Amine odor reduction of polyurethane foam

Abstract

To provide a catalyst composition capable of sufficiently removing amine odor of a polyurethane foam even under high-temperature environments.SOLUTION: A catalyst composition for producing a polyurethane foam includes: an amine compound (A) expressed by the following general formula (1); and an essential oil constituent (B) having an isoprene skeleton. [R1-R5 each independently represent H, an alkyl group, a hydroxyl group, a hydroxymethyl group, or an alkoxy group].SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to reducing the amine odor of polyurethane foams. [Background technology]

[0002] In recent years, higher standards have been set for the physical properties of polyurethane products, and in polyurethane foams for automobiles and bedding and furniture, there is a demand for reducing the unpleasant odors.

[0003] Amine catalysts used in the production of polyurethane foams have a unique unpleasant odor, such as a fishy or burnt smell, and are one of the main causes of the amine odor of polyurethane foams.

[0004] As a method for reducing the odor of amines, for example, Patent Document 1 proposes an odor masking agent using an aliphatic aldehyde compound having 6 to 15 carbon atoms and / or an ester-based fragrance composition, and Patent Document 2 proposes an odor masking agent using a composition containing an ether, a terpene and / or a terpenoid, and an oxime.

[0005] Furthermore, as a method for reducing the amine odor of polyurethane foam, for example, Patent Document 3 proposes a method for reducing the odor of polyurethane foam by using a reactive amine catalyst and at least one glycol selected from the group consisting of ethylene glycol and polyethylene glycol. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 8-302383 [Patent Document 2] JP 2018-115324 A [Patent Document 3] JP 2017-105999 A Summary of the Invention [Problem to be solved by the invention]

[0007] Both Patent Documents 1 and 2 are characterized by using a fragrance composition to mask the odor of an amine catalyst, but there are problems in that a combination of multiple masking agents must be used, and that the masking effect weakens after molding of a polyurethane foam, making it impossible to sufficiently reduce the amine odor of the foam.

[0008] Furthermore, in Patent Document 3, there was a problem that even if a reactive amine catalyst was used, the amine odor of the foam could not be sufficiently removed in a high temperature environment due to the influence of impurities remaining in the catalyst. [Means for solving the problem]

[0009] As a result of intensive research conducted by the present inventors to solve the above problems, they discovered that an amine catalyst composition comprising a specific essential oil component added to a specific reactive amine catalyst shown below can reduce the amine odor of polyurethane foams foamed using the amine catalyst composition, and thus completed the present invention.

[0010] That is, the present disclosure relates to a catalyst composition for producing a polyurethane foam, as described below, and a method for producing a polyurethane foam using the catalyst composition.

[0011] [1] The following general formula (1)

[0012] [ka]

[0013] [In the above general formula (1), R 1 , R 2 , R 3 , R 4 and R 5each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a hydroxymethyl group, or an alkoxy group having 1 to 4 carbon atoms. a and b each independently represent 0 or 1, and satisfy the relationship a+b=1. A catalyst composition for producing polyurethane foam, comprising an amine compound (A) represented by the formula: and an essential oil component (B).

[0014] [2] The catalyst composition according to the above [1], wherein the amine compound (A) is 1,4-diazabicyclo[2.2.2]octane-2-methanol.

[0015] [3] The catalyst composition according to [1] or [2] above, wherein the essential oil component (B) comprises at least one selected from the group consisting of citronellal, isobornyl acetate, hydrocitronellal, citronellol, 2-phenylethyl alcohol, benzyl acetate, cis-3-hexenol, geraniol, gamma decanolactone, citronellyl acetate, linalool, terpineol, β-ionone, thymol, rose oxide, bergamot oil, cedarwood oil, and eucalyptus oil.

[0016] [4] The catalyst composition according to [1] or [2] above, wherein the essential oil component (B) comprises at least one selected from the group consisting of citronellal, isovinyl acetate, citronellol, cis-3-hexenol, citronellyl acetate, linalool, β-ionone, thymol, rose oxide, bergamot oil, cedarwood oil, and eucalyptus oil.

