JP6876185B1 - Urea resin composition and polyurea foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To have excellent flame retardancy and shape retention at the time of combustion, to suppress deterioration with time in a moist heat environment, to have excellent adhesiveness to an adherend at the time of coating, and to cause cracks even when exposed to flame. Provided is a urea resin composition capable of providing a polyurea foam that is difficult to enter and is hard to carbonize. A urea resin composition containing a polyisocyanate compound (A), a polyamine compound (B), a trimerization catalyst, a foaming agent, a foam stabilizer and a flame retardant, and the content of the polyamine compound (B) is A urea resin composition, which is 2.0% by mass when the total amount of the urea resin composition is 100% by mass. [Selection diagram] None

Description

The present invention relates to a urea resin composition and a polyurea foam.

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 as to have an isocyanate index of 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 compound, a polyol compound, a trimerization catalyst, a foaming agent, a foam stabilizer and an additive, and the trimerization catalyst is a nitrogen-containing aromatic compound, a carboxylate alkali metal salt, and a tertiary ammonium salt. And at least one selected from the group consisting of quaternary ammonium salts, 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 agent. A flame retardant urethane resin composition comprising a combination of at least one selected from the group consisting of a flame retardant, 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

In the invention of Patent Document 1, although the flame retardancy is improved by the nurate bond, many urethane bonds are formed, and there is a possibility that the flame retardancy may not be sufficient. Further, the invention of Patent Document 2 describes that high flame retardancy is imparted by adding red phosphorus (powder) as a flame retardant and incorporating an isocyanurate ring, but the powder flame retardant By using, for example, it is considered that poor adhesion (excitement) to the adherend occurs when spray-applied, and there is a possibility that the foam material may fall off or the heat insulating performance may be deteriorated due to a change with time. Patent Document 2 does not particularly mention this point. Furthermore, the inventions of Patent Documents 1 and 2 relate to deterioration over time due to temperature and humidity, which is important when used as a heat insulating material or a heat insulating material for construction applications, ships for transporting oil and gas, refrigerators and the like. No verification was made, and there was a risk of deterioration over time in a moist heat environment. In addition to these, the inventions of Patent Documents 1 and 2 may be cracked or carbonized when they come into contact with a flame due to a fire or the like when used for building purposes, for example, and the strength is significantly reduced. There was a risk of causing the collapse of the building.

Therefore, an object of the present invention is that it has excellent flame retardancy and shape retention during combustion, which cannot be solved by urethane foam, can suppress deterioration over time in a moist heat environment, and adheres to an adherend during coating. It is an object of the present invention to provide a urea resin composition capable of providing a polyurea foam having excellent properties, being less likely to crack even when exposed to flames, and being less likely to be carbonized.

The present inventors have diligently studied toward the realization of the above object, and a urea resin composition containing a polyisocyanate compound, a polyamine compound, a trimerization catalyst, a foaming agent, a foam stabilizer and a flame retardant can solve the above problems. This has led to the completion of the present invention. That is, the present invention is as follows.

The present invention (1)
A urea resin composition containing a polyisocyanate compound (A), a polyamine compound (B), a trimerization catalyst, a foaming agent, a defoaming agent and a flame retardant.
The urea resin composition is characterized in that the content of the polyamine compound (B) is 2.0% by mass or more when the total amount of the urea resin composition is 100% by mass.
The present invention (2)
The urea resin composition of the invention (1), characterized in that the amine value of the polyamine compound (B) is 50 to 1000 mg KOH / g.
The present invention (3)
The polyisocyanate compound (A) is the urea resin composition of the invention (1) or (2), characterized in that the NCO% is 10 to 35%.
The present invention (4)
The urea resin composition according to any one of the inventions (1) to (3), wherein the polyisocyanate compound (A) is an aromatic isocyanate.
The present invention (5)
The flame retardant is a urea resin composition according to any one of the inventions (1) to (4), which comprises red phosphorus.
The present invention (6)
The flame retardant comprises 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. The urea resin composition according to any one of the inventions (1) to (5).
The present invention (7)
A polyurea foam obtained by foaming and curing the urea resin composition according to any one of the inventions (1) to (6).
The present invention (8)
^{The polyurea foam has a total calorific value of 8.5 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. The polyurea foam according to the invention (7).

According to the present invention, it has excellent flame retardancy and shape retention during combustion, can suppress deterioration over time in a moist heat environment, has excellent adhesion to an adherend during coating, and is in contact with flame. It is possible to provide a urea resin composition capable of providing a polyurea foam that is less likely to crack and is less likely to be carbonized.

1. 1. Urea Resin Composition The urea resin composition of the present invention is a urea resin composition containing a polyisocyanate compound (A), a polyamine compound (B), a trimerization catalyst, a foaming agent and a flame retardant, and preferably a foam stabilizer. is there.

