine compound (a1) absorbing carbon dioxide is heated from 23°C to 250°C at a temperature increase rate of 10°C / min, and the temperature at which the amount of heat absorbed accompanying the desorption of carbon dioxide reaches a maximum is measured, and this temperature is defined as the maximum dissociation temperature of carbon dioxide. Here, the cyclic polyamine compound (a1) absorbing carbon dioxide can be prepared by, for example, allowing 5 mmol of the cyclic polyamine compound (a1) to stand in air at 23°C and 50% RH for 24 hours.

[0102] From the viewpoint of further improving carbon dioxide absorption and foaming properties, the acid dissociation constant (pKa) of the cyclic polyamine compound (a1) is preferably 8.0 or more, more preferably 8.5 or more, and even more preferably 9.0 or more. Also, from the viewpoint of improving the dissociation of carbon dioxide and further improving foaming properties, it is preferably 12.0 or less, more preferably 11.5 or less, and even more preferably 11.0 or less.

[0103] The acid dissociation constant of the cyclic polyamine compound (a1) is a value determined by the following measurement method based on an acid-base titration method.

[0104] (1) 0.2 g of the cyclic polyamine compound (a1) was dissolved in 30 mL of purified water.

[0105] (2) The solution obtained in the above (1) is titrated with a 0.1 N perchloric acid-acetic acid solution using a potentiometric automatic titrator (eg, AT-610 manufactured by Kyoto Electronics Co., Ltd.) to calculate the acid dissociation constant (pKa).

[0106] In addition, the temperature during measurement was set to 25±2°C.

[0107] From the viewpoint of suppressing weight loss during heat treatment when carbon dioxide is dissociated, the molecular weight of the cyclic polyamine compound (a1) is preferably 110 or more, more preferably 120 or more, and even more preferably 130 or more. Furthermore, from the viewpoint of further improving carbon dioxide absorption and foaming properties, it is preferably 250 or less, more preferably 200 or less, and even more preferably 180 or less.

[0108] From the viewpoint of suppressing weight loss during heat treatment when carbon dioxide is dissociated, the maximum endothermic temperature of the cyclic polyamine compound (a1) measured by the following method is preferably 130° C. or higher, more preferably 140° C. or higher, and further preferably 150° C. or higher. From the viewpoint of improving carbon dioxide absorption and foaming properties, it is preferably 260° C. or lower, more preferably 230° C. or lower, further preferably 210° C. or lower, and further preferably 190° C. or lower.

[0109] (method)

[0110] The cyclic polyamine compound (a1) is heated from 23°C to 350°C at a temperature increase rate of 10°C / min, and the temperature at which the amount of heat absorbed by the volatilization of the cyclic polyamine compound (a1) reaches a maximum is measured. This temperature is defined as the maximum endothermic temperature of the amine compound (a1).

[0111] From the viewpoint of further improving the carbon dioxide absorption and foaming properties, the amine value of the cyclic polyamine compound (a1) is preferably 400 mgKOH / g or more, more preferably 500 mgKOH / g or more, more preferably 600 mgKOH / g or more, more preferably 650 mgKOH / g or more, and more preferably 700 mgKOH / g or more. Also, it is preferably 1500 mgKOH / g or less, more preferably 1400 mgKOH / g or less, more preferably 1300 mgKOH / g or less, more preferably 1100 mgKOH / g or less, more preferably 1000 mgKOH / g or less, and more preferably 850 mgKOH / g or less. The amine value represents the amount of amine in the compound, and refers to the number of mg of potassium hydroxide (KOH) equivalent to the acid required to neutralize 1 g of the compound.

[0112] The amine value can be measured by the following method in accordance with JIS K7237-1995.

[0113] (1) 0.1 g of the cyclic polyamine compound (a1) was dissolved in 20 mL of acetic acid.

[0114] (2) The solution obtained in the above (1) is titrated with a 0.1 N perchloric acid-acetic acid solution using a potentiometric automatic titrator (eg, AT-610 manufactured by Kyoto Electronics Co., Ltd.), thereby calculating the amine value.

[0115] From the viewpoint of improving foaming properties, the mass increase rate of the cyclic polyamine compound (a1) calculated by the following formula when the cyclic polyamine compound (a1) is left to stand for one week in an air environment of 23°C and 50%RH is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 18% by mass or more, further preferably 20% by mass or more, further preferably 23% by mass or more. Furthermore, it is preferably 50% by mass or less, more preferably 45% by mass or less, further preferably 40% by mass or less, further preferably 30% by mass or less, further preferably 28% by mass or less.

[0116] Mass increase rate of cyclic polyamine compound (a1) [mass %] = 100 × mass increase of cyclic polyamine compound (a1) (g) / (mass of cyclic polyamine compound (a1) (g) + mass increase of cyclic polyamine compound (a1) (g))

[0117] Specifically, the mass increase rate of the cyclic polyamine compound (a1) can be measured by the method described in Examples.

[0118] The reaction product (A) of the cyclic polyamine compound (a1) and carbon dioxide can be obtained, for example, by contacting the cyclic polyamine compound (a1) with a gas containing carbon dioxide and reacting the cyclic polyamine compound (a1) with carbon dioxide. That is, in a preferred method for producing the reaction product (A) of the cyclic polyamine compound (a1) and carbon dioxide, the cyclic polyamine compound (a1) is contacted with a gas containing carbon dioxide and reacted with the cyclic polyamine compound (a1) with carbon dioxide.

