Polyurethane foam and vehicle indoor member

Abstract

The air permeability of the polyurethane foam is improved by reducing the cyclic siloxane or not using the cyclic siloxane. The polyurethane foam is obtained from a composition obtained by mixing a polyol, a polyisocyanate, and a tin catalyst. The composition contains a hydrocarbon having 5-50 carbon atoms (inclusive).

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a polyurethane foam and an interior member of a vehicle.

[0002] This application is based on Japanese Patent Application No. 2023-35388 filed on March 8, 2023, the content of which is incorporated herein by reference in its entirety for all purposes. BACKGROUND

[0003] Patent Literature 1 discloses a technique of adding a cyclic siloxane in order to improve the air permeability of a polyurethane foam.

[0004] PRIOR ART DOCUMENTS PATENT LITERATURE Patent Literature 1: Japanese Patent Application Publication No. 2011-037987 SUMMARY PROBLEMS TO BE SOLVED BY THE INVENTION However, cyclic siloxanes are subject to various restrictions. In addition, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and octamethylcyclotetrasiloxane are listed in the nineteenth SVHC (Substance of Very High Concern) list of the European REACH regulation.

[0005] The present disclosure is made in view of the above, and aims to improve the air permeability of a polyurethane foam without using a cyclic siloxane or by reducing the amount of a cyclic siloxane. The present disclosure can achieve this in the following manner.

[0006] MEANS FOR SOLVING THE PROBLEM [1] A polyurethane foam obtained from a composition in which a polyol, a polyisocyanate, and a tin catalyst are mixed, The composition contains a hydrocarbon having 5 or more and 50 or less carbon atoms.

[0007] EFFECT OF THE INVENTION According to the present disclosure, the air permeability of a polyurethane foam can be improved without using a cyclic siloxane or by reducing the amount of a cyclic siloxane. BRIEF DESCRIPTION OF DRAWINGS

[0008] Figure 1 is a drawing of an interior member of a vehicle having a polyurethane foam of an embodiment. DETAILED DESCRIPTION

[0009] Here, a preferred example of the present disclosure is shown.

[0010] [2] The polyurethane foam according to [1], wherein the polyol contains a polyester polyol.

[0011] [3] The polyurethane foam according to [1] or [2], the composition containing a flame retardant.

[0012] [4] The polyurethane foam according to any one of [1] to [3], the polyurethane foam having a ventilation amount of 25 L / min or more based on JIS K6400-7 A method:2012.

[0013] [5] The polyurethane foam according to any one of [1] to [4], the composition containing 5.0 parts by mass or less of the hydrocarbon with respect to 100 parts by mass of the polyol.

[0014] [6] An indoor member of a vehicle having the polyurethane foam according to any one of [1] to [5].

[0015] Hereinafter, the present disclosure will be described in detail. Furthermore, in the present specification, in a description using "~" for a numerical range, unless otherwise specified, the lower limit value and the upper limit value are included. For example, for a description of "10~20", the lower limit value of "10" and the upper limit value of "20" are included. That is, "10~20" means the same as "10 or more and 20 or less". In addition, in the present specification, the upper limit value and the lower limit value of each numerical range can be arbitrarily combined.

[0016] 1. Polyurethane foam The polyurethane foam can be obtained from a composition (hereinafter referred to as "polyurethane resin composition") in which a polyol, a polyisocyanate, and a tin catalyst are mixed. The composition contains a hydrocarbon having 5 or more and 50 or less carbon atoms.

[0017] (1) Polyol The polyol is not particularly limited. Various polyols can be used alone or in combination with two or more.

[0018] As the polyol, polyether polyol, polyester polyol, polyether ester polyol, polycarbonate diol, carbon-carbon bond main chain type polyol can be exemplified.

[0019] The polyether polyol can be exemplified by polyoxypropylene-polyoxyethylene polyol, polymer polyol, polyoxytetramethylene glycol, for example.

[0020] The polyester polyol can be exemplified by condensation type polyester polyol of aliphatic or aromatic type, polycaprolactone polyol, for example.

[0021] The carbon-carbon bond main chain type polyol can be exemplified by polybutadiene polyol, isoprene polyol, and the like polyolefin type polyol, acrylic polyol, for example.

[0022] (1.1) Polyether polyol As the polyether polyol, for example, a polyether polyol or polytetramethylene ether glycol obtained by adding one or two or more of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, epichlorohydrin, styrene oxide, etc. to one or two or more of the following initiators (compounds) is exemplified.