The urea resin composition of the present invention is characterized in that the content of the polyamine compound (B) is 2.0% by mass or more when the total amount of the urea resin composition is 100% by mass.

The urea resin composition of the present invention can form a polyurea foam by foaming and curing.

2. Raw material of urea resin composition 2-1. Polyisocyanate compound (A)
The polyisocyanate compound (A) according to the present invention is not particularly limited as long as it does not inhibit the effect of the present invention. Examples of the polyisocyanate compound (A) include monomer-type polyisocyanates and polymer-type polyisocyanates. The monomer-type polyisocyanate is a compound in which a plurality of isocyanate groups are present at the ends of the monomer structure. The polymer-type polyisocyanate is a compound in which a plurality of isocyanate groups are present at the ends of the polymer structure. These polyisocyanate compounds (A) can be used alone or in combination of two or more.

The monomer-type polyisocyanate is, for example, as a bifunctional polyisocyanate compound, 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), m-phenylenediisocinate. , P-phenylenediisocyanate, 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 2,2'-diphenylmethane diisocyanate (2,2) '-MDI), hydrogenated MDI, xylylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylenedisonate, 3,3'-dimethoxy-4,4'-biphenylenediisocyanate, polymethylene polyphenyl poly Aromatic ones such as isocyanate, 1,5-naphthalenediocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, tetramethylxylene diisocyanate (TMXDI), cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane- Alicyclic type such as 4,4'-diisocyanate and methylcyclohexane diisocyanate, alkylene type such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate and lysine diisocyanate;
As trifunctional or higher functional polyisocyanates, 1-methylbenzol-2,4,6-triisocyanate, 1,3,5-trimethylbenzol-2,4,6-triisocyanate, biphenyl-2,4,4'-triisocyanate Isocyanate, 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-undecantriisocyanate, bicycloheptane triisocyanate, 1,8- Diisocyanatomethyloctane, etc .;
Further, these modified products, derivatives and the like; can be included. These polyisocyanate compounds can be used alone or in combination of two or more. Since the monomer-type polyisocyanate compound forms the urea skeleton of the polyurea foam, it can be freely selected in consideration of the desired properties of the polyurea foam. Among these monomer-type polyisocyanates, aromatic isocyanates are preferable, MDI or modified products or derivatives of MDI are more preferable, and monomeric MDI and crude MDI are further preferable, because they are excellent in reactivity. These suitable aromatic isocyanates are preferable in terms of safety in the working environment because they are excellent in reactivity when used as a polyurea foam for a spraying method. Further, in the monomeric MDI and the crude MDI having the same NCO%, the crude MDI containing a polynuclear body is excellent in flame retardancy because it has an excellent isocyanurate conversion rate.

The polymer-type polyisocyanate compound includes a polyol compound and a polyamine compound (D) that have been prepolymerized by reacting an excess amount of the polyisocyanate compound (C). The polyamine compound (D) and the polyisocyanate compound (C) are raw materials for producing a polymer-type polyisocyanate, and the polyamine compound (B) and the polyisocyanate which are the raw materials of the urea resin composition according to the present invention. It is not included in each of the compounds (A). Here, the polyisocyanate compound (C) may be the same as or different from the polyisocyanate compound (A).

Examples of such a polyol compound include polyester polyols and polyether polyols. Some polyester polyols are obtained by a condensation reaction between a polyhydric alcohol and a polyvalent carboxylic acid. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, butanediol, butylene glycol, glycerin, and trimethylolpropane. Examples of the polyvalent carboxylic acid include glutaric acid, adipic acid, maleic acid, phthalic acid, terephthalic acid, isophthalic acid and the like. These can be used alone or in combination of two or more. Further, polyester polyols obtained by ring-opening condensation of caprolactone, methyl valerolactone and the like can be mentioned.

As the polyether polyol, for example, an oxide such as ethylene oxide, propylene oxide, trimethylene oxide, or butylene oxide is addition-polymerized with a polyhydric alcohol such as ethylene glycol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane, and sorbitol. I can mention things. These can be used alone or in combination of two or more.

The polyisocyanate compound (B) to be reacted with these polyol compounds is not particularly limited as long as the effect of the present invention is not impaired, and is obtained by modifying aliphatic or aromatic polyisocyanates, mixtures thereof, and modifying them. The modified polyisocyanate to be used can be mentioned.

The polyamine compound (D) is not particularly limited as long as it does not inhibit the effect of the present invention. Examples of the polyamine compound (D) include aliphatic polyamines such as triethylenetetramine, aromatic polyamines such as metaphenylenediamine, and alicyclic polyamines such as isophoronediamine. Specifically, 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, dimethylthio Toluene diamine can be mentioned. This can be used alone or in combination of two or more. Further, the polyamine compound (D) may be the same as or different from the polyamine compound (B) described later.

