JP2024038933A - Resin foam-forming composition and foam body - Google Patents

Abstract

To provide techniques that can provide a novel resin foam-forming composition with superior foamability, for example, under low temperature conditions.SOLUTION: A resin foam-forming composition according to the present disclosure comprises an aromatic polyamine (A), and an active hydrogen-containing compound (B) represented by the formula [B].SELECTED DRAWING: None

Description

The present invention relates to compositions for forming resin foams (e.g., compositions for producing polyurea foams) and foams (e.g., polyurea foams).

In recent years, foams using polyamine compounds as raw materials (for example, polyurea foams) have been proposed as foams (Patent Documents 1 and 2).

Patent No. 6876185 Patent No. 6925554

An object of the present invention is, for example, to provide a technique that can provide a novel composition for forming a foamed resin that has excellent foamability even under low temperature conditions.

The first aspect of the present invention is
aromatic polyamine (A);
An active hydrogen-containing compound (B) represented by the following formula [B],
A composition for forming a foamed resin containing the following.

(In formula [B], R ^B2 is a divalent hydrocarbon group that may have a heteroatom, R ^B1 is a group represented by either -NR ^B1a H or -SH, R ^B3 is a group represented by -NR ^B3a H, -SH, or -OH, and R ^B1a and R ^B3a are each independently hydrogen or a hydrocarbon group having 8 or less carbon atoms. )

The composition for forming a foamed resin may contain a trimerization catalyst.

The second aspect of the invention is
As the first liquid, the foamed resin forming composition of the first aspect;
This is a two-component composition for forming a foamed resin, which includes a composition containing a polyisocyanate as a second component.

The third aspect of the present invention is
aromatic polyamine (A);
An active hydrogen-containing compound (B) represented by the following formula [B],
polyisocyanate and
It is a foam obtained by foaming a composition for forming a foamed resin containing.

(In formula [B], R ^B2 is a divalent hydrocarbon group that may have a heteroatom, R ^B1 is a group represented by either -NR ^B1a H or -SH, R ^B3 is a group represented by -NR ^B3a H, -SH, or -OH, and R ^B1a and R ^B3a are each independently hydrogen or a hydrocarbon group having 8 or less carbon atoms. )

According to the present invention, for example, a technique is provided that can provide a novel composition for forming a foamed resin that has excellent reactivity or foamability even under low-temperature conditions.

Hereinafter, the composition for forming a foamed resin and the foam according to the present invention will be described in detail, but the present invention is not limited thereto.

In the following, when a certain compound is described, its isomers are also described at the same time.

In the following, when an upper limit value and a lower limit value are described separately, a numerical range that is a combination of any upper limit value and any lower limit value is substantially disclosed.

In addition, the explanation of the content/content ratio of each component (solid content) in the composition for forming a foamed resin can be read as the explanation of the content/content ratio of each component in the foam, to the extent that there is no particular contradiction. .

Here, the composition for forming a foamed resin contains an active hydrogen compound (an aromatic polyamine (A) described later and an active hydrogen-containing compound (B) described later) (first reaction component), and a polyisocyanate compound (described later) (first reaction component). A two-component system liquid comprising a first liquid containing no active hydrogen compound (first reaction component) and a second liquid containing a polyisocyanate compound (second reaction component); can do. Other additives may be distributed to the first liquid or the second liquid in consideration of the reactivity of each component.

In this way, storage stability can be improved by dividing each component in the composition for forming a foamed resin into a plurality of compositions and creating a system liquid that is mixed at the time of use. When the foamed resin forming composition is a two-component system solution, it can be used in a spray construction method in which the first and second components are mixed at a construction site, foamed/cured, and sprayed at the same time. can. By using the foam forming composition, which is a two-component system liquid, in the spraying method, it is possible to easily perform insulation construction.

Further, the first liquid according to the present disclosure (a composition containing an aromatic polyamine (A) described below and an active hydrogen-containing compound (B) described below) can be used in combination with any polyisocyanate, so that it can be used at low temperatures. Effects such as improvement in reactivity or foamability are expected.

In the following, the first liquid, the second liquid, the system liquid (a two-part composition in which the first liquid and the second liquid are managed separately), and the first liquid and the second liquid are mixed. The compositions obtained will be explained without making any particular distinction.

<<<<Composition of composition for forming resin foam>>>>
The composition for forming a foamed resin according to the present disclosure preferably contains an aromatic polyamine (A) and an active hydrogen-containing compound (B).
In addition, from another perspective, the composition for forming a foamed resin according to the present disclosure includes, as a first liquid, an aromatic polyamine (A) and an active hydrogen-containing compound (B). It is preferable that the composition be a two-component foamed resin-forming composition, which contains a polyisocyanate as a second component.
The composition for forming a foamed resin preferably contains a trimerization catalyst and/or a resinization catalyst.
The composition for forming resin foam may contain other additives.
Each component will be explained below.