[0119] The gas containing carbon dioxide can be carbon dioxide alone or a mixture of carbon dioxide and an inert gas. As the gas containing carbon dioxide, it is convenient to use air, which is preferred. Here, "inert gas" refers to a gas that does not affect the reaction when obtaining the polyurea resin foam described later. As the inert gas, nitrogen, oxygen, etc. can be listed.

[0120] Preferably, the method further comprises the step of contacting the cyclic polyamine compound (a1) with carbon dioxide in a gas containing carbon dioxide and having a carbon dioxide concentration of 0.01% by volume to 10% by volume to obtain a reactant (A).

[0121] The carbon dioxide concentration is preferably 0.01% by volume or more, more preferably 0.02% by volume or more, further preferably 0.03% by volume or more, and preferably 10% by volume or less, more preferably 5% by volume or less, further preferably 1% by volume or less, further preferably 0.5% by volume or less, further preferably 0.1% by volume or less. In addition, the gas having a carbon dioxide concentration of 0.01% by volume or more and 10% by volume or less is further preferably air.

[0122] There is no limitation on the method of contacting the cyclic polyamine compound (a1) with a gas containing carbon dioxide. Preferably, the cyclic polyamine compound (a1) is stored in a gas containing carbon dioxide at 30° C. or less while stirring or shaking until the mass increase rate reaches the target range. There is no limitation on the pressure when the cyclic polyamine compound (a1) is contacted with a gas containing carbon dioxide. Preferably, the cyclic polyamine compound (a1) is stored under atmospheric pressure or under pressure, and more preferably, it is stored under atmospheric pressure.

[0123] The time for contacting the gas containing carbon dioxide can be adjusted according to the temperature, pressure, and amount of carbon dioxide contained in the gas shown above. When air is used as the gas containing carbon dioxide and stored under atmospheric pressure, the time for contacting the gas containing carbon dioxide is preferably 1 hour or more, more preferably 1 day or more, further preferably 5 days or more, further preferably 10 days or more, further preferably 15 days or more, and further preferably 30 days or more. There is no upper limit, but it is preferably 100 days or less.

[0124] The reaction product (A) of the cyclic polyamine compound (a1) and carbon dioxide preferably contains at least one selected from the group consisting of carbamic acid, carbamates, carbonates, and bicarbonates.

[0125] The reaction product (A) of the cyclic polyamine compound (a1) and carbon dioxide forms a salt as described above, but the molar ratio of the portion derived from the cyclic polyamine compound (a1) contained in the reactant (A) to the portion derived from carbon dioxide [cyclic polyamine compound (a1) / carbon dioxide] is preferably 70 / 30 to 30 / 70, more preferably 60 / 40 to 40 / 60, and further preferably 55 / 45 to 45 / 55.

[0126] The water content in the reactant (A) is preferably 50% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, and further preferably 5% by mass or less. By setting the water content within the above range, foaming properties can be improved.

[0127] The reaction product (A) of the cyclic polyamine compound (a1) and carbon dioxide can be obtained by contacting the cyclic polyamine compound (a1) with a gas containing carbon dioxide as described above, and it is preferred that no moisture is added at this time.

[0128] <Polyisocyanate compound (B)>

[0129] The polyisocyanate compound (B) is not particularly limited as long as it contains a compound having two or more isocyanate groups, and a conventionally known compound can be used. The polyisocyanate compound (A) is preferably a compound having two or more isocyanate groups.

[0130] Examples of the diisocyanate compound having two isocyanate groups include aliphatic isocyanate compounds such as 1,6-hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, methylene diisocyanate, isopropylidene diisocyanate, lysine diisocyanate, lysine diisocyanate methyl ester, and 1,5-octylene diisocyanate; 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), norbornene diisocyanate, hydrogenated toluene diisocyanate, methylcyclohexane diisocyanate, isopropylidene diisocyanate, and the like; alicyclic isocyanate compounds such as 2,4-toluene diisocyanate or 2,6-toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate, p-xylylene diisocyanate or m-xylylene diisocyanate (XDI), toluidine diisocyanate, p-phenylene diisocyanate, diphenyl ether diisocyanate, diphenyl sulfone diisocyanate, dianisidine diisocyanate, tetramethyl-m-xylylene diisocyanate and other aromatic isocyanate compounds, etc.

[0131] Examples of the isocyanate compound having three or more isocyanate groups include triphenylmethane triisocyanate, thiophosphoric acid triphenyl isocyanate, polymethylene polyphenylene polyisocyanate (POLYMERIC MDI), and trimers of HDI and TDI, namely, isocyanurate-modified products and biuret-modified products.

[0132] The isocyanate compound (B) can be used alone or in combination of two or more.

[0133] Among these, the polyisocyanate compound (B) is preferably a diisocyanate having two isocyanate groups, more preferably at least one selected from the group consisting of isophorone diisocyanate (IPDI), 1,6-hexamethylene diisocyanate (HDI) and 4,4'-diphenylmethane diisocyanate (MDI), further preferably at least one selected from the group consisting of isophorone diisocyanate (IPDI) and 1,6-hexamethylene diisocyanate (HDI), and even more preferably isophorone diisocyanate (IPDI).