The NCO% of the polyisocyanate compound (A) is not limited as long as it does not inhibit the effect of the present invention, and can be, for example, 5 to 40%, preferably 10 to 35%. When the NCO% of the polyisocyanate compound (A) is large, a polyurea foam having high shape retention during combustion, low thermal conductivity, and capable of suppressing deterioration over time in a moist heat environment can be obtained. That is, it is possible to obtain a polyurea foam having excellent flame retardancy and shape retention during combustion, capable of suppressing deterioration over time in a moist heat environment, and having excellent adhesion to an adherend during coating.

The NCO% (isocyanate content) of the polyisocyanate compound (A) is the method A (toluene / Measure according to dibutylamine, hydrochloric acid method).

2-2. Polyamine compound (B)
Polyamine compounds form urea bonds by reacting with isocyanates. The urea bond has features such as excellent water resistance, corrosion resistance, and chemical resistance such as acid and alkali.

The polyamine compound (B) is not particularly limited as long as it does not inhibit the effect of the present invention. Examples of the polyamine compound (B) include aliphatic polyamines such as triethylenetetramine, aromatic polyamines such as metaphenylenediamine, and alicyclic polyamines such as isophoronediamine. Specifically, 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, dimethylthio Toluenediamine can be mentioned, and examples of commercially available products are Iharacuremin MT, Iharacuremin M liquid product, CUA-4, Cure Hard MED, Erasmer 250P, Erasmer 1000P manufactured by Kumiai Chemical Industry Co., Ltd .; manufactured by Ronza Japan Co., Ltd. Lonzacure M-DEA, Lonzacure M-MIPA, Lonzacure M-DIPA, Lonzacure M-CDEA; Albemar EtaCure 100, EtaCure 300, EtaCure 410, EtaCure 420; EtaCure 420; Can be mentioned. These can be used alone or in combination of two or more.

The amine value of the polyamine compound (B) is not particularly limited as long as it does not inhibit the effect of the present invention, but can be, for example, 50 to 1000 mg KOH / g, preferably 200 to 1000 mg KOH / g, and 450 to 1000 mg. KOH / g is more preferable, and 500 to 1000 mg KOH / g is even more preferable. When the amine value of the polyamine compound is within such a range, it has excellent flame retardancy and shape retention during combustion, can suppress deterioration over time in a moist heat environment, and adheres to the adherend during coating. It is possible to obtain a urea resin composition capable of providing a polyurea foam having excellent properties, which is less likely to crack even when exposed to flames, and which is less likely to be carbonized. In particular, a total calorie test using a cone calorimeter according to the ISO-5660 standard (a test showing flame retardancy, which may be abbreviated as a concaro total calorimeter test) and a volume change rate at 600 ° C. It shows an excellent effect in that it can prevent the formation of a carbonized layer in the test of shape retention) and the flame contact evaluation.

The amine value of the polyamine compound is the total amine value described in JIS K1557-7: 2011 "Plastic-Polyurethane Raw Material Polyurethane Test Method-Part 7: How to Determine Basicity (Nitrogen Content and Total Amine Value Display)". Measure according to the measuring method.

In addition to the polyamine compound of the present invention, a polyol compound can be added as long as the effect of the present invention is not impaired. The polyol compound can react with the polyisocyanate compound (A) to form a urethane bond to form a part of the skeleton of the polyurea foam. However, since the urethane bond has higher flammability than the urea bond, the flame retardancy of the polyurea foam may decrease. Therefore, the content of the polyol compound can be 1/5 or less by mass ratio with respect to the content of the polyamine compound, preferably 1/10 or less, and more preferably not containing the polyol compound.

2-3. Trimerization catalyst The trimerization catalyst according to the present invention is not particularly limited as long as the effects of the present invention are not impaired. Examples of the trimerization catalyst 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 Class ammonium salts; diazabicycloundecene (DBU), etc .; these can be used alone or in combination of two, among which tertiary amines, organic metal salts, etc. It is more preferable to use diazabicycloundecene, and it is more preferable to use tertiary amines and diazabicycloundecene. By using these suitable trimerization catalysts, excellent flame retardancy and during combustion It is possible to obtain a foam having a shape-retaining property, suppressing deterioration over time in a moist heat environment, and having excellent adhesion to an adherend during coating.

2-4. Foaming agent The foaming agent according to the present invention is not particularly limited as long as the effect of the present invention is not impaired. 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.

2-5. Foaming agent The antifoaming agent according to the present invention is not particularly limited as long as the effect of the present invention is not impaired. Examples of the foam stabilizer include silicone compounds and nonionic surfactants. These can be used alone or in combination of two or more.

