JP2023184459A - Urea resin composition, method for producing polyurea foam, and polyurea foam - Google Patents

Abstract

To provide a technique capable of providing a new polyurea foam having excellent adhesive strength, for example, even when being coated under a low temperature condition.SOLUTION: There is provided a composition that is one production raw material of a polyurea foam, and is a composition containing polyamine, a carboxylic acid metal salt, a Lewis base compound and/or an organometallic compound.SELECTED DRAWING: None

Description

The present invention relates to a urea resin composition (for example, a composition for producing a polyurea foam), a method for producing a polyurea foam, and a polyurea foam.

In recent years, polyurea foam has been proposed as an alternative material to urethane foam (Patent Documents 1 and 2).

Patent No. 6876185 Patent No. 6925554

An object of the present invention is to provide a technique capable of providing a novel polyurea foam having excellent adhesive strength even when coated under low temperature conditions.

The first aspect of the present invention is
polyamine and
carboxylic acid metal salt,
A polyamine-containing composition containing a Lewis base compound and/or an organometallic compound. The term "polyamine-containing composition" as used herein means a raw material composition necessary for preparing polyurea.
Moreover, the second aspect of the present invention is
polyamine and
A polyamine-containing composition containing a resinization catalyst, the polyamine-containing composition having a peak temperature of 40° C. or higher during the reaction when polyurea is obtained from a polyisocyanate and the composition under the following reaction conditions. .
(Reaction conditions)
The composition and the polyisocyanate (each cooled to 5° C.) are mixed in a 500 mL polypropylene disposable cup (10 cm in diameter) and stirred for 10 seconds at 3000 rpm using a hand mixer. After stirring, measure the temperature of the system using a thermocouple. The highest temperature until polyurea is obtained is defined as the peak temperature.
Moreover, the third aspect of the present invention is
As a first liquid, the polyamine-containing composition of the first aspect, or as a first liquid, the polyamine-containing composition of the second aspect, which further contains a trimerization catalyst;
This is a two-component urea resin composition containing a polyisocyanate-containing composition as a second component.
Moreover, the fourth aspect of the present invention is
polyisocyanate and
polyamine and
carboxylic acid metal salt,
This is a method for producing a polyurea foam from a urea resin composition containing a Lewis base compound and/or an organometallic compound.
Moreover, the fifth aspect of the present invention is
carboxylic acid metal salt,
A polyurea foam containing a Lewis base compound and/or an organometallic compound.

Note that the above problem can also be solved by the following aspects.
This aspect (A1) is
polyamine and
polyisocyanate and
carboxylic acid metal salt,
A composition containing a Lewis base compound and/or an organometallic compound.
This aspect (A2) is
The composition according to aspect (A1), wherein the Lewis base compound is an amine compound.
This aspect (A3) is
polyamine and
polyisocyanate and
The present invention is a composition containing a resin-forming catalyst, and has a peak temperature of 40° C. or higher during the reaction when polyurea is obtained from the composition under the following reaction conditions.
(Reaction conditions)
After stirring the composition for 10 seconds at a rotational speed of 3000 rpm, the temperature of the system is measured using a thermocouple. The highest temperature until polyurea is obtained is defined as the peak temperature.
This aspect (A4) is
The composition is
The first liquid is a composition containing the polyamine, the carboxylic acid metal salt, the Lewis base compound, and/or the organometallic compound, or the first liquid is a composition containing the polyamine and the three metal salts. A composition containing a quantification catalyst and the resinization catalyst;
The composition according to any one of the embodiments (A1) to (A3) is a two-component composition containing the polyisocyanate-containing composition as the second component.
This aspect (A5) is
polyisocyanate and
polyamine and
carboxylic acid metal salt,
This is a method for producing a polyurea foam from a composition containing a Lewis base compound and/or an organometallic compound.
This aspect (A6) is
The method according to aspect (A5), wherein the Lewis base compound is an amine compound.
This aspect (A7) is
carboxylic acid metal salt,
A polyurea foam containing a Lewis base compound and/or an organometallic compound.
This aspect (A8) is
The polyurea foam according to the embodiment (A7), wherein the Lewis base compound is an amine compound.

According to the composition according to the present invention, when used as a raw material for producing a polyurea foam, it is possible to provide a polyurea foam having excellent adhesive strength even when applied under low temperature conditions, for example. In addition, the composition according to the present invention has the effect of having high reactivity at low temperatures, for example, when producing solid polyurea or polyurea foam. Furthermore, the composition according to the present invention also has the effect of imparting excellent material strength (compressive strength, brittleness) to the foam immediately after foaming.

Further, according to the method for producing a polyurea foam and the polyurea foam according to the present invention, it is possible to provide a polyurea foam that has excellent adhesive strength even at low temperatures, for example. Furthermore, according to the method for producing a polyurea foam and the polyurea foam according to the present invention, excellent material strength (compressive strength, brittleness) can be imparted to the foam immediately after foaming.

FIG. 1 is a diagram showing the results of the peak temperature during the reaction when polyurea is obtained from a polyisocyanate and a polyamine-containing composition.

Hereinafter, one embodiment of the present invention will be described. Note that the present invention is not limited to this form. In addition, as a form different from the form explained below, "carboxylic acid metal salt" and "Lewis base compound and/or organometallic compound" in the form explained below are used as "trimerization catalyst" and "resinization catalyst" and "resinization catalyst", respectively. Catalyst (urea conversion catalyst)" is also included.

The polyamine-containing composition that is one raw material for preparing polyurea according to this embodiment contains a polyamine, a carboxylic acid metal salt, a Lewis base compound, and/or an organometallic compound. Here, the "polyamine-containing composition" means a raw material for producing polyurea (polyurea foam or solid polyurea). When actually producing polyurea, not only the polyamine-containing composition but also polyisocyanate is used. Moreover, when manufacturing a polyurea foam, a foaming agent and a foam stabilizer are preferably used. In addition, flame retardants are preferably used when producing flame retardant polyureas (eg, polyurea foams). Therefore, in the following, we will focus on flame-retardant polyurea foam, and explain the urea resin composition (i.e., the polyamine-containing composition, polyisocyanate, blowing agent, and foam stabilizer according to the present embodiment) as raw materials for producing the polyurea foam. A composition containing a flame retardant (hereinafter referred to as a "composition for producing a polyurea foam") will be described in detail.

