JP6876186B1 - Resin composition and foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a foam and its raw material whose compressive strength is hard to deteriorate even in a bad environment (particularly under high temperature and high humidity) while ensuring basic characteristics (flame retardancy, shape retention, etc.) as a flame-retardant material. A resin composition is provided. SOLUTION: A resin component containing an isocyanate-terminated prepolymer having at least two or more isocyanate groups obtained from a compound having two or more active hydrogens and a polyisocyanate; a polyamine; a trimerization catalyst; and a flame retardant. A resin composition comprising; a foaming agent and a; a foam stabilizer. [Selection diagram] None

Description

The present invention relates to resin compositions and foams.

Urethane foam is used as a heat insulating material and a heat insulating material for construction applications, ships for transporting oil and gas, and electric appliances such as refrigerators. In particular, in reinforced concrete construction and the like, a method of constructing urethane foam by a spraying method is used because heat insulation construction is easy. The spraying method is a method of forming a urethane foam heat insulating structure by spraying a stock solution of urethane foam onto the building frame at the same time using a spraying device.

In general, polyurethane resin has excellent elasticity, flexibility, and tensile strength, and also has excellent wear resistance and impact strength. However, since the urethane foam alone has high flammability, studies have been made to improve the flame retardancy of the urethane foam.

As such a urethane foam, Patent Document 1 describes for forming a water-foaming hard polyisocyanurate foam composed of an organic polyphenylmethane polyisocyanate, a polyol, a trimerization catalyst, water as a foaming agent, a foam stabilizer, and a flame retardant. The composition is disclosed. The invention of Patent Document 1 is a primary and / or secondary polyol obtained by using an active hydrogen-containing compound as a polymerization initiator, presenting an acid catalyst, and performing ring-open polymerization of a chlorinated epoxy compound. It is characterized by containing a chlorinated polyether polyol having a hydroxyl group, and is characterized in that an organic polyphenylmethane polyisocyanate and a polyol are blended so that the isocyanate index is 120 to 400. It has been shown that the urethane foam using the composition for forming a water-foamed hard polyisocyanurate foam of Patent Document 1 is excellent in a working environment and the like and is excellent in flame retardancy.

Patent Document 2 includes a polyisocyanate, a polyol, a trimerization catalyst, a foaming agent, a foam stabilizer and an additive, and the trimerization catalyst includes a nitrogen-containing aromatic compound, a carboxylate alkali metal salt, a tertiary ammonium salt and 4 It is at least one selected from the group consisting of quaternary ammonium salts, and the additive contains red phosphorus as an essential component, and in addition to red phosphorus, a phosphate ester, a phosphate-containing flame retardant, a bromine-containing flame retardant, and a boron-containing flame retardant. , A flame retardant urethane resin composition comprising at least one selected from the group consisting of an antimony-containing flame retardant and a metal hydroxide is disclosed. The urethane foam using the flame-retardant urethane resin composition of Patent Document 2 is easy to handle, has excellent flame retardancy, and can form a foam that maintains a constant shape when heated. It is shown.

Japanese Unexamined Patent Publication No. 2013-023510 Japanese Unexamined Patent Publication No. 2017-075326

Here, it is preferable that the physical properties of the flame-retardant material do not change with time even in a poor environment (particularly, under high temperature and high humidity). In particular, the present inventors have found that the flame retardant effect decreases with time as the compressive strength deteriorates. Therefore, the present invention ensures the basic characteristics (flame retardancy, shape retention, etc.) as a flame-retardant material, and the foam and foam whose compressive strength does not easily deteriorate even in a poor environment (particularly under high temperature and high humidity). The main subject is to provide a resin composition as a raw material thereof. In addition, the flame-retardant material is preferably not only flame-retardant but also a material in which the spread of fire does not easily proceed even in the event of a fire. As a result of proceeding with verification from this point of view, the present inventors have confirmed that although the conventional urethane foam has excellent flame retardancy, the spread of fire tends to proceed unexpectedly. Therefore, an object of the present invention is to provide a foam capable of suppressing the progress of fire spread and a resin composition as a raw material thereof while ensuring flame retardancy.

The present invention (1) comprises a resin component containing an isocyanate-terminated prepolymer having at least two or more isocyanate groups, which is obtained from a compound having two or more active hydrogens and polyisocyanate; a polyamine; and a trimerization catalyst; A resin composition comprising a flame retardant, a foaming agent, and a foam stabilizer.
The present invention (2) is the resin composition of the invention (1), wherein the NCO% of the isocyanate-terminated prepolymer is 10 to 35% by mass.
The present invention (3) is the resin composition of the invention (1) or (2), wherein the resin composition further contains a polyisocyanate different from the isocyanate-terminated prepolymer.
The present invention (4) is the resin composition according to any one of the inventions (1) to (3), wherein the compound having two or more active hydrogens is at least one selected from polyols, polyamines and polythiols. is there.
The present invention (5) is a resin composition according to any one of the above inventions (1) to (4), wherein the trimerization catalyst is an organometallic salt, a quaternary ammonium salt or a nitrogen-containing heterocyclic compound.
In the present invention (6), the resin composition is any one of the inventions (1) to (5), further containing red phosphorus.
In the present invention (7), the resin composition is at least selected from the group consisting of a phosphate ester, a phosphate-containing flame retardant, a bromine-containing flame retardant, a boron-containing flame retardant, an antimony-containing flame retardant, and a metal hydroxide. The resin composition of the invention (6), which further contains one flame retardant.
The present invention (8) is a foam obtained from any one of the resin compositions of the inventions (1) to (7).
The present invention (9) is the foam of the present invention (8), wherein the isocyanurate formation rate in the foam is 20% or more and 50% or less.

