Urethane resin composition, raw material composition thereof, and raw material kit

Abstract

This invention provides a urethane resin composition that allows for the production of urethane resin foams with excellent flame retardancy and high mechanical strength without the use of carboxylic acid-based metal salt catalysts. [Solution] According to one aspect of the present invention, a urethane resin composition comprising a polyisocyanate compound, cardanol, a triglyceride of a fatty acid, a tertiary amine catalyst containing an ether compound and / or an imidazole compound having two or more morpholine rings, and a quaternary ammonium salt catalyst, but without a carboxylic acid-based metal salt catalyst as a trimerizing catalyst, wherein the foam pieces formed from the urethane resin composition have an apparent total density of 60 kg / m³ as measured in accordance with JIS K 7222:2005. 3 The following urethane resin composition is provided.

Description

[Technical Field]

[0001] This invention relates to a urethane resin composition, a raw material composition thereof, and a raw material kit. [Background technology]

[0002] Concrete reinforced with steel bars is used for the exterior walls of apartment buildings, detached houses, public facilities, and commercial buildings. Furthermore, to prevent condensation and improve insulation, sprayed rigid polyurethane foam is applied to these concrete structures. However, simply spraying rigid polyurethane resin foam may result in the foam burning if a fire or other incident occurs inside the building.

[0003] Therefore, various techniques have been proposed to impart flame retardancy to this rigid polyurethane resin foam (see, for example, Patent Document 1). Furthermore, it has been shown that when making rigid polyurethane foam flame retardant, a quaternary ammonium salt catalyst, a potassium octylate catalyst (carboxylic acid-based metal salt catalyst), and a tertiary amine catalyst can be used in combination as catalysts. However, in this case, our inventors' investigations revealed that the density (especially the apparent overall density) of the rigid polyurethane resin foam tends to be high. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2006-291101 [Overview of the project] [Problems that the invention aims to solve]

[0005] In view of the above circumstances, the present invention aims to provide a urethane resin composition that can produce a urethane resin foam having excellent flame retardancy and high mechanical strength without using a carboxylic acid-based metal salt catalyst. [Means for solving the problem]

[0006] According to one aspect of the present invention, a urethane resin composition comprising a polyisocyanate compound, cardanol, a fatty acid triglyceride, a tertiary amine catalyst containing an ether compound and / or an imidazole compound having two or more morpholine rings, and a quaternary ammonium salt catalyst, but without a carboxylic acid-based metal salt catalyst as a trimerizing catalyst, wherein the foam pieces formed from the urethane resin composition have an apparent total density of 60 kg / m³ as measured in accordance with JIS K 7222:2005. 3 The following urethane resin composition is provided.

[0007] According to one aspect of the present invention, a urethane resin foam can be obtained that has excellent flame retardancy and high mechanical strength, and in which the increase in apparent overall density is suppressed, without the use of a carboxylic acid-based metal salt catalyst. [Modes for carrying out the invention]

[0008] The following describes the urethane resin composition, its raw material composition, and raw material kit according to this embodiment with specific examples. However, the urethane resin composition according to this embodiment is not limited to the specific examples shown below, and can be modified as appropriate, as long as the effects are not hindered. Furthermore, the components shown below can be combined with each other. In this specification, the content of X in Y refers to the proportion (mass%) of X in the total amount of Y (100% by mass).

[0009] <Urethane resin composition> The urethane resin composition according to this embodiment comprises a polyisocyanate compound, cardanol, a tertiary amine catalyst containing a fatty acid triglyceride, an ether compound and / or an imidazole compound having two or more morpholine rings, and a quaternary ammonium salt catalyst. Furthermore, such a urethane resin composition does not contain a carboxylic acid-based metal salt catalyst as a trimerizing catalyst. With such a urethane resin composition, a urethane resin foam having excellent flame retardancy and high mechanical strength can be obtained without using a carboxylic acid-based metal salt catalyst.

[0010] [Polyisocyanate compounds] Examples of polyisocyanate compounds include aromatic polyisocyanates such as diphenylmethane diisocyanate and tolylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate and cyclohexylene diisocyanate, aliphatic polyisocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate, and modified versions thereof (e.g., modified versions containing urethane groups, carbodiimide groups, allophanate groups, urea groups, biuret groups, isocyanurate groups, or xazolidone groups). These polyisocyanate compounds may be used individually or in combination of two or more.

[0011] The number-average molecular weight of the polyisocyanate compound is not particularly limited, but is preferably 30 g / mol or more and 3000 g / mol or less, more preferably 50 g / mol or more and 2500 g / mol or less, even more preferably 70 g / mol or more and 2000 g / mol or less, and particularly preferably 100 g / mol or more and 1500 g / mol or less.

[0012] The isocyanate index is expressed as a percentage of the equivalent ratio of isocyanate groups of a polyisocyanate compound to the hydroxyl groups of a polyol compound. In this specification, when calculating the isocyanate index, the polyol compound shall include diamine polyols, aromatic polyester polyols, bisphenol polyols, and other polyols, as well as cardanol (cardanol is originally a monool). The isocyanate index is not particularly limited, but is preferably 120 or higher, more preferably over 170, even more preferably between 180 and 1000, even more preferably between 200 and 800, particularly preferably between 250 and 600, and most preferably between 300 and 600.

[0013] [Cardanol] Cardanol is a compound in which a linear hydrocarbon group (alkyl group or alkenyl group) with approximately 15 carbon atoms and 0, 1, 2, or 3 double bonds is bonded to the m-position of phenol. A urethane resin foam obtained from a urethane resin composition containing cardanol forms a carbonized layer when it comes into contact with a flame. This carbonized layer prevents the urethane resin composition from further spreading or melting, thereby suppressing the rate of heat generation.

