JP2023089975A - Foam-forming composition and foam - Google Patents

Abstract

To provide a foam-forming composition that enables the production of a foam having excellent performance.SOLUTION: A foam-forming composition comprises an active hydrogen compound comprising two or more active hydrogen atoms, a polyisocyanate compound, and a flame retardant, wherein the flame retardant comprises a flame retardant A which is a compound having a cyclic structure comprising a heterocyclic ring or an aromatic ring, and a functional group comprising an ethylenic or acetylenic unsaturated carbon bond.SELECTED DRAWING: None

Description

The present invention relates to foam-forming compositions and foams.

Since foams are light-weight materials having thermal insulation properties, they are used in various applications such as building applications, ships for oil and gas transportation, heat insulating materials for electric appliances such as refrigerators, and heat insulating materials. However, in some cases, the thermal insulation and flame retardancy of foams are not sufficient, and various studies have been conducted to improve the thermal insulation and flame retardancy of foams.

For example, Patent Literature 1 discloses a foam that uses halogenated ester glycol or the like and has excellent flame retardancy.

Further, Patent Document 2 discloses a foam having excellent flame retardancy and the like, which uses polyethylene glycol, phthalic acid-derived ester polyol, and Mannich polyol as polyols.

Patent No. 5625954 JP 2011-157528 A

However, the foams according to the prior art are sometimes insufficient in various performances including flame retardancy.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a foam-forming composition capable of producing a foam having excellent performance.

The present inventors have conducted intensive research, found that the above problems can be solved by a foam-forming composition containing specific components, and completed the present invention. That is, the present invention is as follows.

The present invention comprises an active hydrogen compound having two or more active hydrogens, a polyisocyanate compound, and a flame retardant,
A foam-forming composition comprising a flame retardant A, wherein the flame retardant is a compound having a cyclic structure containing a heterocyclic ring or an aromatic ring and a functional group containing an ethylenically or acetylenically unsaturated carbon bond. is.

The active hydrogen compound preferably contains a polyol compound or a polyamine compound.
It is preferred that the flame retardant contains a nitrogen-containing heterocycle.
It is preferable that a flame retardant B other than the flame retardant A is further included as the flame retardant.

The present invention may be a foam obtained by foaming and curing the foam-forming composition.

The present invention may be a polyurethane foam containing, as a flame retardant, a compound having a cyclic structure containing a heterocyclic ring or an aromatic ring and a functional group containing an ethylenically or acetylenically unsaturated carbon bond. .

The present invention is a polyurea foam containing, as a flame retardant, a compound having a cyclic structure containing a heterocyclic or aromatic ring and a functional group containing an ethylenically or acetylenically unsaturated carbon bond, good too.

The present invention also includes all inventions in which any two or more of the configurations listed above are combined.

ADVANTAGE OF THE INVENTION According to this invention, the composition for foam formation which can manufacture the foam which has the outstanding performance can be provided.

The foam-forming composition and foam according to the present invention will be described in detail below, but the present invention is not limited thereto.

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

In addition, the description of the content/content ratio of each component (solid content) in the foam-forming composition can be read as the description of the content/content ratio of each component in the foam, as long as there is no contradiction. .

<<<<Foam Forming Composition>>>>
The foam-forming composition includes an active hydrogen compound (a compound containing two or more active hydrogens), a polyisocyanate, and a flame retardant.

<<<Active Hydrogen Compound>>>
Examples of compounds having two or more active hydrogens include polyol compounds, polyhydric phenol compounds, polyamine compounds, alkanolamine compounds, and polythiol compounds.

The compound having two or more active hydrogens is preferably a polyol compound and/or a polyamine compound.

The polyol compound is not particularly limited, and may include polyester polyol, polycarbonate polyol, polyether polyol, polyester ether polyol, and the like.

The polyester polyol is not particularly limited, and for example,
Carboxylic acid component [aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid, aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, alicyclic dicarboxylic acids such as hexahydrophthalic acid, hexahydroterephthalic acid and hexahydroisophthalic acid, or their acid esters or acid anhydrides] and a polyol component [ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1, 3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1, 9-nonanediol, etc., or a mixture thereof] and a polyester polyol such as polypropylene glycol obtained by a dehydration condensation reaction;
Polylactone diols obtained by ring-opening polymerization of lactone monomers such as ε-caprolactone and methyl valerolactone;
etc. can be mentioned.

Examples of polycarbonate polyols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexane. At least one polyhydric alcohol such as diol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, diethylene carbonate, dimethyl carbonate, diethyl and those obtained by reacting carbonate and the like.

Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol obtained by polymerizing cyclic ethers such as ethylene oxide, propylene oxide and tetrahydrofuran, respectively, and copolyethers thereof. It can also be obtained by polymerizing the above cyclic ether using a polyhydric alcohol such as glycerin or trimethylolethane.

Polyester ether polyols include, for example, aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid, aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, alicyclic Dicarboxylic acids such as hexahydrophthalic acid, hexahydroterephthalic acid and hexahydroisophthalic acid, or their acid esters or acid anhydrides and glycols such as diethylene glycol or propylene oxide adducts, or mixtures thereof Those obtained by a dehydration condensation reaction can be mentioned.

Examples of polyalkylene polyol include polyalkylene glycol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutadiene polyol, polyethylene glycol-polypropylene glycol copolymer, polyethylene glycol-polytetramethylene glycol copolymer, polypropylene glycol-polytetramethylene glycol. A methylene glycol copolymer and the like can be mentioned.

The polyhydric phenol compound is not particularly limited, and examples thereof include monocyclic polyhydric phenols such as pyrogallol and hydroquinone; bisphenols such as bisphenol A, bisphenol F and bisphenol sulfone; and the like.

The polyamine compound is not particularly limited, and examples thereof include aliphatic polyamines, aromatic polyamines, and alicyclic polyamines.
Specifically, N,N-bis(sec-butylaminophenyl)methane, 4,4-methylene-bis(2-methylcyclohexylamine), 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, 4,4'-methylenebis(2-isopropyl-6-methylaniline), 4,4'-methylenebis(2,6-diisopropylaniline), 4,4'- Mention may be made of methylenebis(3-chloro-2,6-diethylaniline), 3,5-diethyltoluene-2,4-diamine, dimethylthiotoluenediamine.

Polythiol compounds are not particularly limited and include, for example, bis-(2-hydrothioethyloxy)methane, dithioethylene glycol, dithioerythritol, and dithiothreitol.

Alkanolamine compounds are not particularly limited, and examples include diethanolamine, ethanolisopropanolamine, diisopropanolamine, ethanol-2-hydroxybutylamine, isopropanol-2-hydroxybutylamine, triethanolamine, N-methylaminoethanol, N-normal Butylethylaminoethanol, N-tert-butylaminoethanol, N-ethylaminoethanol, N-benzylaminoethanol, N-(2-hydroxyethyl)piperazine and the like.

Here, the type of resin can be changed by changing the type of active hydrogen compound or catalyst contained in the foam-forming composition. For example, using a polyol compound as an active hydrogen compound to obtain a polyurethane foam or a polyisocyanurate foam, using a polyamine compound as an active hydrogen compound to obtain a polyurea foam, or using a polythiol compound as an active hydrogen compound. This makes it possible to obtain a polythiourethane resin, and the like.

The hydroxyl value of the polyol compound and polyhydric phenol compound is preferably 50 to 1000 mgKOH/g, more preferably 80 to 850 mgKOH/g, even more preferably 100 to 700 mgKOH/g.

Here, the hydroxyl value is a value measured according to JIS-K0070.

The mercapto value (SH value) of the polythiol compound is preferably 50-1000 mgKOH.
Here, the mercapto group value of the polythiol compound is obtained by the following method. Mercapto group value (SH value; mgKOH/g): Weigh the sample in a 100 mL (milliliter) sample bottle (the mass is in grams and read accurately to four decimal places), acetic anhydride-tetrahydrofuran solution (anhydrous in 100 mL of solution Accurately add 5 mL of 4-dimethylaminopyridine-tetrahydrofuran solution (containing 1 g of 4-dimethylaminopyridine in 100 mL of solution) and 10 mL of 4-dimethylaminopyridine-tetrahydrofuran solution to dissolve the sample completely, then stir at room temperature for 1 hour. . Then, exactly 1 mL of ultrapure water is added and stirred at room temperature for 30 minutes, followed by titration with a 0.5M potassium hydroxide-ethanol solution (indicator: phenolphthalein).
The SH value is calculated by the following formula.
SH value (mgKOH/g) = 28.05 x (BA)/S
(Wherein, S is the sample collection amount (g), A is the amount of 0.5M potassium hydroxide-ethanol solution required for titration of the sample (mL), B is the 0.5M hydroxide required in the blank test Represents the amount (mL) of potassium-ethanol solution.)

The amine value of the polyamine compound is preferably 50-1000 mgKOH/g, more preferably 50-800 mgKOH/g.
Here, the amine value of the polyamine compound is all described in JIS K1557-7:2011 "Plastics-Polyurethane raw material polyol test method-Part 7: Determination of basicity (nitrogen content and total amine value display)" Measured by the method for measuring amine value.

