Compositions for foam production and foams

Abstract

The present invention provides a foam manufacturing composition that exhibits excellent reactivity at low temperatures and can be used to produce a foam that can serve as a substitute for rigid polyurethane foam. [Solution] One embodiment of the present invention is a composition for producing foam. The composition for producing foam contains a plurality of amine compounds having a plurality of amine groups selected from primary amine groups and secondary amine groups. In the composition for producing foam, the molar percentage of primary amine groups relative to the total of primary and secondary amine groups is greater than 0 mol%. The composition for producing foam further contains an amine compound having a tertiary amine group.

Description

[Technical Field]

[0001] This invention relates to a composition for producing foam and a foam. [Background technology]

[0002] Foam is used as insulation in buildings such as apartment buildings and detached houses, and rigid polyurethane foam is widely used.

[0003] For example, Patent Document 1 discloses a polyol composition for spray coating that has excellent flame retardancy and can be sprayed even at low temperatures without dripping, by containing 10 to 56 parts by weight of catalyst per 100 parts by weight of polyol. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2018-100404 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, technologies using rigid polyurethane foam have limitations in improving reactivity at low temperatures, and there was a need for technologies that could further suppress adhesion failures (peeling from the substrate).

[0006] Therefore, the object of the present invention is to provide a foam manufacturing composition that exhibits excellent reactivity at low temperatures and can be used as a substitute for rigid urethane foam. [Means for solving the problem]

[0007] The inventors of this invention have conducted diligent research and discovered that the above problems can be solved by a foam manufacturing composition using a predetermined amine compound as a raw material, and have completed the present invention. That is, the present invention is as follows.

[0008] One form of the present invention is a composition for producing a foam. The composition for producing a foam contains a plurality of amine compounds having a plurality of amine groups selected from primary amine groups and secondary amine groups. In the composition for producing a foam, the molar percentage of the primary amine group with respect to the total of the primary amine group and the secondary amine group is more than 0 mol%. The composition for producing a foam further contains an amine compound having a tertiary amine group.

[0009] The amine compound having a tertiary amine group is preferably a compound having a total carbon number of 10 or more. The composition for producing a foam is preferably for spraying.

[0010] Another form of the present invention is a foam produced using the composition for producing a foam.

[0011] Still another form of the present invention is a catalyst for producing a polyurea foam containing a tertiary amine compound having a total carbon number of 10 or more.

Effects of the Invention

[0012] According to the present invention, it is an object to provide a composition for producing a foam that is excellent in reactivity at low temperatures and can produce a foam that can be an alternative to a rigid urethane foam.

Modes for Carrying Out the Invention

[0013] In the following, when a certain compound is described, its isomers are also considered to be described at the same time.

[0014] In the following, when an upper limit value and a lower limit value are separately described, a numerical range obtained by combining any upper limit value and any lower limit value is considered to be substantially disclosed.

[0015] Hereinafter, the composition of the composition for producing a foam, the physical properties / properties of the composition for producing a foam, the method for producing a foam using the composition for producing a foam, and the use / usage method of the foam will be specifically described, but the present invention is not limited thereto.

[0016] <<<Composition of the composition for producing a foam>>> The composition for producing a foam contains an amine compound having a primary amine group and / or a secondary amine group (hereinafter referred to as the first amine compound). Further, the composition for producing a foam according to the present disclosure preferably contains an isocyanate compound. More specifically, the composition for producing a foam according to the present disclosure is preferably a composition that reacts the first amine compound and the isocyanate compound to form a urea resin foam (a composition for producing a urea resin foam).

[0017] Here, when the first amine compound and the isocyanate compound are mixed, the reaction proceeds rapidly. Therefore, when the composition for producing a foam according to the present disclosure contains an amine compound and an isocyanate compound, it is preferable that the first amine compound and the isocyanate compound are held in a separated state. That is, the composition for producing a foam according to the present disclosure may be a multi-liquid type (for example, two-liquid type) system liquid including a first liquid containing the first amine compound and not containing the isocyanate compound, and a second liquid not containing the first amine compound and containing the isocyanate compound. In this case, other additives may be distributed to the first liquid, the second liquid, or a liquid other than the first liquid and the second liquid (for example, the third liquid) in consideration of the reactivity of each component. Thus, by dividing each component in the composition for producing a foam into a plurality of compositions and using it as a system liquid to be mixed at the time of use, the storage stability can be enhanced. When the composition for producing a foam is a multi-liquid type system liquid, it can be used in a spraying method in which each liquid (for example, the first liquid and the second liquid) is mixed at a construction site or the like, and spraying is performed while foaming and curing. By using the composition for producing a foam, which is a multi-liquid type system liquid, in the spraying method, it is possible to easily perform heat insulation construction.

[0018] As described above, the foam manufacturing composition according to this disclosure may be a multi-liquid composition (system liquid) comprising a first liquid containing a first amine compound and a second liquid containing a component such as an isocyanate compound that can react with the first amine compound. Alternatively, the foam manufacturing composition according to this disclosure may be a composition (first liquid) capable of producing foam by being combined with another composition (second liquid) containing a component such as an isocyanate compound that can react with the first amine compound.