1. Composition for manufacturing polyurea foam (urea resin composition)
The composition for producing a polyurea foam according to this embodiment comprises (A) a polyisocyanate, (B) a polyamine, (C) a carboxylic acid metal salt, and (D) a Lewis base compound and/or an organometallic compound. , and preferably further includes (E) a foaming agent, (F) a foam stabilizer, and (G) a flame retardant. Here, by using (C) and (D) together, it is possible to provide a polyurea foam having excellent adhesive strength even when coated under low temperature conditions. To be more specific, resin formation progresses preferentially, and reaction heat is more likely to be generated. Thereby, the foaming agent with a low boiling point can be easily vaporized to foam the resin, and the temperature inside the foam can be increased. This temperature increase allows trimerization to proceed efficiently. In addition, when foaming is performed on a face material or structure such as a wooden board or metal, a resin conversion reaction progresses at the interface between the foam and the face material, which develops sufficient material strength even at low temperatures, and allows for adhesion to the face material or structure. Improves sex. In addition, the brittleness of the foam immediately after foaming can be suppressed, and a strong foam can be obtained. Furthermore, according to the composition according to this embodiment, excellent material strength (compressive strength, brittleness) can be imparted to the foam immediately after foaming.

Here, the composition for producing a polyurea foam according to the present embodiment may be of a one-part type (one-component type) or a two-part type (two-part type), and is preferably a two-part type (system liquid). A two-part type is a combination of compositions in which a polyamine and a polyisocyanate are contained separately. Components other than these (polyamine and polyisocyanate) are preferably included in the composition on the polyamine side. In the case of a two-part type, specifically, the first liquid preferably contains (B) a polyamine, (C) a carboxylic acid metal salt, (D) a Lewis base compound, and/or an organometallic compound. , (E) a foaming agent, (F) a foam stabilizer, and (G) a flame retardant, and the second liquid is (A) a polyamine-containing composition containing polyisocyanate. . However, flame retardants, foam stabilizers, blowing agents, dispersants, and/or other additives that do not react with (A) polyisocyanate may be mixed into the composition on the (A) polyisocyanate side. Each component will be explained in detail below.

1-1. Component/Composition 1-1-1. (A) Polyisocyanate The polyisocyanate according to this embodiment is not particularly limited as long as it has a plurality of isocyanate groups. For example, examples of polyisocyanates include monomer-type polyisocyanates and polymer-type polyisocyanates. Here, the monomer type polyisocyanate is a compound in which a plurality of isocyanate groups are present at the ends of the monomer structure. A polymer type polyisocyanate is a compound in which a plurality of isocyanate groups are present at the ends of a polymer structure. The polyisocyanates may be used alone or in combination. The monomer type polyisocyanate and the polymer type polyisocyanate will be explained in detail below.

<Monomer type polyisocyanate>
Monomeric polyisocyanates include, for example, 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), m-phenylene diisocyanate, and p-phenylene diisocyanate as difunctional polyisocyanates. Phenyl diisocyanate, 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 2,2'-diphenylmethane diisocyanate (2,2'-MDI) , hydrogenated MDI, xylylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, polymethylene polyphenyl polyisocyanate, 1,5- Aromatic ones such as naphthalene diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, and tetramethylxylene diisocyanate (TMXDI); cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, Alicyclic ones such as methylcyclohexane diisocyanate; alkylene-based ones such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, lysine diisocyanate, and 1,8-diisocyanatomethyloctane. be able to. Examples of trifunctional or higher functional polyisocyanates include 1-methylbenzole-2,4,6-triisocyanate, 1,3,5-trimethylbenzole-2,4,6-triisocyanate, and biphenyl-2,4,4'-triisocyanate. Isocyanate, diphenylmethane-2,4,4'-triisocyanate, methyldiphenylmethane-4,6,4'-triisocyanate, 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate, triphenyl Methane-4,4',4''-triisocyanate, polymeric MDI, lysine ester triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,6,11-undecane triisocyanate, bicycloheptane triisocyanate, etc. Also, for example, modified products or derivatives of these may be used. Examples of modified products or derivatives of these include isocyanurate compounds of diisocyanates, adduct compounds of diisocyanates, biuret compounds of diisocyanates, and allophanate compounds of diisocyanates. , carbodiimide-modified compounds of diisocyanates.

Among the monomeric polyisocyanates, aromatic isocyanates are preferred, MDI or modified products or derivatives of MDI are more preferred, and monomeric MDI or crude MDI is even more preferred. For example, when using the composition in a spraying method, aromatic isocyanate has excellent reactivity and can ensure safety in the working environment. Further, crude MDI is particularly preferred because it has excellent flame retardancy. In particular, from the viewpoint of increasing adhesive strength, it is most preferable to use monomeric MDI and crude MDI in combination.

<Polymer type polyisocyanate>
Examples of the polymer type polyisocyanate include those obtained by making a prepolymer by reacting an active hydrogen compound having two or more active hydrogen groups with an excess amount of polyisocyanate. Here, examples of the active hydrogen compound having two or more active hydrogen groups include polyols and/or polyamines. Here, the polyisocyanate and polyamine that are raw materials for the polymer-type polyisocyanate are not particularly limited. Regarding the polyisocyanate, for example, the above-mentioned examples of monomer-type polyisocyanate can be mentioned, and for the polyamine, for example, the following examples can be mentioned. (B) Examples of polyamines can be mentioned. The polyol, which is a raw material for the polymer-type polyisocyanate, will be described in detail below.

(polyol)
Examples of polyols include polyester polyols and polyether polyols. Examples of polyester polyols include those obtained by a condensation reaction between a polyhydric alcohol and a polyhydric carboxylic acid. Here, examples of the polyhydric alcohol include ethylene glycol, propylene glycol, butanediol, butylene glycol, glycerin, and trimethylolpropane. Further, examples of the polyhydric carboxylic acid include glutaric acid, adipic acid, maleic acid, phthalic acid, terephthalic acid, and isophthalic acid. These polyhydric alcohols and/or polyhydric carboxylic acids may be used singly or in combination. Furthermore, polyester polyols obtained by ring-opening condensation of caprolactone, methylvalerolactone, etc. may also be used. On the other hand, polyether polyols include, for example, addition polymerization of oxides such as ethylene oxide, propylene oxide, trimethylene oxide, and butylene oxide to polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane, and sorbitol. I can list things that I did. These polyhydric alcohols and/or oxides may be used alone or in combination.

<NCO%>
The NCO% of the polyisocyanate is not particularly limited, and is, for example, 5 to 40%, preferably 10 to 35%, and more preferably 15 to 35%. Within this range, it is possible to provide a polyurea foam having higher initial adhesive strength. Here, the NCO% (isocyanate content) of the polyisocyanate is determined by method A (toluene/dimethyl Butylamine, hydrochloric acid method).