The alkanolamine compound preferably has a hydroxyl value of 50 to 1000 mgKOH/g. Moreover, the amine value of the alkanolamine compound is more preferably 50 to 800 mgKOH/g.

Active hydrogen-containing compounds can be used alone or in combination.

<<<polyisocyanate compound>>>
The polyisocyanate compound is not limited as long as it is a compound having multiple isocyanate groups, and may be aromatic, aliphatic or alicyclic.

Examples of bifunctional 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'-diphenylmethanedianate (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), Aromatics such as hydrogenated XDI, tetramethylxylene diisocyanate (TMXDI);
Cycloaliphatic ones such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, methylcyclohexane diisocyanate;
Alkylene compounds such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and lysine diisocyanate;
etc.

Tri- or higher functional polyisocyanates include, for example, 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, 1 , 8-diisocyanatomethyloctane and the like.

Further, the polyisocyanate compound may be a modified product or derivative of the above compound.

In addition, the polyisocyanate compound has a terminal isocyanate group obtained by reacting the polyisocyanate compound in an excess amount with respect to the active hydrogen compound containing two or more active hydrogens (for example, the polyol compound described above). It may contain a prepolymer having

The polyisocyanate compound preferably contains one or more selected from MDI, TDI, and modified or derivatives thereof, more preferably monomeric MDI and/or crude MDI.

These polyisocyanate compounds can be used alone or in combination.

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

<<<<flame retardant>>>>
The foam-forming composition preferably contains, as a flame retardant, a compound having a cyclic structure containing a heterocyclic ring or an aromatic ring and a functional group containing an ethylenically or acetylenically unsaturated carbon bond. Such a compound is hereinafter referred to as flame retardant A.

Moreover, the foam-forming composition preferably further contains a flame retardant having a structure different from that of the flame retardant A. The flame retardant other than the flame retardant A is hereinafter referred to as a flame retardant B.

<<<flame retardant A>>>
Flame retardant A is a compound having a cyclic structure containing a heterocyclic ring or an aromatic ring and a functional group containing an ethylenically or acetylenically unsaturated carbon bond. For example, flame retardant A is a compound having a functional group containing an ethylenically or acetylenically unsaturated carbon bond as at least one substituent of a cyclic structure containing a heterocyclic ring or an aromatic ring.

When a polyurethane foam, a polyurea foam, or the like contains the flame retardant A, it is presumed that the flame retardancy is improved by the following mechanism of action. When the foam is exposed to high heat, the foam resin skeleton is thermally decomposed (when burned) to generate radicals. This radical reacts with the unsaturated bond of the flame retardant A to temporarily form a crosslinked structure. As a result, the heat resistance of the foam is improved because the cyclic structure is incorporated in the resin skeleton of the foam. In addition, the cyclic structure is likely to form carbonization, and carbonization can be expected to have the effect of retarding the spread of fire from the surface to the inside.

The flame retardant A may have one cyclic structure or two or more cyclic structures in one molecule.

Aromatic rings and heterocyclic rings may have appropriate substituents. Examples of such substituents include alkyl groups having 1 to 4 carbon atoms and carbonyl groups.

When flame retardant A has a plurality of cyclic structures, the cyclic structures may be bonded to each other through single bonds, or may be bonded via carbon atoms, oxygen atoms, or the like. For example, the flame retardant A may contain a biphenyl structure or a diphenylmethane structure in its skeleton.

Cyclic structures may include polycyclic structures (eg, naphthalene and nadimide rings) in which multiple rings are bonded together by sharing two or more atoms. Also in this case, the cyclic structure may be a heterocyclic aromatic ring, such as an indole structure.

A heterocycle can be, for example, a 3- to 12-membered ring or a 4- to 8-membered ring.

The heteroatom contained in the heterocyclic ring may be 1 or 2 or more. Heteroatoms are, for example, oxygen, nitrogen, sulfur, phosphorus, silicon, and the like.

Preferably the heterocycle contains nitrogen as a heteroatom. In other words, flame retardant A preferably contains a nitrogen-containing heterocycle. Cyclic structures containing nitrogen-containing heterocycles include a pyrrolidine group, imidazolidine ring, maleimide ring, phthalimide ring, triazine ring, isocyanurate ring, nadimide ring, glycoluril ring and the like. It is particularly preferred that the flame retardant A has an isocyanurate ring. By using the flame retardant A containing such a heterocyclic ring, the flame retardancy, shape retention, etc. of the foam can be enhanced.