According to the present invention, while ensuring the basic characteristics (flame retardancy, shape retention, etc.) as a flame-retardant material, the foam and foam whose compressive strength is hard to deteriorate even in a poor environment (particularly under high temperature and high humidity) It becomes possible to provide a resin composition as a raw material thereof. Further, according to the present invention, it is possible to provide a foam capable of suppressing the progress of fire spread and a resin composition as a raw material thereof while ensuring flame retardancy.

FIG. 1 is an absorption spectrum chart of the foam according to Example 1 obtained by infrared spectroscopic analysis.

The present invention preferably comprises a resin component comprising an isocyanate-terminated prepolymer having at least two or more isocyanate groups, obtained from an active hydrogen compound having two or more active hydrogens and a polyisocyanate; with a polyamine; trimerization. A foam obtained by reacting a resin composition containing a catalyst, a flame retardant, a foaming agent, and a foam stabilizer. The "resin component" in the present specification and claims is an isocyanate-terminated prepolymer and a polyamine, and when a polyisocyanate is contained, this is also a resin component. Ingredients other than these are not considered to be resin components within the scope of this specification and claims. Hereinafter, the foam, the method for producing the foam, the physical properties of the foam, and the use of the foam will be described in order.

≪Effervescent foam≫
<Overall structure>
The foam according to the present invention is preferably a closed cell type. Here, the density of the foam foam is preferably 10 to 200 / ^{m 3,} more preferably from 10 to 100 kg / ^{m 3,} and still more preferably from 10 to 50 kg / ^{m 3} ..

<Chemical structure>

(Isocyanurate ring content (isocyanurate conversion rate))
The isocyanurate conversion rate in the foam according to the present invention is preferably 20% or more and 50% or less, and preferably 25% or more and 40% or less. Here, the isocyanurate conversion rate is a value calculated by the following equation 1.

(Equation 1)
Isocyanurate conversion rate (%) = P1 / (P1 + P2 + P3 + P4) x 100

Here, P1 is a peak area derived from the isocyanurate structure contained in the absorption spectrum of the foam obtained by infrared spectroscopic analysis. P2 is a peak area derived from C = O of the urea structure included in the absorption spectrum of the foam obtained by infrared spectroscopy. P3 is a peak area derived from C = O of the urethane structure and the isocyanate structure contained in the absorption spectrum of the foam obtained by the infrared spectroscopic analysis. P4 is a peak area derived from NH contained in the urethane structure and the urea structure contained in the absorption spectrum of the foam obtained by the infrared spectroscopic analysis. More specifically, P1 is the area of the peak derived from the isocyanurate structure contained in the absorption spectrum of the foam obtained by the infrared spectroscopic analysis, and the area of the peak derived from the nurate ring in the vicinity of ^{wave number 1410 cm-1.} Is. P1 is a peak area with a wave number in the range of 1380 to 1430 cm ^-1. P1 indicates the content of the isocyanurate structure formed by the reaction of the isocyanate group derived from the raw material. P2 is a peak area derived from C = O of the urea structure included in the absorption spectrum of the foam obtained by infrared spectroscopic analysis, and a peak derived from C = O of the urea bond ^{having a wave number of about 1595 cm -1.} The area of. P2 is a peak area with a wave number in the range of 1550 to 1640 cm- ^1. P2 indicates the content of the urea structure formed by the reaction of the isocyanate group derived from the raw material. P3 is the peak area derived from C = O of the urethane structure and the isocyanurate structure contained in the absorption spectrum of the foam obtained by the infrared spectroscopic analysis, and is the peak area of the C = O bond in the vicinity of ^{wave number 1710 cm -1.} The area. P3 is a peak area with a wave number in the range of 1680 to 1730 cm- ^1. P3 indicates the content of the urethane structure and the isocyanurate structure formed by the reaction of the isocyanate group derived from the raw material. P4 is a peak area derived from NH contained in the urethane structure and urea structure contained in the absorption spectrum of the foam obtained by infrared spectroscopic analysis, and is derived from NH having a wave number of 1510 cm ^-1. The area of the peak. P4 is a peak area with a wave number in the range of 1470 to 1550 cm ^-1. P4 indicates the content of the urethane structure and the urea structure contained in the foam, and indicates the content of the urethane structure and the urea structure formed by the reaction of the isocyanate group derived from the raw material. Therefore, the sum of P1 to P4 indicates the total number of reacted isocyanate groups derived from the raw material. Therefore, the isocyanurate conversion rate is a value indicating the ratio of the isocyanate groups derived from the reacted raw materials to those having an isocyanurate structure.

≪Manufacturing method of foam≫
<Raw material for foam>
Suitable raw materials for the foam according to the present invention are resin components containing an isocyanate-terminated prepolymer having at least two or more isocyanate groups, obtained from a compound having two or more active hydrogens and polyisocyanate; and polyamines; A resin composition containing a catalyst (including a trimerization catalyst), a flame retardant, a foaming agent, and a foam stabilizer. As the raw material, another resin component (for example, a polyisocyanate different from the isocyanate-terminated prepolymer) or another component may be used. Hereinafter, each raw material will be described in detail.