1-1-2. (B) Polyamine The polyamine according to this embodiment is not particularly limited as long as it is an active hydrogen compound having two or more amino groups (a primary amino group or a secondary amino group). For example, an aliphatic polyamine, Examples include aromatic polyamines and alicyclic polyamines. Specifically, triethylenetetramine, metaphenylenediamine, isophoronediamine, 4,4'-diamino-3,3'-dichlorodiphenylmethane, trimethylene-bis(4-aminobenzoate), 4,4'-diamino-3, 3'-diethyl-5,5'-dimethyldiphenylmethane, polytetramethylene oxide-di-p-aminobenzoate, 2,2',6,6'-tetraethyl-4,4'-methylene dianiline, 4,4' -Methylenebis(2-isopropyl-6-methylaniline), 4,4'-methylenebis(2,6-diisopropylaniline), 4,4'-methylenebis(3-chloro-2,6-diethylaniline), 3,5 -diethyltoluene-2,4-diamine, dimethylthiotoluene diamine, N-(3-aminomethylbenzyl)-2-phenylethan-1-amine, and polyamide amine. The polyamines may be used alone or in combination. Examples of commercially available products include Gascamin 240 manufactured by Mitsubishi Gas Chemical Co., Ltd., Iharakyumin MT, Iharakyumin M liquid product manufactured by Kumiai Chemical Industry Co., Ltd., CUA-4, Cure Hard MED, Elasmer 250P, Elasmer 1000P; Lonzacure M-DEA, Lonzacure M-MIPA, Lonzacure M-DIPA, Lonzacure M-CDEA manufactured by Lonza Japan; Ettacure 100, Ettacure 300, Ettacure 410, Ettacure 420 manufactured by Albemarle; Evo VERSALINK740 manufactured by Nik Nutrition &Care; ANCAMINE2049 manufactured by Evonik may be mentioned.

The amine value of the polyamine is not particularly limited, and is, for example, 50 to 1000 mgKOH/g, preferably 200 to 1000 mgKOH/g, more preferably 450 to 1000 mgKOH/g, and still more preferably 500 to 1000 mgKOH/g. It is. When the amine value of the polyamine is within this range, it is possible to provide a polyurea foam with higher initial adhesive strength. Here, the amine value of the polyamine is the total amine value described in JIS K1557-7:2011 "Plastics - Polyurethane raw material polyol test method - Part 7: How to determine basicity (nitrogen content and total amine value display)" It can be measured by a method of measuring valence.

Note that the composition according to this embodiment may contain other active hydrogen compounds in addition to the polyamine. Examples of other active hydrogen compounds include alcohols such as primary alcohols, secondary alcohols, and tertiary alcohols, polyol compounds, and thiol compounds. Alcohols and polyol compounds can react with polyisocyanate to form urethane bonds and form part of the skeleton of the polyurea foam. The content of other active hydrogen compounds in the entire composition for producing polyurea foam is preferably 1/5 or less, and 1/10 or less, of the polyamine content in terms of mass ratio. is more preferable, and it is even more preferable not to contain it. In addition, in the case of a two-component type, other active hydrogen compounds are contained in the polyamine-containing composition.

1-1-3. (C) Carboxylic Acid Metal Salt The carboxylic acid metal salt according to this embodiment is not particularly limited as long as it is a salt containing a carboxylic acid ion and a metal ion as an anion component and a cation component, respectively. Here, the carboxylic acid metal salt can function as an isocyanate trimerization catalyst. That is, when manufacturing a polyurea foam, an isocyanurate structure can be formed in the polyurea foam. Each component will be explained in detail below.

<Carboxylic acid>
Examples of carboxylic acids constituting carboxylic acid metal salts include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, octylic acid, caproic acid (hexanoic acid), caprylic acid (octanoic acid), capric acid (decanoic acid), Aliphatic monocarboxylic acids having 1 to 18 carbon atoms such as undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, heptadecanoic acid, stearic acid, trifluoroacetic acid, phenylacetic acid, chloroacetic acid, glycolic acid, lactic acid; cyclo Alicyclic monocarboxylic acids such as pentanecarboxylic acid and cyclohexanecarboxylic acid; benzoic acid, methylbenzoic acid, ethylbenzoic acid, propylbenzoic acid, isopropylbenzoic acid, butylbenzoic acid, isobutylbenzoic acid, tert-butylbenzoic acid, salicylic acid , anisic acid, ethoxybenzoic acid, propoxybenzoic acid, isopropoxybenzoic acid, butoxybenzoic acid, nitrobenzoic acid, fluorobenzoic acid, resorcinic acid, naphthalenecarboxylic acid, biphenylcarboxylic acid, and other aromatic monomers having 7 to 14 carbon atoms. Carboxylic acid; aromatic polycarboxylic acid having 7 to 14 carbon atoms such as phthalic acid, isophthalic acid, terephthalic acid, nitrophthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid, naphthalene dicarboxylic acid; oxalic acid , malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, methylmalonic acid, ethyl Chilimalonic acid, propylmalonic acid, butylmalonic acid, dimethylmalonic acid, diethylmalonic acid, methylethylmalonic acid, methylsuccinic acid, ethylsuccinic acid, methylethylsuccinic acid, maleic acid, citraconic acid, itaconic acid, etc. with 1 or more carbon atoms 18 aliphatic polycarboxylic acids; alicyclic polycarboxylic acids having 6 to 18 carbon atoms, such as cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methylhexahydrophthalic acid, and methyltetrahydrophthalic acid; Can be mentioned. Among these, carboxylic acids having 6 to 16 carbon atoms are preferred, and aliphatic monocarboxylic acids having 6 to 16 carbon atoms are more preferred, since higher initial adhesive strength can be achieved.

<Metal>
Further, the metal constituting the carboxylic acid metal salt is not particularly limited, and suitable examples include alkali metals such as lithium, sodium, and potassium; and alkaline earth metals such as magnesium and calcium. Among these, potassium is the most preferred. Employing suitable metals can provide polyurea foams with higher initial bond strength.

1-1-4. (D) Lewis base compound and/or organometallic compound <Lewis base compound>
The Lewis base compound according to this embodiment is not particularly limited as long as it is a compound having at least one electron pair that is not used for covalent bonding and can be donated. Suitable Lewis base compounds are amine compounds, such as cyclic amine compounds, aromatic or cycloaliphatic amines (eg imidazoles and tertiary amines). Specific examples include cyclic amine compounds such as imidazole, 1,2-dimethylimidazole, 1-methyl-4-isopropylimidazole, and TEDA; aromatic and alicyclic amines such as triethylenediamine, dimethylbenzylamine, and dicyclohexylmethylamine. can be mentioned. This Lewis acid-base compound can function as a polyurea resin conversion catalyst (urea conversion catalyst). Note that a compound having the functions of both a resin forming catalyst and a foaming catalyst is referred to as a resin forming catalyst. Here, by combining the above-mentioned carboxylic acid metal salt and Lewis base compound, the activity of the resin formation reaction at low temperature can be improved. Specifically, even at low temperatures, the entire reaction can be activated without reducing the reactivity of the amine compound. In addition, by combining the aforementioned carboxylic acid metal salt and Lewis base compound, a polyurea foam having higher initial adhesive strength can be provided.