[0023] (1.1.1) Initiator (1.1.1.1) Polyol and alkylene oxide adduct of polyol Examples of polyol: [Di-functional alcohol] Ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, propylene glycol [Tri-functional alcohol] Glycerol, trimethylolpropane [Tetra-functional alcohol] Pentaerythritol [Hexa-functional alcohol] Sorbitol [Octa-functional alcohol] Sucrose (1.1.1.2) Alkylene oxide adduct of polyphenol Examples of alkylene oxide adduct of polyphenol: Alkylene oxide adduct of bisphenol A (1.1.1.3) Polyhydroxy compound Examples of polyhydroxy compound: Phosphoric acid, phenylphosphoric acid, polyphosphoric acid (e.g., trimetaphosphoric acid and tetrametaphosphoric acid), etc. (1.1.1.4) Phenol-aniline-formaldehyde ternary condensate (1.1.1.5) Aniline-formaldehyde condensate (1.1.1.6) Polyamine Examples of polyamine: Ethylenediamine, diethylenetriamine, triethylenetetramine, methylenebis-o-chloroaniline, 4,4- and 2,4'-diphenylmethanediamine, 2,4-toluenediamine, 2,6-toluenediamine, etc.

[0024] (1.1.1.7) Alkanolamine Examples of alkanolamine: Triethanolamine, diethanolamine, etc. (1.1.2) Polymer polyol The polymer polyol is a polyol obtained by graft polymerization of an ethylenically unsaturated compound such as acrylonitrile, styrene, alkyl methacrylate, etc. with the polyether polyol described above.

[0025] (1.2) Polyester polyol The polyester polyol is a polyester polyol obtained by condensation of one or two or more compounds having at least two hydroxyl groups with one or two or more compounds having at least two carboxyl groups, or a ring-opening polymer of a cyclic ester such as caprolactone, methylvalerolactone, etc.

[0026] Examples of the compound having at least two hydroxyl groups Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, tetramethylene glycol, neopentyl glycol, methyl pentanediol, butyl ethyl propylene glycol, hexamethylene glycol, decamethylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol.

[0027] Examples of the compound having at least two carboxyl groups Malonic acid, maleic acid, succinic acid, adipic acid, tartaric acid, pimelic acid, azelaic acid, sebacic acid, oxalic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimellitic acid.

[0028] (1.3) Polycarbonate polyols As the polycarbonate polyol, for example, a polyol obtained by an ester exchange reaction of a low-molecular polyol such as butanediol and hexanediol with a low-molecular carbonate such as propylene carbonate and diethyl carbonate can be mentioned.

[0029] (1.4) Polyolefin-based polyols As the polyolefin-based polyol, a polybutadiene polyol, a polyisoprene polyol, a hydrogenated polybutadiene polyol, a hydrogenated polyisoprene polyol can be exemplified.

[0030] (1.5) Plant-derived polyols As the polyol, in addition to the above polyols, a plant-derived polyol can also be included. As the plant-derived polyol, for example, a castor oil-based polyol, a soybean oil-based polyol, a palm oil-based polyol, a palm kernel oil-based polyol, a coconut oil-based polyol, a cashew oil-based polyol, an olive oil-based polyol, a cottonseed oil-based polyol, a safflower oil-based polyol, a sesame oil-based polyol, a sunflower seed oil-based polyol, a flaxseed oil-based polyol, and the like can be mentioned. In the plant-derived polyol, the number of functional groups of the hydroxyl groups in 1 molecule is usually 2 to 3.

[0031] As the castor oil-based polyol, a castor oil, a reaction product of castor oil and a polyol, an esterification reaction product of castor oil fatty acid and a polyol, and the like can be mentioned. As the polyol reacted with castor oil or castor oil fatty acid, a divalent polyol such as ethylene glycol, diethylene glycol, propylene glycol, or the like, or a polyol of three or more valences such as glycerol, trimethylolpropane, hexanetriol, sorbitol, and the like can be mentioned.

[0032] As the soybean oil-based polyol, polyols derived from soybean oil such as a reaction product of soybean oil and a polyol, an esterification reaction product of a soybean oil fatty acid and a polyol, and the like can be given. As the polyol which is reacted with soybean oil or a soybean oil fatty acid, the same substances as those described above in the case of castor oil can be used. The same applies to palm oil-based polyols, cashew oil-based polyols, and the like as the soybean oil-based polyols. Furthermore, the various polyols exemplified as the plant-derived polyols can be used alone or two or more kinds thereof can be used in combination.

[0033] (1.6) Suitable for Flame Lamination Method In the case where the polyurethane foam is used in the flame lamination method, it is preferable that the polyol contains a polyester polyol.