(Isocyanate-terminated prepolymer)
The isocyanate-terminated prepolymer is a compound having at least two or more isocyanate groups, which is obtained from a compound having two or more active hydrogens and a polyisocyanate. Here, the weight average molecular weight of the prepolymer is preferably in the range of 300 to 5000, more preferably in the range of 300 to 4000, and even more preferably in the range of 400 to 3000. The weight average molecular weight of the prepolymer can be measured by a gel permeation chromatography (GPC) method (standard polymer = polystyrene). The isocyanate-terminated prepolymer can be obtained, for example, by blending an excess amount of polyisocyanate than the number of moles of a compound having two or more active hydrogens (for example, Patent 5121699, Patent 4883490).

-Compound having 2 or more active hydrogens Here, the compound having 2 or more active hydrogens, which is one raw material of the prepolymer, includes, for example, polyols, polyhydric phenols, polyamines, alkanolamines, polythiols and the like. Can be done. The compound having two or more active hydrogens is preferably at least one selected from polyols, polyamines and polythiols, and is preferably polyols and / or polyamines. Hereinafter, they will be described in order.

The polyol is not particularly limited, and examples thereof include polyester polyols, polycarbonate polyols, polyether polyols, polyester ether polyols, and the like. Of these, polyester polyols are preferable, and polyester polyols using an aliphatic dicarboxylic acid as a raw material are particularly preferable.

The polyester polyol is not particularly limited, and includes, 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 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, neopentylglycol, 1,8-octane Polyester polyols such as polypropylene glycol obtained by dehydration condensation reaction with diols, 1,9-nonanediols, etc., or mixtures thereof; polylactones obtained by ring-open polymerization of lactone monomers such as ε-caprolactone and methylvalerolactone. Examples thereof include diols. Examples of the polycarbonate polyol 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, and diethylene carbonate, dimethyl carbonate, diethyl. Examples thereof include those obtained by reacting with carbonate and the like. Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol and the like obtained by polymerizing cyclic ethers such as ethylene oxide, propylene oxide and tetrahydrofuran, and copolyethers thereof. It can also be obtained by polymerizing the above cyclic ether using a polyhydric alcohol such as glycerin or trimethylolethane. Examples of the polyester ether polyol include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid, and aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid. Dicarboxylic acids such as hexahydrophthalic acid, hexahydroterephthalic acid and hexahydroisophthalic acid, or acid esters or acid anhydrides thereof, and glycols such as diethylene glycol or propylene oxide adduct, or mixtures thereof. Examples thereof include those obtained by the dehydration condensation reaction.

The polyhydric phenols are 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.

The polyamine is not particularly limited, and examples thereof include aliphatic polyamines, aromatic polyamines, and alicyclic polyamines. Specifically, 4,4-methylenebis (N-sec-butylaniline), 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'- Methylenebis (3-chloro-2,6-diethylaniline), 3,5-diethyltoluene-2,4-diamine, dimethylthiotoluenediamine can be mentioned.

The polythiol is not particularly limited, and examples thereof include bis- (2-hydrothioethyroxy) methane, dithioethylene glycol, dithioerythritol, and dithiothreitol.

The alkanolamine is not particularly limited, and examples thereof include diethanolamine, ethanolisopropanolamine, diisopropanolamine, ethanol-2-hydroxybutylamine, isopropanol-2-hydroxybutylamine, and triethanolamine.

The hydroxyl value of the polyol and the polyhydric phenol is preferably 50 to 1000 mgKOH / g, more preferably 80 to 850 mgKOH / g, and 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 polythiol is preferably 50 to 1000 mgKOH. Here, the mercapto base value of polythiol is determined by the following method. Mercapto base value (SH value; mgKOH / g): Weigh the sample into a 100 mL (milliliter) sample bottle (mass is accurately read to the 4th digit after the decimal point in grams), and anhydrous acetic acid- tetrahydrofuran solution (anhydrous in 100 mL of solution). Exactly add 5 mL (containing 4 g of acetic acid) and 10 mL of 4-dimethylaminopyridine- tetrahydrofuran solution (containing 1 g of 4-dimethylaminopyridine in 100 mL of solution) to completely dissolve the sample, and then stir at room temperature for 1 hour. Then, 1 mL of ultrapure water was added accurately, and the mixture was stirred at room temperature for 30 minutes and then titrated with a 0.5 M potassium hydroxide-ethanol solution (indicator: phenolphthalein). The SH value was calculated by the following formula.
SH value (mgKOH / g) = 28.05 × (BA) / S
(However, in the formula, S is the sample collection amount (g), A is the amount of 0.5 M potassium hydroxide-ethanol solution required for titration of the sample (mL), and B is 0.5 M hydroxide required in the blank test. Represents the amount (mL) of potassium-ethanol solution.)

The amine value of the polyamine is preferably 50 to 1000 mgKOH / g, more preferably 50 to 800 mgKOH / g. The amine value of polyamine is the total amine value described in JIS K1557-7: 2011 "Plastic-Polyurethane Raw Material Polyurethane Test Method-Part 7: How to Obtain Basicity (Nitrogen Content and Total Amine Value Display)". It is measured by the measuring method of.

The hydroxyl value of the alkanolamine is preferably 50 to 1000 mgKOH / g. Further, the amine value of the alkanolamine is more preferably 50 to 800 mgKOH / g.

In addition, you may use a combination of a plurality of kinds of compounds having 2 or more active hydrogens.

