Composition for producing foam and foam

Abstract

To provide a composition for producing a foam, which can produce a foam having excellent performance that can be a substitute for a rigid urethane foam.SOLUTION: An embodiment of the present invention is a composition for producing a foam, comprising a monoamine having an aromatic group and a polydiamine having an aromatic group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a foam-producing composition and a foam. [Background technology]

[0002] Foams are used as heat insulating materials for buildings such as apartment buildings and detached houses, and rigid urethane foams are widely used as such foams.

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

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2018-100404 Summary of the Invention [Problem to be solved by the invention]

[0005] However, techniques using rigid urethane foams have not always been able to provide sufficient performance.

[0006] Therefore, an object of the present invention is to provide a foam-producing composition that can be used to produce foams with excellent performance and that can be used as an alternative to rigid urethane foams. [Means for solving the problem]

[0007] The present inventors have conducted extensive research and found that the above-mentioned problems can be solved by using a foam-producing composition that uses a specific amine compound as a raw material, and have thus completed the present invention.

[0008] One aspect of the present invention is a foam-producing composition comprising an aromatic monoamine and an aromatic polyamine.

[0009] The aromatic monoamine is preferably benzylamine or dibenzylamine. The foam-producing composition is preferably for spray application.

[0010] Another aspect of the present invention is a foam produced using the foam-producing composition. [Effects of the Invention]

[0011] An object of the present invention is to provide a foam-producing composition that can be used to produce foams with excellent performance and that can serve as an alternative to rigid urethane foams. DETAILED DESCRIPTION OF THE INVENTION

[0012] In the following, when a compound is described, its isomers are also described.

[0013] Hereinafter, when an upper limit value and a lower limit value are separately described, it is considered that a numerical range combining any upper limit value and any lower limit value is substantially disclosed.

[0014] The composition of the foam-producing composition according to the present disclosure, the physical properties / properties of the foam-producing composition, the method for producing a foam using the foam-producing composition, and applications / uses of the foam will be specifically described below, but the present invention is not limited thereto.

[0015] <<<Composition of foam manufacturing composition>>> The foam-producing composition includes an amine compound. Preferably, the foam-producing composition according to the present disclosure also includes an isocyanate compound. More specifically, the foam-producing composition according to the present disclosure is preferably a composition for forming a urea resin foam by reacting an amine compound with an isocyanate compound (a composition for producing a urea resin foam).

[0016] Here, when an amine compound and an isocyanate compound are mixed, the reaction proceeds rapidly. Therefore, when the foam-producing composition according to the present disclosure contains an amine compound and an isocyanate compound, it is preferable that the amine compound and the isocyanate compound are maintained in a separated state. That is, the foam-producing composition according to the present disclosure may be a multi-component (e.g., two-component) system liquid comprising a first component containing an amine compound but not an isocyanate compound, and a second component containing an isocyanate compound but not an amine compound. In this case, other additives may be distributed to the first component, the second component, or a component other than the first and second components (e.g., a third component) in consideration of the reactivity of each component. In this way, by dividing the components of the foam-producing composition into multiple components and forming a system liquid that is mixed at the time of use, storage stability can be improved. When the foam-producing composition is a multi-component system liquid, it can be used in a spraying method in which components (e.g., the first and second components) are mixed at a construction site, foamed, cured, and sprayed simultaneously. By using a foam-producing composition, which is a multi-component system liquid, in the spraying method, it is possible to easily carry out heat insulation construction.

[0017] As described above, the foam-producing composition according to the present disclosure may be a multi-liquid composition (system liquid) containing a first liquid containing an amine compound and a second liquid containing a component capable of reacting with the amine compound, such as an isocyanate compound. The foam-producing composition according to the present disclosure may also be a composition (first liquid) that can produce a foam by combining it with another composition (second liquid) containing a component capable of reacting with the amine compound, such as an isocyanate compound.

[0018] The foam-producing composition according to the present disclosure may also contain other additives.

[0019] The amine compound, isocyanate compound, and other components will be described below, without making any particular distinction between the first liquid, the second liquid, the system liquid (a multi-liquid composition in which the first liquid and the second liquid are separately managed), and the composition obtained by mixing the first liquid and the second liquid.