<Structure example>
Table 1 shows structural examples of suitable amine compounds. In the table below, R ¹¹ and R ¹² are each independently hydrogen or a hydrocarbon group having 1 to 18 carbon atoms (preferably 1 to 4 carbon atoms) (for example, a methyl group or an isopropyl group). be.

<Organometallic compound>
The organometallic compound according to this embodiment is not particularly limited as long as it is a compound containing a chemical bond between a metal and carbon, and examples thereof include organotin compounds, organolead compounds, organobismuth compounds, and organozinc compounds. This organometallic compound can function as a polyurea resinization catalyst. Here, by combining the above-mentioned carboxylic acid metal salt and organometallic compound, the activity of the resin formation reaction at low temperature can be improved. Specifically, even at low temperatures, the entire reaction can be activated without reducing the reactivity of the amine compound. In addition, by combining the aforementioned carboxylic acid metal salt and organometallic compound, a polyurea foam having higher initial adhesive strength can be provided.

<Structure example>
Table 2 shows structural examples of suitable organometallic compounds. For example, in the following formula, one of R ₁ to R ₄ is hydrogen, and the remaining three are each independently a hydrocarbon group (for example, a hydrocarbon group having 1 to 18 carbon atoms). (e.g., a methyl group or a butyl group) or a sulfur-containing hydrocarbon group (e.g., a mercapto group substituted with a hydrocarbon group having 1 to 18 carbon atoms, such as -S-C ₈ H ₁₇ , -S-C ₁₂ H ₂₅ It is a compound that is a mercapto group substituted with 1 to 18 hydrocarbon groups, such as -S-C ₈ H ₁₇ , -S-C ₁₂ H ₂₅ ). Further, in the following formula, R ₁ to R ₄ are each independently a hydrocarbon group (for example, a hydrocarbon group having 1 to 18 carbon atoms, such as a methyl group, an ethyl group, a butyl group, etc.). It is a compound that is a group). In addition, in the following formula, R ₁ to R ₃ are each independently a hydrocarbon group (for example, a hydrocarbon group having 1 to 18 carbon atoms, such as a methyl group, an ethyl group, a butyl group, etc.). It is a compound that is a group). Furthermore, in the following formula, R ₁ to R ₂ are each independently a hydrocarbon group (for example, a hydrocarbon group having 1 to 18 carbon atoms, such as a methyl group, an ethyl group, a butyl group, etc.). It is a compound that is a group).

1-1-5. (E) Foaming agent The foaming agent according to this embodiment is not particularly limited. Examples of the blowing agent include water, hydrocarbons (preferably C4 to C6), hydrofluoroolefins, and carbon dioxide gas. Specifically, cyclopentane, HFO (1336mzz), and HFO (1233zd) can be mentioned. These may be used alone or in combination.

1-1-6. (F) Foam stabilizer The foam stabilizer according to this embodiment is not particularly limited. Examples of the foam stabilizer include silicone compounds and nonionic surfactants. These can be used alone or in combination.

1-1-7. (G) Flame retardant The flame retardant according to this embodiment is not particularly limited. For example, red phosphorus; phosphoric acid ester; phosphate-containing flame retardant; bromine-containing flame retardant; boron-containing flame retardant; antimony-containing flame retardant; metal hydroxide; and a cyclic structure containing a heterocycle or an aromatic ring; Compounds having a functional group containing an ethylenic or acetylenic unsaturated carbon bond; and the like. These may be used alone or in combination. Among these, it is preferable that at least one selected from red phosphorus, phosphoric acid ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant, antimony-containing flame retardant, and metal hydroxide is included. In particular, it is more preferable to include red phosphorus. In addition to red phosphorus, phosphoric acid esters; phosphate-containing flame retardants; bromine-containing flame retardants; boron-containing flame retardants; antimony-containing flame retardants; metal hydroxides; and cyclic structures containing heterocycles or aromatic rings. and a functional group containing an ethylenic or acetylenic unsaturated carbon bond. Note that flame retardants other than these flame retardants may be included. Each component will be explained in detail below. Examples of the phosphoric acid ester include triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, tricylenyl phosphate, tris (t-butylated phenyl) phosphate, tris (i-propylated phenyl) phosphate, 2-ethylhexyl Aromatic phosphate esters such as diphenyl phosphate; aromatic esters such as 1,3-phenylene bis(diphenyl phosphate), 1,3-phenylene bis(dixylenyl) phosphate, resorcinol bis(diphenyl) phosphate, and bisphenol A bis(diphenyl phosphate) Condensed phosphate ester; halogen-containing phosphate esters such as tris(dichloropropyl) phosphate, tris(β-chloropropyl) phosphate, tris(chloroethyl) phosphate; 2,2-bis(chloromethyl)trimethylenebis(bis( 2-chloroethyl) phosphate), halogen-containing condensed phosphoric acid esters such as polyoxyalkylene bisdichloroalkyl phosphate; and the like. Phosphate-containing flame retardants include, for example, monophosphates such as ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate; monosodium phosphate, disodium phosphate, and trisodium phosphate. Sodium salts such as sodium, monosodium phosphite, disodium phosphite, sodium hypophosphite; monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite , potassium salts such as potassium hypophosphite; lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, lithium hypophosphite; phosphoric acid Barium salts such as barium dihydrogen, barium hydrogen phosphate, tribarium phosphate, barium hypophosphite; Magnesium salts such as magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, magnesium hypophosphite; Calcium salts such as dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, and calcium hypophosphite; Zinc salts such as zinc phosphate, zinc phosphite, and zinc hypophosphite; Aluminum salts such as dialuminum phosphate, tertiary aluminum phosphate, aluminum phosphite, and aluminum hypophosphite; etc. can be mentioned. Examples of the polyphosphate include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, and aluminum polyphosphate. Bromine-containing flame retardants include, for example, pentabromodiphenyl ether; octabromodiphenyl ether; decabromodiphenyl ether; tetrabromobisphenol A (TBBA), TBBA-epoxy oligomer, TBBA-polycarbonate oligomer, TBBA-bis(dibromopropyl ether), TBBA- TBBA compounds such as bis(aryl ether); bisphenylpentamethane, 1,2-bis(2,4,6-tribromophenoxy)ethane, 2,4,6-tris(2,4,6-tribromophenoxy) )-Multi-benzene ring compounds such as 1,3,5-triazine, 2,6-dibromophenol, and 2,4-dibromophenol; Brominated styrene compounds such as brominated polystyrene and polybrominated styrene; ethylene bistetrabromophthalimide Phthalic acid compounds such as; cycloaliphatic compounds such as hexabromocyclododecane; polyacrylic acid brominated aromatic ester compounds such as poly(pentabromophenyl acrylate); and the like. Boron-containing flame retardants include, for example, borax; boron oxides such as diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide; boric acid, lithium borate, sodium borate, Examples include boric acid compounds such as potassium borate, cesium borate, magnesium borate, calcium borate, barium borate, zirconium borate, zinc borate, aluminum borate, and ammonium borate. Examples of antimony-containing flame retardants include antimony oxides such as antimony trioxide and antimony pentoxide; antimonates such as sodium antimonate and potassium antimonate; pyroantimonates such as sodium pyroantimonate and potassium pyroantimonate; etc. can be mentioned. These can be used alone or in combination. Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, and the like. As other flame retardants, known flame retardants can be used. Examples of other flame retardants include chlorine compounds such as chlorinated paraffin; nitrogen compounds such as hindered amine and melamine cyanurate; and cellulose. Examples of compounds having a cyclic structure containing a heterocycle or an aromatic ring and a functional group containing an ethylenically or acetylenically unsaturated carbon bond include triallyl isocyanurate (TAIC), trimetyyl isocyanurate (TMAIC), Triallyl cyanurate (TAC), ethoxylated isocyanuric acid triacrylate (TEAIC), tetraallyl glycol urylate (TA-G), alkyl diallyl isocyanurate (LCAIC), phenylene bismaleimide (PBMI), bisallylnadimide ( BANI), diallyl phthalate (DAP), diallyl isophthalate (iso-DAP), and methacryloyl group-terminated polyphenylene ether oligomer (DA-PPE).