Flame retardant A preferably has 2 or more functional groups containing ethylenic or acetylenic unsaturated carbon bonds in one molecule, preferably 2 to 5, and may have 2 to 4. Preferably, it is particularly preferable to have 2 to 3.

Functional groups containing ethylenically or acetylenically unsaturated carbon bonds include, for example, functional groups containing alkenyl groups or alkynyl groups (having, for example, 2 to 8 or 2 to 5 carbon atoms). An alkenyl group or alkynyl group may be linear or branched.

Moreover, the functional group containing an ethylenically or acetylenically unsaturated carbon bond may contain an ester bond, an ether bond, or the like. For example, a functional group containing an ethylenically or acetylenically unsaturated carbon bond may be a (meth)acryloyl group, a (meth)acryloyloxy group, or a (meth)acryloyloxyalkyl group (the alkyl moiety may be linear or branched). It may be of any shape, or it may be a long chain, preferably having 1 to 5 or 2 to 3 carbon atoms.

Moreover, from the viewpoint of enhancing flame retardancy and shape retention, the flame retardant A is preferably a compound containing an ethylenically or acetylenically unsaturated carbon bond at its terminal portion. More specifically, the flame retardant A is preferably a compound having an allyl group, a (meth)acryloyloxy group, or a (meth)acryloyloxyalkyl group (the alkyl moiety has 2 to 3 carbon atoms). .

The molecular weight of the flame retardant A is preferably 100-1500, more preferably 120-1200, even more preferably 150-500.

The flame retardant A is preferably liquid at 20° C. from the viewpoint of uniform dispersibility of the flame retardant in the foam and enhancement of flame retardancy and shape retention.

Preferred flame retardants A include triallyl isocyanurate (TAIC), trimethylisocyanurate (TMAIC), triallyl cyanurate (TAC), ethoxylated isocyanuric acid triacrylate (TEAIC), tetraallylglycolurylate (TA- G), alkyl diallyl isocyanurate (LCAIC), phenylene bismaleimide (PBMI), bisallyl nadiimide (BANI), diallyl dilate (DAP), dialiph isophthalate (iso-DAP), methacryloyl group-terminated polyphenylene ether oligomer ( DA-PPE) and the like.

Flame retardant A can be used alone or in combination.

The content of the flame retardant A in the foam-forming composition is not particularly limited, but is 1 to 50 parts by mass, 1 to 40 parts by mass, 2 to 30 parts by mass, 5 parts by mass with respect to 100 parts by mass of the active hydrogen compound. It is preferably up to 25 parts by mass, or 10 to 20 parts by mass.

From another point of view, the content of the flame retardant A in the foam-forming composition is 0.5 parts per 100 parts by mass of the total amount of the active hydrogen compound and the polyisocyanate (or the amount of the resin component). It is preferably 20 parts by mass, 1.0 to 15 parts by mass, 1.5 to 10 parts by mass, or 3 to 7 parts by mass.

<<<flame retardant B>>>
Flame retardant B is a flame retardant having a structure different from that of flame retardant A, and includes a phosphate ester, a phosphate-containing flame retardant, a bromine-containing flame retardant, a boron-containing flame retardant, an antimony-containing flame retardant, a metal hydroxide, Other flame retardants are included.

Phosphate esters include, for example, triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(t-butylated phenyl) phosphate, tris(i-propylated phenyl) phosphate, 2-ethylhexyl Aromatic phosphoric acid esters such as diphenyl phosphate; Condensed phosphoric acid ester; Halogen-containing phosphoric acid esters such as tris (dichloropropyl) phosphate, tris (β-chloropropyl) phosphate, tris (chloroethyl) phosphate; 2,2-bis (chloromethyl) trimethylene bis (bis ( 2-chloroethyl)phosphate), halogen-containing condensed phosphates such as polyoxyalkylenebisdichloroalkylphosphate;

Phosphate-containing flame retardants include, for example, monophosphates such as ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen 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, 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; aluminum salts such as aluminum diphosphate, aluminum tertiary phosphate, aluminum phosphite, and aluminum hypophosphite;

Examples of polyphosphate include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate, and aluminum polyphosphate.

Bromine-containing flame retardants include, for example, pentabromodiphenyl ether; octabromodiphenyl ether; decabromodiphenyl ether; tetrabromobisphenol A (TBBA); - TBBA compounds such as bis(aryl ethers); bisphenylpentamethane, 1,2-bis(2,4,6-tribromophenoxy)ethane, 2,4,6-tris(2,4,6-tribromo phenoxy)-1,3,5-triazine, 2,6-dibromophenol, 2,4-dibromophenol and other multi-benzene ring compounds; brominated polystyrene, polybrominated styrene and other brominated styrene compounds; ethylenebistetrabromo phthalic acid compounds such as phthalimide; cycloaliphatic compounds such as hexabromocyclododecane; special brominated flame retardants such as tris(2,3-dibromopropyl)isocyanurate;

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.