-Polyisocyanate The polyisocyanate is not limited as long as it is a compound having a plurality of isocyanate groups, and may be any of aromatic, aliphatic and alicyclic. For example, as the bifunctional polyisocyanate, 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), m-phenylenediisocyanate, p-phenylenediisocyanate, etc. 4,4'-Diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diocyanate (2,4'-MDI), 2,2'-diphenylmethane diisocyanate (2,2'-MDI), hydrogen Added MDI, xylylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylenediisonate, 3,3'-dimethoxy-4,4'-biphenylenediisocyanate, polymethylenepolyphenylpolyisocyanate, 1,5- Aromatic ones such as naphthalenediocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, tetramethylxylene diisocyanate (TMXDI), cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate. , Alicyclic type such as methylcyclohexanediisocyanate, alkylene type such as butane-1,4-diisocyanate, hexamethylenediisocyanate, isopropylene diisocyanate, methylenediisocyanate, lysinediisocyanate; -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, polypeptide MDI, lysine ester triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,6,11-undecantryisocyanate, bicycloheptane triisocyanate, 1,8-diisocyanatomethyloctane, etc. It can also contain these modified products, derivatives, etc .; these polyisocyanates can be used alone or in combination of two, among which MDI, TDI, or MDI. Or a modified form of TDI Alternatively, derivatives are preferable, and monomeric MDI and crude MDI are more preferable.

-Isocyanate index The isocyanate index of the resin composition, which is a raw material for producing a prepolymer, is preferably 200 to 600, and more preferably 200 to 500. Here, the isocyanate index is a value obtained by multiplying the ratio of the number of moles of all active hydrogens of the resin composition containing all the raw materials to the number of moles of isocyanate groups in the polyisocyanate by 100 (number of moles of NCO / activity). The number of moles of hydrogen x 100).

-Other components As described above, the essential raw materials for the isocyanate-terminated prepolymer according to the present invention are a compound having two or more active hydrogens and a polyisocyanate. However, as long as there are two or more isocyanate groups at the ends of the prepolymer (for example, isocyanate groups at both ends of the main chain, isocyanate groups at one end of the main chain + isocyanate groups in the side chains, and isocyanate groups in multiple side chains). A polymerizable component that forms a part of the prepolymer skeleton, a component for modifying a side chain, or the like may be used. As described above, the "terminal" does not mean only both ends, but is a concept in which two or more isocyanate groups need to be present at any part of the skeleton.

Here, the NCO% in the prepolymer is preferably 10 to 35% by mass, more preferably 15 to 30% by mass, and particularly preferably 17 to 28% by mass. The NCO% (isocyanate content) of the prepolymer is the method A (toluene / di) of JIS K1603-1: 2007 "Plastic-Polyurethane Raw Material Aromatic Isocyanate Test Method Part 1: How to Obtain Isocyanate Group Content". Measure according to butylamine, hydrochloric acid method).

(Polyamine)
The polyamine is not particularly limited, and examples thereof include aliphatic polyamines, aromatic polyamines, and alicyclic polyamines. Specifically, 4,4-methylenebis (N-sec-butylaniline), diethyldiaminotoluene, 4,4-phenylenebis (N-sec-butylaniline), 4,4-methylenebis (N-sec-butylaniline) , 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'-methylenebis (3-chloro-2,6-diethylaniline), 3,5- Examples thereof include diethyltoluene-2,4-diamine and dimethylthiotoluenediamine.

The amine value of the polyamine is preferably 50 to 1000 mgKOH / g, more preferably 50 to 800 mgKOH / g. The amine value of polyamine is the total amine value described in JIS K1557-7: 2011 "Plastic-Polyurethane Raw Material Polyurethane Test Method-Part 7: How to Obtain Basicity (Nitrogen Content and Total Amine Value Display)". It is measured by the measuring method of.

(catalyst)
The catalyst includes a trimerization catalyst. Here, examples of the trimerization catalyst include metal oxides such as lithium oxide, sodium oxide, and potassium oxide; methoxysodium, ethoxysodium, propoxysodium, butoxysodium, methoxypotassium, ethoxypotassium, propoxypotassium, butoxypotassium, and the like. Alkoxides; organic metal salts such as potassium acetate, potassium octylate, potassium caprylate, iron oxalate; 2,4,6-tris (dimethylaminomethyl) phenol, N, N', N "-tris (dimethylamino) Tertiary amines such as propyl) hexahydrotriazine, triethylenediamine, 1,3,5-tris (dimethylaminopropyl) hexahydro-s-triazine; derivatives of ethyleneimine; acetylacetone chelates of alkali metals, aluminum and transition metals Class, quaternary ammonium salt; nitrogen-containing heterocyclic compound such as diazabicycloundecene (DBU); these can be used alone or in combination of two or more. It is more preferable to use an organic metal salt, a quaternary ammonium salt, or a nitrogen-containing heterocyclic compound. Further, a foaming catalyst or a resinification catalyst may be contained.