[0017] [5] The catalyst composition according to any one of the above [1] to [4], wherein the weight ratio of the amine compound (A) to the essential oil component (B) is 0.005 to 0.5 parts by weight of the essential oil component (B) per 100 parts by weight of the amine compound (A).

[0018] [6] A method for producing a polyurethane foam, comprising reacting a polyol with a polyisocyanate in the presence of the catalyst composition according to any one of [1] to [5] above. Effect of the Invention

[0019] The catalyst composition of the present invention can reduce the amine odor generated from polyurethane foam as compared to the catalyst compositions of the prior art. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] In the present disclosure, the catalyst composition contains an amine compound (A) represented by the above general formula (1) and an essential oil component (B).

[0021] In the above general formula (1), R 1 , R 2 , R 3 , R 4 and R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a hydroxymethyl group, or an alkoxy group having 1 to 4 carbon atoms.

[0022] The alkyl group having 1 to 4 carbon atoms is not particularly limited, but examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

[0023] The alkoxy group having 1 to 4 carbon atoms is not particularly limited, but examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group.

[0024] Specific examples of the amine compound (A) represented by the above general formula (1) include the following compounds (exemplary compounds 1 to 28), but the present invention is not limited thereto.

[0025] [ka]

[0026] In the present disclosure, the amine compound (A) is, in terms of being able to further reduce the amine odor, 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom, a methyl group, an ethyl group, or a hydroxymethyl group (provided that R 1 , R 2 , R 3 , R 4 and R 5 In the above general formula (1), R 1 , R 2 , R 3 , R 4 and R 5 are all methyl groups, or in the above general formula (1), R 1 , R 2 , R 3 , R 4 and R 5 is preferably a hydrogen atom, and more preferably, in the above general formula (1), R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom or a methyl group, and more preferably, in the above general formula (1), R 1 , R 2 , R 3 , R 4 and R 5 are all hydrogen atoms (1,4-diazabicyclo[2.2.2]octane-2-methanol).

[0027] The method for producing the amine compound (A) represented by the above general formula (1) is not particularly limited, but it can be produced, for example, by a cyclization reaction of dihydroxyalkylpiperazines (see, for example, JP-A-2010-37325).

[0028] The method for producing the amine compound (A) represented by the general formula (1) is not particularly limited, but it can be produced, for example, by the method described in Khimiya Geterotsiklicheskikh Soedinenil, 10, 1404 (1980), WO 95 / 18104 pamphlet, etc. It can also be produced by intramolecular cyclization of ethylene oxide adducts of hydroxyalkylpiperazines derived by the method described in Journal of Medicinal Chemistry (1993), 36 (15), 2075-2083, or JP 2010-120887 A. Furthermore, it can be produced, for example, by the method described in JP 2010-37325 A, that is, by cyclization reaction of dihydroxyalkylpiperazines.

[0029] In the present disclosure, the content of the amine compound (A) relative to the entire catalyst composition is not particularly limited, but is, for example, preferably in the range of 1 to 80% by weight, and more preferably in the range of 3 to 50% by weight.

[0030] In the present disclosure, the essential oil component (B) is not particularly limited, but is preferably an essential oil component selected from, for example, terpenes, terpenoids, aromatic compounds, etc. having an isoprene skeleton.

[0031] In addition, the essential oil component (B) preferably contains at least one selected from the group consisting of citronellal, isobornyl acetate, hydrocitronellal, citronellol, 2-phenylethyl alcohol, benzyl acetate, cis-3-hexenol, geraniol, gamma decanolactone, citronellyl acetate, linalool, terpineol, β-ionone, thymol, rose oxide, bergamot oil, cedarwood oil, and eucalyptus oil, and more preferably contains at least one selected from the group consisting of citronellal, isobornyl acetate, citronellol, cis-3-hexenol, citronellyl acetate, linalool, β-ionone, thymol, rose oxide, bergamot oil, cedarwood oil, and eucalyptus oil.