1-1-8. Other Additive Components In addition to the above-mentioned additive components, the composition for producing a polyurea foam according to the present embodiment may further contain other additive components. Examples of other additive components include those known as additives, such as foaming catalysts, balance catalysts, antioxidants, ultraviolet absorbers, antibacterial agents, and dispersants. Furthermore, the composition for producing a polyurea foam according to the present embodiment may contain other trimerization catalysts in addition to the above-mentioned carboxylic acid metal salt. Other trimerization catalysts include, but are not particularly limited to, metal oxides such as lithium oxide, sodium oxide, and potassium oxide; methoxy sodium, ethoxy sodium, propoxy sodium, butoxy sodium, methoxy potassium, ethoxy potassium, propoxy potassium, butoxy Alkoxides such as potassium; 2,4,6-tris(dimethylaminomethyl)phenol, N,N',N''-tris(dimethylaminopropyl)hexahydrotriazine, triethylenediamine, 1,3,5-tris(dimethyl Tertiary amines such as (aminopropyl) hexahydro-s-triazine; derivatives of ethyleneimine; chelates of acetylacetone of alkali metals, aluminum, and transition metals; quaternary ammonium salts; diazabicycloundecene (DBU), etc. Can be mentioned.

1-2. Formulation/Composition 1-2-1. (A) Polyisocyanate The content of polyisocyanate in the composition for producing polyurea foam is, for example, 100 to 1000 parts by mass when the total content of polyamine in the composition for producing polyurea foam is 100 parts by mass. It is. Here, when monomeric MDI is used as at least a part of the polyisocyanate, the preferable lower limit of the content of monomeric MDI is 30% by mass, 35% by mass, 40% by mass based on the total mass of polyisocyanate. mass%, 45 mass%, 50 mass%, 55 mass%, 60 mass%, 65 mass%, 70 mass%, 72.5 mass%, 75 mass%, and the preferable upper limit values are 100 mass%, 97 mass% .5% by mass, 95% by mass, 92.5% by mass, 90% by mass, 87.5% by mass, 85% by mass, and 82.5% by mass.

1-2-2. (B) Polyamine The content of polyamine in the composition for producing polyurea foam is, for example, 2.0% by mass or more, preferably 5% by mass or more, when the total amount of the composition for producing polyurea foam is 100% by mass. The content is .0% by mass or more, more preferably 8.0% by mass or more. The upper limit of the polyamine content is, for example, 40.0% by mass or less, preferably 30.0% by mass or less, and more preferably 20.0% by mass or less. From another point of view, the polyamine content is such that the composition for producing a polyurea foam has an isocyanate index of preferably 200 to 600, more preferably 200 to 500. Here, the isocyanate index is the value obtained by multiplying the ratio of the number of moles of active hydrogen in the composition for producing polyurea foam to the number of moles of isocyanate groups in the polyisocyanate by 100 (number of moles of NCO/active hydrogen number of moles x 100). When the isocyanate index of the composition for producing a polyurea foam is within this range, a sufficient isocyanurate structure is formed and the isocyanurate conversion rate can be made appropriate. Therefore, the polyurea foam can have excellent flame retardancy.

1-2-3. (C) Carboxylic acid metal salt The content of the carboxylic acid metal salt (or the total amount of trimerization catalyst) in the composition for producing polyurea foam is based on the total content of polyamine in the composition being 100 parts by mass. , for example, 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, more preferably 5 to 20 parts by weight, and even more preferably 10 to 20 parts by weight. Within this range, a polyurea foam particularly excellent in initial adhesive strength can be provided. In addition, it has a particularly high reactivity in the formation of isocyanurate structures even at low temperatures.

1-2-4. (D) Lewis base compound and/or organometallic compound The content of the total amount of the Lewis base compound and the organometallic compound (or the total amount of resinization catalyst) in the composition for producing polyurea foam is, for example, When the total content of polyamine in the composition for body production is 100 parts by weight, it is 1 to 50 parts by weight, preferably 5 to 40 parts by weight, and more preferably 10 to 40 parts by weight. Within this range, a polyurea foam particularly excellent in initial adhesive strength can be provided. In addition, it has particularly high reactivity in converting polyurea into a resin even at low temperatures.

1-2-5. (Mc)/(Md) ratio Here, the ratio of the mass (Mc) of the carboxylic acid metal salt (or trimerization catalyst) to the total mass (Md) of the Lewis base compound and the organometallic compound (or resinization catalyst) The lower limit value of {(Mc)/(Md)} is preferably 0.1, 0.15, 0.2, 0.25, 0.3, and the upper limit value is preferably 5, 4. 5, 4, 3.5, 3, 2.5. Within this range, a polyurea foam particularly excellent in initial adhesive strength can be provided. In addition, it has particularly high reactivity in the formation of isocyanurate structures and in the resinization of polyurea, even at low temperatures.

1-2-6. (E) Blowing agent The content of the blowing agent in the composition for producing polyurea foam is, for example, 1 to 80 parts by mass when the total content of polyamine in the composition for producing polyurea foam is 100 parts by mass. and preferably 50 to 80 parts by mass.

1-2-7. (F) Foam stabilizer The content of the foam stabilizer in the composition for producing polyurea foam is, for example, 0.1 when the total content of polyamine in the composition for producing polyurea foam is 100 parts by mass. ~20 parts by mass.