2-6. Flame Retardant The flame retardant according to the present invention is not particularly limited as long as the effect of the present invention is not impaired, and for example, red phosphorus, phosphoric acid ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant, and the like. Examples thereof include antimony-containing flame retardants and metal hydroxides. These can be used alone or in combination of two or more. Of these, it is preferable to contain at least one selected from red phosphorus or phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant, antimony-containing flame retardant and metal hydroxide, and red. In addition to phosphorus, it is more preferable to contain at least one selected from a phosphoric acid 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. It may further contain a phosphoric acid ester and further contain at least one selected from a chlorine-containing phosphoric acid 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. It is preferable to include a red phosphorus, a phosphoric acid ester, and a bromine-containing flame retardant. When the urea resin composition of the present invention contains these flame retardants, it has excellent flame retardancy and shape retention during combustion when the urea resin composition is foamed and cured, and over time in a moist heat environment. It is possible to obtain a polyurea foam that can suppress deterioration and has excellent adhesion to an adherend during coating. In addition, other flame retardants other than these flame retardants can be included.

The phosphoric acid ester according to the present invention is not particularly limited as long as it does not inhibit the effect of the present invention. Examples of the phosphoric acid ester include triphenyl phosphate, cresyldiphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (t-butylated phenyl) phosphate, tris (i-propylated phenyl) phosphate, and 2-ethylhexyl. Aromatic phosphates such as diphenyl phosphate;
Aromatic condensed phosphates such as 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (dixylenyl) phosphate, resorcinol bis (diphenyl) phosphate, and bisphenol A bis (diphenyl phosphate);
Halogen-containing phosphate esters such as tris (dichloropropyl) phosphate, tris (β-chloropropyl) phosphate, tris (chloroethyl) phosphate;
Halogen-containing condensed phosphoric acid esters such as 2,2-bis (chloromethyl) trimethylenebis (bis (2-chloroethyl) phosphate) and polyoxyalkylene bisdichloroalkyl phosphate; and the like can be mentioned. These can be used alone or in combination of two or more.

The phosphate-containing flame retardant according to the present invention is not particularly limited as long as the effect of the present invention is not impaired. Examples of the phosphate-containing flame retardant include ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate as monophosphates;
Sodium salts such as monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphate, disodium phosphate, sodium hypophosphite;
Potassium salts such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, potassium hypophosphite;
Lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphate, dilithium phosphite, lithium hypophosphite;
Barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, tribarium phosphate, barium hypophosphite, magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, magnesium hypophosphite, etc. salt;
Calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, calcium hypophosphite;
Zinc salts such as zinc phosphate, zinc phosphate, zinc hypophosphite, aluminum primary phosphate, aluminum dibasic phosphate, aluminum triphosphate, aluminum phosphite, aluminum hypophosphite and the like Salt; etc. can be mentioned.
Examples of the polyphosphate include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate, aluminum polyphosphate and the like. These can be used alone or in combination of two or more.

The bromine-containing flame retardant according to the present invention is not particularly limited as long as the effect of the present invention is not impaired. 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-tribromophenoxy) -1,3,5-triazine, Polybenzene ring compounds such as 2,6-dibromophenol and 2,4-dibromophenol;
Brominated styrene compounds such as brominated polystyrene and polybrominated styrene;
Phthalic acid compounds such as ethylenebistetrabromophthalimide;
Cyclic aliphatic compounds such as hexabromocyclododecane; and the like can be mentioned. These can be used alone or in combination of two or more.

The boron-containing flame retardant according to the present invention is not particularly limited as long as the effect of the present invention is not impaired. 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.

The antimony-containing flame retardant according to the present invention is not particularly limited as long as the effect of the present invention is not impaired. 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; pyroantimonates such as sodium pyroantimonate and potassium pyroantimonate; And so on. These can be used alone or in combination of two or more.

The metal hydroxide according to the present invention is not particularly limited as long as the effect of the present invention is not impaired. Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide and the like. These can be used alone or in combination of two or more.

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. These can be used alone or in combination of two or more.

2-7. Other Additives In addition to the above additives, other additives may be added to the resin composition according to the present invention as long as the effects of the present invention are not impaired. As other additives, known additives such as a resin (urea) catalyst, a foaming catalyst, a balance catalyst, an antioxidant, an ultraviolet absorber, an antibacterial agent, and a dispersant can be added.

3. 3. Method for Producing Urea Resin Composition The urea resin composition of the present invention is prepared by previously mixing a polyisocyanate compound (A), a polyamine compound (B), a catalyst, a foaming agent, a foam stabilizer, a flame retardant and other additives. A known method can be used as the mixing method of the urea resin composition. When used in the spraying method, a mixed solution in which raw materials other than polyisocyanate are mixed in advance and the polyisocyanate compound (A) can be mixed and used in the spraying device immediately before the construction of the polyurea foam. ..