[0019] Furthermore, the foam manufacturing composition according to this disclosure includes an amine compound having a tertiary amine group (hereinafter referred to as the second amine compound) as an amine compound different from the first amine compound. When a two-component system liquid containing the second amine compound is constructed, it is preferable that the second amine compound is mixed with the first liquid which contains the first amine compound but does not contain the isocyanate compound.

[0020] Furthermore, the foam manufacturing composition relating to this disclosure may also contain other additives.

[0021] The first amine compound, the second amine compound, the isocyanate compound, and other components will be described below. In the following, the first liquid, the second liquid, the system liquid (a multi-liquid composition in which the first and second liquids are separated and managed), and the composition obtained by mixing the first and second liquids will not be particularly distinguished in the description.

[0022] <<First amine compound>> The first amine compound is an amine compound having a primary amine group and / or a secondary amine group. Preferably, the first amine compound is an amine compound (polyamine compound) having multiple amine groups selected from primary and secondary amine groups. The polyamine compound may be difunctional or trifunctional or more.

[0023] The first amine compound may be any of the following: an aliphatic polyamine compound, an aromatic polyamine compound, an alicyclic polyamine compound, etc.

[0024] Examples of the first amine compound include triethylenetetramine, phenylenediamine, xylylenediamine, 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'-methylenedianiline, and 4,4'-methylenebis(2-isopropyl-6-methyl Examples include diline, 4,4'-methylenebis(2,6-diisopropylaniline), 4,4'-methylenebis(3-chloro-2,6-diethylaniline), 4,4'-methylenebis[N-(1-methylpropyl)aniline], 3,5-diethyltoluene-2,4-diamine, dimethylthiotoluenediamine, N-(3-aminomethylbenzyl)-2-phenylethane-1-amine, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), polyamidoamine, etc. Polyamine compounds may also include modified forms and derivatives of these compounds.

[0025] The first amine compound may be a commercially available product. Examples of commercially available first amine compounds include Gascamin 240 from Mitsubishi Gas Chemical Company; Iharacureamine MT, Iharacureamine M liquid, CUA-4, Heartcure 10, Curehard MED, Elastomer 250P, Elastomer 1000P from Kumiai Chemical Industry Co., Ltd.; Lonzacure M-DEA, Lonzacure M-MIPA, Lonzacure M-DIPA, Lonzacure M-CDEA from Lonza Japan Co., Ltd.; Etacure 100, Etacure 300, Etacure 410, Etacure 420 from Albemarle Co., Ltd.; VERSALINK 740 from Evonik Nutrition & Care Co., Ltd.; ANCAMINE 2049 from Evonik Co., Ltd.; Fujicure from T&K TOKA Co., Ltd.; Daitokral from Daito Sangyo Co., Ltd.; and others.

[0026] The amine value of the first amine compound is not particularly limited as long as it does not inhibit the effects of the present disclosure, but is preferably, for example, 50 mg KOH / g or more, 100 mg KOH / g or more, 200 mg KOH / g or more, or 300 mg KOH / g or more, and is also preferably 1000 mg KOH / g or less, 800 mg KOH / g or less, 600 mg KOH / g or less, or 500 mg KOH / g or less. The amine value can be measured by the method for measuring the total amine value described in JIS K1557-7:2011 "Plastics - Test methods for polyol raw materials for polyurethane - Part 7: Determination of basicity (expression of nitrogen content and total amine value)".

[0027] Furthermore, it is preferable to use multiple polyamine compounds in combination. By combining multiple polyamine compounds in this way, it is easier to form a foam with excellent adhesion to the structure and a low density. In addition, by combining multiple polyamine compounds, the effect when the molar percentage of primary amine groups in the composition is within a predetermined range, as described later, can be further enhanced.

[0028] The first amine compound preferably includes a diamine compound having two secondary amine groups (preferably an aromatic diamine compound) and a diamine compound having two primary amine groups or having one primary amine group and one secondary amine group.

[0029] In the foam manufacturing composition, the molar percentage of primary amine groups relative to the total of primary and secondary amine groups is preferably greater than 0 mol%, 1 mol% or more, 5 mol% or more, 10 mol% or more, 15 mol% or more, or 20 mol% or more. The upper limit of the molar percentage of primary amine groups is not particularly limited, but for example, it is 90 mol%, 80 mol%, 70 mol%, 60 mol%, or 50 mol%. By having the ratio of primary and secondary amine groups within such a range, the reactivity during foaming (when the first amine compound and the isocyanate compound are mixed) can be made appropriate.

[0030] <<Second amine compound>> The second amine compound is an amine compound having a tertiary amine group.

[0031] The second amine compound may have only one tertiary amine group, or it may have two or more (preferably five or fewer, or four or fewer) tertiary amine groups.

[0032] The second amine compound may be any of the following: an aliphatic amine compound, an aromatic amine compound, an alicyclic amine compound, etc.

[0033] The second amine compound may or may not have a hydroxyl group. When a hydroxyl group is used as the second amine compound, the hydroxyl group reacts with the isocyanate compound, etc., which can prevent the volatilization of the second amine compound during foam production. When a hydroxyl group is not used as the second amine compound, storage stability and other properties may be improved.