[0020] In the present disclosure, an amine compound refers to a compound that contains an amine group (a primary amine group or a secondary amine group) as an active hydrogen group and does not contain any active hydrogen groups other than the amine group (a hydroxyl group or a thiol group). In other words, in the present disclosure, even if a compound contains an amine group, a compound that contains an active hydrogen group other than the amine group (for example, an amino alcohol compound) is not considered to be an amine compound.

[0021] <<Amine compounds>> The amine compound preferably contains an aromatic monoamine and an aromatic polyamine. By using such amine compounds in combination, the reactivity during foaming (when the amine compound and the isocyanate compound are mixed) can be made appropriate, and the flame retardancy of the resulting foam can be improved. The aromatic amine is a compound having an aromatic ring and an amino group. In the aromatic amine, the amino group may be directly bonded to the aromatic ring or may be bonded to another site.

[0022] Examples of the monoamine having an aromatic group include aniline, methylaniline, dimethylaniline (1,5-dimethylaniline, 3,4-dimethylaniline, etc.), trimethylaniline (2,4,6-trimethylaniline, etc.), ethylaniline, aminocetophenone, benzylamine, dibenzylamine, phenylethylamine, phenylpropylamine, naphthylamine, aminobiphenyl, etc. The monoamine having an aromatic group may be used alone or in combination.

[0023] The aromatic polyamine may be bifunctional or trifunctional or higher. The aromatic polyamine is preferably an aromatic diamine.

[0024] Examples of aromatic polyamines include phenylenediamine, xylylenediamine, 4,4'-diamino-3,3'-dichlorodiphenylmethane, trimethylene-bis(4-aminobenzoate), 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, Examples of suitable polyamines include polytetramethylene oxide-di-p-aminobenzoate, 2,2',6,6'-tetraethyl-4,4'-methylenedianiline, 4,4'-methylenebis(2-isopropyl-6-methylaniline), 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, 3,5-diethyltoluene-2,6-diamine, dimethylthiotoluenediamine, and N-(3-aminomethylbenzyl)-2-phenylethan-1-amine. The aromatic polyamines may be used alone or in combination. The aromatic polyamine preferably contains two or more selected from these aromatic polyamines.

[0025] The amine compound may include modified products, derivatives, etc. of these.

[0026] The amine compound may be a commercially available product. Examples of commercially available aromatic polyamines include Gaskamine 240 manufactured by Mitsubishi Gas Chemical Company, Inc.; Iharacamine MT, Iharacamine M liquid, CUA-4, and Heartcure 10 manufactured by Kumiai Chemical Industry Co., Ltd.; Lonzacure M-DEA, Lonzacure M-DIPA, and Lonzacure M-CDEA manufactured by Lonza Japan; and Ethacure 100, Ethacure 300, Ethacure 410, and Ethacure 420 manufactured by Albemarle Corporation.

[0027] The amine value of the aromatic monoamine is preferably 200 or more, or 250 or more, and preferably 800 or less, or 600 or less. The amine value of the aromatic polyamine is preferably 200 or more, or 300 or more, and preferably 1000 or less, or 800 or less.

[0028] The molecular weight of the aromatic monoamine and the molecular weight of the aromatic polyamine are preferably 1,000 or less, 800 or less, or 500 or less, respectively.

[0029] In the foam-producing composition, the ratio of the content of aromatic monoamine to the content of aromatic polyamine (monoamine / polyamine) is preferably 0.01 or more, 0.02 or more, or 0.03 or more, and is preferably 0.20 or less, 0.15 or less, 0.10 or less, or 0.08 or less. When the ratio of the content of aromatic polyamine to the content of aromatic monoamine falls within such a range, the above-mentioned effects can be further enhanced.

[0030] In the foam-producing composition, the ratio of the total content of aliphatic amines and alicyclic amines to the total content of aromatic amines (total content of aromatic monoamines and aromatic polyamines) [(aliphatic amines + alicyclic amines) / aromatic amines] is preferably 0.50 or less, 0.30 or less, 0.10 or less, 0.05 or less, or 0.01 or less.

[0031] <<Isocyanate compounds>> The isocyanate compound is not particularly limited, and may be bifunctional, trifunctional or higher functional.

[0032] The isocyanate compound may be an aromatic polyisocyanate or an aliphatic polyisocyanate. The aliphatic polyisocyanate may be a cyclic or chain polyisocyanate.