<<<Aromatic polyamine (A)>>>
The aromatic polyamine (A) is not particularly limited as long as it is a polyamine having one or more aromatic rings in its structure. More specifically, the aromatic polyamine (A) is an amino group selected from the group consisting of a primary amino group and a secondary amino group (hereinafter sometimes referred to as an active amino group). Examples include those having more than one.

The number of active amino groups contained in one molecule of the aromatic polyamine (A) is not particularly limited as long as it is 2 or more, and is preferably 5 or less, 3 or less, or 2, etc. When the number of active amino groups in the aromatic polyamine (A) is within this range, the reactivity or foamability at low temperatures can be improved.

The number of aromatic rings contained in one molecule of aromatic polyamine (A) is not particularly limited as long as it is 1 or more, and is preferably 5 or less, 3 or less, 2 or less, or 2, etc. When the number of aromatic rings in the aromatic polyamine (A) is within this range, the reactivity or foamability at low temperatures can be improved.

The molecular weight of the aromatic polyamine (A) is preferably 1500 or less, 1000 or less, 750 or less, or 500 or less, and preferably 108 or more, 150 or more, 200 or more, or 250 or more. When the molecular weight of the aromatic polyamine (A) is within such a range, the reactivity or foamability at low temperatures can be improved.

The amine value of the aromatic polyamine (A) is not particularly limited, and is preferably 50 mgKOH/g or more, 200 mgKOH/g or more, 300 mgKOH/g or more, 450 mgKOH/g or more, or 500 mgKOH/g or more, and It is preferably 1000 mgKOH/g or less, 900 mgKOH/g or less, 800 mgKOH/g or less, or 650 mgKOH/g or less. When the amine value of the aromatic polyamine (A) is within this range, it becomes easy to produce a foam having excellent adhesive properties.

The amine value of the aromatic polyamine (A) is as 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 the method of measuring total amine value.

As mentioned above, the aromatic polyamine (A) has at least two active amino groups. The aromatic polyamine (A) preferably has an aromatic ring in the main skeleton between the first active amino group and the second active amino group.
Examples of such preferable aromatic polyamines (A) include compounds represented by the following formula [A].

(In formula [A], R ^A1 and R ^A3 are each independently hydrogen or a hydrocarbon group having 8 or less carbon atoms, and R ^A2 is a divalent group containing an aromatic ring.)

Preferred specific examples of the aromatic polyamine (A) include metaphenylenediamine, 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, Examples include 5-diethyltoluene-2,4-diamine, dimethylthiotoluene diamine, and N-(3-aminomethylbenzyl)-2-phenylethan-1-amine.

The aromatic polyamine (A) may be used alone or in combination.

<<<Active hydrogen-containing compound (B)>>>
The active hydrogen-containing compound (B) is a compound represented by the following formula [B].

In the formula [B], R ^B2 is a divalent hydrocarbon group that may have a hetero atom (for example, a nitrogen atom, an oxygen atom, a sulfur atom, etc.), and R ^B1 is -NR ^B1a H, -SH, R ^B3 is a group represented by -NR ^B3a H, -SH, or -OH, and R ^B1a and R ^B3a each independently represent hydrogen or It is a hydrocarbon group having 8 or less carbon atoms.

In formula [B], R ^B2 preferably has 8 or less carbon atoms, 2 to 7, 2 to 6, or 2 to 4 carbon atoms.

In formula [B], examples of R ^B2 having a hetero atom include those having an ester bond, an ether bond, a sulfide bond, an amide bond, an amino group, and the like. As R ^B2 having a hetero atom, one having an ether bond is preferable.

In formula [B], R ^B2 preferably has an oxygen atom as a hetero atom (for example, R ^B2 has an ether bond) or does not have a hetero atom, and R ^B2 does not have a hetero atom. is more preferable.

In formula [B], R ^B2 preferably has a linear or branched structure or does not contain an aromatic ring.

In formula [B], R ^B2 preferably does not contain an active hydrogen-containing group (a primary amino group, a secondary amino group, a hydroxyl group, a mercapto group, etc.).

In formula [B], combinations of (R ^B1a , R ^B3a ) include (-NR ^B1a H, -NR ^B3a H), (-NR ^B1a H, -SH), (-NR ^B1a H, -OH), (-SH, -SH), (-SH, -OH) exist. The active hydrogen-containing compound (B) may have any of these structures. Note that in this embodiment, the combination of (-NR ^B1a H, -SH) and the combination of (-SH, -NR ^B3a H) can be considered to be equivalent.