The content of the polyamine compound (B) is 2.0% by mass or more, preferably 5.0% by mass or more, preferably 8.0% by mass, when the total amount of the urea resin composition is 100% by mass. The above is more preferable. The upper limit of the content of the polyamine compound (B) can be, for example, 40.0% by mass or less, preferably 30.0% by mass or less, and more preferably 20.0% by mass or less. From another viewpoint, the content of the polyamine compound (B) can be blended so that the isocyanate index of the urea resin composition is 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 compound (A) by 100 (NCO). Number of moles / number of moles of active hydrogen × 100). When the isocyanate index of the resin composition is within such a range, sufficient isocyanurate is formed, and the isocyanurate conversion rate can be made appropriate. Therefore, the flame retardancy of the polyurea foam can be made excellent.

The content of the polyisocyanate compound (A) can be 100 to 1000 parts by mass when the total content of the polyamine compound (B) in the urea resin composition is 100 parts by mass.

The content of the defoaming agent can be 0.1 to 20 parts by mass when the total content of the polyamine compound (B) in the urea resin composition is 100 parts by mass.

The content of the flame retardant can be 10 to 200 parts by mass, preferably 30 to 150 parts by mass, when the total content of the polyamine compound (B) in the urea resin composition is 100 parts by mass. More preferably, 50 to 100 parts by mass. When the content of the flame retardant is within such a range, a polyurea foam having excellent flame retardancy can be obtained.

The content of red phosphorus contained in the flame retardant can be 100 parts by mass or less, and 5 to 40 parts by mass, when the total content of the polyamine compound (B) in the urea resin composition is 100 parts by mass. Parts are preferable, and 25 to 40 parts by mass are more preferable. When the content of red phosphorus is within such a range, a polyurea foam having more excellent flame retardancy can be obtained, and deterioration with time in a moist heat environment can be suppressed. In particular, it is possible to suppress thermal decomposition of the foam and prevent the formation of a carbonized layer in the flame contact evaluation described later.
The total content of the flame retardant selected from the phosphate ester, the phosphate-containing flame retardant, the bromine-containing flame retardant, the boron-containing flame retardant, the antimony-containing flame retardant and the metal hydroxide is the polyamine in the resin composition. When the total content of the compound is 100 parts by mass, it can be 10 to 200 parts by mass. In addition, the total of the red phosphorus content (Fp) and the flame retardant selected from the phosphate ester, the phosphate-containing flame retardant, the bromine-containing flame retardant, the boron-containing flame retardant, the antimony-containing flame retardant and the metal hydroxide. The ratio (Fp / Ft) to the content (Ft) is not particularly limited, but can be, for example, 0.0 to 1, preferably 0.0 to 0.8, and 0.09 to 0.73. Is more preferable, and 0.45 to 0.73 is even more preferable. When these flame retardants are blended in such a range, a polyurea foam having excellent flame retardancy and shape retention during combustion and capable of suppressing deterioration over time in a moist heat environment can be obtained.

The content of the trimerization catalyst can be 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, when the total content of the polyamine compound in the resin composition is 100 parts by mass. ~ 20 parts by mass is more preferable, and 10 to 20 parts by mass is further preferable. When the content of the trimerization catalyst is within such a range, isocyanurate formation is sufficient, polyurea foam has excellent flame retardancy and shape retention during combustion, and can suppress deterioration over time in a moist heat environment. Can be obtained.

When the content of a catalyst other than the quantification catalyst (resinification catalyst, foaming catalyst, etc.) is blended, the content of the catalyst other than the quantification catalyst is 100 mass by mass of the total content of the polyamine compound in the resin composition. In the case of parts, it can be 1 to 10 parts by mass. A compound having both a resinification catalyst and a foaming catalyst action shall be blended as a resinification catalyst.

4. Uses of urea resin composition The urea resin composition of the present invention is used as a raw material for polyurea foams used for construction applications, ships for transporting oil and gas, heat insulating materials for electric appliances such as refrigerators, and heat insulating materials. Further, in a reinforced concrete construction or the like, since heat insulation construction is easy, it can be used as a urea resin composition for a spraying method.

The polyurea foam can be formed by foaming and curing the urea resin composition of the present invention. Known methods can be used for foaming and curing. When used as a urea resin composition for the spraying method, a mixture in which raw materials other than the polyisocyanate compound (A) are mixed in advance is placed in the equipment for the spraying method, and then the polyisocyanate compound (A) is mixed. Can be used as a polyurea foam by foaming and curing in.

^{The polyurea foam can have a total calorific value of 25 MJ / m 2} or less after 20 minutes, measured under the condition of heating with a ^{radiant heat intensity of 50 kW / m 2} , in accordance with the ISO-5660 test method. , 8.5 MJ / m ² or less is preferable. When the total calorific value of the polyurea foam is within such a range, the polyurea foam has particularly excellent flame retardancy.