[0034] The flame lamination method is a method for adhering other members such as a surface material to the polyurethane foam. In the flame lamination method, a flame is brought into contact with the surface of the polyurethane foam and is caused to melt, and by causing the melted portion to exhibit adhesiveness, the other members are adhered to the polyurethane foam. In the case where the polyester polyol is contained, the polyurethane foam is easily fused by the flame, and sufficient adhesiveness can be obtained. Furthermore, the polyester polyol is not limited to use for the flame lamination method. For example, the polyester polyol can be used for the purpose of adjusting various physical properties of the polyurethane foam and the like.

[0035] The content of the polyester polyol is not particularly limited. In the case where the total polyol is 100 parts by mass, the content of the polyester polyol is preferably 0.5 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 15 parts by mass or less, and further preferably 3 parts by mass or more and 10 parts by mass or less.

[0036] The weight average molecular weight of the polyester polyol is not particularly limited. The number average molecular weight of the polyester polyol is preferably 200 or more and 4500 or less, more preferably 500 or more and 3500 or less, and further preferably 800 or more and 2500 or less. Furthermore, the weight average molecular weight of the polyester polyol can be measured by a gel permeation chromatography (GPC) method. In the case where the polyol is a commercially available product, the catalog value can be adopted as the weight average molecular weight.

[0037] The hydroxyl value of the polyester polyol is not particularly limited. The hydroxyl value of the polyester polyol is preferably 80 mgKOH / g or more and 350 mgKOH / g or less, more preferably 100 mgKOH / g or more and 300 mgKOH / g or less, and further preferably 150 mgKOH / g or more and 250 mgKOH / g or less.

[0038] The number of functional groups of the polyester polyol is not particularly limited. The number of functional groups of the polyester polyol is preferably 2.0 or more, more preferably 2.1 or more, and further preferably 2.2 or more. The number of functional groups of the polyester polyol is, for example, 4.0 or less.

[0039] From the viewpoint of ensuring the softness of the polyurethane foam, a polyester polyol is preferably used in combination with a polyether polyol. The polyether polyol used in combination with the polyester polyol is not particularly limited.

[0040] The content of the polyether polyol used in combination is, for example, preferably 80 parts by mass or more and 99.5 parts by mass or less, more preferably 85 parts by mass or more and 99 parts by mass or less, and further preferably 90 parts by mass or more and 97 parts by mass or less, based on 100 parts by mass of the polyol as a whole.

[0041] The weight average molecular weight, the hydroxyl value, and the number of functional groups of the polyether polyol used in combination are not particularly limited.

[0042] The weight average molecular weight of the polyether polyol described above is preferably 500 or more and 10,000 or less, more preferably 1,000 or more and 6,000 or less, and further preferably 1,500 or more and 4,000 or less. The weight average molecular weight of the polyether polyol can be measured by a gel permeation chromatography (GPC) method.

[0043] The hydroxyl value of the polyether polyol described above is preferably 40 mgKOH / g or more and 300 mgKOH / g or less, more preferably 45 mgKOH / g or more and 150 mgKOH / g or less, and further preferably 50 mgKOH / g or more and 80 mgKOH / g or less.

[0044] The number of functional groups of the polyether polyol described above is preferably 2.0 or more, more preferably 2.1 or more, and further preferably 2.2 or more. The number of functional groups of the polyester polyol is, for example, 4.0 or less.

[0045] (2) Catalyst The polyurethane resin composition contains a tin catalyst. The inventors of the present application have conducted intensive studies based on the knowledge that if the amount of the tin catalyst to be formulated is increased, the air permeability of the polyurethane foam decreases. As a result, it has been newly found that by formulating a hydrocarbon when the tin catalyst is formulated, the air permeability of the polyurethane foam can be improved, and thus the technology of the present disclosure has been developed.

[0046] As the tin catalyst, one or more selected from the group consisting of tin (II) octoate (tin (II) 2-ethylhexanoate, stannous octoate), tin (II) acetate, tin (II) octoate, stannous dioleate, tin (II) neodecanoate, tin (II) dilaurate, dibutyl tin oxide, dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin dichloride, dioctyl tin dilaurate, dibutyl tin maleate, and dioctyl tin diacetate can be used.

[0047] The amount of the tin catalyst to be incorporated in the polyurethane resin composition is not particularly limited. From the viewpoint of sufficiently promoting the polyurethane-forming reaction, the amount of the tin catalyst to be incorporated is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and further preferably 0.06 parts by mass or more, relative to 100 parts by mass of the polyol. On the other hand, from the viewpoint of maintaining various physical properties of the polyurethane foam and the viewpoint of manufacturing cost, the amount of the tin catalyst to be incorporated is preferably 1.0 parts by mass or less, more preferably 0.5 parts by mass or less, and further preferably 0.2 parts by mass or less. From these viewpoints, the amount of the tin catalyst to be incorporated is preferably 0.01 parts by mass or more and 1.0 parts by mass or less, more preferably 0.03 parts by mass or more and 0.5 parts by mass or less, and further preferably 0.06 parts by mass or more and 0.2 parts by mass or less, relative to 100 parts by mass of the polyol. Also, the amount of the tin catalyst to be incorporated can be 0.17 parts by mass or less, 0.15 parts by mass or less, or 0.13 parts by mass or less.