In formula [B], combinations of (R ^B1a , R ^B3a ) include (-NR ^B1a H, -NR ^B3a H), (-NR ^B1a H, -SH), (-NR ^B1a H, -OH), Alternatively, (-SH, -OH) is preferable.

In formula [B], when the combination of (R ^B1a , R ^B3a ) is (-NR ^B1a H, -NR ^B3a H), R ^B1a and R ^B3a each independently represent hydrogen or a group having 4 or less carbon atoms. It is preferably a hydrocarbon group, more preferably hydrogen or a hydrocarbon group having 2 or less carbon atoms, even more preferably hydrogen or a hydrocarbon group having 1 carbon number, and hydrogen or a hydrocarbon group having 1 carbon number. It is particularly preferable that at least one of R ^B1a and R ^B3a is hydrogen.

In formula [B], when the combination of (R ^B1a , R ^B3a ) is (-NR ^B1a H, -SH), R ^B1a is preferably hydrogen or a hydrocarbon group having 4 or less carbon atoms, and hydrogen Alternatively, it is more preferably a hydrocarbon group having 2 or less carbon atoms, even more preferably hydrogen or a hydrocarbon group having 1 carbon number, and particularly preferably hydrogen.

In formula [B], when the combination of (R ^B1a , R ^B3a ) is (-NR ^B1a H, -OH), R ^B1a is preferably a hydrocarbon group having 8 or less carbon atoms; is more preferably a hydrocarbon group of 7 or less.

The active hydrogen-containing compound (B) preferably has a molecular weight of 60 to 1,500, 60 to 1,000, 60 to 750, or 60 to 500.

The active hydrogen value of the active hydrogen-containing compound (B) is 100 to 3000 (mgKOH/g), 150 to 2500 (mgKOH/g), 200 to 2000 (mgKOH/g), or 250 to 1500 (mgKOH/g). It is preferable that The active hydrogen value is determined as [(56100×number of functional groups)/molecular weight].

By using such an active hydrogen-containing compound (B), the reactivity or foamability at low temperatures can be improved. Specifically, by using the active hydrogen-containing compound (B), the entire reaction can be activated without reducing the reactivity of the amine compound even at low temperatures. Therefore, polyurea foams with higher initial bond strength can be provided.

In the foamed resin forming composition, when the total amount of the aromatic polyamine (A) content and the active hydrogen-containing compound (B) content is 100 parts by mass, the content of the active hydrogen-containing compound (B) is preferably 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, or 5 parts by mass or more, and 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, and 25 parts by mass or less. , or preferably 20 parts by mass or less. By setting the content of the active hydrogen-containing compound (B) within such a range, the reactivity or foamability at low temperatures can be improved. In addition, it is easy to produce a foam with excellent flame retardancy.

Here, the aromatic polyamine (A) and the active hydrogen-containing compound (B) are compounds having different structures. The active hydrogen-containing compound (B) is a combination of (R ^B1a , R ^B3a ) in formula [B], (-NR ^B1a H, -SH), (-NR ^B1a H, -OH), (-SH, - When the aromatic polyamine (A) has a group represented by NR ^B3a H), (-SH, -SH) or (-SH, -OH), the aromatic polyamine (A) is a compound having a structure other than these. Also when the active hydrogen-containing compound (B) has a group represented by (-NR ^B1a H, -NR ^B3a H) as a combination of (R ^B1a , R ^B3a ) in formula [B], the active hydrogen-containing compound (B) has a different structure from the aromatic polyamine (A). As a specific example, the aromatic polyamine (A) is a compound having an aromatic ring in the main skeleton between one active amino group and another active amino group (for example, a compound represented by the above-mentioned formula [A]). In this case, the active hydrogen-containing compound (B) is a compound that does not have an aromatic ring in the main skeleton between one active amino group and another active amino group (for example, in the above formula [B], R ^B2 is preferably a compound having no aromatic ring.

The composition for forming a foamed resin according to the present disclosure may contain a polyamine or polyol other than the aromatic polyamine (A). The total content of polyamines and polyols other than the aromatic polyamine (A) in the composition for forming a foamed resin is expressed as a mass ratio with respect to the content of the active hydrogen-containing compound (B) in the composition for forming a foamed resin. , 1/2 or less, 1/5 or less, 1/10 or less, 1/20 or less, or 1/50 or less, and the foamed resin forming composition contains polyamines and polyols other than aromatic polyamines. It is more preferable not to do so. In addition, when it is said that a composition does not contain a certain component, it is permissible for the composition to contain the certain component as an unavoidable component.