[0134] <Aromatic polyamine compound (C)>

[0135] The foamable resin-forming composition of the present invention contains an aromatic polyamine compound (C).

[0136] The "aromatic polyamine compound (C)" in the foamable resin-forming composition of the present invention refers to a polyamine having an amino group directly bonded to an aromatic ring.

[0137] This is probably because the aromatic polyamine compound (C) starts to react at the same time as the foaming of the foamable resin-forming composition starts, and therefore the molecular weight of the obtained foamable polyurea-based resin increases, and the foaming property further improves.

[0138] The aromatic polyamine compound (C) has multiple amino groups in one molecule, but when there is only one aromatic ring in one molecule of the aromatic polyamine compound (C), multiple amino groups are present on one aromatic ring. When there are multiple aromatic rings in one molecule of the aromatic polyamine compound (C), one or more amino groups are present on one aromatic ring. However, the aromatic polyamine compound (C) preferably has multiple aromatic rings in one molecule and one amino group on one aromatic ring.

[0139] The aromatic ring of the aromatic polyamine compound (C) is preferably at least one selected from the group consisting of a five-membered ring and a six-membered ring, and more preferably a six-membered ring.

[0140] The number of amino groups in the aromatic polyamine compound (C) is preferably 2 or more, and is preferably 6 or less, more preferably 4 or less, further preferably 3 or less, and further preferably 2 or less.

[0141] The amino group is preferably an amino group having a nitrogen-hydrogen bond, more preferably at least one amino group selected from the group consisting of a primary amino group and a secondary amino group, and still more preferably a primary amino group.

[0142] The aromatic polyamine compound (C) is preferably a compound represented by the following formula (III).

[0143] [Chemistry 7]

[0144]

[0145] (In formula (III), X is a divalent organic group.)

[0146] X may be a divalent organic group, and may be at least one selected from the group consisting of an alkylene group optionally having a substituent, a polyoxyalkylene group optionally having a substituent, an ether bond, an ester bond, an amide bond, and a single bond, and may be an organic group obtained by combining these.

[0147] The aromatic polyamine compound (C) is more preferably a compound represented by the following formula (IIIa). The compound represented by formula (IIIa) is polytetramethylene oxide-diparaaminobenzoate.

[0148] [Chemistry 8]

[0149]

[0150] (In formula (IIIa), n is preferably 1 to 20.)

[0151] From the viewpoint of improving foaming properties, n is preferably 1 to 20, more preferably 2 to 15, further preferably 2 to 10, and further preferably 2 to 6.

[0152] Examples of commercially available products of the compound represented by the above formula (IIIa) include "ELASMER 1000P" (molecular weight 1238, amine value 84.8 mgKOH / g), "ELASMER 650P" (molecular weight 888, amine value 126 mgKOH / g), and "ELASMER 250P" (molecular weight 488, amine value 220 mgKOH / g) manufactured by Kumiai Chemical Industry Co., Ltd.; "ETHACURE 100PLUS" (molecular weight 178, amine value 89 mgKOH / g), "ETHACURE 300" (molecular weight 214, amine value 107 mgKOH / g), and "ETHACURE 420" (molecular weight 310, amine value 155 mgKOH / g) manufactured by Mitsui Chemicals Fine Chemicals Co., Ltd.

[0153] The aromatic polyamine compound (C) can be used alone or in combination of two or more.

[0154] The molecular weight of the aromatic polyamine compound (C) is preferably 300 to 5000, more preferably 300 to 2000, further preferably 300 to 1500, further preferably 300 to 1000, further preferably 300 to 700, further preferably 400 to 600. When the molecular weight of the aromatic polyamine compound (C) is within the above range, the foaming property can be improved, and further, flexibility can be imparted to the obtained polyurea resin foam.

[0155] The amine value of the aromatic polyamine compound (C) is preferably 50 to 1000 mgKOH / g, more preferably 50 to 600 mgKOH / g, further preferably 50 to 400 mgKOH / g, further preferably 50 to 300 mgKOH / g, further preferably 70 to 300 mgKOH / g, further preferably 80 to 300 mgKOH / g, further preferably 100 to 300 mgKOH / g. The amine value represents the amount of amine in the compound, and refers to the number of mg of potassium hydroxide (KOH) equivalent to the acid required to neutralize 1 g of the compound. By setting the amine value of the aromatic polyamine compound (C) to the above range, the foaming property can be improved, and further, the obtained polyurea resin foam can be given flexibility.

[0156] The amine value can be measured by the following method in accordance with JIS K7237-1995.

[0157] (1) 0.1 g of an aromatic polyamine compound (C) was dissolved in 20 mL of acetic acid.

[0158] (2) The solution obtained in the above (1) is titrated with a 0.1 N perchloric acid-acetic acid solution using a potentiometric automatic titrator (eg, AT-610 manufactured by Kyoto Electronics Co., Ltd.), thereby calculating the amine value.

[0159] <Composition of Foaming Resin Forming Composition>

[0160] As described above, the foamable resin-forming composition contains the reaction product (A) of the cyclic polyamine compound (a1) and carbon dioxide, the polyisocyanate compound (B) and the aromatic polyamine compound (C), and preferably has the following composition.