[0014] Cardanol is also the main component of industrial cashew nut shell liquid. Therefore, when adding cardanol, industrial cashew nut shell liquid may be used. The cardanol content in industrial cashew nut shell liquid is usually between 70% and 90% by mass, but it may be increased to 90% or more by various purification methods such as distillation. Here, "industrial cashew nut shell liquid" refers to a product obtained by heat-treating natural cashew nut shell liquid. Natural cashew nut shell liquid mainly contains anacardic acid, but heat treatment causes the carboxyl group at the ortho position of this anacardic acid to decarboxylate, changing it into cardanol. In this specification, cardanol is used as a concept that includes not only cardanol itself but also polyol compounds obtained by chemically modifying (polyolizing) cardanol. Examples of polyolization methods include ring opening after epoxidation of the double bond in the side chain of cardanol, addition of alkylene oxide to the phenolic hydroxyl group, and introduction of a hydroalkyl group to the aromatic ring by an aldehyde or the like.

[0015] The content of cardanol is not particularly limited, but is preferably 1% by mass or more and 30% by mass or less, more preferably 2% by mass or more and 25% by mass or less, still more preferably 3% by mass or more and 20% by mass or less, and particularly preferably 4% by mass or more and 15% by mass or less, based on 100% by mass of the urethane resin composition. When the content of cardanol is not less than the required amount, the carbonized layer forming ability can be further improved, and the heat release rate can be reduced. In addition, when the content of cardanol is not more than the required amount, the mechanical strength of the urethane resin foam can be further improved. The content of cardanol is not particularly limited, but the mass ratio (content of cardanol / content of fatty acid triglyceride) is preferably 1 or more and 15 or less, more preferably 1.5 or more and 10 or less, still more preferably 2 or more and 7 or less, and particularly preferably 3 or more and 5 or less, relative to the content of fatty acid triglyceride described later.

[0016] [Fatty acid Triglyceride] Fatty acid triglyceride (hereinafter sometimes simply referred to as "triglyceride") is a compound in which fatty acids are ester-bonded to the three hydroxyl groups of glycerin. When the urethane resin composition contains triglyceride, the flexibility of the urethane resin foam obtained from the urethane resin composition and the adhesion to various members (objects to be adhered) can be improved.

[0017] The number of carbon atoms in the fatty acid is not particularly limited, but is preferably 8 or more and 30 or less, more preferably 10 or more and 25 or less, still more preferably 12 or more and 22 or less, and particularly preferably 14 or more and 20 or less. Either saturated fatty acids or unsaturated fatty acids can be used as the fatty acid. In addition, hydroxy fatty acids having a hydroxyl group may be used as the fatty acid.

[0018] Specific examples of fatty acids include, for instance, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecyl acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, (9,12,15)-linolenic acid, (6,9,12)-linolenic acid, eleostearic acid, arachidic acid, meadic acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, cerotic acid, montanic acid, melissic acid, ricinoleic acid, ricineradicic acid, cereronic acid, and dihydroxystearic acid.

[0019] Fatty acids may be used individually or in combination of two or more types. That is, a single triglyceride may contain only one type of fatty acid, or it may contain two or three types of fatty acids. Furthermore, regarding the combination of fatty acid types and glycerol bonding positions, only one type of triglyceride may be used, or a combination of multiple different types of triglycerides may be used. The triglycerides are preferably those containing hydroxy fatty acids, such as one or more of castor oil, rescera oil, etc.

[0020] Castor oil may be used as the triglyceride. The proportion of fatty acids in castor oil is as follows: palmitic acid: 0.5% to 1.5% by mass, stearic acid: 0.5% to 1.5% by mass, oleic acid: 2.5% to 4% by mass, linoleic acid: 4% to 5% by mass, linolenic acid: 0.5% to 1.5% by mass, ricinoleic acid: 87% to 91% by mass, and dihydroxystearic acid: 0.5% to 1.5% by mass.

[0021] The triglyceride content is not particularly limited, but is preferably 0.1% to 20% by mass, more preferably 0.2% to 15% by mass, even more preferably 0.5% to 10% by mass, and particularly preferably 1% to 5% by mass, based on 100% by mass of the urethane resin composition. A triglyceride content above the required amount enhances the flexibility and adhesion to various components of the urethane resin foam obtained from the urethane resin composition. Furthermore, a triglyceride content below the required amount further suppresses the heat generation rate of the urethane resin obtained from the urethane resin composition.

[0022] [Diamine polyols] The urethane resin composition according to this embodiment preferably further contains a diamine polyol. The inclusion of a diamine polyol in the urethane resin composition can accelerate the urethane formation reaction during the formation of a urethane resin foam.

[0023] Examples of diamine polyols are not particularly limited, but include compounds obtained by adding an alkylene oxide to a diamine. Examples of diamines include one or more of ethylenediamine, butylenediamine, or their alkyl derivatives, or N-hydroxyalkyl derivatives (e.g., N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine). On the other hand, examples of alkylene oxides include one or more of ethylene oxide, propylene oxide, or tetrahydrofuran.

[0024] The content of diamine polyols is not particularly limited, but is preferably 0.1% to 20% by mass, more preferably 0.2% to 15% by mass, even more preferably 0.5% to 10% by mass, and particularly preferably 1% to 5% by mass, based on 100% by mass of the urethane resin composition. A diamine polyol content above the required amount can further promote the urethaneization reaction when forming the urethane resin foam. Furthermore, a diamine polyol content below the required amount can maintain a low amount of urethane bonds (in other words, an increase in the amount of nurate bonds, which are highly flame-retardant trimerized bonds), thereby further enhancing the flame retardancy of the urethane resin foam.

[0025] [Aromatic polyester polyols] The urethane resin composition according to this embodiment preferably further contains an aromatic polyester polyol. By including an aromatic polyester polyol in the urethane resin composition, a carbonized layer is more easily formed when the urethane resin foam formed from this composition comes into contact with a flame.

[0026] Aromatic polyester polyols are not particularly limited, but examples include polymers obtained by dehydration condensation of aromatic polybasic acids and polyhydric alcohols. Examples of polybasic acids include one or more of the following: terephthalic acid, isophthalic acid, phthalic acid, or derivatives thereof. On the other hand, examples of polyhydric alcohols include one or more of the following: bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, triethylene glycol, 1,6-hexane glycol, neopentyl glycol, etc.