Antimony-containing flame retardants include, for example, antimony oxides such as antimony trioxide and antimony pentoxide; antimonate salts such as sodium antimonate and potassium antimonate; pyroantimonate salts such as sodium pyroantimonate and potassium pyroantimonate; etc. can be mentioned.

Examples of metal hydroxides include aluminum hydroxide and magnesium hydroxide.

Other flame retardants include chlorine compounds such as chlorinated paraffin; nitrogen compounds such as hindered amines and melamine cyanurate; cellulose;

Flame retardant B can be used alone or in combination.

Flame retardant B preferably contains a phosphate ester.

By combining the flame retardant A and the flame retardant B, a flame retardant action in different temperature zones or a flame retardant action by a different mechanism of action is produced, and the flame retardancy of the foam can be improved.

The content of the flame retardant B in the foam-forming composition is not particularly limited. / (content of flame retardant B in foam-forming composition) is 0.10 to less than 1.00, 0.10 to 0.80, 0.15 to 0.70, or 0.25 to 0.25 60 is preferred.

Here, the foam-forming composition may or may not contain red phosphorus as the flame retardant B. The foam-forming composition does not contain red phosphorus, for example, when the red phosphorus content (solid content ratio) in the foam-forming composition is less than 0.10% by mass, less than 0.05% by mass. , or less than 0.01% by mass.

<<<<Other Ingredients>>>>
The foam-forming composition may contain other components depending on the use of the foam. Other components include catalysts, foaming agents, foam stabilizers, and the like. Moreover, other components may contain another component.

<<<catalyst>>>
The catalyst is not particularly limited, and known catalysts can be used.

Examples of the catalyst include catalysts that promote the reaction between the active hydrogen compound and the polyisocyanate compound. Such a catalyst can be appropriately selected according to the active hydrogen compound to be used and the foam to be produced.

For example, if it is desired to produce urethane foam, the catalyst may include a urethanization catalyst. Examples of the urethanization catalyst include amine-based catalysts such as triethylamine and tetramethylguanidine, tin-based catalysts such as stannus octoate, and metal catalysts such as phenylmercuric propionate and lead octenate.

The catalyst may also contain a trimerization catalyst. Examples of trimerization catalysts include metal oxides such as lithium oxide, sodium oxide and potassium oxide; alkoxides such as methoxysodium, ethoxysodium, propoxysodium, butoxysodium, methoxypotassium, ethoxypotassium, propoxypotassium and butoxypotassium organic metal salts such as potassium acetate, potassium octylate, potassium caprylate, iron oxalate; 2,4,6-tris(dimethylaminomethyl)phenol, N,N',N"-tris(dimethylaminopropyl)hexa tertiary amines such as hydrotriazine, triethylenediamine, 1,3,5-tris(dimethylaminopropyl)hexahydro-s-triazine; derivatives of ethyleneimine; acetylacetone chelates of alkali metals, aluminum and transition metals, 4 ammonium salts; nitrogen-containing heterocyclic compounds such as diazabicycloundecene (DBU);

Moreover, the catalyst may contain a foaming catalyst or a resin-forming catalyst.

Foaming catalysts include, for example, N,N-dimethylaminoethanol, N,N,N',N',N''-pentamethyldiethylenetriamine, bis(2-dimethylaminoethyl) ether, N,N,N' , N′,N″-pentamethyldipropylenetriamine, N,N-dimethylaminoethoxyethanol, N,N,N′-trimethylaminoethoxyethanol, N,N,N′,N″,N′″ ,N'''-hexamethyltriethylenetetramine, N,N,N',N''-tetramethyl-N''-(2-hydroxylethyl)triethylenediamine, N,N,N',N''- Examples include tertiary amines such as tetramethyl-(2-hydroxylpropyl)triethylenediamine and organic acid salts thereof, morpholine compounds, and piperazine compounds, and one or more of these can be used.