The polyurea foam can have an isocyanurate conversion rate of 25 to 40% calculated by the following formula (1) based on the absorption spectrum obtained by infrared spectroscopic analysis. The isocyanurate conversion rate indicates the degree of the trimerization reaction of polyisocyanate, and the polyurea foam has excellent flame retardancy as long as the isocyanurate conversion rate is within such a range.
(Equation 1)
Isocyanurate conversion rate (%) = P1 / (P1 + P2 + P3 + P4) x 100
P1: Peak area derived from the isocyanurate structure contained in the absorption spectrum of the polyurea foam obtained by infrared spectroscopic analysis P2: C of the urea structure contained in the absorption spectrum of the polyurea foam obtained by infrared spectroscopic analysis = Peak area P3 derived from O: Peak area P4 derived from C = O of urethane structure and isocyanurate structure contained in the absorption spectrum of polyurea foam obtained by infrared spectroscopy: Obtained by infrared spectroscopy The peak area derived from the urethane structure contained in the absorption spectrum of the polyurea foam and NH contained in the urea structure.

P1 is the area of the peak derived from the isocyanurate structure contained in the absorption spectrum of the polyurea foam obtained by the infrared spectroscopic analysis, and is the area of the peak derived from the nurate ring in the vicinity of ^{wave number 1410 cm-1.} 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 of the raw material polyisocyanate compound (A).

P2 is a peak area derived from C = O of the urea structure included in the absorption spectrum of the polyurea foam obtained by infrared spectroscopic analysis, and is derived from C = O of the urea bond ^{having a wave number of about 1595 cm-1.} The area of the peak. 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 of the raw material polyisocyanate compound (A).

P3 is a peak area derived from C = O of the urethane structure and the isocyanurate structure contained in the absorption spectrum of the polyurea foam obtained by infrared spectroscopic analysis, and is a peak of C = O bond in the vicinity of ^{wave number 1710 cm -1.} The area of. 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 groups of the raw material polyisocyanate compound (A).

P4 is a peak area derived from the urethane structure contained in the absorption spectrum of the polyurea foam obtained by infrared spectroscopic analysis and NH contained in the urea structure, and is derived from NH having a wave number of 1510 cm ^-1. The area of the peak to be 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 polyurea foam, and indicates the content of the urethane structure and the urea structure formed by the reaction of the isocyanate group of the raw material polyisocyanate compound (A).

Therefore, the sum of P1 to P4 indicates the total number of reacted isocyanate groups of the raw material polyisocyanate compound (A). Therefore, the isocyanurate conversion rate is a value indicating the ratio of the isocyanate groups of the polyisocyanate compound (A), which is the reacted raw material, having an isocyanurate structure.

The density of the polyurea foam is not particularly restricted so long as it does not inhibit the effect of the present invention, it can be 10 to 200 / ^{m 3,} preferably ^{10~100kg / m 3, 10~55kg / m} 3 Gayori preferable. When the density of the polyurea foam is within such a range, a polyurea foam having excellent thermal conductivity and excellent flame retardancy can be obtained.

The density of polyurea foam is measured according to JIS K7222: 2005 "Foam plastics and rubber-How to determine the apparent density".

<< Preparation of resin composition >>
<Raw materials>
(Polyamine compound)
-Etacure 420 (manufactured by Albemarle, amine value: 562 mgKOH / G)
・ Erasmer 250P (manufactured by Kumiai Chemical Industry Co., Ltd., amine value: 254 mgKOH / g)
-ANCAMINE2049 (manufactured by Evonik, amine value: 484 mgKOH / g)
・ Erasmer 1000P (manufactured by Kumiai Chemical Industry Co., Ltd., amine value: 93 mgKOH / g)
(Polyol compound (B))
-Maximol RLK-505 (manufactured by Kawasaki Kasei Chemicals, hydroxyl value: 250 mgKOH / g)
(Flame retardants)
-Tris phosphate (2-chloropropyl) (TMCPP, chlorine-containing phosphate ester)
-Resorcinol bis (diphenyl) phosphate (PFR, phosphate ester)
・ Red phosphorus / aluminum hypophosphite (phosphate-containing flame retardant)
・ Decabromodiphenyl oxide (flame retardant containing bromine)
・ Zinc borate (boron-containing flame retardant)
・ Antimony trioxide (flame retardant containing antimony)
・ Aluminum hydroxide (metal hydroxide flame retardant)
(Foaming agent)
・ SF2937F (Silicone-based surfactant manufactured by Toray Dow Corning)
(catalyst)
・ Bismuth niethylhexanoate (bismuth-based resinification catalyst)
・ N, N-dimethylaminoethanol (foaming catalyst)
・ TOYOCAT-TRX (manufactured by Tosoh Co., Ltd., quantification catalyst)
・ Diazabicycloundecene (triquantization catalyst)
・ 1,3,5-Tris (dimethylaminopropyl) hexahydro-s-triazine (trimerization catalyst)
・ Potassium octylate (triquantization catalyst)
(Foaming agent)
・ Opteon1100 (manufactured by Mitsui Chemours FluoroProducts, HFO-1336mzz (Z))
(Polyisocyanate compound (A))
・ Millionate MR-200 (manufactured by Tosoh, NCO%: 30.9%, Crude MDI)
-Foam Light MI (BASF INOC Polyurethane NCO%: 33.3%, Monomeric MDI)