(Flame retardants)
Red phosphorus is suitable as the flame retardant. Further, it is preferable to use at least one selected from a phosphate ester, a phosphate-containing flame retardant, a bromine-containing flame retardant, a boron-containing flame retardant, an antimony-containing flame retardant and a metal hydroxide in combination with red phosphorus. .. In addition to these, other flame retardants can be further included. Specifically, examples of the phosphate ester include triphenyl phosphate, cresyldiphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (t-butylated phenyl) phosphate, and tris (i-propylated phenyl). Aromatic phosphates such as phosphate and 2-ethylhexyl diphenyl phosphate; 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (diphenylenyl) phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl phosphate) ) And other aromatic condensed phosphate esters; halogen-containing phosphate esters such as tris (dichloropropyl) phosphate, tris (β-chloropropyl) phosphate, tris (chloroethyl) phosphate; 2,2-bis (chloromethyl) tri Halogen-containing condensed phosphoric acid esters such as methylene bis (bis (2-chloroethyl) phosphate) and polyoxyalkylene bisdichloroalkyl phosphate; and the like can be mentioned. Examples of the phosphate-containing flame retardant include ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate as monophosphate; monosodium phosphate, disodium phosphate, and triphosphate. Sodium salts such as sodium, monosodium phosphite, disodium phosphite, sodium hypophosphite; monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite , Potassium salts such as potassium hypophosphite; lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, lithium hypophosphite; phosphoric acid Barium salts such as barium dihydrogen, barium hydrogen phosphate, tribarium phosphate, barium hypophosphite, magnesium salts such as magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, magnesium hypophosphite; Calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, calcium hypophosphite; zinc salts such as zinc phosphate, zinc phosphite, zinc hypophosphite, primary aluminum phosphate, di Aluminum salts such as aluminum diphosphate, tertiary aluminum phosphate, aluminum phosphite, aluminum hypophosphite; and the like. Examples of the polyphosphate include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate, aluminum polyphosphate and the like. Examples of the bromine-containing flame retardant include pentabromodiphenyl ether; octabromodiphenyl ether; decabromodiphenyl ether; tetrabromobisphenol A (TBBA), TBBA-epoxy oligomer, TBBA-polycarbonate oligomer, TBBA-bis (dibromopropeel ether), and TBBA. TBBA compounds such as −bis (aryl ether); 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 polybenzene ring compounds; brominated styrene compounds such as brominated polystyrene and polybrominated styrene; ethylene bistetrabromo Phtal acid compounds such as phthalimide; cyclic aliphatic compounds such as hexabromocyclododecane; and the like can be mentioned. Examples of the boron-containing flame retardant include boric acid; boron oxide such as diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide; boric acid, lithium borate, sodium borate, etc. Examples thereof include boric acid compounds such as potassium borate, cesium borate, magnesium borate, calcium borate, barium borate, zirconium borate, zinc borate, aluminum borate, and ammonium borate. Examples of the boron-containing flame retardant include antimony oxide such as antimony trioxide and antimony pentoxide; antimonyates such as sodium antimonate and potassium antimonate; and pyroantimonates such as sodium pyroantimonate and potassium pyroantimonate; And so on. These can be used alone or in combination of two or more. Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide and the like. As the other flame retardant, a known flame retardant can be used. Examples of other flame retardants include chlorine compounds such as chlorinated paraffin; nitrogen compounds such as hindered amine and melamine cyanurate; cellulose; and the like.

(Foaming agent)
Examples of the foaming agent include water, hydrocarbons (preferably C4 to C6), hydrofluoroolefins, and carbon dioxide gas. Specific examples thereof include cyclopentane, HFO (1336 mzz), and HFO (1233 zd). These can be used alone or in combination of two or more. The foaming agent may or may not contain water. However, when at least one of the foaming agents is water, it is preferably 2 parts by mass or less, more preferably 1 part by mass or less, and 0 parts by mass with respect to 100 parts by mass of the resin component. It is particularly preferable that the amount is .75 parts by mass or less.

(Foaming agent)
Examples of the foam stabilizer include silicone compounds and nonionic surfactants. These can be used alone or in combination of two or more.

(Other additives)
The resin composition according to the present invention may further contain other additives in addition to the above additives. In particular, it is preferable to contain polyisocyanate. The polyisocyanate is not limited as long as it is a compound having a plurality of isocyanate groups, and may be aromatic, aliphatic, or alicyclic. For example, the above-mentioned polyisocyanate can be exemplified as a raw material for producing an isocyanate-terminated prepolymer. In particular, MDI or a modified version or derivative of MDI is preferable, and monomeric MDI is more preferable. Further, as other additives, known additives such as antioxidants, ultraviolet absorbers and antibacterial agents can be added.

Here, when polyisocyanate is further contained, the prepolymer / isocyanate ratio (mass ratio) is preferably 20/80 to 95/5, and more preferably 30/70 to 70/30. It is particularly preferable that the ratio is 40/60 to 67.5 / 27.5.

The resin composition can be prepared, for example, by adding and mixing each component. At this time, for example, when preparing a resin composition in which polyisocyanate and / or polyamine is further blended as a resin component in addition to the prepolymer, (1) polyisocyanate and / or polyamine is added separately from the prepolymer. (2) When preparing the prepolymer, polyisocyanate and / or polyamine exceeding the equivalent ratio may be added, and as a result, unreacted polyisocyanate and / or polyamine may be present.

≪Manufacturing method of foam≫
The foam of the present invention can be produced, for example, by premixing an isocyanate-terminated prepolymer, a polyamine, a catalyst, a foaming agent, a foam stabilizer and a flame retardant to prepare a resin composition, and foaming and curing the resin composition. .. A known method can be used as a method for mixing the resin composition and a method for foaming and curing. When used in the spraying method, a mixed solution in which a raw material having no isocyanate group is mixed in advance and a raw material having an isocyanate group can be mixed and used in a spraying device immediately before the construction of the foam. ..

The blending amount of the isocyanate-terminated prepolymer is preferably 1 to 100% by mass, more preferably 10 to 100 parts by mass, and further preferably 10 to 10% by mass, based on the total mass of the resin component. It is 90% by mass, and particularly preferably 20 to 80% by mass.

The blending amount of the polyisocyanate is preferably 1 to 80% by mass based on the total mass of the resin component.