[0034] The second amine compound is preferably a compound represented by the following formula 1.

[0035] [ka]

[0036] In formula 1, R 1 , R 2 Each of these is independently a hydrocarbon group (e.g., an alkyl group) having 1 to 10, 1 to 5, or 1 to 3 carbon atoms. 1 , R 2 It is preferable that it be a methyl group. In formula 1, R 3 R is a substituent with a total number of carbon atoms of 5 or more, 8 or more, or 10 or more (the upper limit for the number of carbon atoms is, for example, 20 or 15). 3 Examples include alkyl groups that may or may not have a hydroxyl group at their terminus, hydrocarbon groups containing an aromatic ring, and hydrocarbon groups containing a tertiary amine group.

[0037] A compound represented by formula 1, and R 3Examples of the compound having a hydrocarbon group containing a tertiary amine group include, for example, a compound represented by the following formula (2).

[0038] [Chemical formula]

[0039] In formula (2), R 4 , R 7 , R 10 are each independently an alkylene group having 1 to 5 carbon atoms or 2 to 4 carbon atoms, and R 5 , R 6 , R 8 , R 9 , R 11 , R 12 are each independently an alkyl group having 1 to 5 carbon atoms or 1 to 3 carbon atoms.

[0040] The second amine compound is preferably a compound having 10 or more carbon atoms in total. The upper limit of the total carbon number is not particularly limited, but is, for example, 25, 20, or 15. By using such a second amine compound, storage stability and the like can be improved.

[0041] From the viewpoint of controlling reactivity and the like in the composition for producing a foam, the second amine compound preferably does not have a primary amine group and a secondary amine group. Further, the second amine compound preferably does not have a heterocyclic ring (for example, a heterocyclic ring containing nitrogen as a heteroatom).

[0042] In the composition for producing a foam, the content of the second amine compound is preferably 0.1 part by mass or more, 0.5 part by mass or more, 1 part by mass or more, or 2 part by mass or more, and preferably 20 parts by mass or less, 15 parts by mass or less, or 10 parts by mass or less when the total amount of the first amine compound is 100 parts by mass.

[0043] The second amine compound functions as a catalyst (resin-forming catalyst) in a foam manufacturing composition. Furthermore, when the second amine compound is used in combination with the first amine compound or other amine compounds, the reactivity of the first amine compound or other amine compounds can be optimized, and reactivity at low temperatures can be improved.

[0044] In other words, the second amine compound (an amine compound having a tertiary amine group) can be preferably used as a catalyst for the production of polyurea foam (particularly a catalyst for the production of spray-applied polyurea foam) when reacting an amine compound such as the first amine compound with an isocyanate compound to form a polyurea foam. In this case, as mentioned above, from the viewpoint of improving storage stability, the second amine compound is particularly preferably a compound with a total of 10 or more carbon atoms.

[0045] <<Isocyanate compounds>> The isocyanate compound is not particularly limited. The isocyanate compound may be bifunctional or trifunctional or more.

[0046] The isocyanate compound may be an aromatic polyisocyanate or an aliphatic polyisocyanate. Furthermore, the aliphatic polyisocyanate may be cyclic or chain-like.

[0047] As bifunctional aromatic polyisocyanates, 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), m-phenylenediisocyanate, p-phenylenediisocyanate, 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethandianate (2,4'-MDI), 2,2'-diphenylmethane diisocyanate (2, Examples include 2'-MDI), hydrogenated MDI, xylylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylenediisocyanate, 3,3'-dimethoxy-4,4'-biphenylenediisocyanate, polymethylene polyphenyl polyisocyanate, 1,5-naphthalenediisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, tetramethylxylene diisocyanate (TMXDI), and others.

[0048] Examples of difunctional aliphatic polyisocyanates include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexane diisocyanate, methylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and isopropyl diisocyanate.

[0049] Examples of isocyanate compounds with three or more functions include 1-methylbenzol-2,4,6-triisocyanate, 1,3,5-trimethylbenzol-2,4,6-triisocyanate, biphenyl-2,4,4'-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, methyldiphenylmethane-4,6,4'-triisocyanate, 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate, triphenylmethane-4,4',4"-triisocyanate, polymeric MDI, lysine ester triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,6,11-undecane triisocyanate, bicycloheptane triisocyanate, and 1,8-diisocyanatomethyloctane.

[0050] The isocyanate compounds may also include modified forms, derivatives, etc.

[0051] These may be used individually or in combination.

[0052] The amount of isocyanate compound in the foam manufacturing composition is preferably such that the isocyanate index in the foam manufacturing composition is 150-800, 200-600, or 200-500. The isocyanate index is the value obtained by multiplying the ratio of the number of moles of isocyanate groups in the isocyanate compound to the total number of moles of active hydrogen in the foam manufacturing composition by 100 (moles of NCO / moles of active hydrogen × 100).

[0053] From another perspective, the content of the isocyanate compound in the foam manufacturing composition is preferably 100 to 1000 parts by mass, or 100 to 500 parts by mass, when the total amount of the first amine compound is 100 parts by mass.