<<<Polyisocyanate>>>
The polyisocyanate according to the present disclosure is not particularly limited as long as it has a plurality of isocyanate groups.
Examples of polyisocyanates include monomer type polyisocyanates and polymer type polyisocyanates. A monomeric polyisocyanate is a compound in which a plurality of isocyanate groups are present at the ends of a 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.

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. Can be done.
Further, the polyisocyanate may be a modified product or a derivative thereof. Examples of these modified products and derivatives include isocyanurate compounds of diisocyanates, adduct compounds of diisocyanates, biuret compounds of diisocyanates, allophanate compounds of diisocyanates, and carbodiimide-modified compounds of diisocyanates.

The monomeric polyisocyanate is preferably an aromatic isocyanate, more preferably MDI or a modified product or derivative of MDI, and even more preferably monomeric MDI and/or crude MDI. For example, when a composition for forming a foamed resin is used in a spraying method, aromatic isocyanate has excellent reactivity, so it is easy to ensure safety in the working environment. Furthermore, when the polyisocyanate contains monomeric MDI and/or crude MDI, the flame retardance of the resulting foam can be further improved.

Examples of the polymer type polyisocyanate include those obtained by making a prepolymer by reacting a compound having two or more active hydrogen-containing groups with an excess amount of polyisocyanate.

Examples of the polyisocyanate constituting the polymer type polyisocyanate include the aforementioned examples of the monomer type polyisocyanate.

Examples of the compound having two or more active hydrogen-containing groups constituting the polymeric polyisocyanate include polyols and/or polyamines.

Examples of the polyamine include aromatic polyamine (A) and polyamines other than aromatic polyamine (A) (aliphatic polyamine, alicyclic polyamine, etc.).

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.

The polyisocyanates may be used alone or in combination.

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, a foam having higher initial adhesive strength can be provided. The NCO% (isocyanate content) of polyisocyanate is determined by method A (toluene/dibutylamine, hydrochloric acid (Act).

The content of polyisocyanate in the composition for forming a foamed resin is preferably such that the isocyanate index in the composition for forming a foamed resin is 150 to 800, 200 to 600, or 200 to 500. The isocyanate index is the value obtained by multiplying the ratio of the number of moles of all active hydrogens in the composition for forming a foamed resin to the number of moles of isocyanate groups in the polyisocyanate by 100 (number of moles of NCO/number of moles of active hydrogen). ×100).

In another aspect, the content of polyisocyanate in the composition for forming a foamed resin is based on the total amount of the content of the aromatic polyamine (A) and the content of the active hydrogen-containing compound (B) of 100 parts by mass. In this case, the amount is, for example, 100 to 1000 parts by mass, or 100 to 500 parts by mass.

<<<Trimerization catalyst>>>
The composition for forming a foamed resin according to the present disclosure preferably contains a trimerization catalyst. When the composition for forming a foamed resin according to the present disclosure contains a trimerization catalyst, the flame retardance of the foam can be improved.

The trimerization catalyst is not particularly limited, and includes carboxylic acid metal salts; metal oxides such as lithium oxide, sodium oxide, and potassium oxide; methoxy sodium, ethoxy sodium, propoxy sodium, butoxy sodium, methoxy potassium, ethoxy potassium, propoxy Alkoxides such as potassium and butoxypotassium; 2,4,6-tris(dimethylaminomethyl)phenol, N,N',N"-tris(dimethylaminopropyl)hexahydrotriazine, triethylenediamine, 1,3,5- Tertiary amines such as tris(dimethylaminopropyl)hexahydro-s-triazine; derivatives of ethyleneimine; chelates of acetylacetone of alkali metals, aluminum, and transition metals; quaternary ammonium salts; diazabicycloundecene (DBU) and so on.

Preferably, the trimerization catalyst is a carboxylic acid metal salt. The carboxylic acid metal salt is not particularly limited as long as it contains a carboxylic acid ion and a metal ion as an anionic component and a cationic component, respectively.

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.

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 bond strength.

In the composition for forming a foamed resin, the content of the trimerization catalyst (for example, carboxylic acid metal salt) is such that the total amount of the aromatic polyamine (A) and the active hydrogen-containing compound (B) is 100% In terms of parts by weight, it is, 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 foam with particularly excellent initial adhesive strength is provided. In addition, it has high reactivity in forming isocyanurate structures even at low temperatures.

<<<Resinization catalyst>>>
It is preferable that the composition for forming a foamed resin according to the present disclosure includes a resinization catalyst.

The resinification catalyst is preferably a Lewis base compound or an organometallic compound (e.g., an organotin compound, an organolead compound, an organobismuth compound, or an organozinc compound).

<<Lewis base compound>>
The Lewis base compound according to the present disclosure is not particularly limited as long as it is a compound that has at least one electron pair that is not used for covalent bonding and can donate.