[0027] The number-average molecular weight of aromatic polyester polyols is not particularly limited, but is preferably 50 g / mol or more and 3000 g / mol or less, more preferably 100 g / mol or more and 2500 g / mol or less, even more preferably 200 g / mol or more and 2000 g / mol or less, and particularly preferably 300 g / mol or more and 1500 g / mol or less.

[0028] The content of aromatic polyester polyols is not particularly limited, but is preferably 0.5% to 30% by mass, more preferably 1% to 20% by mass, even more preferably 2% to 15% by mass, and particularly preferably 3% to 10% by mass, based on 100% by mass of the urethane resin composition. A content of aromatic polyester polyols above the required amount can further promote the urethane formation reaction when forming a urethane resin foam from this urethane resin composition. Furthermore, a content of aromatic polyester polyols below the required amount can improve the compatibility of each component in the urethane resin composition.

[0029] [Bisphenol-based polyols] The urethane resin composition according to this embodiment preferably further contains a bisphenol polyol. By including a bisphenol polyol in the urethane resin composition, the flame retardancy of the urethane resin foam formed from this urethane resin composition can be further enhanced. Bisphenol-based polyols are not particularly limited, but examples include compounds obtained by adding an alkylene oxide (one or more of ethylene oxide, propylene oxide, or tetrahydrofuran) to bisphenol.

[0030] Examples of bisphenols include one or more of bisphenol A, bisphenol F, and bisphenol S, but it is preferable to use bisphenol A. This makes it possible to further enhance the flame retardancy of the urethane resin foam formed from the urethane resin composition. The number-average molecular weight of the bisphenol polyol is not particularly limited, but is preferably 50 g / mol or more and 3000 g / mol or less, more preferably 100 g / mol or more and 2500 g / mol or less, even more preferably 200 g / mol or more and 2000 g / mol or less, particularly preferably 300 g / mol or more and 1500 g / mol or less, and most preferably 400 g / mol or more and 1000 g / mol or less.

[0031] The content of bisphenol polyols is not particularly limited, but is preferably 0.5% to 30% by mass, more preferably 1% to 20% by mass, even more preferably 2% to 15% by mass, and particularly preferably 3% to 10% by mass, based on 100% by mass of the urethane resin composition. A bisphenol polyol content above the required amount can further enhance the flame retardancy of the urethane resin foam formed from this urethane resin composition. Furthermore, a bisphenol polyol content below the required amount can further enhance the toughness of the urethane resin foam.

[0032] [Other polyols] The urethane resin composition according to this embodiment may or may not contain other polyols in addition to the polyols described above. If the urethane resin composition contains other polyols, the content thereof is not particularly limited, but may be 0.1% to 40% by mass, 0.2% to 35% by mass, 0.5% to 30% by mass, or 1% to 25% by mass, based on 100% by mass of the urethane resin composition.

[0033] [Foam stabilizer] The urethane resin composition according to this embodiment preferably further contains a foam stabilizer (for example, a surfactant). By including a foam stabilizer in the urethane resin composition, the dispersibility of air bubbles in the urethane resin composition can be improved, and the air bubble structure of the resulting urethane resin foam can be adjusted. Examples of foam stabilizers that can be used include polyoxyalkylene-based foam stabilizers such as polyoxyalkylene alkyl ethers, and silicone-based foam stabilizers such as organopolysiloxanes.

[0034] The content of the foam stabilizer is not particularly limited, but it is preferably 0.05% to 10% by mass, more preferably 0.1% to 5% by mass, even more preferably 0.2% to 3% by mass, particularly preferably 0.5% to 2% by mass, and most preferably 0.5% to 0.7% by mass, based on 100% by mass of the urethane resin composition. By having a foam stabilizer content of the required amount or more, the dispersibility of bubbles in the urethane resin composition can be improved, and the bubble structure of the formed urethane resin foam can be adjusted. Furthermore, by having a foam stabilizer content of the required amount or less, the dimensional stability of the urethane resin foam formed from such urethane resin composition can be improved.

[0035] [Amine-based catalysts] The urethane resin composition according to this embodiment preferably further contains an amine-based catalyst. The urethane resin composition can promote the reaction between the polyisocyanate compound and water by containing an amine-based catalyst. As an amine catalyst, for example, one of the following may be used alone: ​​an aliphatic amine, an aromatic amine, or a heterocyclic amine, or two or more may be used in combination.

[0036] The urethane resin composition according to this embodiment includes a tertiary amine catalyst containing an ether compound and / or an imidazole compound having two or more morpholine rings as an amine catalyst. By including such a tertiary amine catalyst in the urethane resin composition, the urethane formation reaction during the formation of the urethane resin foam can be sufficiently promoted. Therefore, the flame retardancy and mechanical strength (compressive strength) of the urethane resin foam can be improved without using a carboxylic acid-based metal salt catalyst (for example, potassium octoate catalyst) which has the effect of enhancing flame retardancy.

[0037] Examples of ether compounds having two or more morpholine rings (hereinafter sometimes simply referred to as "ether compounds") include bis(2-morpholinoethyl) ether (DMDEE) and bis(2,2-dimorpholinoethyl) ether. These may be used individually or in combination of two or more. In particular, the ether compound is preferably bis(2-morpholinoethyl) ether. This is because bis(2-morpholinoethyl) ether is especially effective in improving the flame retardancy and mechanical strength (compressive strength) of urethane resin foam.

[0038] Examples of imidazole compounds include imidazole and 1,2-dimethylimidazole (an imidazole derivative). The content of the ether compound and / or the imidazole compound is preferably 0.01% to 10% by mass, more preferably 0.05% to 7.5% by mass, even more preferably 0.1% to 5% by mass, and particularly preferably 0.5% to 1% by mass, based on 100% by mass of the urethane resin composition. By including the ether compound in such amounts in the urethane resin composition, the above effects can be further improved.

[0039] The tertiary amine catalyst may include, for example, aliphatic compounds such as triethylamine, bis(2-dimethylaminoethyl) ether (BDMAEE), N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA), N,N,N'-trimethylaminoethyl-ethanolamine, and N-methyl,N'-dimethylaminoethylpiperazine, as well as alicyclic compounds such as N-methylmorpholine.