[0033] Examples of bifunctional aromatic polyisocyanates include 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), m-phenylene diisocyanate, p-phenylene 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-naphthalene diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, tetramethylxylene diisocyanate (TMXDI), etc.

[0034] Examples of bifunctional 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 isopropylene diisocyanate.

[0035] Examples of tri- or higher functional isocyanate compounds include 1-methylbenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene-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.

[0036] The isocyanate compound may include modified compounds, derivatives, etc. of these compounds.

[0037] These may be used alone or in combination.

[0038] The content of the isocyanate compound in the foam-producing composition is preferably an amount such that the foam-producing composition has an isocyanate index of 150 to 800, 200 to 600, or 200 to 500. The isocyanate index refers to the ratio of the number of moles of all active hydrogens in the foam-producing composition to the number of moles of isocyanate groups in the isocyanate compound multiplied by 100 (number of moles of NCO / number of moles of active hydrogen × 100).

[0039] From another perspective, the content of the isocyanate compound in the foam-producing composition is preferably 100 to 1,000 parts by mass or 100 to 500 parts by mass, relative to 100 parts by mass of the total amount of the amine compounds.

[0040] <<Other ingredients>> Examples of other components include flame retardants, antioxidants, ultraviolet absorbers, antibacterial agents, etc. The other components may include additives that function when producing foams (e.g., blowing agents, foam stabilizers, trimerization catalysts, resinification catalysts), etc. The foam-producing composition may also include active hydrogen-containing compounds other than amine compounds (e.g., polyol compounds, polythiol compounds, aminoalcohol compounds, etc.).

[0041] <Flame retardant> Examples of flame retardants include red phosphorus, phosphoric acid 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 containing a heterocyclic or aromatic ring and a functional group containing an ethylenic or acetylenic unsaturated carbon bond. The flame retardant may also contain other flame retardants in addition to these flame retardants. These may be used alone or in combination.

[0042] 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); halogen-containing phosphate esters such as tris(dichloropropyl)phosphate, tris(β-chloropropyl)phosphate, and tris(chloroethyl)phosphate; and halogen-containing condensed phosphate esters such as 2,2-bis(chloromethyl)trimethylenebis(bis(2-chloroethyl)phosphate) and polyoxyalkylenebisdichloroalkylphosphate.

[0043] Examples of the phosphate-containing flame retardant include monophosphates, such as ammonium salts such as 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 aluminum monophosphate, aluminum diphosphate, aluminum triphosphate, aluminum phosphite, and aluminum hypophosphite. Examples of polyphosphates include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, and aluminum polyphosphate.

[0044] 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; phthalic acid compounds such as ethylene bistetrabromophthalimide; cyclic aliphatic compounds such as hexabromocyclododecane; and brominated polyacrylic acid aromatic ester compounds such as poly(pentabromophenyl acrylate).

[0045] 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.

[0046] Examples of antimony-containing flame retardants include antimony oxides such as antimony trioxide and antimony pentoxide; antimonates such as sodium antimonate and potassium antimonate; and pyroantimonates such as sodium pyroantimonate and potassium pyroantimonate.

[0047] Examples of metal hydroxides include aluminum hydroxide and magnesium hydroxide.

[0048] 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), trimethyl isocyanurate (TMAIC), triallyl cyanurate (TAC), ethoxylated isocyanuric acid triacrylate (TEAIC), tetraallyl glycol urate (TA-G), alkyl diallyl isocyanurate (LCAIC), phenylene bismaleimide (PBMI), bisallylnadimide (BANI), diallyl phthalate (DAP), diallyl isophthalate (iso-DAP), and methacryloyl-terminated polyphenylene ether oligomer (DA-PPE).

[0049] Other flame retardants include, for example, chlorine compounds such as chlorinated paraffin; nitrogen compounds such as hindered amines and melamine cyanurate; cellulose; and the like.

[0050] The content of the flame retardant in the foam-producing composition is preferably 10 parts by mass or more, 30 parts by mass or more, or 50 parts by mass or more, and is preferably 300 parts by mass or less, 250 parts by mass or less, or 200 parts by mass or less, relative to 100 parts by mass of the total amount of the amine compounds.