[0032] In the present disclosure, the catalyst composition may contain the amine compound (A) and the essential oil component (B) in any ratio. The content of the essential oil component (B) relative to the amine compound (A) is not particularly limited, but in terms of further reducing the amine odor, the content of the essential oil component (B) is preferably in the range of 0.005 to 0.5% by weight, more preferably in the range of 0.01 to 0.1% by weight, relative to 100 parts by weight of the amine compound (A).

[0033] Polyurethane foam can be produced by reacting polyols and polyisocyanates in the presence of the above catalyst composition. The method for producing polyurethane foam can also be carried out in the presence of raw materials such as additional catalysts, blowing agents (including water), surfactants, flame retardants, crosslinking agents, chain extenders, colorants, antioxidants, linking agents, and other conventionally known additives, in addition to the catalyst composition for producing polyurethane foam, polyols, and polyisocyanates, as necessary.

[0034] The catalyst composition for producing polyurethane foam is used to promote various reactions such as the urethane reaction (resinization reaction) between polyols and polyisocyanates, and the urea reaction (foaming reaction) between polyisocyanates and water.

[0035] Here, the mixture of the catalyst composition for producing polyurethane foam and the polyols can be used as a polyol raw material blend liquid. The polyol raw material blend liquid may contain the additional catalyst, blowing agent (including water), surfactant, flame retardant, crosslinking agent, chain extender, colorant, antioxidant, linking agent, and other conventionally known additives.

[0036] The polyols are not particularly limited, and examples thereof include conventionally known polyether polyols, polyester polyols, polymer polyols, flame-retardant polyols, etc. These polyols can be used alone or in combination as appropriate mixtures.

[0037] The polyether polyol is not particularly limited, but examples thereof include those produced by an addition reaction of a compound having at least two active hydrogen groups (specific examples include polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and pentaerythritol, amines such as ethylenediamine, and alkanolamines such as ethanolamine and diethanolamine) as a starting material with an alkylene oxide (specific examples include ethylene oxide and propylene oxide) [see, for example, the method described in Gunter Oertel, "Polyurethane Handbook" (1985) Hanser Publishers (Germany), pp. 42-53].

[0038] The polyester polyol is not particularly limited, but examples thereof include those obtained by reacting a dibasic acid with a glycol, waste materials from the production of nylon, trimethylolpropane, pentaerythritol waste, waste materials from phthalic acid-based polyesters, and polyester polyols derived from the treatment of waste materials (see, for example, the description in "Polyurethane Resin Handbook" by Keiji Iwata (1987), published by the Nikkan Kogyo Shimbun, p. 117).

[0039] The above-mentioned polymer polyol is not particularly limited, but examples thereof include polymer polyols obtained by reacting the above-mentioned polyether polyol with an ethylenically unsaturated monomer (e.g., butadiene, acrylonitrile, styrene, etc.) in the presence of a radical polymerization catalyst.

[0040] The flame-retardant polyol is not particularly limited, but examples thereof include phosphorus-containing polyols obtained by adding alkylene oxide to a phosphoric acid compound, halogen-containing polyols obtained by ring-opening polymerization of epichlorohydrin or trichlorobutylene oxide, and phenol polyols.

[0041] The polyols are not particularly limited, but preferably have an average hydroxyl value in the range of 20 to 1000 mgKOH / g, more preferably have an average hydroxyl value in the range of 20 to 100 mgKOH / g when producing a flexible polyurethane foam resin or a semi-rigid polyurethane foam resin, and more preferably have an average hydroxyl value in the range of 100 to 800 mgKOH / g when producing a rigid polyurethane foam resin.

[0042] In the present disclosure, the polyisocyanates may be conventionally known ones and are not particularly limited, but examples thereof include aromatic polyisocyanates such as tolylene diisocyanate (hereinafter sometimes referred to as "TDI"), diphenylmethane diisocyanate (hereinafter sometimes referred to as "MDI"), naphthylene diisocyanate, xylylene diisocyanate, etc., aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as dicyclohexyl diisocyanate, isophorone diisocyanate, etc., and mixtures thereof. Among these, TDI and its derivatives, or MDI and its derivatives are preferred, and these may be used alone or in combination.