[0054] <<Other ingredients>> Other components include flame retardants, antioxidants, ultraviolet absorbers, and antibacterial agents. Other components may also include additives that function during the production of the foam (e.g., foaming agents, foam stabilizers, trimerizing catalysts, resinification catalysts). Furthermore, the foam production composition may also contain active hydrogen-containing compounds other than the first amine compound (e.g., polyol compounds and polythiol compounds).

[0055] <Flame retardant> Examples of 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; and compounds having a cyclic structure including a heterocyclic or aromatic ring and a functional group containing an ethylenically or acetylenely unsaturated carbon bond. Furthermore, the flame retardant may also contain other flame retardants besides those listed above. These may be used individually or in combination.

[0056] Examples of phosphate esters include aromatic phosphate esters such as triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(t-butylated phenyl) phosphate, tris(i-propylated phenyl) phosphate, and 2-ethylhexyl diphenyl phosphate; aromatic condensed phosphate 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); halogenated phosphate esters such as tris(dichloropropyl) phosphate, tris(β-chloropropyl) phosphate, and tris(chloroethyl) phosphate; and halogenated condensed phosphate esters such as 2,2-bis(chloromethyl)trimethylene bis(bis(2-chloroethyl) phosphate) and polyoxyalkylene bisdichloroalkyl phosphate.

[0057] Examples of phosphate-containing flame retardants include monophosphates such as ammonium salts like ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate; sodium salts such as monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, disodium phosphite, and sodium hypophosphite; potassium salts such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, and potassium hypophosphite; lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, and lithium hypophosphite; barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, tribarium phosphate, and barium hypophosphite; magnesium salts such as magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, and magnesium hypophosphite; calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, and calcium hypophosphite; zinc salts such as zinc phosphate, zinc phosphite, and zinc hypophosphite; and aluminum salts such as monoaluminum phosphate, dialuminum phosphate, trialuminum phosphate, aluminum phosphite, and aluminum hypophosphite. Examples of polyphosphates include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate amide, and aluminum polyphosphate.

[0058] Examples of bromine-containing flame retardants include pentabromodiphenyl ether; octabromodiphenyl ether; decabromodiphenyl ether; TBBA compounds such as tetrabromobisphenol A (TBBA), TBBA-epoxy oligomer, TBBA-polycarbonate oligomer, TBBA-bis(dibromopropyl ether), and TBBA-bis(aryl ether); polybenzene ring compounds such as bisphenylpentamethane, 1,2-bis(2,4,6-tribromophenoxy)ethane, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, 2,6-dibromophenol, and 2,4-dibromophenol; brominated styrene compounds such as brominated polystyrene and polybrominated styrene; phthalate compounds such as ethylenebistetrabromophthalimide; cyclic aliphatic compounds such as hexabromocyclododecane; and polyacrylic acid brominated aromatic ester compounds such as poly(pentabromophenyl acrylate).

[0059] Examples of boron-containing flame retardants include borax; boron oxides such as diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide; and boric acid compounds such as boric acid, lithium borate, sodium borate, potassium borate, cesium borate, magnesium borate, calcium borate, barium borate, zirconium borate, zinc borate, aluminum borate, and ammonium borate.

[0060] Examples of antimony-containing flame retardants include antimony oxides such as antimony trioxide and antimony pentoxide; antimonate salts such as sodium antimonate and potassium antimonate; and pyroantimonate salts such as sodium pyroantimonate and potassium pyroantimonate.

[0061] Examples of metal hydroxides include aluminum hydroxide and magnesium hydroxide.

[0062] Compounds having a cyclic structure containing a heterocyclic or aromatic ring and a functional group containing an ethylenically or acetylenely unsaturated carbon bond include triallyl isocyanurate (TAIC), trimethyl isocyanurate (TMAIC), triallyl cyanurate (TAC), ethoxylated isocyanurate triacrylate (TEAIC), tetraallyl glycolurate (TA-G), alkyldiallyl isocyanurate (LCAIC), phenylene bismaleimide (PBMI), bisallyl nadiimide (BANI), diallyl phthalate (DAP), diaryl isophthalate (iso-DAP), and methacryloyl-terminated polyphenylene ether oligomer (DA-PPE).

[0063] Other flame retardants include, for example, chlorine compounds such as chlorinated paraffins; nitrogen compounds such as hindered amines and melamine cyanurates; cellulose; and the like.

[0064] In the foam manufacturing composition, the flame retardant content is preferably 10 parts by mass or more, 30 parts by mass or more, or 50 parts by mass or more, when the total amount of the first amine compound is 100 parts by mass, and is also preferably 300 parts by mass or less, 250 parts by mass or less, or 200 parts by mass or less.

[0065] <Foaming agent> The blowing agent is not particularly limited. Examples of blowing agents include water, hydrocarbons (preferably hydrocarbons having 4 to 6 carbon atoms, more preferably cyclopentanes), hydrofluoroolefins [HFO(1336mzz), HFO(1233zd), etc.], and carbon dioxide. These may be used individually or in combination.