Suitable Lewis base compounds are amine compounds with one active amino group or without active amino groups, such as cyclic amine compounds, aromatic or cycloaliphatic amines (e.g. imidazoles and tertiary amines). ).

Specific examples of suitable Lewis base compounds include cyclic amine compounds such as imidazole, 1,2-dimethylimidazole, 1-methyl-4-isopropylimidazole, and TEDA; aromatic compounds such as triethylenediamine, dimethylbenzylamine, and dicyclohexylmethylamine; and alicyclic amines.

This Lewis acid-base compound can function as a resinization catalyst (ureation catalyst) in polyurea foams. 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 reactivity or foamability 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 the present disclosure is, for example, an organotin compound, an organolead compound, an organobismuth compound, an organozinc compound, etc. (eg, a nonionic compound).

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, the reactivity of the amine compound is not easily reduced even at low temperatures, and the entire reaction can be activated. 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, a suitable organotin compound is represented by the following formula, in which (1) one of R ¹ to R ⁴ is hydrogen, and the remaining three are independently hydrocarbon groups (for example, carbon atoms 1 to 18 (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 ), (2) 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 or a butyl group) or a compound that is a sulfur-containing hydrocarbon group (for example, 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 ). .
In addition, a suitable organic lead compound is such that 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).

In the composition for forming a foamed resin, the content of the resinization catalyst (for example, the total content of Lewis base compounds and organometallic compounds (for example, organotin compounds, organolead compounds, organobismuth compounds, organozinc compounds)) is , when the total content of the aromatic polyamine (A) and the content of the active hydrogen-containing compound (B) is 100 parts by mass, it is, for example, 1 to 50 parts by mass, preferably 5 to 40 parts by mass. and more preferably 10 to 40 parts by mass. Within this range, a foam with particularly excellent initial adhesive strength can be provided. In addition, it has particularly high reactivity in converting polyurea into a resin even at low temperatures.

<<<Other additive ingredients>>>
The composition for forming a foamed resin according to the present disclosure may contain other additive components. Examples of other additive components include those known as additives, such as foaming agents, foam stabilizers, flame retardants, foaming catalysts, balance catalysts, antioxidants, ultraviolet absorbers, antibacterial agents, and dispersants. Can be done. When producing flame retardant foams (eg polyurea foams) it is preferred to use flame retardants.

<<Foaming agent>>
The blowing agent according to the present disclosure is not particularly limited. Examples of the blowing agent include water, hydrocarbons (preferably having 4 to 6 carbon atoms), hydrofluoroolefins, and carbon dioxide gas. Specifically, cyclopentane, HFO (1336mzz), and HFO (1233zd) can be mentioned. These may be used alone or in combination.

In the composition for forming a foamed resin, the content of the blowing agent is, for example, 1 when the total amount of the aromatic polyamine (A) content and the active hydrogen-containing compound (B) content is 100 parts by mass. ~80 parts by weight, preferably 50 to 80 parts by weight.

<<Foam stabilizer>>
The foam stabilizer according to the present disclosure is not particularly limited. Examples of the foam stabilizer include silicone compounds and nonionic surfactants. These can be used alone or in combination.

In the composition for forming a foamed resin, the content of the foam stabilizer is, for example, when the total amount of the aromatic polyamine (A) content and the active hydrogen-containing compound (B) content is 100 parts by mass. The amount is 0.1 to 20 parts by mass.

<<Flame retardant>>
The flame retardant according to the present disclosure is not particularly limited. Flame retardants include, for example, red phosphorus; phosphoric acid esters; phosphate-containing flame retardants; bromine-containing flame retardants; boron-containing flame retardants; antimony-containing flame retardants; metal hydroxides; and heterocycles or aromatic rings. Compounds having a cyclic structure and a functional group containing an ethylenically or acetylenically unsaturated carbon bond; etc. can be mentioned. In other words, flame retardants include red phosphorus, phosphate esters, phosphate-containing flame retardants, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, metal hydroxides, heterocycles or aromatic rings. It is preferable that the compound contains one or more components selected from the group consisting of compounds having a cyclic structure containing a cyclic structure and a functional group containing an ethylenically or acetylenically unsaturated carbon bond (including two or more components). is more preferable). Moreover, the flame retardant may contain other flame retardants other than these flame retardants. These may be used alone or in combination.

Further, the flame retardant preferably contains red phosphorus, and more preferably contains red phosphorus and a flame retardant other than red phosphorus.

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.

Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, and the like.

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).

Other flame retardants include, for example, chlorine compounds such as chlorinated paraffin; nitrogen compounds such as hindered amine and melamine cyanurate; and cellulose.