[0043] Examples of the TDI and its derivatives include a mixture of 2,4-TDI and 2,6-TDI, a terminal isocyanate prepolymer derivative of TDI, etc. Examples of MDI and its derivatives include a mixture of MDI and its polymer polyphenylpolymethylene diisocyanate, a diphenylmethane diisocyanate derivative having a terminal isocyanate group, etc.

[0044] Among these polyisocyanates, TDI and its derivatives, MDI and its derivatives, or both of them are preferably used for flexible polyurethane foam resins and semi-rigid polyurethane foam resin products, while a mixture of MDI and its polymer polyphenylpolymethylene diisocyanate is preferably used for rigid polyurethane foam resins.

[0045] The mixing ratio of the polyisocyanates and polyols is not particularly limited, but is generally preferably in the range of 40 to 400, more preferably in the range of 50 to 200, and further preferably in the range of 60 to 120, when expressed in terms of isocyanate index ([isocyanate group] / [active hydrogen group capable of reacting with isocyanate group]×100).

[0046] In the above-mentioned method for producing polyurethane foam, the catalyst may be the catalyst composition for producing polyurethane foam of the present invention alone, or may be used in combination with other foaming catalysts, organometallic catalysts, carboxylate metal salt catalysts, or quaternary ammonium salt catalysts as additional catalysts, if necessary. The additional catalysts may be incorporated in the catalyst composition of the present invention beforehand, or may be prepared separately from the catalyst composition of the present invention and then mixed with polyols together with the catalyst composition of the present invention for use.

[0047] The foaming catalyst may be a catalyst represented by the following formula (4):

[0048] [ka]

[0049] [In the above general formula (4), R 6 , R 7 , R 10 , and R 11 R each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have at least one group selected from the group consisting of a hydroxyl group, an amino group, a methylamino group, and a dimethylamino group. 8 and R 9 each independently represents an alkyl group having 1 to 8 carbon atoms, n is an integer of 0 to 2, and m is an integer of 0 to 2.] Examples of the amine compounds include those represented by the following formula:

[0050] In the above general formula (4), R 6 , R 7 , R 10, and R 11 each independently represents a hydrogen atom, or an alkyl group having 1 to 8 carbon atoms which may have at least one group selected from the group consisting of a hydroxy group, an amino group, a methylamino group, and a dimethylamino group.

[0051] R 6 , R 7 , R 10 , and R 11 are not particularly limited, and examples of the groups that can be independently selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, a hydroxymethyl group, a hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, a 4-hydroxybutyl group, an aminomethyl group, an aminoethyl group, a 1-aminopropyl group, a 2-aminopropyl group, a 3-aminopropyl group, a 1-aminobutyl group, a 2-aminobutyl group, a 3-aminobutyl group, a 4-aminobutyl group, an N-monomethylaminomethyl group, an N-monomethylaminoethyl group, an N-monomethylamino-1-propyl group, an N-monomethylaminoethyl group, an N-monomethylamino-2-propyl ... and preferably each independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, a hydroxyethyl group, a 2-hydroxypropyl group, an aminomethyl group, an aminoethyl group, a 3-aminopropyl group, an N-monomethylaminomethyl group, an N-monomethylaminoethyl group, an N-monomethylamino-3-propyl group, an N,N-dimethylaminomethyl group, an N,N-dimethylaminoethyl group, an N,N-dimethylamino-3-propyl group, and the like.

[0052] In the above general formula (4), R 8and R 9 each independently represents an alkyl group having 1 to 8 carbon atoms.

[0053] The alkyl group having 1 to 8 carbon atoms is not particularly limited, but examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group.

[0054] R 8 and R 9 With regard to the curing properties in the production of polyurethane foam, it is preferable that each of them is independently a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or an n-butyl group, and it is more preferable that each of them is independently an ethyl group or an n-propyl group.