1-2-8. (G) Flame retardant The content of the flame retardant in the composition for producing polyurea foam is, for example, 10 to 300 parts by mass when the total content of polyamine in the composition for producing polyurea foam is 100 parts by mass. and preferably 50 to 250 parts by mass. Within this range, high flame retardance can be achieved while maintaining the high initial adhesive strength of the polyurea foam. Each flame retardant will be mentioned below. First, the content of red phosphorus in the composition for producing polyurea foam is, for example, 100 parts by mass or less, when the total content of polyamine in the composition for producing polyurea foam is 100 parts by mass, and 5 parts by mass or less. ~50 parts by weight is preferred, and 25 to 50 parts by weight is more preferred. Within this range, high flame retardance can be achieved while maintaining the high initial adhesive strength of the polyurea foam. In addition, the total content of flame retardants selected from phosphate esters, phosphate-containing flame retardants, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, and metal hydroxides is the composition for producing polyurea foam. When the total content of polyamine in the product is 100 parts by mass, it is, for example, 10 to 200 parts by mass. Within this range, high flame retardance can be achieved while maintaining the high initial adhesive strength of the polyurea foam.

1-3. Physical properties/composition 1-3-1. Peak temperature The peak temperature of the composition for producing polyurea foam according to the present embodiment under the following reaction conditions (peak temperature during reaction to obtain polyurea) is preferably 40°C or higher, more preferably 45°C or higher, More preferably, the temperature is 50°C or higher. Note that the upper limit is not particularly limited, and is, for example, 100°C. Here, the reaction conditions for measuring the peak temperature are as follows.
(Reaction conditions)
A polyamine-containing composition {however, in this evaluation item, a composition consisting of a polyamine, a flame retardant (TCPP), and a resinization catalyst} and a polyisocyanate (each cooled to 5°C) were placed in a polypropylene 500 mL disposable cup (diameter 10 cm). and stirred for 10 seconds at 3000 rpm using a hand mixer. After stirring, measure the temperature of the system using a thermocouple. The highest temperature until polyurea is obtained is defined as the peak temperature. By combining the above-mentioned polyamine and resinization catalyst in the composition for producing a polyurea foam, the peak temperature under the above-mentioned reaction conditions can be obtained.

1-3-2. Cream time The cream time at 5° C. of the composition for producing a polyurea foam according to the present embodiment is, for example, 1 to 120 seconds, preferably 2 to 70 seconds. When the cream time at 5° C. of the composition for producing a polyurea foam is within this range, more excellent effects can be achieved in terms of obtaining sufficient liquid flowability and wettability and adhesion to the building body. Here, the cream time refers to the time from the time when the polyamine-containing composition and the polyisocyanate are mixed until just before the mixture starts foaming, becomes a creamy liquid, and starts expanding. It is measured with the naked eye as the time when the color of the mixture solution begins to take on a white color. More specifically, polyamine, various catalysts, blowing agent, foam stabilizer, and flame retardant are measured into a 500 mL disposable cup. These are mixed and stirred and mixed for 5 minutes at room temperature at a rotation speed of 1000 rpm using a hand mixer to prepare a polyamine-containing composition (first liquid). Then, the polyamine-containing composition (first liquid) and the polyisocyanate composition (second liquid) made of polyisocyanate were stored in a refrigerator set at 5°C, and the respective temperatures were kept at 5±2°C. do. Next, the polyamine-containing composition (first liquid) and the polyisocyanate composition (second liquid) were mixed, stirred for 3 seconds at a rotation speed of 3000 rpm using a hand mixer, and then placed in a foaming wooden box (170 mm x 170mm x 170mm) and foamed and hardened. In addition, 5 degreeC shows that the polyisocyanate and the polyamine containing composition were each maintained at 5 degreeC, and were mixed.

1-3-3. Rise Time The rise time at 5° C. of the composition for producing polyurea foam according to the present embodiment is, for example, 1 to 100 seconds, preferably 1 to 50 seconds. Here, the rise time at 5°C is the time from when the polyamine-containing composition and polyisocyanate are mixed and stirred at 5°C to start foaming until the foaming height of the foam completely stops changing. represents. More specifically, polyamine, various catalysts, blowing agent, foam stabilizer, and flame retardant are measured into a 500 mL disposable cup. These are mixed and stirred and mixed for 5 minutes at room temperature at a rotation speed of 1000 rpm using a hand mixer to prepare a polyamine-containing composition (first liquid). Then, the polyamine-containing composition (first liquid) and the polyisocyanate composition (second liquid) made of polyisocyanate were stored in a refrigerator set at 5°C, and the respective temperatures were kept at 5±2°C. do. Next, the polyamine-containing composition (first liquid) and the polyisocyanate composition (second liquid) were mixed, stirred for 3 seconds at a rotation speed of 3000 rpm using a hand mixer, and then placed in a foaming wooden box (170 mm x 170mm x 170mm) and foamed and hardened.

2. Method for producing polyurea foam First, in the case of a two-component type (two-component type) composition for producing a polyurea foam according to the present embodiment, the composition includes a polyamine, a catalyst, a blowing agent, a foam stabilizer, and a flame retardant. (for example, red phosphorus or red phosphorus and other flame retardants) and other additive components as necessary, and a second solution containing polyisocyanate are prepared by mixing. The composition for producing a polyurea foam may be mixed by any known method. Specifically, raw materials other than the polyisocyanate are mixed in a container using a mixer (e.g., a stirrer equipped with a propeller-type stirring blade) (e.g., stirred at 2000 rpm for 5 minutes using the above-mentioned stirrer), and the polyamine-containing composition is prepared. Prepare a liquid (first solution). Subsequently, the polyisocyanate (second liquid) and the polyamine-containing composition (first liquid) are each cooled to a predetermined temperature (for example, 10±1° C.). Thereafter, a polyurea foam can be obtained by mixing the polyisocyanate and the polyamine-containing composition (for example, stirring at 2000 rpm for 5 seconds using the above-mentioned stirrer), foaming and curing.

In addition, when using the spraying method, a polyamine-containing composition (first liquid) and polyisocyanate (second liquid), which are mixed with raw materials other than polyisocyanate in advance, are supplied to a spray gun using a pump or the like. (Open the spray gun nozzle at this time). A polyurea foam can then be obtained by mixing the polyamine-containing composition and isocyanate in a chamber within a spray gun and spraying the mixture onto the building frame.

3. Polyurea foam 3-1. Ingredients The polyurea foam according to the present embodiment contains a carboxylic acid metal salt, a Lewis base compound, and/or an organometallic compound. Incidentally, these components are as described in the above composition section.

3-2. Content 3-2-1. Carboxylic acid metal salt The lower limit of the content of the carboxylic acid metal salt contained in the polyurea foam according to the present embodiment is, for example, 0.01% by mass or more, when the total mass of the polyurea foam is 100% by mass. 0.05% by mass or more, 0.1% by mass or more, 0.25% by mass or more, 0.5% by mass or more, 0.75% by mass or more, and the upper limit is, for example, 20% by mass or less, 15% by mass % or less, 12.5% by mass or less, 10% by mass or less, 7.5% by mass or less, 5% by mass or less, and 2.5% by mass or less.