[0040] The content of the amine-based catalyst is not particularly limited, but is preferably 0.1% to 20% by mass, more preferably 0.2% to 10% by mass, even more preferably 0.5% to 5% by mass, and particularly preferably 1% to 4% by mass, based on 100% by mass of the urethane resin composition. A content of amine-based catalyst above the required amount allows for more appropriate promotion of the reaction between the polyisocyanate compound and water. Furthermore, a content of amine-based catalyst below the required amount allows for appropriate maintenance of the foaming rate in the urethane resin composition.

[0041] [Trimerization catalyst] The urethane resin composition according to this embodiment preferably further contains a trimerizing catalyst. By including a trimerization catalyst, the urethane resin composition can react with the isocyanate groups contained in the polyisocyanate compound to trimerize them and promote the formation of an isocyanurate ring.

[0042] Examples of trimerization catalysts include nitrogen-containing aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine; carboxylic acid metal salts such as potassium acetate, potassium 2-ethylhexanoate, and potassium octoate; tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, and triphenylammonium salt; quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, tetraphenylammonium salt, and (2-hydroxypropyl)(2-hydroxyethyl)dimethylammonium salt. The anions that pair with tertiary and quaternary ammonium compounds are not particularly limited, but include, for example, halide ions (e.g., fluoride ions, chloride ions, bromide ions, iodide ions), inorganic acid-derived anions (e.g., nitrate ions, nitrite ions, hydrogen sulfate ions, sulfate ions, dihydrogen phosphate ions, monohydrogen phosphate ions, phosphate ions, bicarbonate ions, carbonate ions, perchlorate ions), organic acid-derived anions (e.g., formate ions, acetate ions, propionate ions, 2-ethylhexanoate ions, benzoate ions, lactate ions, citrate ions), sulfonic acid-derived anions (e.g., methanesulfonate ions, p-toluenesulfonate ions, trifluoromethanesulfonate ions), and weakly coordinating anions (e.g., BF 4- , PF 6- SbF 6- , NTf 2- Examples include:

[0043] The urethane resin composition according to this embodiment contains a quaternary ammonium salt (catalyst) as a trimerizing catalyst. The quaternary ammonium salt (catalyst) has a high effect in promoting the formation of isocyanurate rings, and therefore can improve the flame retardancy of the urethane resin foam. Furthermore, as described above, by using ether compounds and / or imidazole compounds as tertiary amine catalysts, the use of carboxylic acid-based metal salts (catalysts), which are generally used to flame retardate urethane resin foams, can be omitted.

[0044] The lower limit of the trimerizing catalyst content is not particularly limited, but it can be 0.05% by mass or more, 0.1% by mass or more, 0.2% by mass or more, 0.3% by mass or more, 0.4% by mass or more, 0.5% by mass or more, 0.6% by mass or more, 0.7% by mass or more, 0.8% by mass or more, 0.9% by mass or more, 1% by mass or more, 1.1% by mass or more, 1.15% by mass or more, 1.2% by mass or more, 1.25% by mass or more, or 1.3% by mass or more, based on 100% by mass of the urethane resin composition. On the other hand, the upper limit of the trimerizing catalyst content is not particularly limited, but it can be 10% by mass or less, 9% by mass or less, 8% by mass or less, 7% by mass or less, 6% by mass or less, 5% by mass or less, 4% by mass or less, 3% by mass or less, or 2% by mass or less, based on 100% by mass of the urethane resin composition. By having a trimerizing catalyst content of the required amount or more, the formation of isocyanurate rings can be promoted, and the flame retardancy of the urethane resin foam can be improved. Furthermore, by keeping the trimerization catalyst content below the required amount, clogging of the spray gun's mixing section due to the rapid formation of isocyanurate rings can be prevented.

[0045] [Urethane metal catalyst] The urethane resin composition according to this embodiment preferably further contains a urethane metal catalyst. The urethane resin composition, by containing a urethane metal catalyst, can promote the reaction between the polyisocyanate compound and the cardanol and various polyol compounds mentioned above. Examples of urethane metal catalysts include metal salts or metal complexes containing lead, tin, bismuth, copper, zinc, cobalt, nickel, etc., with metal salts containing bismuth (bismuth-based metal salt catalysts) being particularly preferred. Specific examples of urethane metal catalysts include bismastris (2-ethylhexanoate), dinormal butyltin dilaurate, lead 2-ethylhexanoate, and bismuth 2-ethylhexanoate.

[0046] The content of the urethane metal catalyst is not particularly limited, but is preferably 0.005% to 1% by mass, more preferably 0.01% to 0.5% by mass, even more preferably 0.02% to 0.3% by mass, and particularly preferably 0.02% to 0.2% by mass, based on 100% by mass of the urethane resin composition. A content of urethane metal catalyst above the required amount promotes the formation of isocyanurate rings, thereby improving the flame retardancy of the urethane resin foam. Furthermore, a content of urethane metal catalyst below the required amount prevents clogging of the spray gun's mixing section due to rapid isocyanurate ring formation.

[0047] [Flame retardant] The urethane resin according to this embodiment preferably further contains a flame retardant. For example, one or more of the following can be used as flame retardants: phosphate ester flame retardants, phosphate-containing flame retardants, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, and metal hydroxide-based flame retardants.

[0048] (Phosphate ester-based flame retardant) Examples of phosphate ester-based flame retardants include monophosphate esters and condensed phosphate esters. Specific examples of monophosphate esters include tris(β-chloropropyl) phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, and tributoxyethyl phosphate. Specific examples of condensed phosphate esters include trialkyl polyphosphates, resorcinol polyphenyl phosphates, resorcinol poly(di-2,6-xylyl) phosphates, or condensates thereof.

[0049] (Phosphate-containing flame retardant) A phosphate-containing flame retardant contains phosphate. As the phosphate, one or more types can be used, for example, from among monophosphates, pyrophosphates, polyphosphates, etc. (Bromine-containing flame retardant) Bromine-containing flame retardants are flame retardants that contain compounds with bromine in their molecular structure. As a bromine-containing flame retardant, for example, aromatic brominated compounds can be used.