In the composition for forming a foamed resin, the content of the flame retardant is, for example, 5 parts when the total amount of the aromatic polyamine (A) content and the active hydrogen-containing compound (B) content is 100 parts by mass. -200 parts by weight is preferred, and 25-150 parts by weight is more preferred.

When the composition for forming a foamed resin contains red phosphorus as a flame retardant, the content of red phosphorus in the composition for forming a foamed resin is determined by the content of the aromatic polyamine (A) and the content of the active hydrogen-containing compound (B). When the total amount is 100 parts by weight, for example, it is preferably 50 parts by weight or less, more preferably 1 to 50 parts by weight, and even more preferably 5 to 40 parts by weight.

When the composition for forming a foamed resin contains a flame retardant other than red phosphorus as a flame retardant, the content of the flame retardant other than red phosphorus in the composition for forming a foamed resin is determined by the content and activity of the aromatic polyamine (A). When the total amount including the content of the hydrogen-containing compound (B) is 100 parts by mass, for example, it is preferably 5 to 150 parts by mass, more preferably 20 to 100 parts by mass.

When the content of the flame retardant in the composition for forming a foamed resin is within this range, the foamed resin produced has an improved flame retardancy, low-temperature reactivity or foamability, etc. in a well-balanced manner. Forming compositions are easy to obtain.

<<<<Physical properties/properties of foamed resin forming composition>>>>
＜＜＜Cream Time＞＞＞
The cream time at 5° C. of the composition for forming a foamed resin according to the present disclosure is, for example, 1 to 120 seconds, preferably 2 to 70 seconds. When the cream time at 5° C. of the composition for forming a foamed resin 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, cream time refers to a first liquid containing an aromatic polyamine (A) and an active hydrogen-containing compound (B) (first reaction component) but not containing a polyisocyanate compound (second reaction component), and an aromatic polyamine (A) and the second liquid that does not contain the active hydrogen-containing compound (B) (first reaction component) but contains a polyisocyanate compound (second reaction component), the mixture starts foaming and forms a cream. This refers to the time just before it becomes a liquid and begins to expand. Visually, it is determined as the time when the solution color of the mixture begins to change color. Note that 5° C. indicates that the first liquid and the second liquid were mixed while being maintained at 5° C., respectively.
In addition, when the composition for forming resin foam contains other components, they shall be mixed in advance with the first liquid.

＜＜＜Rise Time＞＞＞
The rise time at 5° C. of the composition for forming a foamed resin 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 first liquid and the second liquid are mixed and stirred at 5°C to start foaming until the foaming height of the foam completely stops changing. represents.
In addition, when the composition for forming resin foam contains other components, they shall be mixed in advance with the first liquid.

<<<<Method for manufacturing foam>>>>
The composition for forming a foamed resin according to the present disclosure can be produced by a known method.
For example, in the case of a two-component type (two-component type), first, an aromatic polyamine (A), an active hydrogen-containing compound (B), a catalyst, a blowing agent, a foam stabilizer, and a flame retardant, as necessary. A first liquid containing the additives and other additive components, and a second liquid containing polyisocyanate are prepared.
The first liquid is prepared, for example, by mixing raw materials other than the polyisocyanate with a mixer in a container. The stirring conditions are, for example, stirring at 2000 rpm for 5 minutes using a stirrer equipped with a propeller type stirring blade.
Subsequently, the first liquid and the second liquid are each cooled to a predetermined temperature (for example, 10±1° C.). Thereafter, a polyurea foam can be obtained by mixing the first liquid and the second liquid, foaming and curing the mixture. The stirring condition is, for example, stirring using the above-mentioned stirrer at 2000 rpm for 5 seconds.

In addition, when using the composition for forming a foamed resin according to the present disclosure in a spraying method, a first liquid in which raw materials other than polyisocyanate are mixed in advance and a second liquid containing polyisocyanate are pumped into a spray gun. etc. are used to supply each. At this time, open the spray gun nozzle. Then, by mixing the first liquid and polyisocyanate in a chamber within a spray gun and spraying the mixture onto the building frame, a foam (for example, polyurea foam) can be obtained.

<<<<Foam>>>>
The components contained in the foam according to the present disclosure are as described above.

<<<Physical properties/properties of foam>>>
＜＜Density＞＞
The density of the foam is not particularly limited, and is, for example, 10 to 200 kg/m ³ , preferably 10 to 100 kg/m ³ , and more preferably 25 to 75 kg/m ³ . When the density of the foam is within this range, the foam tends to have excellent thermal conductivity and flame retardancy. The density of the foam is measured according to JIS K7222:2005 "Foamed plastics and rubber - How to determine apparent density."