The blending amount of the polyamine is preferably 0.1 to 30% by mass, more preferably 0.1 to 15% by mass, and further preferably 0.1 by mass, based on the total mass of the resin component. It is 10% by mass.

The blending amount of the defoaming agent may be preferably 0 to 10 parts by mass with respect to 100 parts by mass of the resin component.

The blending amount of the trimerization catalyst is, for example, 0.1 part by mass or more and 15 parts by mass or less, preferably 1 part by mass or more and 10 parts by mass or less, more preferably, with respect to 100 parts by mass of the resin component. Is 1.5 parts by mass or more and 8.0 parts by mass or less, and more preferably 1.8 parts by mass or more and 6.0 parts by mass or less.

The blending amount of the foaming catalyst is preferably 0 to 5 parts by mass with respect to 100 parts by mass of the resin component.

The blending amount of red phosphorus is preferably 0 to 30 parts by mass, and more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the resin component.

The blending amount of the flame retardant other than red phosphorus is preferably 0 to 50 parts by mass, and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the resin component.

≪Physical properties of foam≫
<Residual weight>
The residual weight (600 ° C.) of the foam according to the present invention is preferably 30% by weight or more, more preferably 35% by weight or more, and further preferably 40% by weight or more. Is. The value of the residual weight is a value measured according to the method described in the examples. Similarly, the residual weight of the foam according to the present invention (held at 300 ° C. for 30 minutes) is preferably 60% by weight or more, more preferably 70% by weight or more, and 80% by weight. The above is more preferable. The value of the residual weight is a value measured according to the method described in the examples. When the residual weight is in the above range, the collapse of the flame-retardant material at a high temperature is suppressed, and as a result, the spread of fire can be suppressed.

<Volume change rate>
The foam tends to expand at a high temperature (for example, 300 ° C.) and shrink when exposed to a higher temperature (for example, 400 ° C.). If the rate of change in volume from expansion to contraction is small, the spread of fire due to deformation of the adherend is suppressed. Therefore, the volume change rate of the foam according to the present invention is preferably less than 120% (300 ° C.), more preferably less than 100% (300 ° C.), based on the original volume. Yes, and more preferably less than 80% (300 ° C.). Further, the difference between the volume change rate at 300 ° C. and the volume change rate at 400 ° C. of the foam according to the present invention is preferably 150% or less, more preferably 100% or less, and is 80. It is more preferably within%. Further, when exposed to a higher temperature (for example, 500 ° C.), the residue at the high temperature becomes an important parameter, so how much remains after heating becomes an important factor. From this point of view, the volume change rate of the foam according to the present invention is preferably within ± 50% (500 ° C.) and within ± 40% (500 ° C.) based on the original volume. It is more preferable that it is within ± 30% (500 ° C.). The value of the volume change rate is a value measured according to the method described in the examples.

<Limited oxygen index>
The critical oxygen index of the foam according to the present invention is preferably 27% or more, more preferably 29% or more, and even more preferably 32% or more. The upper limit is not limited, but is, for example, 35. The value of the critical oxygen index is a value measured according to the method described in the examples.

<Flame retardant>
^{The foam according to the present invention has a total calorific value of 25 MJ / m 2} or less after 20 minutes as measured under the condition of heating with a ^{radiant heat intensity of 50 kW / m 2} in accordance with the ISO-5660 test method. It is possible, and 8.5 MJ / m ² or less is preferable.

<Rate of change in compression strength>
The foam according to the present invention preferably has a change rate (%) of compression strength of 20% or more and 50% or less before and after wet heat treatment (80 ° C. × RH 85% × 1 month), and is less than 20%. Is more preferable.

≪Use of foam≫
The foam of the present invention is suitably used as a heat insulating material and a heat insulating material for construction applications, ships for transporting oil and gas, electric appliances such as refrigerators, and the like. In particular, in reinforced concrete construction and the like, it can be used as a foam for the spraying method because heat insulation construction is easy.

<< Preparation of resin composition >>
<Raw materials>
(Prepolymer)
Polyol A-1: Phthalate polyol (OHV = 250)
Polyol A-2: Phthalate polyol (OHV = 200)
-Polyol A-3: Aliphatic / phthalate polyol (OHV = 250)
-Polyamine B-1: 4,4-methylenebis (N-sec-butylaniline) (amine value: 526)
-Polyisocyanate I-1: Monomeric MDI
-Polyisocyanate I-2: Crude MDI (NCO%: 31.4%)
(Polyisocyanate)
-Polyisocyanate I-2: Crude MDI (NCO%: 31.4%)
(Polyamine)
-Polyamine B-1: 4,4-methylenebis (N-sec-butylaniline) (amine value: 526)
-Polyamine B-2: diethyldiaminotoluene (amine value: 486)
-Polyamine B-3: 4,4-phenylenebis (N-sec-butylaniline) (amine value: 637)
-Polyamine B-4: Aniline-terminated PTMG (amine value: 250)
(Triquantization catalyst)
-CT-1: 1,3,5-tris (dimethylaminopropyl) hexahydro-s-triazine-CT-2: diazabicycloundecene (DBU)
・ CT-3: Quaternary ammonium salt ・ CT-4: Potassium acetate (flame retardant)
-FL-1: Red phosphorus-FL-2: TCPP (halogen-containing phosphoric acid ester)
FL-3: PFR (phosphate ester)
FL-4: Ammonium polyphosphate (phosphate)
FL-5: Poly (pentabromophenyl acrylate) (bromine type)
・ FL-6: Zinc borate (boron type)
・ FL-7: Antimony trioxide (antimony type)
・ FL-8: Aluminum hydroxide (metal hydroxide)
(Foaming agent)
・ FA-1: Hydrofluoroolefin ・ FA-2: Water (foaming agent)
-FS-1: Silicon-based surfactant