[0051] <Foaming agent> The blowing agent is not particularly limited. Examples of the blowing agent include water, hydrocarbons (preferably hydrocarbons having 4 to 6 carbon atoms, more preferably cyclopentane), hydrofluoroolefins [HFO(1336mzz), HFO(1233zd), etc.], carbon dioxide gas, etc. These may be used alone or in combination.

[0052] The content of the blowing agent in the foam-producing composition is preferably 10 parts by mass or more, 20 parts by mass or more, or 30 parts by mass or more, and is preferably 100 parts by mass or less, 80 parts by mass or less, or 70 parts by mass or less, relative to 100 parts by mass of the total amount of the amine compounds.

[0053] <Foam stabilizer> The foam stabilizer is not particularly limited. Examples of the foam stabilizer include silicone compounds and nonionic surfactants. These may be used alone or in combination.

[0054] The content of the foam stabilizer in the foam-producing composition is preferably 0.1 parts by mass or more, 1 part by mass or more, or 5 parts by mass or more, and is preferably 30 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less, relative to 100 parts by mass of the total amount of the amine compounds.

[0055] <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.]; ethyleneimine derivatives; acetylacetone chelates of alkali metals, aluminum, and transition metals; quaternary ammonium salts; diazabicycloundecene (DBU); and the like.

[0056] Examples of carboxylic acids that can be used to form metal carboxylates include aliphatic monocarboxylic acids having 1 to 18 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, octylic 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; Alicyclic monocarboxylic acids such as hexanecarboxylic acid; aromatic monocarboxylic acids having 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, resorcylic acid, naphthalenecarboxylic acid, and biphenylcarboxylic acid. Carboxylic acids; aromatic polycarboxylic acids having 7 to 14 carbon atoms, such as phthalic acid, isophthalic acid, terephthalic acid, nitrophthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid, and naphthalenedicarboxylic 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, and ethyl chirimalonic acid. and alicyclic polycarboxylic acids having 6 to 18 carbon atoms, such as cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methylhexahydrophthalic acid, methyltetrahydrophthalic acid, etc. 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 the ability to achieve higher initial adhesive strength.

[0057] The metal constituting the metal carboxylate is not particularly limited, and examples thereof include alkali metals (for example, lithium, sodium, and potassium) and alkaline earth metals (for example, magnesium and calcium).

[0058] The content of the trimerization catalyst in the foam-producing composition is preferably 1 part by mass or more, 5 parts by mass or more, or 10 parts by mass or more, and is preferably 50 parts by mass or less, 40 parts by mass or less, or 30 parts by mass or less, relative to 100 parts by mass of the total amount of the amine compounds.

[0059] <<<Physical properties / properties>>> <<Cream Time (CT)>> The cream time of the foam-producing composition is preferably 1 to 120 seconds, 1 to 60 seconds, or 1 to 30 seconds. When the cream time of the foam-producing composition is within this range, foams with excellent performance are likely to be formed when the composition is applied to a spraying method or the like. The cream time of the foam-producing composition is measured by the method described below.

[0060] <<Tuck Free Time (TFT)>> The tack-free time of the foam-producing composition is preferably 100 seconds or less, 80 seconds or less, or 50 seconds or less. When the tack-free time of the foam-producing composition is within this range, foams with excellent performance are likely to be formed when the composition is applied to a spraying method or the like. The tack-free time of the foam-producing composition is measured by the method described below.

[0061] <<Rise Time (RT)>> The rise time of the foam-producing composition is preferably 150 seconds or less, 120 seconds or less, 100 seconds or less, 50 seconds or less, 30 seconds or less, 20 seconds or less, or 15 seconds or less. The lower limit of the rise time is, for example, 1 second, 3 seconds, or 5 seconds. When the rise time of the foam-producing composition is within this range, foams with excellent performance are likely to be formed when applied to a spraying method or the like. Furthermore, by shortening the rise time, it becomes possible to spray a second layer on top of the first layer without any time delay after spraying the first layer, thereby shortening the application time in multi-layer spraying. The rise time of the foam-producing composition is measured by the method described below.

[0062] Peak Temperature (PT) The peak temperature of the foam-producing composition (the peak temperature during the reaction until a 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-producing composition is measured by the method described below.