<<<Applications>>>
Applications of the foam according to the present disclosure include, for example, architectural applications {walls, ceilings, roofs, floors, pipe covers (foam insulation materials for residential piping), etc.}; fittings (windows, shoji screens, doors, sliding doors, transoms, etc.) ; Ships and storage tanks for transporting oil and gas; Vehicles (engines, batteries, ceilings, floors, door panels, etc.); Aircraft; ; Heat retaining material, heat insulating material, cold/heat resistance mitigation material for earth retaining walls; Underground filling reinforcing material during ground subsidence prevention work and road construction; Injection repair material for civil engineering such as tunnels, bridges, floating piers, etc.; Filling of structures such as unnecessary basements materials; energy absorbing materials; waterproof materials; water-stop 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 foam for spraying construction methods.

Hereinafter, urethane foam will be specifically explained with reference to Examples and Reference Examples, but the present invention is not limited thereto.

<<Aromatic polyamine>>
(A-1)
Ettacure 420 (manufactured by Albemarle)
4,4'-methylenebis[N-(1-methylpropyl)aniline]
Amine value: 529mgKOH/g

<<Aromatic polyol (substitute component for aromatic polyamine)>>
(A-2)
Fantor SV-208 (manufactured by Hitachi Chemical)
Aromatic polyester polyol

<<Active hydrogen-containing compound>>
(B-1)
Amino alcohol MMA (manufactured by Nippon Nyukazai Co., Ltd.)
N-methylaminoethanol (B-2)
Amino alcohol MEM (manufactured by Nippon Nyukazai Co., Ltd.)
N-ethylaminoethanol (B-3)
Amino alcohol MBM (manufactured by Nippon Nyukazai Co., Ltd.)
N-butylaminoethanol (B-4)
N-benzylaminoethanol (manufactured by Alkyl Amines Chemicals)
(B-5)
A2010 (manufactured by Koei Chemical Co., Ltd.)
4-Aminobutanol (B-6)
B3070 (manufactured by Koei Chemical Co., Ltd.)
3-methylaminopropylamine (B-7)
1,6-diaminohexane (manufactured by Tokyo Chemical Industry Co., Ltd.)
(B-8)
B1010 (manufactured by Koei Chemical Co., Ltd.)
Bis(3-aminopropyl)ether (B-9)
B1050 (manufactured by Koei Chemical Co., Ltd.)
α,ω-bis(3-methylaminopropyl) polyethylene glycol ether (B-10)
Aminoethyl mercaptan (manufactured by Tokyo Chemical Industry Co., Ltd.)
(B-11)
2-Mercaptoethanol (manufactured by Toyobo Co., Ltd.)
(B-12)
Ethylene glycol (manufactured by Wako Pure Chemical Industries)

Table 3 shows the specific structures of the compounds (B-1) to (B-12).

<<Polyisocyanate>>
(C-1)
MR-200 (manufactured by Tosoh Corporation)
Crude MDI
NCO%: 30.9%
(C-2)
Luplanate MI (manufactured by BASF INOAC Polyurethane)
Monomeric MDI

<<Catalyst>>
(D-1)
KL-No. 110 (manufactured by Kao Corporation)
1-Methylimidazole resin formation catalyst (D-2)
DABCO T-120 (manufactured by Evonik)
Dibutylbis(dodecylthio)stannane resin formation catalyst (D-3)
K-Zero G (manufactured by Momentive Performance Materials)
Potassium octylate trimerization catalyst

<<Other additive ingredients>>
<Foaming agent>
(E-1)
HFO (hydrofluoroolefin)
<Foam stabilizer>
(F-1)
Silicone foam stabilizer Polyalkylene ether silicone copolymer <Flame retardant>
(G-1)
TCPP (tris(1-chloro-2-propyl)phosphate)
(G-2)
TAIC (trialyl isocyanurate)
(G-3)
red phosphorus

<<<Preparation of foam>>>
According to the formulations shown in Tables 4 and 5, the first reaction component (aromatic polyamine, polyol compound, active hydrogen compound), various catalysts, blowing agent, foam stabilizer, and flame retardant were measured into a 500 mL disposable cup. These were 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 first liquid.
Then, the first liquid and the second liquid consisting of polyisocyanate, which is the second reaction component, were stored in a refrigerator set at 5°C, so that the respective temperatures were 5±2°C.
Next, the first liquid and the second liquid are mixed, stirred for 3 seconds at a rotation speed of 3000 rpm using a hand mixer, and poured into a foaming wooden box (170 mm x 170 mm x 170 mm) to foam and harden. A foam was obtained.

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

＜＜Density＞＞
The surface layer part of the foam produced by the above manufacturing method was removed, and a core part having a size of 100 mm x 100 mm x 100 mm was taken out.
To determine the volume of the core, the length, width, and thickness were measured using calipers.
The weight of the core portion was measured to the second decimal place using an electronic balance.
The density was calculated from the obtained volume and weight.