[0050] (Boron-containing flame retardant) Boron-containing flame retardants are flame retardants that contain compounds with boron in their molecular structure. Examples of boron-containing flame retardants that can be used include borax, boron oxide, boric acid, and borates. (Antimony-containing flame retardant) Antimony-containing flame retardants are flame retardants that contain compounds with antimony in their molecular structure. Examples of antimony-containing flame retardants that can be used include antimony oxide, antimony salts, and pyroantimony salts.

[0051] (Metal hydroxide-based flame retardant) Examples of metal hydroxide-based flame retardants include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, titanium hydroxide, zinc hydroxide, and copper hydroxide. (Red phosphorus) The urethane resin composition according to this embodiment preferably does not contain red phosphorus, or if it does contain red phosphorus, it is preferably more than 0% by mass and less than 3% by mass relative to 100% by mass of the urethane resin composition. In this case, a decrease in the adhesion of the urethane resin foam to various components can be prevented.

[0052] The amount of flame retardant is not particularly limited, but is preferably 1% to 50% by mass, more preferably 2% to 40% by mass, even more preferably 3% to 30% by mass, and particularly preferably 4% to 20% by mass, based on 100% by mass of the urethane resin composition. A flame retardant content above the required amount can enhance flame retardancy. Furthermore, a flame retardant content below the required amount allows for more appropriate foaming of the urethane resin composition.

[0053] [Foaming agent] The urethane resin composition according to this embodiment preferably contains a foaming agent. By including a foaming agent in the urethane resin composition, the foaming of the urethane resin foam formed from this urethane resin composition can be promoted. Examples of foaming agents that can be used include water, low-boiling-point hydrocarbons, chlorinated aliphatic hydrocarbon compounds, fluorine compounds, hydrofluorocarbons, hydrochlorofluorocarbon compounds, ether compounds, or mixtures thereof, as well as inorganic physical foaming agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas.

[0054] The amount of foaming agent is not particularly limited, but is preferably 1% to 30% by mass, more preferably 2% to 25% by mass, even more preferably 3% to 20% by mass, and particularly preferably 4% to 15% by mass, based on 100% by mass of the urethane resin composition. By having a foaming agent content of the required amount or more, the urethane resin foam can be given appropriate foaming properties. Conversely, by having a foaming agent content of less than the required amount, the mechanical strength of the urethane resin foam can be further increased.

[0055] [Other additives] The urethane resin composition according to this embodiment may contain an inorganic filler. As the inorganic filler, for example, one selected from silica, alumina, titanium oxide, talc, clay, mica, glass fiber, glass beads, aluminum nitride, boron nitride, silicon nitride, carbon fiber, potassium titanate, lead zirconate titanate, stainless steel fiber, slag fiber, fly ash, silica-alumina fiber, alumina fiber, silica fiber, zirconia fiber, etc., may be used alone, or two types thereof may be used in combination. In the urethane resin composition according to the present embodiment, if necessary, additives such as phenolic, amine, sulfur and other antioxidants, heat stabilizers, metal deactivators, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, tackifier resins, tackifiers such as polybutene and petroleum resins, and bifenthrin-based termiticides can be used.

[0056] [Physical Properties etc. of Urethane Resin Composition] In the present embodiment, a foam piece formed from the urethane resin composition (a mixture of a first raw material and a second raw material described later) has an overall apparent density measured in accordance with JIS K 7222:2005 of 60 kg / m 3 or less, more preferably 51 kg / m 3 or more and 59 kg / m 3 or less, and even more preferably 53 kg / m 3 or more and 58 kg / m 3 or less. As described above, using an ether compound having two or more morpholine rings and / or an imidazole compound as the tertiary amine catalyst can prevent an increase in the density (overall apparent density) of the urethane resin foam. A specific method for measuring the density will be described later.

[0057] A foam piece formed from the urethane resin composition according to the present embodiment preferably has a compressive strength measured in accordance with JIS A 9526:2022 of 245 kPa or more, more preferably 245 kPa or more and 500 kPa or less, and even more preferably 250 kPa or more and 480 kPa or less. A specific method for measuring the compressive strength will be described later. The foam pieces formed from the urethane resin composition according to this embodiment preferably have an oxygen index of 26 or higher, and more preferably 26.5 or higher, as measured in accordance with JIS K 7201-2:2021. The oxygen index may also be 30 or lower, 28 or lower, or 27 or lower. The specific method for measuring the oxygen index will be described later.

[0058] The urethane resin composition according to this embodiment is used by spraying it onto structures such as buildings, furniture, automobiles, trains, and ships. In this way, a urethane resin foam layer can be formed on the surface of the structure. Specifically, the urethane resin composition may be separated into a polyisocyanate compound and other components, mixed while spraying, and then sprayed onto the surface of a structure, etc., or the polyisocyanate compound and other components may be mixed and then sprayed onto the surface of a structure, etc.

[0059] The urethane resin composition according to this embodiment hardens through a reaction, and therefore its viscosity changes over time. For this reason, before using the urethane resin composition according to the present invention, the urethane resin composition is divided into two or more parts to prevent it from reacting and hardening. Then, when using the urethane resin composition, the raw materials or raw material compositions of the divided urethane resin composition are mixed to obtain the urethane resin composition according to this embodiment.

[0060] When dividing a urethane resin composition into two or more raw materials or raw material compositions, the components should be divided in such a way that curing does not begin with each component of the divided urethane resin composition alone, but only after the components of the urethane resin composition are mixed together. Most typically, this involves dividing the composition into two parts: a polyisocyanate compound and the other components. The latter raw material composition will be described below.

[0061] <Raw material composition> The raw material composition according to this embodiment is a raw material composition for a urethane resin composition used in combination with a polyisocyanate compound. Specifically, this raw material composition contains cardanol, a fatty acid triglyceride, a tertiary amine catalyst containing an ether compound and / or an imidazole compound having two or more morpholine rings, and a quaternary ammonium salt catalyst, but does not contain a carboxylic acid-based metal salt catalyst as a trimerizing catalyst.

[0062] In one embodiment, this raw material composition may further contain a diamine polyol, an aromatic polyester polyol, a bisphenol polyol, other polyols, a foam stabilizer, other amine catalysts, other trimerizing catalysts, a urethane metal catalyst, a flame retardant, and a blowing agent. The specific types of each component are the same as those described in the section on urethane resin compositions, so a detailed explanation is omitted here. The content of each component in this raw material composition will be described below.