<Preparation of foam>
(Preparation of mixed solution and foam used for evaluation other than adhesiveness evaluation)
In a 500 mL polypropylene disposable cup, the contents of polyamine compounds, polyol compounds, trimmerization catalysts, flame retardants, foaming agents, defoaming agents, and other additives are added to each of Examples and Comparative Examples shown in Tables 1 to 3. Weighed and used as a mixed solution of each Example and Comparative Example. Each mixture was stirred and mixed at 2000 rpm for 5 minutes using a stirrer equipped with a propeller type stirring blade to obtain a polyamine mixture and a polyol mixture of each Example and Comparative Example. The mixture was placed in a cooling furnace at 10 ° C., and the obtained polyamine mixture and the polyisocyanate having the contents shown in Tables 1 to 3 were individually cooled to 10 ± 1 ° C. The polyamine mixture and polyol mixture of each example and comparative example, and polyisocyanate are stirred and mixed at 2000 rpm for 5 seconds at 2000 rpm using a stirrer equipped with a propeller type stirring blade to foam and cure, and each example and comparative example and the polyisocyanate are mixed. A foam of a comparative example was obtained.
In the adhesiveness evaluation, the polyamine mixed solution and the polyol mixed solution of each Example and Comparative Example and the polyisocyanate whose contents shown in Tables 1 to 3 were weighed were individually cooled to 10 ± 1 ° C. The mixture was mixed with a hand spray for spraying rigid urethane foam, which will be described later, and sprayed onto an object to form a foam for evaluation of adhesiveness.

<< 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 Equation 1. The measurement was performed at three points of the upper part, the central part, and the bottom part with respect to the rising direction of the foam, and the average value was taken. The measurement results are shown in Tables 1 to 3. The evaluation was judged according to the following evaluation criteria, and the results are shown in Tables 1 to 3.
(Observation peak)
P1: Peak area derived from the isocyanurate structure contained in the absorption spectrum of the foam obtained by infrared spectroscopy (observation range: 1380 to 1430 cm ^-1 )
P2: Peak area derived from C = O of the urea structure included in the absorption spectrum of the polyurea foam obtained by infrared spectroscopic analysis (observation range: 1550 to 1640 cm ^-1 )
P3: Peak area derived from C = O of urethane structure and isocyanurate structure contained in the absorption spectrum of the foam obtained by infrared spectroscopic analysis (observation range: 1680 to 1730 cm ^-1 )
P4: Polyurea structure included in the absorption spectrum of the foam obtained by infrared spectroscopic analysis and peak area derived from NH contained in the urea structure (observation range: 470 to 1550 cm ^-1 )
(Equation 1)
Isocyanurate conversion rate = P1 / (P1 + P2 + P3 + P4) x 100
(Evaluation criteria)
2 points: Over 35 1 point: 30 or more and 35 or less 0 points: Less than 30

<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 1-3.

<Measurement of thermal conductivity>
JIS A1412-1: 2016 "Measuring method of thermal resistance and thermal conductivity of thermal insulating material-Part 1: Protective thermal plate method" GHP method) ”was measured. The results are shown in Tables 1-3.

<Rate of change in compression hardness before and after wet heat treatment>
The foams of Examples and Comparative Examples 24 hours after foaming were subjected to wet heat treatment for 1 month in an environment of 80 ° C. and RH 85%, and the rate of change in compression hardness before and after the wet heat treatment was measured. The compressive hardness before and after the wet heat treatment was measured with a 25% compressive load at 25 ° C. as the compressive hardness. The measurement was carried out by the D method described in JIS K6400-2: 2012 "Soft foam material-Physical characteristics-Part 2: Hardness and compressive stress-How to obtain strain characteristics". The evaluation was judged according to the following evaluation criteria, and the results are shown in Tables 1 to 3.
・ Judgment criteria 3 points: The rate of change in compression hardness before and after wet heat treatment is 10% or less 1 point: The rate of change in compression hardness before and after wet heat treatment is more than 10% and less than 20% 0 points: Before and after wet heat treatment The rate of change in compression hardness of is 20% or more.