<Preparation of prepolymer>
A predetermined amount of the polyisocyanate shown in Tables 1 to 4 was charged at 25 ° C. in a 5 L polyethylene container equipped with a mechanical stirrer, an anchor type stirring blade, and a nitrogen introduction pipe, and the liquid temperature of the isocyanate was set to 25 ° C. Here, a predetermined amount of the polyol or polyamine shown in Tables 1 to 4 was added stepwise so that the liquid temperature did not exceed 80 ° C. From the time when the addition of the polyol or polyamine was completely completed, the mixture was stirred at a stirring speed of 60 rpm for 2 hours, and the above isocyanate was reacted with the polyol or polyamine to obtain an NCO group-terminated prepolymer. The NCO group content of the obtained prepolymer was measured in accordance with JIS K1603-1 (Method A), and it was confirmed that the NCO group content was within the specified range.

<Preparation of resin composition>
In a 500 mL polypropylene disposable cup, polyamines, trimmer catalysts, flame retardants, foaming agents, defoamers, and other additives were added to each of the blended amounts of Examples and Comparative Examples shown in Tables 1 to 4 and each was weighed. A mixed solution of Examples and Comparative Examples was used. Each mixture was stirred and mixed at 2000 rpm for 5 minutes using a stirrer equipped with a propeller-type stirring blade to obtain the first compositions of Examples and Comparative Examples. The first composition obtained in a cooling furnace at 10 ° C. and the second composition (prepolymer and optionally polyisocyanate) in which the blending amounts shown in Tables 1 to 4 were weighed were individually 10 ± 1. Cooled to ° C. The first composition and the second composition of each Example and Comparative Example were stirred and mixed at 2000 rpm for 5 seconds using a stirrer equipped with a propeller type stirring blade to foam and cure, and the first composition and the second composition of each Example and Comparative Example were foamed and cured. A foam was obtained. In the table, the description of "Example 35" shall be read as "Comparative Example 3".

<< Evaluation >>
<Measurement of isocyanurate conversion rate>
The infrared absorption spectrum of each of the foams of Examples and Comparative Examples 24 hours after foaming was measured using a Fourier transform infrared spectrophotometer (FT-IR, model FT / IR-4200 manufactured by Nippon Kogaku Co., Ltd.). .. The measurement was performed by the ATR method using a diamond prism, and the total number of times was set to 50. The isocyanurate group content in the foam was calculated from the formula (1). The measurement was performed at three points of the upper part, the central part, and the lower part with respect to the rising direction of the foam, and the average value was shown. The results are shown in Tables 1-4.

<Measurement of residual weight (600 ° C)>
Collect 3 to 5 mg from the center of the foam of each Example and Comparative Example 24 hours after foaming, fill the sample in an aluminum pan, and use a DG / DTA measuring device (SII model TG / DTA7200). The weight loss behavior of the sample was observed in the temperature range of 25 ° C. to 600 ° C., and the residual amount (%) of the sample was determined from the remaining weight of the sample at 600 ° C. The measurement was carried out at a heating rate of 10 ° C./min and under a dry air stream (flow velocity: 250 mm / min). The results are shown in Tables 1-4.

<Residual weight (300 ° C x 30 minutes holding)>
The method of collecting the sample and the amount of the sample are the same as <Measurement of residual weight (600 ° C.)>. In the measurement, the temperature was raised at 20 ° C./min from 25 ° C. to 300 ° C., and the sample was heated and held at 300 ° C. for 30 minutes to determine the residual weight.

<Measurement of critical oxygen index>
The skin layer was removed from the foams of each Example and Comparative Example 24 hours after foaming, and 10 samples having a width of 1 cm, a length of 15 cm, and a thickness of 1 cm were cut out. The sample was fixed in a glass tube with a jig and erected vertically on 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 (critical oxygen index) required for combustion was obtained from the ignition time and the fire spread distance.

<Measurement of total calorific value (50 kW x 20 minutes)>
A sample was cut out from the center of each of the foams of Examples and Comparative Examples 24 hours after foaming so as to have a length of 10 cm, a width of 10 cm, and a thickness of 5 cm, and according to the standard of ISO5660 (Building Standard Law No. 2). , The cone calorimeter test of the foam was carried out, and the total calorific value and the maximum calorific value of the sample were measured. The measurement was performed with a radiant heat amount of 50 kW / m ² and a measurement time of 20 minutes. The results are shown in Tables 1-4.

<Volume change rate (300 ° C, 400 ° C, 500 ° C)>
A sample (unheated sample) was cut out from the center of each of the foams of Examples and Comparative Examples 24 hours after foaming so as to have a length of 5 cm, a width of 5 cm, and a thickness of 2.5 cm, and heated to 300 ° C. It was allowed to stand in the furnace for 5 minutes, and the volume change rate was measured. Taking the volume of the unheated sample as 100%, measure the volume after heating at 300 ° C., subtract the volume of the unheated sample from the volume after heating at 300 ° C., divide by the volume of the unheated sample, and multiply by 100. The value was taken as the volume change rate at 300 ° C. Similarly, the sample after heating at 300 ° C. was allowed to stand in an electric furnace heated to 400 ° C. for 5 minutes, and the volume change rate was measured. The volume of the sample after heating at 300 ° C is set to 100%, the volume after heating at 400 ° C is measured, and the value obtained by subtracting the volume after heating at 300 ° C from the volume after heating at 400 ° C is divided by the volume after heating at 300 ° C. The value multiplied by 100 was taken as the volume change rate at 400 ° C. Further, the sample after heating at 400 ° C. was allowed to stand in an electric furnace heated to 500 ° C. for 5 minutes. Then, the volume of the unheated sample is set to 100%, the volume after heating at 500 ° C. is measured, and the value obtained by subtracting the volume of the unheated sample from the volume after heating at 500 ° C. is divided by the volume of the unheated sample to 100. The value multiplied by was taken as the volume change rate at 600 ° C. When it expands, it shows a positive value, and when it contracts, it shows a negative value. The results are shown in Tables 1-4.