[0055] In the above general formula (4), n is an integer of 0 to 2, and m is an integer of 0 to 2.

[0056] The above m and n are preferably each independently 0 or 1 in terms of curing properties in the production of polyurethane foam.

[0057] The foaming catalyst is not particularly limited, but examples thereof include triethanolamine, bis(2-dimethylaminoethyl)ether, N,N,N',N",N"-pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, N,N-dimethylaminoethoxyethanol, N,N,N'-trimethylaminoethylethanolamine, N,N-dimethylaminoethyl-N'-methylaminoethyl-N"-methylaminoisopropanol, N,N-dimethyl-N',N'-bis(2-hydroxypropyl)-1,3-propanediamine, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, bis(3-dimethylaminopropyl)ether, and the like. amine, 2-[[3-(dimethylamino)propyl]methylamino]ethanol, 1-[bis[3-(dimethylamino)propyl]amino]-2-propanol, N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl)ether, N-(3-aminopropyl)-N,N',N'-trimethyl-2,2'-oxybis(ethylamine), 2-[2-(dimethylamino)ethoxy]ethanol, 2-[[2-(dimethylamino)ethyl]methylamino]ethanol, N,N,N',N''-tetramethyl-N''-(2-hydroxypropyl)-diethylenetriamine, N,N-dimethylaminoethanol, or 6-dimethylamino-1-hexanol.

[0058] The organometallic catalyst may be any of those known in the art and is not particularly limited. Examples of the organometallic catalyst include stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, lead octoate, lead naphthenate, nickel naphthenate, and cobalt naphthenate.

[0059] The above-mentioned carboxylate metal salt catalyst may be a conventionally known one, and is not particularly limited, but examples thereof include alkali metal salts and alkaline earth metal salts of carboxylic acids. Here, examples of the carboxylic acid include, but are not particularly limited, aliphatic mono- or di-carboxylic acids such as acetic acid, propionic acid, 2-ethylhexanoic acid, and adipic acid, and aromatic mono- or di-carboxylic acids such as benzoic acid and phthalic acid. In addition, examples of the metal that should form the carboxylate include alkali metals such as lithium, sodium, and potassium, and alkaline earth metals such as calcium and magnesium.

[0060] The above-mentioned quaternary ammonium salt catalyst may be a conventionally known one, and is not particularly limited. Examples of the quaternary ammonium salt catalyst include tetraalkylammonium halides such as tetramethylammonium chloride, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide salts, and tetraalkylammonium organic acid salts such as tetramethylammonium 2-ethylhexanoate, 2-hydroxypropyltrimethylammonium formate, and 2-hydroxypropyltrimethylammonium 2-ethylhexanoate.

[0061] In the above-mentioned method for producing polyurethane foam, the above-mentioned catalyst composition can be used alone or in combination with the above-mentioned other additional catalysts. When these are mixed and used, a solvent such as dipropylene glycol, ethylene glycol, 1,4-butanediol, water, etc. can be used in combination if necessary. The amount of the solvent is not particularly limited, but is preferably 3 times or less by weight relative to the catalyst composition for producing polyurethane foam of the present invention. When the catalyst composition for producing polyurethane foam of the present invention is mixed with the above-mentioned other catalysts, the amount is preferably 3 times or less by weight relative to the total amount of the catalysts.

[0062] In the above-mentioned method for producing a polyurethane foam, the above-mentioned catalyst composition, a mixture of the above-mentioned catalyst composition and the above-mentioned other catalyst, or a mixture of the above-mentioned catalyst composition, the above-mentioned other catalyst, and the above-mentioned solvent may be added to a polyol for use, or each component may be added separately to a polyol for use, without any particular limitation.

[0063] In the above-mentioned method for producing polyurethane foam, when the above-mentioned catalyst composition is added to polyols for use, the amount of the catalyst composition is preferably in the range of 0.03 to 9 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the polyols used, although there are no particular limitations thereon.