[0063] <<How to measure cream time, tack-free time, rise time, and peak temperature>> A first liquid containing an amine compound and maintained at 40°C, and a second liquid containing an isocyanate compound and maintained at 40°C are prepared. The ambient temperature is set to 15±5°C, and a spray gun is used to spray the mixture of the first and second liquids into a wooden box measuring 170 mm x 170 mm x 170 mm. Spraying using a spray gun is described below. After spraying, a thermocouple (metal rod) is inserted into the center of the mixture inside the wooden box to measure the temperature of the mixture at regular intervals. The cream time is the time from the time of spraying until the mixture starts to foam, becomes a creamy liquid, and immediately before it starts to expand (the time when the color of the mixture solution starts to change when confirmed with the naked eye). The tack-free time is the time from the time of spraying until the mixture starts to foam, the foam height of the foam (mixture) changes, the reaction progresses, and the tack on the surface of the foam completely disappears. The rise time is the time from the time of spraying until the foam height of the foam (mixture) stops changing completely. The highest temperature measured by a thermocouple inserted into the mixture until a foam is obtained (until the reaction has completely stopped) is taken as the peak temperature. When the foam-producing composition contains other components, they are mixed in advance with the first liquid.

[0064] <<<Foam manufacturing method>>> The method for producing a foam using the foam-producing composition according to the present disclosure can be carried out by a known method.

[0065] As an example, a case where a urea-based foam is produced using a two-component foam-producing composition containing an amine compound and an isocyanate compound will be described.

[0066] First, a first liquid containing an amine compound and, if necessary, other components, and a second liquid containing an isocyanate compound are prepared. The first liquid is prepared, for example, by mixing raw materials other than the isocyanate compound in a container using a mixer. The mixing conditions are not particularly limited, and mixing can be carried out at an appropriate rotation speed for an appropriate period of time using a mixer equipped with a propeller-type mixing blade, etc. Next, the first liquid and the second liquid are cooled to a predetermined temperature (for example, in the range of 5±5°C) as necessary. Thereafter, the first liquid and the second liquid are mixed, foamed, and cured to obtain a foam (for example, a polyurea foam).

[0067] When the foam-producing composition is used in a spraying method, a first liquid, which is a mixture of raw materials other than the isocyanate compound, and a second liquid containing the isocyanate compound are each supplied to a 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 a chamber within the spray gun, and the mixture is sprayed onto a structure to obtain a foam (e.g., a polyurea foam). In this way, the foam-producing composition is preferably applicable to spraying.

[0068] In addition, when the foam-producing composition is a multi-liquid type consisting of three or more liquids, a step of preparing a composition other than the first liquid and the second liquid (e.g., a third liquid) or a step of mixing the first liquid, the second liquid and another composition (e.g., the third liquid) may be carried out.

[0069] The components contained in the foam are as described above.

[0070] <<<Physical properties / properties of foam>>> <<density>> The density of the foam (core density) is 10 kg / m 3 More than 20kg / m 3 or more than 30 kg / m 3 It is preferable that the saturation is 200 kg / m or more. 3 Below 100kg / m 3 or less than 80 kg / m 3 By setting the density of the foam in this range, the foam is likely to have excellent flame retardancy. The density of the foam is measured in accordance with JIS K7222:2005 "Foamed plastics and rubber - Determination of apparent density."

[0071] <<Nurate ratio>> The nurate content of the foam is preferably 10 to 40%, 15 to 40%, 20 to 40%, 25 to 40%, or 30 to 40%. When the nurate content of the foam is within this range, it is easy to obtain a foam with excellent performance. The nurate content can be adjusted by the isocyanate index, the type of trimerization catalyst, etc. The nurate content of the foam is measured using the method described in Japanese Patent No. 6925554. Specifically, it is a value calculated using 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 isocyanurate structures contained in the absorption spectrum of polyurea foam obtained by infrared spectroscopy P2: Peak area derived from C=O of the urea structure in the absorption spectrum of polyurea foam obtained by infrared spectroscopy P3: Peak area derived from C=O of urethane structure and isocyanurate structure contained in the absorption spectrum of polyurea foam obtained by infrared spectroscopy P4: Peak area derived from NH contained in the urethane structure and urea structure in the absorption spectrum of polyurea foam obtained by infrared spectroscopy

[0072] P1 has a wave number of 1380-1430 cm -1 P2 is the peak area in the wavenumber range of 1550 to 1640 cm -1 P3 is the peak area in the wavenumber range of 1680 to 1730 cm -1 P4 is the peak area in the wavenumber range of 1470 to 1550 cm -1 The nurate content of a foam is a value measured, for example, on a portion cut out from the surface of the foam at a depth of 3 mm.