[0066] In the foam production composition, the content of the foaming agent is preferably 10 parts by mass or more, 20 parts by mass or more, or 30 parts by mass or more, when the total amount of the first amine compound is 100 parts by mass, and also preferably 100 parts by mass or less, 80 parts by mass or less, or 70 parts by mass or less.

[0067] <Foam stabilizer> The foam stabilizer is not particularly limited. Examples of foam stabilizers include silicone compounds and nonionic surfactants. These may be used individually or in combination.

[0068] In the foam production composition, the content of the foam stabilizer is preferably 0.1 parts by mass or more, 1 part by mass or more, or 5 parts by mass or more, when the total amount of the first amine compound is 100 parts by mass, and is also preferably 30 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less.

[0069] <Trimerization catalyst> Examples of trimerization catalysts include metal carboxylates; metal oxides such as lithium oxide, sodium oxide, and potassium oxide; alkoxides such as sodium methoxy, sodium ethoxy, sodium propoxy, sodium butoxy, potassium methoxy, potassium ethoxy, potassium propoxy, and potassium butoxy; tertiary amines such as 2,4,6-tris(dimethylaminomethyl)phenol, triethylenediamine, and triazines [N,N',N''-tris(dimethylaminopropyl)hexahydrotriazine, 1,3,5-tris(dimethylaminopropyl)hexahydro-s-triazine, etc.]; derivatives of ethyleneimines; acetylacetone chelates of alkali metals, aluminum, and transition metals; quaternary ammonium salts; and diazabicycloundecene (DBU).

[0070] Examples of carboxylic acids that make up carboxylic acid metal salts include aliphatic monocarboxylic acids with 1 to 18 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, octic acid, caproic acid (hexanoic acid), caprylic acid (octanoic acid), capric acid (decanoic acid), undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, heptadecanoic acid, stearic acid, trifluoroacetic acid, phenylacetic acid, chloroacetic acid, glycolic acid, and lactic acid; cyclopentanecarboxylic acid, cyclo Alicyclic monocarboxylic acids such as hexahexanecarboxylic acid; aromatic monocarboxylic acids with 7 to 14 carbon atoms such as 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, and biphenylcarboxylic acid. Carboxylic acids; Aromatic polycarboxylic acids with 7 to 14 carbon atoms, such as phthalic acid, isophthalic acid, terephthalic acid, nitrophthalic acid, trimellitic acid, hemimeric acid, trimesic acid, pyromellitic acid, naphthalenedicarboxylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanediic acid, methylmalonic acid, ethyl tirimaloic acid Examples include aliphatic polycarboxylic acids having 1 to 18 carbon atoms, such as methyl malonic acid, propyl malonic acid, butyl malonic acid, dimethyl malonic acid, diethyl malonic acid, methyl ethyl malonic acid, methyl succinic acid, ethyl succinic acid, methyl ethyl succinic acid, maleic acid, citraconic acid, and itaconic acid; and alicyclic polycarboxylic acids having 6 to 18 carbon atoms, such as cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methylhexahydrophthalic acid, and methyltetrahydrophthalic acid. 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, for reasons such as achieving higher initial adhesive strength.

[0071] Furthermore, the metals that constitute the carboxylate metal salt are not particularly limited, and examples include alkali metals (e.g., lithium, sodium, potassium) and alkaline earth metals (e.g., magnesium, calcium).

[0072] In the foam manufacturing composition, the content of the trimerizing catalyst is preferably 1 part by mass or more, 5 parts by mass or more, or 10 parts by mass or more, when the total amount of the first amine compound is 100 parts by mass, and is also preferably 50 parts by mass or less, 40 parts by mass or less, or 30 parts by mass or less.

[0073] <<<Physical properties / properties>>> <<Cream Time>> The cream time of the foam manufacturing composition is preferably 1 to 120 seconds, 1 to 60 seconds, or 1 to 30 seconds. When the cream time of the foam manufacturing composition is within this range, it tends to exhibit excellent liquid flowability and adhesion to the structure. The cream time of the foam manufacturing composition is measured by the method described below.

[0074] <<Geltime>> The gel time of the foam manufacturing composition is preferably 1 to 120 seconds, 2 to 100 seconds, or 3 to 100 seconds. The gel time of the foam manufacturing composition is measured by the method described below.

[0075] <<Rise Time>> The rise time of the foam manufacturing composition is preferably 1 to 150 seconds, 5 to 120 seconds, or 10 to 120 seconds. The rise time of the foam manufacturing composition is measured by the method described below.

[0076] <<Peak Temperature>> The peak temperature of the foam manufacturing composition (the peak temperature in the reaction until the polyurea foam is formed) is preferably 80°C or higher, 100°C or higher, or 120°C or higher. The upper limit of the peak temperature is not particularly limited and is, for example, 200°C or 180°C. The peak temperature of the foam manufacturing composition is measured by the method described below.