[0161] The molar ratio ((A) / (C)) of the reaction product (A) of the cyclic polyamine compound (a1) and carbon dioxide to the aromatic polyamine compound (C) in the foamable resin forming composition is preferably 3 / 7 to 9 / 1, more preferably 3 / 7 to 8 / 2, further preferably 4 / 6 to 8 / 2, further preferably 5 / 5 to 8 / 2, further preferably 5 / 5 to 7 / 3, further preferably 6 / 4 to 7 / 3. By setting the molar ratio of the reaction product (A) of the cyclic polyamine compound (a1) and carbon dioxide to the aromatic polyamine compound (C) within the above range, the foamability can be improved, and further, the obtained polyurea resin foam can be given flexibility.

[0162] The ratio of the total number of amino groups of the cyclic polyamine compound (a1) and the carbon dioxide reactant (A) and the aromatic polyamine compound (C) in the foaming resin forming composition to the number of isocyanate groups of the polyisocyanate compound (B) (the aforementioned number of amino groups / the aforementioned number of isocyanate groups) is preferably 0.5 or more and 1.5 or less. From the viewpoint of improving foamability, the ratio of the number of amino groups in the aforementioned foaming agent (A) to the number of isocyanate groups in the polyisocyanate compound (B) (the aforementioned number of amino groups / the aforementioned number of isocyanate groups) is preferably 0.5 or more, more preferably 0.6 or more, further preferably 0.7 or more, further preferably 0.8 or more, and further preferably 0.9 or more. From the same viewpoint, it is preferably 1.5 or less, more preferably 1.4 or less, further preferably 1.3 or less, further preferably 1.2 or less, and further preferably 1.1 or less.

[0163] The foamable resin forming composition of the present invention may contain a foaming agent other than the reaction product (A) of the cyclic polyamine compound (a1) and carbon dioxide, but preferably contains substantially no foaming agent. The content of the foamable resin forming composition other than the foaming agent (A) is preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 1% by mass or less, further preferably 0.5% by mass or less, further preferably 0.1% by mass or less, further preferably 0% by mass or less, and further preferably contains no foaming agent.

[0164] Examples of the blowing agent other than the reactant (A) include halogen-containing hydrocarbons of the Freon series such as chlorofluorocarbons and fluorocarbons; alicyclic hydrocarbons such as cyclopentane; organic blowing agents such as dinitropentamethylenetetramine, azodicarbonamide, p,p'-oxybisbenzenesulfonylhydrazide; and inorganic blowing agents such as sodium bicarbonate.

[0165] The foamable resin forming composition may further contain other components such as fillers, modifying components such as plasticizers, flow regulating components such as thixotropic agents, pigments, leveling agents, thickeners, elastomer particles, curing accelerators, foam stabilizers, chemical foaming agents, etc. depending on the application.

[0166] The foamable resin-forming composition may contain a solvent, but preferably contains substantially no solvent. By containing no solvent, the composition has high environmental compatibility and can easily obtain a foamed product.

[0167] Among them, from the viewpoint of effectively obtaining the effect of the present invention, when the total solid content contained in the foamable resin forming composition described in the present invention is set to 100% by mass, the total content of the reaction product (A) of the cyclic polyamine compound (a1) and carbon dioxide, the polyisocyanate compound (B) and the aromatic polyamine compound (C) in the foamable resin forming composition is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, further preferably 90% by mass or more, further preferably 95% by mass or more, further preferably 98% by mass or more, further preferably 99% by mass or more, and from the same viewpoint, it is preferably 100% by mass or less.

[0168] <Method for preparing foamable resin-forming composition>

[0169] The method for preparing the foaming resin forming composition is not particularly limited, and the composition can be produced by mixing the reaction product (A) of the cyclic polyamine compound (a1) and carbon dioxide, the polyisocyanate compound (B), the aromatic polyamine compound (C), and other components as required using a known method and apparatus.

[0170] [Polyurea resin foam and method for producing polyurea resin foam]

[0171] The polyurea resin foam of the present invention is obtained by foaming the foaming resin forming composition of the present invention. Therefore, the polyurea resin foam of the present invention contains polyurea having a repeating unit represented by the following general formula (I). The polyurea having a repeating unit represented by the following general formula (I) contained in the polyurea resin foam of the present invention is the same as that described in the above-mentioned [Foaming resin forming composition].

[0172] [Chemistry 9]

[0173]

[0174] (In formula (I), R 1 is a divalent hydrocarbon group which may have a substituent and has a cyclic structure and a divalent organic group which may have a substituent and has an aromatic ring structure, R 2 It is a divalent hydrocarbon group optionally having a substituent. It should be noted that in the divalent organic group having an aromatic ring structure, the aromatic ring is bonded to the nitrogen atom.

[0175] R 1The divalent hydrocarbon group may be substituted and has a cyclic structure, and the divalent organic group may be substituted and has an aromatic ring structure. The divalent hydrocarbon group is derived from the cyclic polyamine compound (a1), and the preferred structure is the same as that of the cyclic polyamine compound (a1). The divalent organic group is derived from the aromatic polyamine compound (C), and the preferred structure is the same as that of the aromatic polyamine compound (C).

[0176] R 2 is a divalent hydrocarbon group which may have a substituent. 2 It is derived from the polyisocyanate compound (B), and preferably has the same structure as that of the polyisocyanate compound (B).