<Rate of change in compression strength>
The skin layer was removed from the foam 24 hours after foaming, and a test piece was cut out to a size of 10 cm in length, 10 cm in width, and 5 cm in thickness. Then, the test piece was allowed to stand in a heating / humid heating furnace at 80 ° C. and a relative humidity of 85% for 1 month to cure the test piece. Regarding the test pieces before and after the moist heat treatment, based on JIS K7220, two flat plates with a length of 15 cm, a width of 15 cm, and a thickness of 1 cm are attached to a material testing machine (AG-10, Shimadzu Corporation), and the test pieces are placed between the flat plates. I sandwiched it. In this state, the test piece was compressed and the compression strength was measured. Three samples were used for each sample, and the average value was taken as the compression strength, and the rate of change in the compression strength of the foam before and after the wet heat treatment was calculated.

<Flame resistance>
It is preferable that the foam according to the present invention does not crack in the cross section when the flame contact test described in the examples is carried out. Further, the thickness of the carbonized layer is preferably 25 mm or less, more preferably 15 mm or less, further preferably 8 mm or less, and particularly preferably 7.5 mm or less. When it has such flame resistance, it is possible to suppress the spread of fire as a result of suppressing the collapse of the flame-retardant material at a high temperature.

<Density>
The apparent densities of the foams of Examples and Comparative Examples 24 hours after foaming were measured by the method described in JIS K7222: 2005 "Foam Plastics and Rubber-How to Determine the Apparent Density". The results are shown in Tables 1-4.

≪Judgment criteria≫
■ Evaluation by foaming profile rise time (RT)
RT ≤ 30 seconds: 4
30 seconds <RT ≤ 60 seconds: 2
60 seconds <RT ≤ 100 seconds: 0
RT ≥ 100 seconds: -1
■ Isocyanurate conversion rate
35 and above: 3
30 or more and less than 35: 2
25 or more and less than 30: 1
Less than 25: 0
■ Total calorific value
Less than 7: 3
7-10: 2
Greater than 10 and less than 16: 1
Greater than 16 or not measurable: 0
■ Residual weight (1) 600 ℃
50 and above: 5
40 or more and less than 50: 4
32 or more and less than 40: 3
22 or more and less than 32: 2
10 or more and less than 22: 1
Less than 10: 0
(2) Hold at 300 ° C for 30 minutes
80% or more: 3
70% or more and less than 80%: 2
60% or more and less than 70%: 1
Less than 60%: 0
■ Volume change rate ・ 300 ℃
Less than 100%: 1
100% or more: 0
・ 400 ℃
Difference from 300 ℃ within 100%: 1
Difference from 300 ° C above 100%: 0
・ 500 ℃
Within ± 30%: 1
Above + 30%, below -30%: 0
■ Rate of change in compression strength
Less than 10%: ○ (2 points)
10% or more and less than 20%: △ (1 point)
20% or more: × (0 points)
■ Presence or absence of cross-section cracks 〇: 2
×: 0
Penetration: -1
■ Depth of carbonized layer
4mm or less: 3
Above 4 mm and below 10 mm: 2
Above 10 mm and below 30 mm: 1
Above 30mm 0
≪Comprehensive judgment≫
◎: 18 or more 〇: 16 to 17
△: 14 to 15
×: 13 points or less

Claims (9)

A resin component containing an isocyanate-terminated prepolymer having at least two or more isocyanate groups obtained from a compound having two or more active hydrogens and a polyisocyanate; a polyamine; a trimerization catalyst; a flame retardant; and a foaming agent. ; and foam stabilizer; only containing resin composition, wherein the isocyanate index at the raw material for producing the isocyanate-terminated prepolymer is 200 to 600. The resin composition according to claim 1, wherein the NCO% of the isocyanate-terminated prepolymer is 10 to 35% by mass. The resin composition according to claim 1 or 2, wherein the resin composition further contains a polyisocyanate different from the isocyanate-terminated prepolymer. The resin composition according to any one of claims 1 to 3, wherein the compound having two or more active hydrogens is at least one selected from polyols, polyamines and polythiols. The resin composition according to any one of claims 1 to 4, wherein the trimerization catalyst is an organometallic salt, a quaternary ammonium salt, or a nitrogen-containing heterocyclic compound. The resin composition according to any one of claims 1 to 5, wherein the resin composition further contains red phosphorus. The resin composition further contains at least one flame retardant selected from the group consisting of a phosphate ester, a phosphate-containing flame retardant, a bromine-containing flame retardant, a boron-containing flame retardant, an antimony-containing flame retardant, and a metal hydroxide. The resin composition according to claim 6. A foam obtained from the resin composition according to any one of claims 1 to 7. The foam according to claim 8, wherein the isocyanurate conversion rate in the foam is 20% or more and 50% or less.

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