Examples of the resinification catalyst include triethylenediamine (TEDA), triethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N ,N′,N′-tetramethylpropylenediamine, N,N,N′,N″,N″-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N′,N″,N′ tertiary amines such as '-pentamethyldipropylenetriamine, N,N,N',N'-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine or Organic acid salts, bismuth tris (2-ethylhexanoate), bismuth tris (neodecanoate), bismuth tris (palmitate), bismuth tris (palmitate), bismuth tetramethylheptanedioate, bismuth octylate, bismuth naphthenate, dibutyltin dilaurate, dibutyltin dimaleate, Organometals such as dibutyltin diacetate, dioctyltin diacetate, tin octylate, dimethyltin dimercaptide, titanium-(2-ethylhexoside), 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2- imidazoles such as ethyl-4-methylimidazole, 2-isopropylimidazole, 1-isobutyl-2-methylimidazole, or N-methyl-N'-(2-dimethylaminoethyl)piperazine, N,N'-dimethylpiperazine, N-methylpiperazine, N-methylmorpholine, N-ethylmorpholine, 1,8-diazabicyclo[5.4.0]undecene-7, 1,1′-(3-(dimethylaminopropyl)imino)bis(2- propanol) and the like, and one or more of these can be used.

These can be used alone or in combination.

The content of the catalyst in the foam-forming composition is not particularly limited. , 0.1 to 15.0 parts by mass or 1.0 to 10.0 parts by mass.

<<<foaming agent>>>
Examples of foaming agents include water, hydrocarbons (preferably C4-C6), hydrofluoroolefins, and carbon dioxide gas. Specific examples include cyclopentane, HFO (1336mzz), and HFO (1233zd). These can be used alone or in combination.

The content of the foaming agent in the foam-forming composition can be appropriately adjusted in consideration of the desired density of the foam.

<<<foam stabilizer>>>
Examples of foam stabilizers include silicone compounds such as polyalkylsiloxane-polyoxyethylene-polyoxypropylene graft copolymers, polyalkylsiloxane-polyoxyethylene-polyoxypropylene linear block copolymers; Surfactants such as fluorine-based hydrocarbon compounds, acrylic-polyoxyalkylene copolymers, polyoxyethylene-polyoxypropylene copolymers, acetylene diol compounds, polyoxyethylene fatty acid esters, polyoxyethylene alkyl ethers, polyoxy Ethylene phenyl ether, polyoxyethylene phenyl ether, polyoxyethylene alkylphenyl ether, glycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, and the like can be mentioned. These can be used alone or in combination.

<<<Additional Ingredients>>>
The foam-forming composition may contain other components such as additives such as antioxidants, ultraviolet absorbers, antibacterial agents, tackifiers, compatibilizers, etc. (known additives etc.).

<<<<Foam>>>>
The foam is obtained by reacting and curing the foam-forming composition containing the active hydrogen compound and the polyisocyanate compound described above. More specifically, the polyisocyanate in the foam-forming composition reacts with the active hydrogen compound to form a resin that serves as the skeleton of the foam. By incorporating the flame retardant into this skeleton, a foam having flame retardancy and the like is formed.

Here, the type of foam obtained differs depending on the type of active hydrogen compound and catalyst used. That is, the basic skeleton of the foam can be selected according to its use.

As an example, it is preferably a polyurethane foam obtained using a polyol compound as the active hydrogen compound.

In other words, the foam is a polyurethane foam containing, as a flame retardant, a compound having a cyclic structure containing a heterocycle or an aromatic ring and a functional group containing an ethylenically or acetylenically unsaturated carbon bond. is preferred.

As another example, it is preferably a polyurea foam obtained using a polyamine compound as the active hydrogen compound.

In other words, the foam is a polyurea foam containing, as a flame retardant, a compound having a cyclic structure containing a heterocycle or an aromatic ring and a functional group containing an ethylenically or acetylenically unsaturated carbon bond. is preferred.

Still further, the foam may be a polyisocyanurate foam, a polythiourethane foam, or the like.

In these foams, the content of the flame retardant A in the foam is, for example, 0.5% by mass to 15.0% by mass, 1.0% by mass to 10.0% by mass, or 2.0% by mass. % to 5.0% by mass.

In addition, the type of each component that can be contained and the content of each component are as described above, so the description is omitted.

A foam can be produced by mixing components such as an active hydrogen compound, a polyisocyanate compound, and a flame retardant by a known method. Specifically, each raw material other than polyisocyanate is placed in a container and mixed with a mixer (for example, a stirrer equipped with a propeller-type stirring blade) (for example, stirred at 2000 rpm for 5 minutes using a stirrer) to contain an active hydrogen compound. Adjust the mixture. Subsequently, the polyisocyanate compound and the mixed liquid containing the active hydrogen compound are each cooled to a predetermined temperature (for example, 10±1° C.). Thereafter, the polyisocyanate compound and the mixed solution containing the active hydrogen compound are mixed (for example, stirred at 2000 rpm for 5 seconds using a stirrer), foamed and cured to obtain a foam. At this time, by injecting a mixture of the polyisocyanate compound and the mixture containing the active hydrogen compound into a mold having a cavity having a predetermined product shape, it is possible to foam-mold a molded article having a predetermined shape.