[0177] The polyurea resin foam of the present invention may be produced by any method as long as the foaming resin forming composition is foam-molded. A preferred method for producing the polyurea resin foam includes the step of foaming the foaming resin forming composition.

[0178] In the step of foaming the foamable resin composition, for example, the foamable resin composition is heated to generate a cyclic polyamine compound (a1) and carbon dioxide from the reactant (A), the foamable resin composition is foamed by the carbon dioxide, and the foamable resin composition is cured by the reaction of the generated cyclic polyamine compound (a1), aromatic polyamine compound (C) and polyisocyanate compound (B). In this way, a polyurea resin foam is obtained.

[0179] The heating temperature and heating time in the step of foaming the foamable resin-forming composition can be appropriately selected, and are preferably 50 to 250° C., more preferably 100 to 200° C., and even more preferably 120 to 180° C. from the viewpoints of reaction speed and productivity, and prevention of raw material decomposition. In addition, the reaction time is preferably 10 minutes to 12 hours, and more preferably 15 minutes to 4 hours.

[0180] The pressure in the step of foaming the foamable resin-forming composition can be appropriately selected, but the foaming is preferably performed under atmospheric pressure.

[0181] The molecular weight of the aromatic polyamine compound (C) used in the method for producing the polyurea resin foam is preferably 300 to 5000, more preferably 300 to 2000, further preferably 300 to 1500, further preferably 300 to 1000, further preferably 300 to 700, further preferably 400 to 600. When the molecular weight of the aromatic polyamine compound (C) is within the above range, the foaming property can be improved, and further, flexibility can be imparted to the obtained polyurea resin foam.

[0182] The amine value of the aromatic polyamine compound (C) used in the method for producing a polyurea resin foam is preferably 50 to 1000 mgKOH / g, more preferably 50 to 600 mgKOH / g, further preferably 50 to 400 mgKOH / g, further preferably 50 to 300 mgKOH / g, further preferably 70 to 300 mgKOH / g, further preferably 80 to 300 mgKOH / g, further preferably 100 to 300 mgKOH / g. The amine value represents the amount of amine in the compound, and refers to the number of mg of potassium hydroxide (KOH) equivalent to the acid required to neutralize 1 g of the compound. By setting the amine value of the aromatic polyamine compound (C) to the above range, the foamability can be improved, and further, the obtained polyurea resin foam can be given flexibility.

[0183] The amine value can be measured by the following method in accordance with JIS K7237-1995.

[0184] (1) 0.1 g of an aromatic polyamine compound (C) was dissolved in 20 mL of acetic acid.

[0185] (2) The solution obtained in the above (1) is titrated with a 0.1 N perchloric acid-acetic acid solution using a potentiometric automatic titrator (eg, AT-610 manufactured by Kyoto Electronics Co., Ltd.), thereby calculating the amine value.

[0186] The method for producing a polyurea resin foam of the present invention preferably further comprises: before the step of foaming the foamable resin forming composition, the step of contacting the cyclic polyamine compound (a1) with a gas containing carbon dioxide to react the cyclic polyamine compound (a1) with carbon dioxide to obtain a reactant (A). In other words, the method for producing a polyurea resin foam of the present invention preferably comprises: contacting the cyclic polyamine compound (a1) with a gas containing carbon dioxide to obtain a reactant (A); and mixing the obtained reactant (A) with a polyisocyanate compound (B) and an aromatic polyamine compound (C) to obtain a foamable resin forming composition.

[0187] The gas containing carbon dioxide can be carbon dioxide alone or a mixture of carbon dioxide and an inert gas. It is convenient and preferred to use air as the gas containing carbon dioxide. Here, "inert gas" refers to a gas that does not affect the reaction when obtaining the polyurea resin foam described later. As the inert gas, nitrogen, oxygen, etc. can be listed.

[0188] Preferably, the method further comprises the step of contacting the cyclic polyamine compound (a1) with carbon dioxide in a gas containing carbon dioxide and having a carbon dioxide concentration of 0.01% by volume to 10% by volume to obtain a reactant (A).

[0189] The carbon dioxide concentration is preferably 0.01% by volume or more, more preferably 0.02% by volume or more, further preferably 0.03% by volume or more, and preferably 10% by volume or less, more preferably 5% by volume or less, further preferably 1% by volume or less, further preferably 0.5% by volume or less, further preferably 0.1% by volume or less. In addition, the gas having a carbon dioxide concentration of 0.01% by volume or more and 10% by volume or less is further preferably air.

[0190] The method for contacting the cyclic polyamine compound (a1) with a gas containing carbon dioxide is not limited, but it is preferred that the cyclic polyamine compound (a1) is stored in a gas containing carbon dioxide at 30° C. or less while being stirred or shaken until the mass increase rate reaches the target range. The pressure at which the cyclic polyamine compound (a1) is contacted with a gas containing carbon dioxide is not limited, but it is preferably stored at atmospheric pressure or under pressure, and more preferably stored at atmospheric pressure.

[0191] The reaction product (A) of the cyclic polyamine compound (a1) and carbon dioxide preferably contains at least one selected from the group consisting of carbamic acid, carbamates, carbonates, and hydrogencarbonates.

[0192] Example

[0193] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the scope of the examples. It should be noted that in the present examples, various measurements were performed by the following methods.

[0194] (Acid dissociation constant (pKa) of cyclic polyamine compounds)

[0195] The acid dissociation constant of the amine compound is determined by the following measurement method.