[0064] In the above-mentioned method for producing a polyurethane foam, a crosslinking agent or a chain extender can be used if necessary. Examples of the crosslinking agent or the chain extender include low molecular weight polyhydric alcohols such as ethylene glycol, 1,4-butanediol, and glycerin, low molecular weight amine polyols such as diethanolamine and triethanolamine, and polyamines such as ethylenediamine, xylylenediamine, and methylenebisorthochloroaniline.

[0065] In the above-mentioned method for producing polyurethane foam, a flame retardant can be used if necessary. Examples of the flame retardant to be used include reactive flame retardants such as propoxylated phosphoric acid obtained by addition reaction of phosphoric acid with alkylene oxide, propoxylated dibutyl pyrophosphate, and other phosphorus-containing polyols, tertiary phosphate esters such as tricresyl phosphate, halogen-containing tertiary phosphate esters such as tris(2-chloroethyl)phosphate and tris(chloropropyl)phosphate, halogen-containing organic compounds such as dibromopropanol, dibromoneopentyl glycol, and tetrabromobisphenol A, and inorganic compounds such as antimony oxide, magnesium carbonate, calcium carbonate, and aluminum phosphate. The amount is not particularly limited and varies depending on the required flame retardancy, but is usually preferably 4 to 20 parts by weight per 100 parts by weight of polyols.

[0066] In the above-mentioned method for producing polyurethane foam, a blowing agent can be used if necessary. The blowing agent is not particularly limited, but examples thereof include fluorocarbon compounds such as 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,2-tetrafluoroethane (HFC-134a), and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), hydrofluoroethers such as HFE-254pc, low-boiling point hydrocarbons, water, liquefied carbon dioxide, dichloromethane, formic acid, and acetone. These may be used alone or in combination of two or more. As the low-boiling point hydrocarbon, a hydrocarbon having a boiling point of -30 to 70°C is usually used, and specific examples thereof include propane, butane, pentane, cyclopentane, hexane, and mixtures thereof.

[0067] The amount of the blowing agent used is not particularly limited since it is determined according to the desired density and foam properties. In general, however, the amount of the blowing agent used is such that the resulting foam density is usually 5 to 1000 kg / m3, preferably 10 to 500 kg / m3. 3 The range is selected to be:

[0068] In the above-mentioned method for producing polyurethane foam, if necessary, a surfactant can be used as a foam stabilizer. Examples of the surfactant used include conventionally known organic silicone surfactants, specifically, nonionic surfactants such as organic siloxane-polyoxyalkylene copolymers and silicone-grease copolymers, or mixtures thereof. The amount of these surfactants used is usually 0.1 to 10 parts by weight per 100 parts by weight of polyol.

[0069] In the above-mentioned method for producing a polyurethane foam, if necessary, a colorant, an antioxidant, a linking agent, and other conventionally known additives can be used. The types and amounts of these additives may be within the usual ranges for the additives used.

[0070] The above-mentioned polyurethane foam manufacturing method is usually carried out by rapidly mixing and stirring the mixture of the above-mentioned raw materials, and then injecting the mixture into a suitable container or mold for foaming. Mixing and stirring may be carried out using a general stirrer or a dedicated polyurethane foaming machine. As the polyurethane foaming machine, for example, a high-pressure, low-pressure, or spray-type device is used.

[0071] Examples of polyurethane foam products obtainable by the above-mentioned polyurethane foam production method include flexible polyurethane foam, semi-rigid polyurethane foam, rigid polyurethane foam, etc. Specifically, the polyurethane foam production method of the present invention is particularly suitable for the production of flexible polyurethane foam car seats used as automobile interior materials, semi-rigid polyurethane foam instrument panels and steering wheels, and heat insulating materials produced from rigid polyurethane foam.