<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. According to the standard, the cone calorimeter total calorific value test of the foam was carried out, and the total calorific value and the maximum heat generation rate 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 1-3. The evaluation was judged according to the following evaluation criteria, and the results are shown in Tables 1 to 3. In addition, "not measurable" in the table means that the expanded sample in the test came into contact with the tip of the spark plug of the cone calorimeter, spark did not occur, and normal measurement could not be performed.
3 points: 7 mJ / ^{m 2} less than 2 points: 7 mJ / ^{m 2} or more 10 MJ / ^{m 2} less than 1 point: 10 MJ / ^{m 2} or more 15 mJ / ^{m 2} less than 0 point: 15 mJ / ^{m 2} or more

<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 1-3. The evaluation was judged according to the following evaluation criteria, and the results are shown in Tables 1 to 3.
5 points: more than 50% 4 points: more than 40% 50% or less 3 points: more than 30% 40% or less 2 points: more than 20% 30% or less 1 point: 10% or more and 20% or less 0 points: less than 10%

<Volume change rate (600 ° C)>
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 5 cm, a width of 5 cm, and a thickness of 5 cm, and allowed to stand in an electric furnace heated to 600 ° C. for 5 minutes. Then, the volume change rate was measured. The volume before heating is set to 100%, the volume after heating is measured, 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. did. When it expands, it shows a positive value, and when it contracts, it shows a negative value. The results are shown in Tables 1-3. The evaluation was judged according to the following evaluation criteria, and the results are shown in Tables 1 to 3.
2 points: less than -25% 1 point: -25% or more and -50% or less 0 points: more than -50%

<Adhesiveness>
The polyamine mixture and polyol mixture of each Example and Comparative Example and the polyisocyanate whose contents are weighed as shown in Tables 1 to 3 are individually cooled to 10 ± 1 ° C., and then hard urethane foam is used. Using a hand spray for spraying (manufactured by ADY), a mixture was sprayed on the surface of a wooden board having a surface temperature of 15 ° C., and foamed on the surface of the wooden board. After that, it was cured for 24 hours, and those having no peeling or floating at the adhesive interface between the wooden board and the foam were evaluated as 1 point, and those having peeling or floating were evaluated as 0 points. The results are shown in Tables 1-3.

<Flame contact test>
A sample was cut out from the foams of each Example and Comparative Example 24 hours after the foaming so as to form a rectangular parallelepiped having a length of 10 cm, a width of 10 cm, and a thickness of 5 cm. 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 for 3 minutes with a gas burner. As the combustion gas, methane gas having a purity of 99.5% or more was used, and the combustion gas was supplied at 0.2 MPa so as to produce a pale flame. The height of the fire was 5 cm, and the distance between the flame and the surface of the sample was 1 cm. After the flame contact, the sample was cut in half and the presence or absence of cracks in the cross section was visually observed. In addition, 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 results are shown in Tables 1-3. The evaluation was judged according to the following evaluation criteria, and the results are shown in Tables 1 to 3. In addition, "not measurable" in the table means that the flame could not be measured because the flame penetrated the sample when the flame was contacted.
(Evaluation criteria for cracks)
1 point: No crack 0 point: With crack (Carbonized layer depth evaluation standard)
3 points: less than 5 mm 1 point: 5 mm or more and 25 or less 0 points: more than 25 mm

Tables 1 to 3 show the comprehensive evaluation of each example and comparative example. The comprehensive evaluation was made by summing up the evaluation results of each of the above-mentioned evaluations and judging by the following evaluation criteria.
⊚: 16 points or more ○: 13 points or more and 15 points or less Δ: 10 points or more and 12 points or less ×: 9 points or less

Claims (9)

A urea resin composition containing a polyisocyanate compound (A), a polyamine compound (B), a trimerization catalyst, a foaming agent, a defoaming agent and a flame retardant.
The content of the polyamine compound (B), is 100% by weight the total amount of the urea resin composition state, and are to 2.0 wt%,
The content of the trimerization catalyst, when the content of the polyamine compound (B) of the urea resin composition is 100 parts by mass, and wherein the 5 to 20 parts by mass der Rukoto, urea resin Stuff. The urea resin composition according to claim 1, wherein the polyamine compound (B) has an amine value of 50 to 1000 mg KOH / g. The urea resin composition according to claim 1, wherein the polyamine compound (B) has an amine value of 450 to 1000 mg KOH / g. The urea resin composition according to any one of claims 1 to 3, wherein the polyisocyanate compound (A) has an NCO% of 10 to 35%. The urea resin composition according to any one of claims 1 to 4 , wherein the polyisocyanate compound (A) is an aromatic isocyanate. The urea resin composition according to any one of claims 1 to 5 , wherein the flame retardant contains red phosphorus. The flame retardant comprises 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. Item 2. The urea resin composition according to any one of Items 1 to 6. A polyurea foam obtained by foaming and curing the urea resin composition according to any one of claims 1 to 7. ^{The polyurea foam has a total calorific value of 8.5 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. The polyurea foam according to claim 8 , wherein the polyurea foam is characterized by this.