[0196] (1) 0.2 g of a cyclic polyamine compound was dissolved in 30 mL of purified water.

[0197] (2) The solution obtained in the above (1) was titrated with a 0.1 N perchloric acid-acetic acid solution using a potentiometric automatic titrator (AT-610 manufactured by Kyoto Electronics Co., Ltd.), thereby calculating the acid dissociation constant (pKa).

[0198] In addition, the temperature during measurement was set to 25±2°C.

[0199] (Amine Values ​​of Cyclic Polyamine Compounds and Aromatic Polyamine Compounds)

[0200] The amine value is measured according to JIS K7237-1995 by the following measurement method.

[0201] (1) 0.1 g of a cyclic polyamine compound or an aromatic polyamine compound is dissolved in 20 mL of acetic acid.

[0202] (2) The solution obtained in the above (1) was titrated with a 0.1 N perchloric acid-acetic acid solution using a potentiometric automatic titrator (AT-610 manufactured by Kyoto Electronics Co., Ltd.), thereby calculating the amine value.

[0203] (Maximum endothermic temperature of cyclic polyamine compounds)

[0204] The DTA measurement of the cyclic polyamine compound was carried out as follows to measure the maximum endothermic temperature of the cyclic polyamine compound. First, the cyclic polyamine compound was subjected to differential scanning calorimetry using a differential thermogravimetric analyzer (product name: DTG-60, manufactured by Shimadzu Corporation) under the conditions of a measurement temperature range of 23 to 350°C, a heating rate of 10°C / min, and a nitrogen atmosphere. The temperature at which the endothermic amount associated with the volatilization of the cyclic polyamine compound reaches the maximum was calculated from the DTA curve thus obtained, and this temperature was set as the maximum endothermic temperature of the cyclic polyamine compound.

[0205] (Maximum dissociation temperature of carbon dioxide (CO2) of cyclic polyamine compounds)

[0206] A carbon dioxide concentration meter and a watch glass were placed in an openable and closable desiccator (internal dimensions: 370 mm × 260 mm × 272 mm). Thereafter, a cyclic polyamine compound (5 mmol) was added to the watch glass in the desiccator, and the door was immediately closed. The cyclic polyamine compound was left to stand in the desiccator for 24 hours in an air environment of 23°C and 50% RH. It should be noted that the initial concentration of carbon dioxide was adjusted to about 400 ppm.

[0207] Next, the cyclic polyamine compound is taken out from the dryer to obtain a cyclic polyamine compound that absorbs carbon dioxide. For the cyclic polyamine compound that absorbs carbon dioxide, DSC measurement is performed as follows to measure the maximum dissociation temperature of carbon dioxide of the cyclic polyamine compound. First, for the cyclic polyamine compound, a differential scanning calorimetry measurement is performed using a differential thermogravimetric meter (product name: DTG-60, manufactured by Shimadzu Corporation) under the conditions of a measurement temperature range of 23 to 250°C, a heating rate of 10°C / minute, and a nitrogen atmosphere. Based on the DSC curve thus obtained, the temperature at which the amount of heat absorbed associated with the release of carbon dioxide reaches the maximum is calculated, and this temperature is set as the maximum dissociation temperature of carbon dioxide of the cyclic polyamine compound.

[0208] (Water Content of the Reaction Product (A) of Cyclic Polyamine Compound (a1) and Carbon Dioxide and Composition of Blowing Agent)

[0209] The water content of the reaction product (A) produced in the production example and the composition of the reaction product were measured using an organic trace element analyzer (MACRO CORDER JM10, manufactured by J-SCIENCE LAB).

[0210] (Evaluation of Foaming Property)

[0211] The foamability of the foaming resin forming composition is evaluated based on the volume increase rate (times, foaming ratio) of the polyurea resin foam. The volume increase rate is the value obtained by dividing the thickness after foaming by the thickness before foaming when foaming is performed in a rectangular container with a fixed bottom shape (bottom area). The larger the volume increase rate, the better the foamability.

[0212] In the examples, the following compounds were used as the cyclic polyamine compound (a1), the polyisocyanate compound (B), and the aromatic polyamine compound (C).

[0213] (Cyclic polyamine compound (a1))

[0214] MXDA: meta-phenylenediamine (acid dissociation constant (pKa): 9.5, amine value: 824 mgKOH / g, maximum endothermic temperature: 183.5°C, carbon dioxide (CO2) maximum dissociation temperature: 135.5°C, manufactured by Mitsubishi Gas Chemical Co., Ltd.)

[0215] (Polyisocyanate compound (B))

[0216] IPDI: Isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0217] HDI: 1,6-hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0218] (Aromatic polyamine compound (C))

[0219] 250P: ELASMER 250P (polytetramethylene oxide-diparaaminobenzoate, molecular weight (catalog value): 488, amine value: 220 mgKOH / g, manufactured by Kumiai Chemical Industry Co., Ltd.)

[0220] 1000P: ELASMER 1000P (polytetramethylene oxide-diparaaminobenzoate, molecular weight (catalog value): 1238, amine value: 84.8 mgKOH / g, manufactured by Kumiai Chemical Industry Co., Ltd.)