[0077] <<Methods for measuring cream time, gel time, rise time, and peak temperature>> Prepare a first solution containing a first amine compound and a second amine compound, kept at 40°C, and a second solution containing an isocyanate compound, also kept at 40°C. Set the ambient temperature to 15±5°C and spray the mixture of the first and second solutions into a 170mm x 170mm x 170mm wooden box using a spray gun. The spraying method using a spray gun will be described later. After spraying, a thermocouple (metal rod) is inserted into the center of the mixture inside the wooden box, and the temperature of the mixture is measured periodically. The cream time is defined as the time from the moment of spraying until just before the mixture begins to foam, become a creamy liquid, and expand. This time is measured visually as the time when the color of the mixture solution begins to change. The gel time is defined as the time from the moment of spraying until the foaming of these mixtures begins, the foaming height of the foam (mixture) changes, the reaction progresses, and the resistance begins to increase when a thermocouple (metal rod) inserted into the mixture is moved. The rise time is defined as the time from the moment of spraying until the change in the foaming height of the foam (mixture) completely stops. The peak temperature is defined as the highest temperature measured by a thermocouple inserted into the mixture during the period until the foam is obtained (until the reaction completely stops). If the foam manufacturing composition contains other components, they should be mixed with the first liquid beforehand.

[0078] << A method for producing foam using the foam production composition relating to this disclosure can be carried out by known methods.

[0079] As an example, we will describe a case in which a urea-based foam is produced using a two-component composition containing a first amine compound and an isocyanate compound.

[0080] First, a first liquid containing a first amine compound, a second amine compound, and other components as needed, and a second liquid containing an isocyanate compound are prepared. The first liquid is prepared, for example, by mixing the raw materials other than the isocyanate compound in a container using a mixer. The stirring conditions are not particularly limited and can be carried out at an appropriate speed and for an appropriate time using a stirrer equipped with a propeller-type stirring blade. Next, the first liquid and the second liquid are cooled to a predetermined temperature (for example, in the range of 5±5℃) as needed. After that, the first liquid and the second liquid are mixed and foamed and cured to obtain a foam (for example, a polyurea foam).

[0081] When using the foam manufacturing composition in a spray application method, a first liquid, which is a mixture of raw materials other than the isocyanate compound, and a second liquid, which contains the isocyanate compound, are supplied to the spray gun using a pump or the like. At this time, the nozzle of the spray gun is opened. The first liquid and the isocyanate compound are then mixed in the chamber inside the spray gun, and the mixture is sprayed onto the structure to obtain a foam (for example, polyurea foam). Thus, the foam manufacturing composition is preferably applicable for spray application.

[0082] Furthermore, if the foam manufacturing composition is a multi-liquid type consisting of three or more liquids, a step of preparing another composition (e.g., a third liquid) other than the first and second liquids, or a step of mixing the first liquid, the second liquid, and the other composition (e.g., the third liquid), may be performed.

[0083] The components contained in the foam are as described above.

[0084] <<<Physical properties / characteristics of foam>>> <<density>> The density of the foam (core density) is 10 kg / m³. 3 More than 20kg / m 3 Above, or 30 kg / m 3 Preferably, it should be 200 kg / m 3 Below 100kg / m 3 The following, or 80 kg / m 3The following is preferable; by setting the density of the foam within this range, it is easier to obtain a foam with excellent flame retardancy. The density of the foam is measured according to JIS K7222:2005 "Foamed plastics and rubber - Method for determining apparent density".

[0085] <<Nurating Rate>> The nurating rate of the foam is preferably 10-40%, 15-40%, 20-40%, 25-40%, or 30-40%. When the nurating rate of the foam is within this range, it is easier to obtain a foam with excellent performance. The nurating rate can be adjusted by the isocyanate index, the type of trimerization catalyst, etc. The nurating rate of the foam is measured using the method described in Japanese Patent No. 6925554. Specifically, it is the value calculated by the following formula (1) based on the absorption spectrum obtained by infrared spectroscopy of the polyurea foam. (Formula 1) Nurate rate (%)=P1 / (P1+P2+P3+P4)×100 P1: Peak area derived from the isocyanurate structure in the absorption spectrum of polyurea foam obtained by infrared spectroscopy. P2: Peak area originating from the C=O structure of the urea structure in the absorption spectrum of the polyurea foam obtained by infrared spectroscopy. P3: Peak area derived from the C=O structure of the urethane and isocyanurate structures in the absorption spectrum of the polyurea foam obtained by infrared spectroscopy. P4: Peak area derived from NH contained in the urethane and urea structures in the absorption spectrum of polyurea foam obtained by infrared spectroscopy.

[0086] P1 has a wave number of 1380-1430 cm. -1 This is the peak area in the range. P2 is the wavenumber range of 1550-1640 cm². -1 This is the peak area in the range. P3 is the wavenumber 1680-1730 cm. -1 This is the peak area in the range. P4 corresponds to a wavenumber of 1470-1550 cm². -1This is the peak area within the specified range. The nurating rate of the foam is, for example, a value measured from a section cut from the surface of the foam to a depth of 3 mm.