[0072] In the present invention, the term "flexible polyurethane foam" generally refers to a reversibly deformable foam having an open cell structure and exhibiting high breathability [see Gunter Oertel, "Polyurethane Handbook" (1985 edition), Hanser Publishers (Germany), pp. 161-233, and Keiji Iwata, "Polyurethane Resin Handbook" (1987 first edition), Nikkan Kogyo Shimbun, pp. 150-221]. The physical properties of the flexible polyurethane foam are not particularly limited, but generally, the density is 10 to 100 kg / m 3 , compressive strength (ILD25%) is in the range of 200-8000kPa, and elongation is in the range of 80-500%.

[0073] Semi-rigid polyurethane foam refers to a reversibly deformable foam that has a higher density and compressive strength than flexible polyurethane foam, but has an open cell structure like flexible polyurethane foam and exhibits high breathability [see Gunter Oertel, "Polyurethane Handbook" (1985 edition) Hanser Publishers (Germany), pp. 223-233, and Keiji Iwata, "Polyurethane Resin Handbook" (1987 first edition) Nikkan Kogyo Shimbun, pp. 211-221]. In addition, the polyol and polyisocyanate raw materials used are the same as those of flexible polyurethane foam, so it is generally classified as a flexible polyurethane foam. The physical properties of semi-rigid polyurethane foam are not particularly limited, but generally, the density is in the range of 40 to 800 kg / m3, the compressive strength (ILD25%) is in the range of 10 to 200 kPa, and the elongation is in the range of 40 to 200%. In the present invention, flexible polyurethane foam may include semi-rigid polyurethane foam depending on the raw materials used and the physical property range of the foam.

[0074] Furthermore, rigid polyurethane foam refers to a foam that has a highly crosslinked closed cell structure and is not reversibly deformable [see Gunter Oertel, "Polyurethane Handbook" (1985 edition), Hanser Publishers (Germany), pp. 234-313, and Keiji Iwata, "Polyurethane Resin Handbook" (1987 first edition), Nikkan Kogyo Shimbun, pp. 224-283]. The physical properties of rigid polyurethane foam are not particularly limited, but generally, it has a density of 10 to 100 kg / m 3 , the compressive strength is in the range of 50 to 1000 kPa. EXAMPLES

[0075] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the text and tables, the parts by weight indicate the weight ratio when the weight of the polyol raw material blend liquid containing at least the catalyst composition for producing polyurethane foam and polyols is taken as 100 parts by weight.

[0076] <Method of manufacturing polyurethane foam> ·raw materials The following raw materials were used:

[0077] Polyol: Sannix FA-921 (OH value = 28 mg KOH / g, manufactured by Sanyo Chemical Industries, Ltd.), Interconnecting agent: QB-8000 (interconnecting agent, manufactured by Toho Chemical Industry Co., Ltd.), Foam stabilizer: NIAX SILICONE Y-10366 (silicone foam stabilizer, manufactured by Momentive Performance Materials Japan, LLC), Blowing agent: Water, Catalyst: the catalyst composition described in the examples, Polyisocyanate liquid: diphenylmethane diisocyanate (Coronate CEF-456, manufactured by Tosoh Corporation, NCO content = 28.7%).

[0078] -Polyurethane foam manufacturing method 100 parts by weight of polyol, 2.0 parts by weight of a connecting agent, 1.0 part by weight of a foam stabilizer, 3.3 parts by weight of a blowing agent (water), and 3.0 parts by weight (Examples 1 to 9, Comparative Example 1) or 1.8 parts by weight (Comparative Example 2) of a catalyst shown in Table 1 are weighed out and thoroughly stirred and mixed to prepare a raw material blend liquid.

[0079] 87.4 g of this polyol raw material blend liquid was weighed into a 300 ml polyethylene cup to prepare a polyol raw material blend liquid. After adjusting the temperature of the obtained polyol raw material blend liquid to 20°C, the polyisocyanate solution adjusted to 20°C was weighed out in an amount such that the isocyanate index [[isocyanate group] (molar ratio) / [OH group] (molar ratio) x 100)] was 100, and placed in the cup of the polyol raw material blend liquid, and quickly stirred with a stirrer at 6000 rpm for 5 seconds. The mixed and stirred mixture was quickly poured into a 2 L polyethylene cup, cured at room temperature for 10 minutes, and a polyurethane foam was obtained. The obtained polyurethane foam was aged at room temperature for more than one week, and then used for odor evaluation.