3-2-2. Lewis base compound and/or organometallic compound The total content of the Lewis base compound and organometallic compound contained in the polyurea foam according to this embodiment is, when the total mass of the polyurea foam is 100% by mass, The lower limit is, for example, 0.001% by mass or more, 0.005% by mass or more, 0.1% by mass or more, 0.125% by mass or more, 0.2% by mass or more, 0.25% by mass or more, 0. 3% by mass or more, 0.4% by mass or more, 0.5% by mass or more, 1% by mass or more, 1.5% by mass or more, 2% by mass or more, 2.5% by mass or more, and the upper limit is, for example , 20% by mass or less, 15% by mass or less, 12.5% by mass or less, 10% by mass or less, 7.5% by mass or less, and 5% by mass or less.

3-2-3. Flame Retardant The content of the flame retardant contained in the polyurea foam according to the present embodiment is, for example, 1 to 60% by mass, preferably 2 to 45% by mass, when the total mass of the polyurea foam is 100% by mass. %. Within this range, high flame retardance can be achieved while maintaining the high initial adhesive strength of the polyurea foam. Further, when using red phosphorus as a flame retardant, the content of red phosphorus contained in the polyurea foam is, for example, 1 to 30% by mass, and is preferably 1 to 30% by mass, when the total mass of the polyurea foam is 100% by mass. is 2 to 25% by mass. Within this range, high flame retardance can be achieved while maintaining the high initial adhesive strength of the polyurea foam. Furthermore, when red phosphorus and other flame retardants are used in combination as a flame retardant, the content (Fp) of red phosphorus in the composition for polyurea foam, phosphoric acid ester, phosphate-containing flame retardant, bromine-containing The ratio (Fp/Ft) of the total content (Ft) of flame retardants selected from flame retardants, boron-containing flame retardants, antimony-containing flame retardants, and metal hydroxides is not particularly limited, and is, for example, 0. 01 to 1, preferably 0.01 to 0.75, more preferably 0.05 to 0.75, still more preferably 0.1 to 0.5. Within this range, high flame retardance can be achieved while maintaining the high initial adhesive strength of the polyurea foam.

3-3. Density The density of the polyurea foam is not particularly limited as long as it does not impede the effects of the present embodiment, and is, for example, 10 to 200 kg/m ³ , preferably 10 to 100 kg/m ³ , more preferably 25 to 75 kg. / ^m3 . When the density of the polyurea foam is within this range, a polyurea foam with excellent thermal conductivity and flame retardancy can be obtained. The density of the polyurea foam is measured according to JIS K7222:2005 "Foamed plastics and rubber - How to determine apparent density."

4. Applications of polyurea foam Applications of the polyurea foam according to this embodiment include, for example, architectural applications {walls, ceilings, roofs, floors, pipe covers (foam insulation materials for residential piping), etc.}; fittings (windows, shoji screens, doors and doors); , sliding doors, transoms, etc.); Ships and storage tanks for oil and gas transportation; Vehicles (engines, batteries, ceilings, floors, door panels, etc.); Aircraft; ;Electrical appliances such as refrigerators;Heat retaining materials, thermal insulation materials, cold-heat resistance mitigation materials for retaining walls;Underground filling reinforcing materials for ground subsidence prevention work and road construction;Injected repair materials for civil engineering applications such as tunnels, bridges, and floating piers;Unnecessary Filling materials for structural parts such as basements; energy absorbing materials; waterproofing materials; water-stopping materials; buoyancy materials; etc. In addition, since it is easy to insulate buildings made of wood or reinforced concrete, it can be used as a polyurea foam for spraying construction methods.

<<Preparation of composition for producing polyurea foam>>
<Raw materials>
(Polyamine)
・Etacure 420 (manufactured by Albemarle, amine value: 529mgKOH/g)
(polyol)
・Phthalate ester polyol (Maximol RLK-505, manufactured by Kawasaki Chemical Industries, Ltd., hydroxyl value: 250mgKOH/g)
(Flame retardants)
・Tris(1-chloro-2-propyl)phosphate (TCPP)
・Red phosphorus (foam stabilizer)
・Polyalkylene ether silicone copolymer (catalyst)
・Potassium octylate (trimerization catalyst)
・1,2-dimethylimidazole (resinization catalyst)
・1-Methyl-4-isopropylimidazole (resinization catalyst)
・Triethylenediamine (resinization catalyst)
・Dimethylbenzylamine (resinization catalyst)
・Dibutyltin dimercaptide (R ₁ and R ₂ are butyl groups; R ₃ and R ₄ are -SC ₁₂ H ₂₅ structure) (resinization catalyst)
・Bismuth 2-ethylhexanoate (resinization catalyst)
(foaming agent)
・Hydrofluoroolefin ・Water (polyisocyanate)
・Millionate MR-200 (manufactured by Tosoh Corporation, NCO%: 30.9%, Crude MDI ^* )
・Luplanet MI (manufactured by BASF, NCO%: 33.5%, monomeric MDI)
*The crude MDI contains about 50% by mass of monomeric MDI.

<Production of foam>
According to the formulations shown in Tables 3 and 4, polyamines, various catalysts, blowing agents, foam stabilizers, and flame retardants were measured into 500 mL disposable cups. These were mixed and stirred and mixed at room temperature for 5 minutes at a rotation speed of 1000 rpm using a hand mixer to produce a polyamine-containing composition (first liquid). Then, the polyamine-containing composition (first liquid) and the polyisocyanate composition (second liquid) made of polyisocyanate were stored in a refrigerator set at 5°C, and the respective temperatures were kept at 5±2°C. did. Next, the polyamine-containing composition (first liquid) and the polyisocyanate composition (second liquid) were mixed, stirred for 3 seconds at a rotation speed of 3000 rpm using a hand mixer, and then placed in a foaming wooden box (170 mm x 170 mm x 170 mm) and was foamed and cured to obtain a foam.

＜＜Evaluation＞＞
The following evaluations were carried out for each Example and Comparative Example regarding the foamability during foaming and the characteristics of the foam. Note that since the evaluation methods for peak temperature, cream time, and rise time have been described above, evaluation methods for other evaluation items will be explained.