[0063] In this raw material composition, the cardanol content is not particularly limited, but is preferably 2% by mass or more and 60% by mass or less, more preferably 4% by mass or more and 50% by mass or less, even more preferably 6% by mass or more and 40% by mass or less, and particularly preferably 8% by mass or more and 30% by mass or less, based on 100% by mass of the raw material composition. In this raw material composition, the triglyceride content is not particularly limited, but is preferably 0.2% to 40% by mass, more preferably 0.4% to 30% by mass, even more preferably 1% to 20% by mass, and particularly preferably 2% to 10% by mass, based on 100% by mass of the raw material composition.

[0064] In this raw material composition, the content of diamine polyol is not particularly limited, but is preferably 0.2% to 40% by mass, more preferably 0.4% to 30% by mass, even more preferably 1% to 20% by mass, and particularly preferably 2% to 10% by mass, based on 100% by mass of the raw material composition. In this raw material composition, the content of aromatic polyester polyols is not particularly limited, but is preferably 1% to 60% by mass, more preferably 2% to 40% by mass, even more preferably 4% to 30% by mass, and particularly preferably 6% to 20% by mass, based on 100% by mass of the raw material composition.

[0065] In this raw material composition, the content of bisphenol polyol is not particularly limited, but is preferably 1% by mass or more and 60% by mass or less, more preferably 2% by mass or more and 40% by mass or less, even more preferably 4% by mass or more and 30% by mass or less, and particularly preferably 6% by mass or more and 20% by mass or less, based on 100% by mass of the raw material composition. In this raw material composition, other polyols may not be included, and if they are included, the content is not particularly limited, but may be 0.2% to 80% by mass, 0.4% to 70% by mass, 1% to 60% by mass, or 2% to 50% by mass, based on 100% by mass of the raw material composition.

[0066] In this raw material composition, the content of the foam stabilizer is not particularly limited, but is preferably 0.1% to 20% by mass, more preferably 0.2% to 10% by mass, even more preferably 0.4% to 6% by mass, particularly preferably 1% to 4% by mass, and most preferably 1% to 1.4% by mass, based on 100% by mass of the raw material composition. In this raw material composition, the content of the amine-based catalyst is not particularly limited, but is preferably 0.2% to 40% by mass, more preferably 0.4% to 20% by mass, even more preferably 1% to 10% by mass, and particularly preferably 2% to 8% by mass, based on 100% by mass of the raw material composition.

[0067] Among amine-based catalysts, the content of ether compounds and / or imidazole compounds is preferably 0.05% to 20% by mass, more preferably 0.1% to 15% by mass, even more preferably 0.2% to 10% by mass, and particularly preferably 1% to 2% by mass, based on 100% by mass of the raw material composition. In this raw material composition, the lower limit of the trimerizing catalyst content is not particularly limited, but it can be 0.1% by mass or more, 0.2% by mass or more, 0.4% by mass or more, 0.6% by mass or more, 0.8% by mass or more, 1% by mass or more, 1.2% by mass or more, 1.4% by mass or more, 1.6% by mass or more, 1.8% by mass or more, 2% by mass or more, 2.2% by mass or more, 2.3% by mass or more, 2.4% by mass or more, 2.5% by mass or more, or 2.6% by mass or more, based on 100% by mass of the raw material composition. On the other hand, the upper limit of the trimerizing catalyst content is also not particularly limited, but it can be 20% by mass or less, 18% by mass or less, 16% by mass or less, 14% by mass or less, 12% by mass or less, 10% by mass or less, 8% by mass or less, 6% by mass or less, or 4% by mass or less, based on 100% by mass of the raw material composition.

[0068] In this raw material composition, the content of the urethane metal catalyst is not particularly limited, but is preferably 0.01% to 2% by mass, more preferably 0.02% to 1% by mass, even more preferably 0.04% to 0.6% by mass, and particularly preferably 0.04% to 0.4% by mass, based on 100% by mass of the raw material composition. In this raw material composition, the content of the flame retardant is not particularly limited, but is preferably 2% by mass or more, more preferably 4% by mass or more and 80% by mass or less, even more preferably 6% by mass or more and 60% by mass or less, and particularly preferably 8% by mass or more and 40% by mass or less, based on 100% by mass of the raw material composition.

[0069] Furthermore, while it is preferable that the raw material composition does not contain red phosphorus, if it does contain red phosphorus, it is preferable that the amount is greater than 0% by mass and less than 1.5% by mass relative to 100% by mass of the raw material composition. In this raw material composition, the content of the foaming agent is not particularly limited, but is preferably 2% by mass or more and 60% by mass or less, more preferably 4% by mass or more and 50% by mass or less, even more preferably 6% by mass or more and 40% by mass or less, and particularly preferably 8% by mass or more and 30% by mass or less, based on 100% by mass of the raw material composition.

[0070] <Raw Material Kit> The raw material kit according to this embodiment is a raw material kit for a urethane resin composition. The raw material kit comprises a first raw material containing cardanol, a fatty acid triglyceride, a tertiary amine catalyst containing an ether compound and / or an imidazole compound having two or more morpholine rings, and a quaternary ammonium salt catalyst, but not a carboxylic acid-based metal salt catalyst as a trimerizing catalyst, and a second raw material containing a polyisocyanate compound. Of these raw material kits, the first raw material corresponds to the raw material composition described above. Furthermore, the content of each component in the raw material kit can be applied by replacing "per 100% by mass of the urethane resin composition" with "per 100% of the total mass of the first and second raw materials" when referring to the content of the urethane resin composition as described above.

[0071] <Urethane foam> The urethane resin foam according to this embodiment includes a polymer formed by bonding cardanol and a polyisocyanate compound, and a polymer formed by bonding a fatty acid triglyceride and a polyisocyanate compound.