[0087] <<<Usage>>> The uses of foam include, for example, building applications {walls, ceilings, roofs, floors, pipe covers (foamed insulation for residential plumbing), etc.}; joinery (windows, shoji screens, doors, fusuma sliding doors, transoms, etc.); ships and storage tanks for transporting oil and gas; vehicles (engines, batteries, ceilings, floors, door panels, etc.); aircraft; transport planes; insulated bags for transporting chemicals; freezers and refrigerators; plant facilities; electrical appliances such as refrigerators; insulation, thermal insulation, and cold resistance mitigation materials for retaining walls; underground filling reinforcement materials for ground subsidence prevention work and road construction; injection repair materials for civil engineering applications such as tunnels, bridges, and floating piers; structural filling materials for unnecessary basements, etc.; energy absorption materials; waterproofing materials; water-stopping materials; buoyancy materials; and more. In addition, in wooden and reinforced concrete buildings, it can be used as a foam for spray application methods because insulation work is easy. [Examples]

[0088] The foam will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following.

[0089] <<<Raw materials>>> <<First amine compound>> • Amine compound 1 Aromatic secondary diamines 4,4'-Methylenebis[N-(1-methylpropyl)aniline] Amine value 362 Molecular weight 310

[0090] • Amine compound 2 Gascamin 240 (product name) Manufactured by Mitsubishi Gas Chemical Company, Inc. Amine value 403 Molecular weight 278 Polyamines containing the amine compound shown in Formula 3 below [ka]

[0091] • Amine compound 3 Daitokral C-4620 (product name) Manufactured by Daito Sangyo Co., Ltd. Amine value 470 Molecular weight 238 Polyamine represented by the following formula 4 [ka]

[0092] <<Second amine compound>> Amine compound A TOYOCAT D60 Manufactured by Tosoh Corporation Tertiary amine compounds represented by the following formula 5 [ka]

[0093] • Amine compound B KL-25 Manufactured by Kao Corporation Tertiary amine compounds represented by the following formula 6 [ka]

[0094] • Amine compound C KL-20 Manufactured by Kao Corporation Tertiary amine compounds represented by the following formula 7 [ka]

[0095] • Amine compound D Polycat-9 Manufactured by Evonik Japan Co., Ltd. Tertiary amine compounds represented by the following formula 8 [ka]

[0096] <<Flame retardant>> Flame retardant 1 TCPP Phosphate ester-based flame retardants (liquid flame retardants) • Flame retardant 2 LA-72 (product name) Hindered amine flame retardants Made by ADEKA Corporation • Flame retardant 3 red phosphorus

[0097] <<Foam stabilizer>> • Foam stabilizer 1 L-6888 (product name) Manufactured by Momentive Performance Materials Japan LLC. Silicone-based foam stabilizer

[0098] <<Catalyst>> Catalyst 1 C-41 (product name) Manufactured by Momentive Performance Materials Japan LLC. Trimerization catalyst (triazine-based) Catalyst 2 K-zero G (product name) Manufactured by Momentive Performance Materials Japan LLC. Trimerization catalyst (potassium octylate)

[0099] <<Foaming agent>> • Foaming agent 1 HFO

[0100] <<Isocyanate compounds>> • Isocyanate compound 1 MR-200 (product name) Manufactured by Tosoh Corporation Crude MDI

[0101] <<<Preparation of Composition for Foam Production>>> The foam production compositions according to Examples 1 to 7 and Comparative Examples 1 to 6 were prepared from a first liquid containing components other than the isocyanate compound and a second liquid which is an isocyanate compound so as to have the compounding amounts (parts by mass) shown in Table 1.

[0102] Table 1 shows the mole % of the primary amine group with respect to the total of the primary amine group and the secondary amine group, and the numerical value of the isocyanate index (INDEX) for each foam production composition.

[0103] <<<Production and Evaluation of Foam>>> Using each foam production composition, the production and evaluation of the foam were carried out. Regarding the production of the foam, a BOX evaluation in which the foam was produced in a frame and evaluated, and a spray evaluation in which the foam was produced by spraying onto a steel plate while using a spray gun [product name: CS01RD, B (manufactured by Graco)] and then evaluated were carried out.

[0104] In Comparative Example 2, clogging occurred in the gun during the spray evaluation. Thus, since the spray evaluation could not be carried out for Comparative Example 2, the BOX evaluation was not carried out either.

[0105] <<BOX Evaluation>> For the foam production compositions according to each example and each comparative example, the first liquid and the second liquid were mixed in a mold to form a foam. When producing the foam, based on the method described above, the cream time (CT), gel time (GT), rise time (RT), and peak temperature (PT) were measured.

[0106] Also, for the obtained foam, based on the method described above, the nuration rate and density (core density) were measured.

[0107] Furthermore, for the obtained foam, based on the following method, the residual NCO%, volume change rate, and ash content were measured.

[0108] <Residual NCO%> The residual NCO% in the foam is calculated by dividing the absorption peak height measured in the foam by the peak height measured in the isocyanate raw material, based on the absorption peak height of the isocyanate group (NCO). More specifically, it is calculated as follows: Remaining NCO(%)=x / y×100 x: Measurement value (peak height) for foam material y: Measured value (peak height) using isocyanate raw material Absorption peak position based on NCO: approximately 2300 cm -1 (Measurement procedure) 1. Measure the IR of only the isocyanate raw material (MR-200 in this example). 2. Measure the IR of the foam. 3. Each chart is 750cm -1 Normalize by peak intensity (match peak height). 4. Determine the peak height from the standardized chart and calculate the remaining NCO% using the above formula.