[0080] <Odor evaluation> Odor evaluation of amine catalysts 40 ml of the amine catalyst was measured and sealed in a 50 ml glass bottle. Seven monitors were asked to smell the contents of the glass bottle and evaluate the odor.

[0081] Foam odor A test piece (8 x 8 x 3 cm) was cut from the core of the foam, placed in a Tedlar bag, and the opening was sealed with a heat sealer. After the air was pushed out of the Tedlar bag, 4 L of nitrogen was filled into the bag using a metering pump. After filling, the bag was sealed and heated in an oven at 80°C for 1 hour. The Tedlar bag was removed from the oven, and seven monitors were asked to smell the inside of the Tedlar bag and evaluate the odor.

[0082] Odor evaluation In the odor evaluation, the amine odor was evaluated as follows. ◎: Very low amine odor (fishy, ​​burnt odor), ○: Low amine odor (fishy, ​​burnt odor), △: Amine odor (fishy, ​​burnt odor) is somewhat strong, ×: The amine odor (fishy, ​​burnt odor) was very strong.

[0083] Examples 1 to 9, Comparative Examples 1 to 2 A catalyst composition for producing urethane foam was prepared by weighing and mixing each component according to Table 1. Since 1,4-diazabicyclo[2.2.2]octane-2-methanol is a solid at room temperature, it was melted at 80°C before mixing each component.

[0084] [Table 1]

[0085] The odor evaluation of the amine catalyst was carried out using the catalyst compositions of Examples 1 to 18 and Comparative Examples 1 and 2. In addition, urethane foam was produced using these catalysts, and the odor evaluation of the foam was carried out. The odor evaluation results are shown in Table 2.

[0086] [Table 2]

[0087] As is clear from Examples 1 to 18 and Comparative Examples 1 and 2, the polyurethane foams using the catalyst compositions of Examples 1 to 18 have a better odor than the polyurethane foams using Comparative Examples 1 and 2. [Industrial Applicability]

[0088] The polyurethane foam produced by using the catalyst of the present invention is useful for producing automobile interior materials such as flexible polyurethane foam car seats, semi-rigid polyurethane foam instrument panels and steering wheels, and rigid polyurethane foam heat insulating materials.

Claims

1. The following general formula (1) 【Chemistry 1】 [In the above general formula (1), R １ , R ２ , R ３ , R ４ and R ５ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a hydroxymethyl group, or an alkoxy group having 1 to 4 carbon atoms. a and b each independently represent 0 or 1, and satisfy the relationship a+b=1. and an essential oil component (B) having an isoprene skeleton.

2. 2. The catalyst composition according to claim 1, wherein the amine compound (A) is 1,4-diazabicyclo[2.2.2]octane-2-methanol.

3. The catalyst composition according to claim 1, wherein the essential oil component (B) comprises at least one selected from the group consisting of citronellal, isobornyl acetate, hydrocitronellal, citronellol, 2-phenylethyl alcohol, benzyl acetate, cis-3-hexenol, geraniol, gamma decanolactone, citronellyl acetate, linalool, terpineol, β-ionone, thymol, rose oxide, bergamot oil, cedarwood oil, and eucalyptus oil.

4. The catalyst composition according to claim 1, wherein the essential oil component (B) comprises at least one selected from the group consisting of citronellal, isovinyl acetate, citronellol, cis-3-hexenol, citronellyl acetate, linalool, β-ionone, thymol, rose oxide, bergamot oil, cedarwood oil, and eucalyptus oil.

5. The catalyst composition according to claim 1, wherein the weight ratio of the amine compound (A) to the essential oil component (B) is 0.005 to 0.5 parts by weight per 100 parts by weight of the amine compound (A).

6. A method for producing a polyurethane foam, comprising reacting a polyol with a polyisocyanate in the presence of the catalyst composition according to any one of claims 1 to 5.

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