Here, the foam-forming composition includes a first composition containing a polyisocyanate compound and no active hydrogen compound, and a second composition containing no polyisocyanate compound and containing an active hydrogen compound. It can be a liquid system liquid. The flame retardant and other additives may be assigned to the first composition or the second composition in consideration of the reactivity of each component. By dividing each component in the foam-forming composition into a plurality of compositions in this manner to form a system liquid to be mixed at the time of use, storage stability can be enhanced. When the foam-forming composition is a two-liquid system liquid, the first composition and the second composition are mixed at a construction site or the like, foamed/cured, and sprayed at the same time. can be used. By using the foam-forming composition, which is a two-component system liquid, in the spraying method, it is possible to easily perform insulation work.

<<<<Usage of foam>>>>
Uses of foams include, for example, architectural uses {walls, ceilings, roofs, floors, pipe covers (foam insulation materials for residential piping), etc.}; Transport ships/storage tanks; vehicles (engines, batteries, ceilings, floors, door panels, etc.); aircraft; Thermal insulation material, insulation material, cold-heat resistance mitigation material; Underground filling reinforcement material for ground subsidence prevention work and road construction; Injection repair material for civil engineering applications such as tunnels, bridges, and floating piers; Structural part filling material for unnecessary basements, etc.; material; waterproof material; water stop material; buoyant material;
In addition, it can be used as a foam for the spraying method in wooden or reinforced concrete buildings, because it is easy to insulate.

EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these.

<<<<raw material for foam forming composition>>>>>
<<<Active Hydrogen Compound>>>
<A-1>
o-Phthalic acid ester polyol (hydroxyl value: 250 mgKOH/g)
<A-2>
N,N-bis(sec-butylaminophenyl)methane (amine value: 527 mgKOH/g)

<<<isocyanate compound>>>
<B-1>
Crude MDI (NCO%: 31.4%)

<<<catalyst>>>
<C-1>
Bismuth 2-hexanoate <C-2>
Quaternary ammonium salt <C-3>
N,N-dimethylaminoethoxyaminoethanol <C-4>
Potassium 2-ethylhexanoate <C-5>
Dibutyltin dilauryl mercaptide <C-6>
1-methylimidazole <C-7>
Hexamethyltriethylenetetramine

<<<flame retardant>>>
<<Flame retardant containing a C=C unsaturated bond and containing a cyclic structure (flame retardant A)>>
<D-1>
TAIC
<D-2>
TAC
<D-3>
TEAIC
<D-4>
DAP
<D-5>
iso-DAP

<<Flame Retardant (Flame Retardant B) Containing a C=C Unsaturated Bond and Not Containing a Ring Structure>>
<D-6>
trimethylolpropane triacrylate

<<Flame retardant containing no C=C unsaturated bond (flame retardant B)>>
<D-7>
TCPP (Phosphate Ester Flame Retardant)
<D-8>
TAIC-6B (brominated flame retardant)

<<<foam stabilizer>>>
<<E-1>>
SF2937F (Silicone-based surfactant manufactured by Dow Corning Toray Co., Ltd.)

<<<foaming agent>>>
<F-1>
Hydrofluoroolefin <F-2>
water

<<<<Foam Production>>>>
Active hydrogen compounds, catalysts, flame retardants, foaming agents, foam stabilizers, and other additives were weighed in 500 mL polypropylene disposable cups, and the amounts of each example and comparative example shown in each table were weighed. and the mixed liquid of the comparative example.
Using a stirrer equipped with a propeller-type stirring blade, each liquid mixture was stirred and mixed at 2000 rpm for 5 minutes to obtain the first composition of each example and comparative example.
The obtained first composition and the second composition (polyisocyanate) obtained by weighing the compounding amount described in each table were individually cooled to 10±1°C in a cooling furnace at 10°C.
Using a stirrer equipped with a propeller-type stirring blade, the first composition and second composition of each example and comparative example were stirred and mixed at 2000 rpm for 5 seconds, and then quickly put into a foaming box for foam molding. rice field.
[Foam box]
A polyethylene film of 0.1 mm thickness×170 mm height×170 mm×170 mm was set in a box of 170 mm height×170 mm×170 mm square.