<Residual isocyanate (NCO) content in foam>
From the foam produced by the above manufacturing method, 2 cm was cut off from the surface layer to take out a core with a size of 100 mm x 100 mm x 100 mm. A test specimen measuring 10 mm x 10 mm x 10 mm was cut out from the center of the core. This specimen was compressed to a thickness of 2 mm, and its infrared absorption spectrum was measured using an infrared spectrophotometer (JASCO Corporation, FT/IR-4200). The measurement was carried out by the ATR method using a diamond prism, and the measurement was carried out 50 times at three points in the rise direction of the foam: the top, the center, and the bottom, and the average value was taken as the average value. From the obtained infrared absorption spectrum, the following formula and the area of each detected peak were derived, and the residual isocyanate content in the foam was calculated.
Residual isocyanate content (%) = P5/(P1+P2+P3+P4)×100 (Formula-1)
P1: Peak area derived from isocyanurate structure (peak derived from nurate ring near wave number 1410 cm ^-1 , wave number range from 1380 to 1430 cm ^-1 )
P2: Peak area derived from C=O of the urea structure (area of the peak derived from C=O of the urea bond near the wave number 1595 cm ^-1 , wave number range from 1550 to 1640 cm ^-1 )
P3: Peak area derived from C=O of isocyanurate structure (area of peak of C=O bond near wave number 1710 cm ^-1 , wave number range from 1680 to 1730 cm ^-1 )
P4: Peak area derived from N-H contained in the urea structure (area of peak derived from N-H near wave number 1510 cm ^-1 , peak area in the wave number range of 1470 to 1550 cm ^-1 )
P5: Peak area derived from isocyanato groups (peak derived from isocyanato groups near wave number 2270 cm ^-1 , wave number range from 2160 to 2380 cm ^-1 )

<Resinization reaction activity>
(Temperature profile/solidification time)
The polyamine-containing composition (in this evaluation, a composition consisting of a polyamine, a flame retardant (TCPP), and a resinization catalyst) and the polyisocyanate composition were cooled to 5°C. The polyamine-containing composition and the polyisocyanate composition were placed in a 500 mL polypropylene disposable cup (diameter 10 cm), and stirred for 10 seconds at 3000 rpm using a hand mixer. The temperature of the system was measured using a thermocouple, and the time until the system solidified was measured using a stopwatch.

(GPC measurement of soluble part)
The solidified products obtained in each Example and Comparative Example were added to tetrahydrofuran (THF) at a concentration of 0.5 wt%. The mixture was shaken and stirred in THF at 23°C for 24 hours to extract soluble components. After removing insoluble components by filtration, the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution ( Mw/Mn) was measured. For measurement, mobile phase: tetrahydrofuran (THF), flow rate: 0.35 mL/min, liquid feeding pressure: 4.0 MPa, internal standard substance: polystyrene, measurement column: polystyrene gel column (manufactured by Tosoh Corporation, TSKgel SuperMultipore HZ-N). , detector: UV (wavelength: 254 nm).

<Density>
From the foam produced by the above manufacturing method, 2 cm was cut off from the surface layer to take out a core with a size of 100 mm x 100 mm x 100 mm. To determine the volume of the core, the length, width, and thickness were measured using calipers. Next, the weight of the core portion was measured to the second decimal place using an electronic balance. Then, the density was calculated from the obtained volume and weight.

<Low temperature adhesion (5℃)>
The polyamine-containing compositions and polyisocyanate compounds prepared in each Example and Comparative Example were evaluated using a simple hand sprayer according to the following procedure.
1) A two-liquid mixing cartridge equipped with a static mixer was filled with a polyamine-containing composition and a polyisocyanate compound.
2) The plywood was cooled in a freezer to a surface temperature of 5°C and sprayed with a spray gun to form a foam.
3) The foam was cut out to a size of 60 mm long x 10 mm wide, and the adhesive strength was measured using a force gauge (manufactured by Amano, 500 N).

<Compressive strength>
The polyamine-containing compositions and polyisocyanate compounds prepared in each Example and Comparative Example were evaluated using a simple hand sprayer according to the following procedure.
1) A two-liquid mixing cartridge equipped with a static mixer was filled with a polyamine-containing composition and a polyisocyanate compound.
2) An aluminum plate (width 210 mm x depth 300 mm x thickness 10 mm) was cooled in a freezer to a surface temperature of 5° C. and sprayed with a spray gun to foam and harden to obtain a foam.
3) 2 cm was cut off from the upper surface of the obtained foam, and a sample was cut out with a size of 5 cm width x 5 cm depth x 4 cm thickness.
4) Measurement was performed in accordance with the method for measuring compressive strength described in JIS A9526.

<Brittleness>
The polyamine-containing compositions and polyisocyanate compounds prepared in each Example and Comparative Example were evaluated using a simple hand sprayer according to the following procedure.
1) A two-liquid mixing cartridge equipped with a static mixer was filled with a polyamine-containing composition and a polyisocyanate compound.
2) An aluminum plate (width 210 mm x depth 300 mm x thickness 10 mm) was cooled in a freezer to a surface temperature of 5° C. and sprayed with a spray gun to foam and harden to obtain a foam.
3) A load of 50 N was applied to the skin layer on the upper part of the foam for 3 seconds using a force gauge equipped with a probe on a disc having a diameter of 10 mm, and the force gauge was separated from the foam.
4) In the area where the force gauge was applied, the skin layer of the foam was brittle and collapsed, which was classified as "brittle", and the part that did not collapse was classified as "not brittle."

The results are shown in Tables 3 and 4. Further, FIG. 1 shows the results of the peak temperature during the reaction when polyurea is obtained from a polyisocyanate composition and a polyamine composition (evaluation item of "temperature profile" of resin-forming reaction activity).

Claims (8)

polyamine and
carboxylic acid metal salt,
A polyamine-containing composition containing a Lewis base compound and/or an organometallic compound. The polyamine-containing composition according to claim 1, wherein the Lewis base compound is an amine compound. polyamine and
A polyamine-containing composition containing a resin-forming catalyst, the polyamine-containing composition having a peak temperature of 40° C. or higher during the reaction when polyurea is obtained from a polyisocyanate and the composition under the following reaction conditions.
(Reaction conditions)
The composition and the polyisocyanate (each cooled to 5° C.) are mixed in a 500 mL polypropylene disposable cup (10 cm in diameter) and stirred for 10 seconds at 3000 rpm using a hand mixer. After stirring, measure the temperature of the system using a thermocouple. The highest temperature until polyurea is obtained is defined as the peak temperature. The polyamine-containing composition according to claim 1 or 2 as the first liquid, or the polyamine-containing composition according to claim 3, which further contains a trimerization catalyst as the first liquid;
A two-part urea resin composition comprising, as a second part, a composition containing polyisocyanate. polyisocyanate and
polyamine and
carboxylic acid metal salt,
A method for producing a polyurea foam from a urea resin composition containing a Lewis base compound and/or an organometallic compound. 6. The method of claim 5, wherein the Lewis base compound is an amine compound. carboxylic acid metal salt,
A polyurea foam containing a Lewis base compound and/or an organometallic compound. The polyurea foam according to claim 7, wherein the Lewis base compound is an amine compound.