[0072] <Method for producing urethane resin composition> There are no particular limitations on the method for producing a urethane resin composition, but for example, a method of mixing the components of the urethane resin composition, a method of suspending the urethane resin composition in an organic solvent or heating and melting it to make it into a paint-like substance, or a method of dispersing it in a solvent to prepare a slurry can be used. Furthermore, if the reaction-curable resin component contained in the urethane resin composition contains a component that is solid at room temperature, a method of melting the urethane resin composition under heating can be used as a method for producing the urethane resin composition.

[0073] More specifically, a urethane resin composition can be prepared by kneading each component using a single-screw extruder, twin-screw extruder, Banbury mixer, kneader mixer, kneading roll, lychee machine, planetary agitator, etc. Alternatively, a urethane resin composition can be prepared by kneading the main component and curing agent of the urethane resin separately with fillers, etc., and then kneading these together immediately before injection using a static mixer, dynamic mixer, etc. Furthermore, a urethane resin composition can also be prepared by similarly kneading each component except the catalyst with the catalyst immediately before injection. The manufacturing methods for raw material compositions and raw material kits are also the same. Furthermore, they may be provided in the following embodiments.

[0074] (1) A urethane resin composition comprising a polyisocyanate compound, cardanol, a fatty acid triglyceride, a tertiary amine catalyst containing an ether compound and / or an imidazole compound having two or more morpholine rings, and a quaternary ammonium salt catalyst, but not containing a carboxylic acid-based metal salt catalyst.

[0075] (2) A urethane resin composition according to (1) above, wherein the ether compound is bis(2-morpholinoethyl) ether.

[0076] (3) A urethane resin composition according to (1) or (2) above, wherein the ether compound and / or the imidazole compound is contained in an amount of 0.01% by mass or more and 10% by mass or less based on 100% by mass of the urethane resin composition.

[0077] (4) In the urethane resin composition described in any one of (1) to (3) above, the foam piece formed from the urethane resin composition has an apparent total density of 60 kg / m³ as measured in accordance with JIS K 7222:2005. 3 The following is a urethane resin composition.

[0078] (5) In the urethane resin composition described in any one of (1) to (4) above, the foam piece formed from the urethane resin composition is a urethane resin composition having a compressive strength of 245 kPa or more as measured in accordance with JIS A 9526:2022.

[0079] (6) In the urethane resin composition described in any one of (1) to (5) above, the foam piece formed from the urethane resin composition is a urethane resin composition having an oxygen index of 26 or higher as measured in accordance with JIS K 7201-2:2021.

[0080] (7) A raw material composition for a urethane resin composition to be used in mixture with a polyisocyanate compound, comprising a tertiary amine catalyst containing cardanol, a fatty acid triglyceride, an ether compound and / or an imidazole compound having two or more morpholine rings, and a quaternary ammonium salt catalyst, but not containing a carboxylic acid-based metal salt catalyst.

[0081] (8) A raw material kit for a urethane resin composition to be used in combination with a polyisocyanate compound, comprising: a first raw material comprising cardanol, a fatty acid triglyceride, a tertiary amine catalyst containing an ether compound and / or an imidazole compound having two or more morpholine rings, and a quaternary ammonium salt catalyst, but not containing a carboxylic acid-based metal salt catalyst; and a second raw material comprising the polyisocyanate compound. Of course, this is not always the case.

[0082] Finally, various embodiments of the present invention have been described, but these are presented as examples and are not intended to limit the scope of the invention. These novel embodiments can be implemented in a variety of other forms, and various omissions, substitutions, and modifications can be made without departing from the spirit of the invention. These embodiments and their variations are included in the scope and spirit of the invention, as well as in the claims and their equivalents. [Examples]

[0083] The following examples will provide a more detailed description of the urethane resin composition, its raw material composition, and raw material kit according to this embodiment, but the present invention is not limited in any way to the following examples.

[0084] 1. Preparation of raw materials for urethane resin composition (A) Cashew nut shell liquid: NX2024 (87% cardanol by mass, manufactured by Cardolite Corporation) (B) Triglycerides: Industrial Grade No. 1 Castor Oil (manufactured by Toyokuni Oil Co., Ltd.) (C) Diamine polyol: NL-270 (manufactured by Sanyo Chemical Industries, Ltd.) Ethylene oxide and propylene oxide adduct of N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine (D) Aromatic polyester polyol: RFK505 (manufactured by Kawasaki Chemical Industries, Ltd.) Terephthalic acid, isophthalic acid, phthalic acid and polyester such as ethylene glycol, diethylene glycol, triethylene glycol, etc. (E) Bisphenol-based polyol: BPE-60 (manufactured by Sanyo Chemical Industries, Ltd.) Bisphenol A ethylene oxide adduct

[0085] (F) Foam stabilizer: SH-193 (manufactured by Dow Toray Industries, Inc.) Block copolymer of dimethylsiloxane and polyether

[0086] (G) Tertiary amine catalyst 1: PC-206 (manufactured by Evonik Japan Co., Ltd.) Aliphatic tertiary amine (H) Tertiary amine catalyst 2: KL-390 (manufactured by Kao Corporation) 1,2-dimethylimidazole dipropylene glycol mixture (I) Tertiary amine catalyst 3: DMDEE (Momentive) bis(2-morpholinoethyl) ether (J) Tertiary amine catalyst 4: KL-21 (manufactured by Kao Corporation) N-methylmorpholine (K) Tertiary amine catalyst 5: KL-12 (manufactured by Kao Corporation) bis(2-dimethylaminoethyl) ether

[0087] (L) Quaternary ammonium salt catalyst: KL-410 (manufactured by Kao Corporation) (M) Carboxylic acid-based metal salt catalyst: K-15 (manufactured by Evonik Japan Co., Ltd.) Potassium octoate (N) Metal salt catalyst: Pb-20 (manufactured by Nippon Chemical Industrial Co., Ltd.) Lead 2-ethylhexanoate (O) Bismuth-based metal salt catalyst: BI-28 (manufactured by Nitto Chemical Co., Ltd.) Bismastris (2-ethylhexanoate)