[0073] <<<Usage>>> The foams are used in, for example, architectural applications (walls, ceilings, roofs, floors, pipe covers (foam insulation for residential piping), etc.); building materials (windows, shoji screens, sliding doors, sliding screens, transoms, etc.); oil and gas transport ships and storage tanks; vehicles (engines, batteries, ceilings, floors, door panels, etc.); aircraft; transport aircraft; pharmaceutical transport cooler bags; freezers and refrigerators; plant facilities; electrical appliances such as refrigerators; insulation materials, thermal insulation materials, and cold and heat 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 fillers for unnecessary basements, etc.; energy absorbers; waterproofing materials; water-stopping materials; buoyancy materials; etc. Furthermore, in wooden and reinforced concrete buildings, etc., the foams can be used as spray-applied insulation because of their ease of application. [Example]

[0074] The foam will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following.

[0075] <<<Raw materials>>> <<Amine compounds>> <Polyamine> Amine Compound 1 Ethacure 420 (product name) Albemarle 4,4'-methylenebis[N-(1-methylpropyl)aniline] A diamine having an aromatic group represented by the following formula (1): Amine number 362 Molecular weight 310 [ka]

[0076] Amine compounds 2 Gaskamin 240 (product name) Mitsubishi Gas Chemical Company, Inc. A polyamine containing an aromatic diamine represented by the following formula (2): Amine number 403 Molecular weight 278 [ka]

[0077] Amine Compounds 3 Heart Cure 10 (product name) Manufactured by Kumiai Chemical Industry Co., Ltd. A polyamine containing a diamine having an aromatic group represented by the following formula (3): Amine number 630 Molecular weight 178 [ka]

[0078] Amine Compounds 4 ClearLink 1000 4,4'-methylenebis(N-sec-butylcyclohexanamine) Alicyclic diamines represented by the following formula (4): Amine number 348 Molecular weight 322 [ka]

[0079] <Monoamine> Amine Compounds 5 benzylamine A monoamine having an aromatic group represented by the following formula (5): [ka]

[0080] Amine compounds 6 Dibenzylamine A monoamine having an aromatic group represented by the following formula (6): [ka]

[0081] <<Other ingredients>> <Amino alcohol> Amino alcohol 1 Amino alcohol MBM (product name) Nippon Nyukazai Co., Ltd. Mono-n-butylethanolamine

[0082] <Flame retardant> Flame retardant 1 TCPP Phosphate ester flame retardant (liquid flame retardant) Flame retardant 2 LA-72 (product name) Hindered amine flame retardants Made by ADEKA Corporation Flame retardant 3 red phosphorus

[0083] <Foam stabilizer> Foam stabilizer 1 L-6888 (product name) Manufactured by Momentive Performance Materials Japan, LLC Silicone foam stabilizer

[0084] <Catalyst> Catalyst 1 C-41 (product name) Manufactured by Momentive Performance Materials Japan, LLC Trimerization catalyst (triazine type) Catalyst 2 K-zero G (product name) Manufactured by Momentive Performance Materials Japan, LLC Trimerization catalyst (potassium octoate)

[0085] <Foaming agent> Foaming agent 1 HFO

[0086] <Isocyanate compounds> Isocyanate Compound 1 MR-200 (product name) Tosoh Corporation Crude MDI

[0087] <<<Preparation of foam-producing composition>>> Compositions for producing foams according to Examples 1 to 4 and Comparative Examples 1 to 3 were prepared, each consisting of a first liquid containing components other than an isocyanate compound and a second liquid which was an isocyanate compound, in the amounts shown in Table 1.

[0088] Table 1 shows the isocyanate index (INDEX) values ​​of each foam-producing composition.