<<<<evaluation>>>>
<<<Measurement of ash content (600 ° C) >>>
Take 3 to 5 mg from the center of the foam of each example and comparative example, fill the sample in an aluminum pan (for measurement at 600 ° C.), ) was used to observe the weight loss behavior of the sample in the temperature range of 25 to 600°C, and the ash content (%) of each foam was determined from the residual weight of the sample at 600°C.
The measurement was performed at a temperature elevation rate of 10° C./min under a dry air stream (flow rate: 250 mm/min).
The ash content was evaluated as follows.
[Ash content at 600°C (%)]
○: 4.5% or more △: 3.0% or more and less than 4.5% ×: less than 3.0%

<<<Measurement of Limiting Oxygen Index>>>
After 24 hours from foaming, the skin layer was removed from the foams of Examples and Comparative Examples, and ten samples each having a width of 1 cm, a length of 15 cm, and a thickness of 1 cm were cut out. A sample was fixed in a glass tube with a jig and stood vertically in a candle burning tester (Toyo Seiki Seisakusho).
After that, based on JIS K7201-2, the upper end of the sample was ignited with a gas burner, and the minimum oxygen concentration required for combustion (limit oxygen index) was determined from the ignition time and the fire spread distance.
The limiting oxygen index was evaluated as follows.
[Limit oxygen index (%)]
○: 25% or more △: 22% or more and less than 25% ×: less than 22%

<<<Heat resistance test>>>
A sample having a length of 5 cm, a width of 5 cm, and a thickness of 5 cm was cut out from the central portion of the foam of each example and comparative example, placed in an electric furnace heated to 300 ° C. for 5 minutes, and the volume change rate was measured. It was measured.
The volume before heating is taken as 100%, and the volume after heating is measured, and the value obtained by subtracting the volume before heating from the volume after heating is divided by the volume before heating and multiplied by 100 to obtain the volume change rate. bottom. A positive value indicates expansion, and a negative value indicates contraction.
The volume change rate was evaluated as follows.
After the heat resistance test, the presence or absence of cracks on the sample surface was visually confirmed.
[Volume change rate]
○: Less than 50% △: 50% or more and less than 70% ×: 70% or more

<<<flame contact test>>>
A rectangular parallelepiped sample having a length of 10 cm, a width of 10 cm, and a thickness of 5 cm was cut out from the foam of each example and comparative example 24 hours after foaming. Each of the obtained samples was placed on a wire mesh having a length of 10 cm, a width of 10 cm and a thickness of 1 mm, and the surface of the sample was indirectly flamed with a gas burner for 3 minutes. Methane gas with a purity of 99.5% or higher was used as the combustion gas, and the combustion gas was supplied at 0.2 MPa to create a pale flame. The flame height was 5 cm and the distance between the flame and the sample surface was 1 cm.
After the flame application, the sample was cut in half and the presence or absence of cracks in the cross section was visually observed.
Also, the maximum distance of the black carbonized portion in the cross section (the length of the carbonized portion from the side surface of the cross section) was measured as the depth of the carbonized layer.
The depth of the carbonized layer was evaluated as follows.
[Carbonized layer thickness (mm)]
○: 8 mm or less △: More than 8 mm and less than 10 mm ×: 10 mm or more

<<<Flame Retardant Test>>>
The foams of each example and comparative example were subjected to a UL94 flame retardancy test in accordance with standard V0, and the presence or absence of cracks and deformation of the burned portion was visually confirmed.

<<<core density>>>
After 24 hours from foaming, the foam of each example and comparative example was cut into pieces of 10 cm × 10 cm × 10 cm, and the apparent density of the cut sample was measured according to JIS K7222: 2005 "Foamed plastics and rubber - Determination of apparent density". Measured by the method described.

Claims (7)

comprising an active hydrogen compound having two or more active hydrogens, a polyisocyanate compound, and a flame retardant;
The flame retardant comprises a flame retardant A which is a compound having a cyclic structure containing a heterocyclic ring or an aromatic ring and a functional group containing an ethylenically or acetylenically unsaturated carbon bond. Body shaping composition. The foam-forming composition of claim 1, wherein the active hydrogen compound comprises a polyol compound or a polyamine compound. 3. The foam-forming composition of claim 1 or 2, wherein the flame retardant comprises a nitrogen-containing heterocycle. 3. The foam-forming composition according to claim 1, further comprising a flame retardant B other than said flame retardant A as said flame retardant. A foam obtained by foaming and curing the foam-forming composition according to claim 1 or 2. A polyurethane foam comprising, as a flame retardant, a compound having a cyclic structure containing a heterocycle or an aromatic ring and a functional group containing an ethylenically or acetylenically unsaturated carbon bond. A polyurea foam comprising, as a flame retardant, a compound having a cyclic structure containing a heterocycle or an aromatic ring and a functional group containing an ethylenically or acetylenically unsaturated carbon bond.