<<Flame retardant>>
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.
The foam was left standing in an environment of 23° C. and RH 50% until there was no change in volume.
The total calorific value of the foam was measured in accordance with the ISO5660-1 test method using a radiant heat amount of 50 kW and a test time of 20 minutes.
A: Total calorific value 10 MJ/m ² or less B: Total calorific value 10 MJ/m ² or more and 11.9 MJ/m ² or more C: Total calorific value 12 MJ/m ² or more

<<Surface tack-free time after spraying, residual isocyanate content in foam>>
A spray machine (Graco, H-RV) was equipped with a spray gun (Graco, Gasmar gun), the raw material temperature was set to 40°C, the hose heater was set to 40°C, and the environmental temperature and surface temperature were set to 5°C. (1 m x 1 m x 10 mm thickness) was sprayed in a thin granular form to form a foam.
The time required for the surface tack of the foam formed on the aluminum plate to completely disappear was measured, and this time was defined as the surface tack free time.
A part of the foam (approximately 10 cm square) was cut out and measured using a Fourier transform infrared spectrophotometer using the ATR method using a diamond prism. value.
Based on the obtained infrared absorption spectrum, the residual isocyanate content in the foam was calculated from the following formula 1 and the area of each detected peak.

(Formula 1)
Residual isocyanate content (%) = P5/(P1+P2+P3+P4) x 100

P1: Peak area derived from the isocyanurate structure (area related to the peak derived from the nurate ring near the wave number 1410 cm ^-1 , area in the wave number range of 1380 to 1430 cm ^-1 )
P2: Peak area derived from C=O of the urea structure (area related to the peak derived from C=O of the urea bond near the wave number 1595 cm ^-1 , area in the wave number range of 1550 to 1640 cm ^-1 )
P3: Peak area derived from C=O in the 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 related to the area of the peak derived from N-H near the wave number 1510 cm ^-1 , and the peak area in the wave number range of 1470 to 1550 cm ^-1 area)
P5: Peak area derived from isocyanate groups (area related to peaks derived from isocyanate groups near wave number 2270 cm ^-1 , area in wave number range of 2160 to 2380 cm ^-1 )

The surface tack free time is preferably less than 400 seconds, more preferably less than 300 seconds, and even more preferably less than 250 seconds.

The residual isocyanate content is preferably 3.0% or less, more preferably 2.0% or less, and even more preferably 1.0% or less.

<<Low temperature adhesive strength>>
The low-temperature adhesive strength of the first and second liquids in each Example and Reference Example was evaluated using a simple hand sprayer according to the following procedure.
A two-liquid mixing cartridge equipped with a static mixer was filled with a polyamine mixture and a polyisocyanate compound.
The plywood was cooled in a freezer to a surface temperature of 5°C and sprayed with a spray gun. A measurement sample was cut out so that the foam that had been foamed and hardened after being sprayed on plywood remained in an area of 10 mm in width x 60 mm in length. This measurement sample was attached to a force gauge (manufactured by Amano, 500N) jig, and the adhesive strength of the foam to the plywood was measured.

The low-temperature adhesive strength is preferably 0.020 N/mm ² or more, more preferably 0.025 N/mm ² or more, and even more preferably 0.030 N/mm ² or more.

Claims (4)

aromatic polyamine (A);
An active hydrogen-containing compound (B) represented by the following formula [B],
A foamed resin forming composition containing.
(In formula [B], R ^B2 is a divalent hydrocarbon group that may have a heteroatom, R ^B1 is a group represented by either -NR ^B1a H or -SH, R ^B3 is a group represented by -NR ^B3a H, -SH, or -OH, and R ^B1a and R ^B3a are each independently hydrogen or a hydrocarbon group having 8 or less carbon atoms. ) The composition for forming a foamed resin according to claim 1, comprising a trimerization catalyst. As the first liquid, the composition for forming a foamed resin according to claim 1 or 2;
A two-component foamed resin forming composition comprising, as a second component, a composition containing polyisocyanate. aromatic polyamine (A);
An active hydrogen-containing compound (B) represented by the following formula [B],
polyisocyanate and
A foam obtained by foaming a composition for forming a foamed resin containing.
(In formula [B], R ^B2 is a divalent hydrocarbon group that may have a heteroatom, R ^B1 is a group represented by either -NR ^B1a H or -SH, R ^B3 is a group represented by -NR ^B3a H, -SH, or -OH, and R ^B1a and R ^B3a are each independently hydrogen or a hydrocarbon group having 8 or less carbon atoms. )