[0221] Example 1

[0222] (1) Production of a reaction product (A) of a cyclic polyamine compound (a1) and carbon dioxide (absorption of carbon dioxide into an amine compound)

[0223] MXDA as a cyclic polyamine compound is placed in a container and left to stand for 1 week in an air environment of 23°C and 50% RH. Thus, MXDA reacts with carbon dioxide in the air to obtain a reaction product of MXDA and carbon dioxide (carbonate of MXDA). Here, in order to suppress uneven reaction, the container containing the cyclic polyamine compound is appropriately shaken so that unreacted MXDA is not generated. The moisture content of the obtained reaction product (carbonate of MXDA) is 0% by mass.

[0224] Next, the mass increase of MXDA was measured, and the mass increase rate of the cyclic polyamine compound was calculated according to the following formula: The mass increase rate was 24.1% by mass.

[0225] Mass increase rate of cyclic polyamine compound [mass %] = 100 × mass increase of cyclic polyamine compound (g) / (initial mass of cyclic polyamine compound (g) + mass increase of cyclic polyamine compound (g))

[0226] (2) Production of foamable resin composition

[0227] IPDI as a polyisocyanate compound (B) and 250P as an aromatic polyamine compound (C) were added to the above-mentioned reactant (A) of MXDA and carbon dioxide (carbonate of MXDA), and the mixture was stirred and mixed for 1 minute to obtain a foaming resin forming composition. It should be noted that the amount of the reactant of MXDA and carbon dioxide and 250P was such that the molar ratio of the reactant of MXDA and carbon dioxide to 250P ((A) / (C)) was 6 / 4, and the amount of IPDI was such that the total number of amino groups of MXDA and 250P / the number of isocyanate groups of IPDI was 1 / 1 in terms of molar ratio.

[0228] (3) Production of polyurea resin foam

[0229] The foaming resin forming composition obtained by (2) was put into a rectangular parallelepiped mold with a bottom surface of 12 cm × 12 cm in a manner to have a thickness of about 3 mm, and heated using a hot air dryer at a heating temperature of 150°C and a heating time of 30 minutes to cure and foam the foaming resin forming composition. Thus, a polyurea resin foam was obtained. In addition, it was visually confirmed that the obtained polyurea resin foam had a foaming structure. In addition, the foamability of the obtained polyurea resin foam was evaluated. The results are shown in Table 1.

[0230] Examples 2 to 4 and Comparative Examples 1 to 2

[0231] Polyurea resin foams were obtained in the same manner as in Example 1 except that the amounts of the reaction product of MXDA and carbon dioxide obtained in the same manner as in Example 1 (1) and 250P were changed to the ratios shown in Table 1. It should be noted that Comparative Example 1 did not use 250P, and Comparative Example 2 did not use the reaction product of MXDA and carbon dioxide.

[0232] The foamability of the obtained polyurea resin foam was evaluated. The obtained results are shown in Table 1.

[0233] [Table 1]

[0234] Table 1

[0235]

[0236] Example 5

[0237] A polyurea-based resin foam was obtained in the same manner as in Example 1 except that IPDI as the polyisocyanate compound (B) was changed to HDI.

[0238] The foamability of the obtained polyurea resin foam was evaluated.

[0239] Examples 6 to 9 and Comparative Examples 3 to 4

[0240] Polyurea resin foams were obtained in the same manner as in Example 5 except that the amounts of the reaction product of MXDA and carbon dioxide obtained in the same manner as in Example 1 (1) and 250P were changed to the ratios shown in Table 2. It should be noted that in Comparative Example 3, 250P was not used, and in Comparative Example 4, the reaction product of MXDA and carbon dioxide was not used.

[0241] The foamability of the obtained polyurea resin foam was evaluated.

[0242] [Table 2]

[0243] Table 2

[0244]

[0245] Example 10

[0246] A polyurea-based resin foam was obtained in the same manner as in Example 1 except that 250P as the aromatic polyamine compound (C) was changed to 1000P.

[0247] The foamability of the obtained polyurea resin foam was evaluated. The obtained results are shown in Table 3.

[0248] Examples 11 to 14 and Comparative Examples 5 to 6

[0249] Polyurea resin foams were obtained in the same manner as in Example 10 except that the amounts of the reaction product of MXDA and carbon dioxide obtained in the same manner as in Example 1 (1) and 1000P were changed to the ratios shown in Table 3. It should be noted that in Comparative Example 5, 1000P was not used, and in Comparative Example 6, the reaction product of MXDA and carbon dioxide was not used.

[0250] The foamability of the obtained polyurea resin foam was evaluated. The obtained results are shown in Table 3.

[0251] [Table 3]

[0252] Table 3

[0253]

[0254] Embodiment 15

[0255] A polyurea-based resin foam was obtained in the same manner as in Example 10 except that IPDI as the polyisocyanate compound (B) was changed to HDI.

[0256] The foamability of the obtained polyurea resin foam was evaluated.

[0257] Examples 16 to 18 and Comparative Examples 7 to 8

[0258] Polyurea resin foams were obtained in the same manner as in Example 15 except that the amounts of the reaction product of MXDA and carbon dioxide obtained in the same manner as in Example 1 (1) and 1000P were changed to the ratios shown in Table 4. It should be noted that in Comparative Example 7, 1000P was not used, and in Comparative Example 8, the reaction product of MXDA and carbon dioxide was not used.

[0259] The foamability of the obtained polyurea resin foam was evaluated.