[0088] (P) Phosphate ester-based flame retardant: TCPP (manufactured by ANHUI RUN YUE TECHNOLOGY CO., LTD.) Tris(β-chloropropyl) phosphate (Q) Foaming agent: LBA (manufactured by Honeywell Japan Co., Ltd.) (E)-1-chloro-3,3,3-trifluoropropene (R) Polyisocyanate: Millionate MR-200 (manufactured by Tosoh Corporation) Polymeric MDI (Monomeric MDI: 40% by mass)

[0089] 2. Preparation of spray foam (urethane resin foam by spray foaming method) The components (A) to (P) described above were weighed into a spray tank and mixed and stirred at room temperature using a hand mixer. Next, the spray tank was sealed and pressurized to an internal pressure of 0.1 MPa. Then, component (Q) was introduced into the spray tank by line mixing and circulated and stirred for 2 hours to obtain the first raw material. This first raw material and the second raw material consisting of polyisocyanate were sprayed onto a physical properties acrylic plywood using a reactor A-25 (manufactured by Graco Corporation) with a D gun (manufactured by Graco Corporation) attached to the end of a hose (hose length 30 m), while heating the hose to 40°C, to produce a spray foam (bottom spray + 3 layers of approximately 20 mm thickness).

[0090] 3. Evaluation 3-1. Isocyanate Index The isocyanate index is the equivalent ratio of isocyanate groups in a polyisocyanate compound to hydroxyl groups in a polyol compound, and is expressed as a percentage in Table 1 below.

[0091] 3-2. Apparent overall density The apparent overall density of the obtained spray foam was measured in accordance with JIS K 7222:2005. 3-3. Compression Thickness The compressive strength of the obtained spray foam was measured in accordance with JIS A 9526:2022.

[0092] 3-4. Oxygen Index A 10 x 10 x 150 mm test specimen (corresponding to specimen type II in Table 2 of JIS K 7201-2:2021) was cut from the obtained spray foam. The oxygen index of this test specimen was measured in accordance with JIS K 7201-2:2021. The oxygen index was measured using the following criteria: top surface ignition, a burning time of 180 seconds after ignition, and a measurement of 50 mm below the top of the test specimen (corresponding to Method A of oxygen index measurement criteria in Table 3 of JIS K 7201-2:2021).

[0093] [Table 1]

[0094] [Table 2] Note that the amounts of each component in Table 1 represent the percentage (mass%) of 100% by mass of the urethane resin composition (total mass of the first and second raw materials).

[0095] As shown in Table 1, using tertiary amine catalyst 2, 1,2-dimethylimidazole (imidazole compound), or tertiary amine catalyst 3, bis(2-morpholinoethyl) ether (DMDEE: an ether compound having two or more morpholine rings), resulted in improved flame retardancy and compressive strength of the spray foam without using potassium octoate (carboxylic acid-based metal salt catalyst) (refer to each example in comparison with Comparative Examples 1 and 5). Furthermore, the spray foams of each example also prevented an increase in the apparent overall density. In particular, the same effect as described above was obtained even when the amount of ether compound and / or imidazole compound used was appropriately adjusted.

[0096] Furthermore, simply increasing the amount of tertiary amine catalyst did not yield the same effect as described above (see Comparative Example 2). Furthermore, using a compound having one morpholine ring as a tertiary amine catalyst did not yield the same effect as described above (see Comparative Example 3), nor did using an ether compound without a morpholine ring yield the same effect as described above (see Comparative Example 4). Furthermore, the same effects as described above can be obtained by using an imidazole compound instead of or in addition to an ether compound as a tertiary amine catalyst, using bis(2,2-dimorpholinoethyl) ether as the ether compound, using reskerella oil as the triglyceride, or using other quaternary ammonium salt catalysts.

Claims

1. A urethane resin composition, Polyisocyanate compounds and Cardanol and, Fatty acid triglycerides, A tertiary amine catalyst containing an ether compound and / or an imidazole compound having two or more morpholine rings, It includes a quaternary ammonium salt catalyst, It does not contain a carboxylic acid-based metal salt catalyst as a trimerizing catalyst. The foam pieces formed from the aforementioned urethane resin composition have an apparent total density of 60 kg / m³, as measured in accordance with JIS K 7222:2005. ３ The following: The foam pieces formed from the urethane resin composition have a compressive strength of 245 kPa or more, as measured in accordance with JIS A 9526:2022. Urethane resin composition.

2. In the urethane resin composition according to claim 1, The aforementioned ether compound is bis(2-morpholinoethyl) ether. Urethane resin composition.

3. In the urethane resin composition according to claim 1, The ether compound and / or the imidazole compound are contained in an amount of 0.01% to 10% by mass relative to 100% by mass of the urethane resin composition. Urethane resin composition.

4. In the urethane resin composition according to claim 1, The foam pieces formed from the urethane resin composition have an oxygen index of 26 or higher, as measured in accordance with JIS K 7201-2:2021. Urethane resin composition.

5. A raw material composition for a urethane resin composition used in combination with a polyisocyanate compound, Cardanol and, Fatty acid triglycerides, A tertiary amine catalyst containing an ether compound and / or an imidazole compound having two or more morpholine rings, It includes a quaternary ammonium salt catalyst, It does not contain a carboxylic acid-based metal salt catalyst as a trimerizing catalyst. The foam pieces formed from the aforementioned urethane resin composition have an apparent total density of 60 kg / m³, as measured in accordance with JIS K 7222:2005. ３ The following: The foam pieces formed from the urethane resin composition have a compressive strength of 245 kPa or more, as measured in accordance with JIS A 9526:2022. A raw material composition for urethane resin compositions.

6. A raw material kit for a urethane resin composition, A first raw material comprising cardanol, a fatty acid triglyceride, a tertiary amine catalyst containing an ether compound and / or an imidazole compound having two or more morpholine rings, and a quaternary ammonium salt catalyst, but without a carboxylic acid-based metal salt catalyst as a trimerizing catalyst, A second raw material containing a polyisocyanate compound, The foam pieces formed from the urethane resin composition, which is a mixture of the first and second raw materials, have an apparent total density of 60 kg / m³ as measured in accordance with JIS K 7222:2005. ３ The following: The foam pieces formed from the urethane resin composition have a compressive strength of 245 kPa or more, as measured in accordance with JIS A 9526:2022. A raw material kit for urethane resin compositions.

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