[0109] The residual NCO% of the foam is preferably 10.0% or less, 9.5% or less, 9.0% or less, 8.5% or less, or 8.0% or less. The lower limit is not particularly limited, but is 0.0%, 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, or 2.5%.

[0110] <Volume change rate> Samples measuring 5 cm in length, 5 cm in width, and 5 cm in thickness were cut from the center of the foam of each example and comparative example, and the samples were left to stand in an electric furnace heated to 300°C or 500°C for 5 minutes, after which the volume change rate was measured. The volume before heating was set to 100%, the volume after heating was measured, and the volume change rate was calculated by subtracting the volume before heating from the volume after heating, dividing the result by the volume before heating, and multiplying by 100. A positive value indicates expansion, and a negative value indicates contraction.

[0111] When the heating temperature is 300°C, the volume change rate (volume change rate at 300°C) is preferably 50% or less, 30% or less, or 20% or less, and preferably 0% or more.

[0112] <Ash content> 3-5 mg was taken from the center of the foam of each example and comparative example, and the sample was placed in an aluminum pan (for measurement at 600°C). The weight loss behavior of the sample was observed in the temperature range of 25-600°C using a TG / DTA analyzer (SII Corporation model TG / DTA7200), and the ash content (%) of each foam was determined from the remaining weight of the sample at 600°C (ash content: remaining weight at 600°C / weight before measurement). The measurements were performed at a heating rate of 10°C / min under a dry airflow (flow velocity: 250 mm / min).

[0113] The ash content is preferably 45.0% or less, 40.0% or less, or 35.0% or less.

[0114] <Storage stability of the system fluid> The first solution was mixed and left to stand at room temperature for one week. After standing for one week, the gel time (GT) of the first solution was measured according to the method described above. The percentage change in gel time after one week of standing was calculated using the initial gel time (gel time without one week of standing) as a baseline. A percentage change of 10% or less was evaluated as "○", a percentage change of more than 10% but 30% or less was evaluated as "△", and a percentage change of more than 30% was evaluated as "×".

[0115] <<Spray Application Evaluation>> <End Cure> Using a spray gun, a mixture of the first liquid and the second liquid, both maintained at 40°C, was sprayed onto a vertically positioned steel plate (ambient temperature: 15±5°C). From the moment of spraying, foaming of these mixtures began, the foaming height of the foam changed, and the time until no contact marks were left when touching the surface near the edges of the foam formed by the reaction was evaluated as edge cure. The evaluation results are shown in Table 1. An edge cure of 300 seconds or less, or 200 seconds or less, was judged to be excellent in practicality, and an edge cure of 150 seconds or less was judged to be particularly excellent in performance.

[0116] <Drip> Using a spray gun, a mixture of the first liquid and the second liquid, both maintained at 40°C, was sprayed onto a vertically positioned steel plate (ambient temperature: 15±5°C). The sprayed mixture was visually inspected to determine whether it flowed downwards while remaining liquid. If it did not flow downwards, it was evaluated as "no dripping," and if it did flow downwards, it was evaluated as "dripping." The evaluation results are shown in Table 1.

[0117] <Structure adhesion> Using a spray gun, a mixture of the first liquid and the second liquid, both maintained at 40°C, was sprayed onto a vertically positioned steel plate (ambient temperature: 15±5°C). Ten minutes after spraying, the resulting foam and steel plate laminate was cut to a size of 10 cm long × 1.5 cm wide. The adhesive strength of the foam to the steel plate was measured using a force gauge (IMADA Digital Force Gauge ZP-100). The measured adhesive strength was evaluated as structural adhesion. The evaluation results are shown in Table 1. In the structural adhesion evaluation, an adhesive strength of 3N or higher, or 5N or higher, is considered to be practical, and an adhesive strength of 20N or higher is considered to have particularly excellent performance.

[0118] [Table 1] [Industrial applicability]

[0119] The foam manufacturing composition according to the present invention allows for easy control of reactivity at low temperatures and enables the production of foams with sufficient performance (for example, foams that can serve as a substitute for rigid polyurethane foams). Therefore, it can be preferably used as a composition for spray application methods in which foams for thermal insulation are manufactured on-site.

Claims

1. It contains multiple amine compounds having multiple amine groups selected from primary and secondary amine groups, The molar percentage of primary amine groups relative to the total of primary and secondary amine groups is greater than 0 mol%, A composition for producing foam, further comprising an amine compound having a tertiary amine group.

2. The foam production composition according to claim 1, wherein the amine compound having a tertiary amine group is a compound with a total of 10 or more carbon atoms.

3. A foam manufacturing composition according to claim 1, which is for spray application.

4. A foam produced using the foam production composition described in any one of claims 1 to 3.

5. A catalyst for the production of polyurea foam, comprising a tertiary amine compound with a total of 10 or more carbon atoms.

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