[0089] <<<Foam production and evaluation>>> For each foam-producing composition according to each Example and Comparative Example, the first and second liquids were mixed in a mold to form a foam. During foam production, the cream time (CT), rise time (RT), tack-free time (TFT), and peak temperature (PT) were measured according to the methods described above.

[0090] Furthermore, the density (core density), residual NCO %, nurate content, volume change rate, and ash content of the obtained foam were measured based on the methods described above.

[0091] <Remaining NCO%> The residual NCO % of the foam is a value calculated by dividing the peak height of absorption due to isocyanate groups (NCO) measured for the foam by the peak height measured for the isocyanate raw material. More specifically, it is calculated as follows: Remaining NCO(%)=x / y×100 x: Measured value in foam (peak height) y: Measured value (peak height) for isocyanate raw material NCO-based absorption peak position: 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 the peak intensity (match the peak height). 4. Obtain the peak height from the normalized chart and calculate the remaining NCO% using the above formula.

[0092] The residual NCO% of the foam is preferably 12.0% or less, 10.0% or less, 8.0% or less, or 6.0% or less. The lower limit is not particularly limited, but is preferably 0.0%, 0.1%, 0.5%, 1.0%, 2.0%, or 2.5%.

[0093] <Volume change rate> A sample measuring 5 cm in length, 5 cm in width, and 5 cm in thickness was cut out from the center of the foam of each Example and Comparative Example, and left to stand in an electric furnace heated to 300°C or 500°C for 5 minutes, and the volume change rate was measured. The volume before and after heating was measured, and the volume after heating was subtracted from the volume before heating, divided by the volume before heating, and multiplied by 100 to obtain the volume change rate. When the sample expanded, the volume change rate was a positive value, and when the sample contracted, the volume change rate was a negative value.

[0094] The volume change rate when the heating temperature is set to 300°C (300°C volume change rate) is preferably 150.0% or less, 100.0% or less, or 50.0% or less. The foam of Comparative Example 3 has a volume change rate of 1.0%, but this is in a state where the volume expanded and then began to shrink. In this way, when the volume expands due to a temperature change and then the volume begins to shrink due to cell destruction or the like, resulting in an extremely low volume change rate (for example, a volume change rate of 10.0% or less), this is excluded from the preferred range.

[0095] <Ash content> From the center of each foam of each Example and Comparative Examples 1 to 3, 3 to 5 mg was collected and placed in an aluminum pan (for measurement at 600°C). The weight loss behavior of the sample was observed over a temperature range of 25 to 600°C using a TG / DTA measuring instrument (TG / DTA7200 manufactured by SII Corporation). The ash content (%) of each foam was calculated from the remaining weight of the sample at 600°C (ash content: remaining weight at 600°C / weight before measurement). The measurement was carried out at a temperature rise rate of 10°C / min under a dry air flow (flow rate: 250 mm / min).

[0096] The ash content is preferably 30.0% or more, 35.0% or more, 40.0% or more, or 45.0% or more.

[0097] [Table 1]

[0098] The foam-producing compositions according to each Example have relatively short RT and TFT times compared to Comparative Example 1, have sufficient reactivity (reactivity at relatively low temperatures), and are therefore suitable for spraying processes, etc. (foams with excellent performance can be easily obtained even when a spraying process is performed). Furthermore, the foam-producing compositions according to each Example do not experience cell destruction or the like at 300°C, and are therefore superior in flame retardancy compared to Comparative Examples 2 and 3. The foam-producing compositions according to each Example also have low residual NCO% and high nurate content. Thus, it is believed that the selection of an amine compound or the like in the foam-producing compositions according to each Example facilitates appropriate reactions, resulting in improved flame retardancy of the resulting foams. [Industrial Applicability]

[0099] When a foam is produced using the foam-producing composition according to the present invention, the rise time and other properties are within an appropriate range, and the resulting foam has excellent flame retardancy. Therefore, the foam-producing composition according to the present invention can be preferably used as a composition for a spraying method in which thermal insulation foam is produced on-site.

Claims

1. A foam-producing composition comprising an aromatic monoamine and an aromatic polyamine.

2. 2. The foam-producing composition according to claim 1, wherein the aromatic monoamine is benzylamine or dibenzylamine.

3. The foam-producing composition according to claim 1, which is for spray application.

4. A foam produced using the foam-producing composition according to any one of claims 1 to 3.

Images