[0260] [Table 4]

[0261] Table 4

[0262]

[0263] It can be seen from Tables 1 to 4 that the foamable resin composition of the examples can produce a polyurea resin foam with improved foamability even without using a conventional foaming agent with a large environmental burden. In addition, the foamable resin composition of the examples can be produced by absorbing carbon dioxide in the environment, thus also contributing to reducing the environmental burden.

Claims

1. A foaming resin forming composition for obtaining a polyurea resin foam, The foamable resin-forming composition contains a reaction product (A) of a cyclic polyamine compound (a1) and carbon dioxide, a polyisocyanate compound (B), and an aromatic polyamine compound (C).

2. The foamable resin-forming composition according to claim 1, wherein The molar ratio ((A) / (C)) of the reaction product (A) of the cyclic polyamine compound (a1) and carbon dioxide to the aromatic polyamine compound (C) in the foaming resin-forming composition is 3 / 7 to 8 / 2.

3. The foamable resin-forming composition according to claim 1 or 2, wherein The amine value of the aromatic polyamine compound (C) is 50 to 600 mgKOH / g.

4. The foamable resin composition according to any one of claims 1 to 3, which is a foamable resin composition for obtaining a polyurea resin foam, wherein the polyurea resin foam comprises a polyurea having a repeating unit represented by the following general formula (I): [Chemistry 1] In formula (I), R 1 is a divalent hydrocarbon group which may have a substituent and has a cyclic structure, or a divalent organic group which may have a substituent and has an aromatic ring structure; R 2 It is a divalent hydrocarbon group which may have a substituent. In the divalent organic group having an aromatic ring structure, the aromatic ring is bonded to a nitrogen atom.

5. The foamable resin-forming composition according to any one of claims 1 to 4, wherein The polyisocyanate compound (B) includes a compound having two or more isocyanate groups.

6. The foamable resin-forming composition according to any one of claims 1 to 5, wherein The cyclic polyamine compound (a1) has an amino group bonded to a primary carbon atom.

7. The foamable resin-forming composition according to any one of claims 1 to 6, wherein The cyclic structure of the cyclic polyamine compound (a1) includes at least one selected from the group consisting of a five-membered ring and a six-membered ring.

8. The foamable resin-forming composition according to any one of claims 1 to 7, wherein The number of amino groups in the cyclic polyamine compound (a1) is 2 or more and 6 or less.

9. The foamable resin-forming composition according to any one of claims 1 to 8, wherein The cyclic polyamine compound (a1) includes at least one selected from the group consisting of xylylenediamine and derivatives thereof, bis(aminomethyl)cyclohexane and derivatives thereof, limonenediamine and derivatives thereof, and isophoronediamine and derivatives thereof.

10. The foamable resin-forming composition according to any one of claims 1 to 9, wherein The content of the blowing agent other than the reaction product (A) of the cyclic polyamine compound (a1) and carbon dioxide is 5% by mass or less.

11. The foamable resin-forming composition according to any one of claims 1 to 10, wherein The ratio of the total number of amino groups of the reaction product (A) of the cyclic polyamine compound (a1) and carbon dioxide and the aromatic polyamine compound (C) in the foaming resin-forming composition to the number of isocyanate groups of the polyisocyanate compound (B) (the number of amino groups / the number of isocyanate groups) is 0.5 or more and 1.5 or less.

12. The foamable resin-forming composition according to any one of claims 1 to 11, wherein The aromatic polyamine compound (C) is a compound represented by the following formula (III): [Chemistry 2] In formula (III), X is a divalent organic group, which is at least one selected from the group consisting of an alkylene group optionally having a substituent, a polyoxyalkylene group optionally having a substituent, an ether bond, an ester bond, an amide bond and a single bond, or a combination thereof.

13. The foamable resin-forming composition according to any one of claims 1 to 12, wherein The aromatic polyamine compound (C) is a compound represented by the following formula (IIIa), [Chemistry 3] In the formula (IIIa), n is preferably 1-20. 14 . A polyurea resin foam obtained by foaming the foaming resin-forming composition according to claim 1 .

15. The polyurea resin foam according to claim 14, comprising a polyurea having a repeating unit represented by the following general formula (I): [Chemistry 4] In formula (I), R 1 is a divalent hydrocarbon group which may have a substituent and has a cyclic structure, or a divalent organic group which may have a substituent and has an aromatic ring structure; R 2 It is a divalent hydrocarbon group which may have a substituent. In the divalent organic group having an aromatic ring structure, the aromatic ring is bonded to a nitrogen atom.

16. The polyurea resin foam according to claim 14 or 15, wherein The amine value of the aromatic polyamine compound (C) is 50 to 600 mgKOH / g. 17 . A method for producing a polyurea resin foam, comprising the step of foaming the foam-forming composition according to claim 1 .

18. The method for producing a polyurea resin foam according to claim 17, comprising: A step of contacting the cyclic polyamine compound (a1) with a gas containing carbon dioxide to obtain a reactant (A); as well as A step of mixing the obtained reaction product (A), a polyisocyanate compound (B) and an aromatic polyamine compound (C) to obtain a foamable resin-forming composition.

19. The method for producing a polyurea resin foam according to claim 17 or 18, wherein: The amine value of the aromatic polyamine compound (C) is 50 to 600 mgKOH / g.

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