[0048] The tin catalyst can be used alone or in combination with other catalysts.

[0049] As the other catalyst, an amine catalyst, a quaternary ammonium salt catalyst can be used. Specific examples of these catalysts are shown.

[0050] As the amine catalyst, a tertiary amine catalyst, triethylene diamine, triethylamine, tripropylamine, triisopropanolamine, tributylamine, trioctylamine, hexadecyl dimethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N,N-dimethylethanolamine, N,N-dimethylamino hexanol, N,N-dimethylaminoethoxyethoxyethanol, N,N-dimethylaminoethoxyethanol, formate and other salts of triethylenediamine, oxyalkylene adducts of the amino group of primary and secondary amines, nitrogen heterocyclic compounds such as N-N-dialkylpiperazine, various N,N',N'-trialkylaminoalkylhexahydrotriazines, and N,N,N",N"-tetramethyldivinyltriamine having an amino group as a functional group can be used.

[0051] In addition, as the quaternary ammonium salt catalyst, tetraalkylammonium halides such as tetramethylammonium chloride, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, and tetraalkylammonium organic acid salts such as tetramethylammonium 2-ethylhexanoate, 2-hydroxypropyltrimethylammonium formate, and 2-hydroxypropyltrimethylammonium 2-ethylhexanoate can be used.

[0052] In the polyurethane resin composition, the allotment amount of the more than one catalyzer selected from the group consisting of amine catalyst and quaternary ammonium salt catalyst is not particularly limited.From the viewpoint of the formation reaction that fully promotes urethane, relative to polyvalent alcohol 100 mass parts, the allotment amount of these catalyzers is preferably more than the 0.01 mass part, more preferably more than the 0.05 mass part, more preferably more than the 0.09 mass part.On the other hand, from the viewpoint of the various physical properties keeping polyurethane foam and the viewpoint of manufacturing cost, be preferably below 3.0 mass parts, more preferably below 2.0 mass parts, more preferably below 1.0 mass parts.From these viewpoints, relative to polyvalent alcohol 100 mass parts, the allotment amount of the more than one catalyzer selected from the group consisting of amine catalyst and quaternary ammonium salt catalyst is preferably below 3.0 mass parts above 0.01 mass part, more preferably below 2.0 mass parts above 0.05 mass part, more preferably below 1.0 mass parts above 0.01 mass part.

[0053] The polyurethane resin composition may contain a metal catalyst other than the tin catalyst. The metal catalyst other than the tin catalyst is not particularly limited, and conventionally known metal catalysts can be used.

[0054] Examples of metal catalysts other than tin catalysts include metal salts of Pb (lead), Bi (bismuth), Ni (nickel), Co (cobalt), Fe (iron), Zr (zinc), Cu (copper), and Zn (zinc), and metal salts of organic acids. More specifically, the following metal catalysts can be used.

[0055] Pb catalyst: lead octoate, lead naphthenate, etc. Bi catalyst: bismuth octanoate, bismuth naphthenate, bismuth neodecanoate, bismuth rosinate, etc. Fe catalyst: iron acetylacetonate, etc. Zr catalyst: zirconium acetylacetonate, etc. Ni catalyst: nickel acetylacetonate, nickel octoate, nickel naphthenate, etc. Co catalyst: cobalt acetylacetonate, cobalt octoate, cobalt naphthenate, etc. (3) Flame retardant The polyurethane resin composition preferably contains a flame retardant. The flame retardant is not particularly limited. Examples of the flame retardant include one or more selected from the group consisting of phosphate flame retardants, phosphate-containing flame retardants, red phosphorus, bromine-containing flame retardants, boric acid-containing flame retardants, antimony-containing flame retardants, and metal hydroxides.

[0056] From the viewpoint of improving flame retardancy, the flame retardant is preferably a phosphoric acid ester-based flame retardant. The phosphoric acid ester-based flame retardant can be a halogen-based phosphoric acid ester-based flame retardant or a non-halogen-based phosphoric acid ester-based flame retardant. As the halogen-based phosphoric acid ester-based flame retardant, for example, one or more selected from the group consisting of a condensation product of tris (1-chloro-2-propyl) phosphate (TCPP), a condensation product of tris-2-chloroethyl phosphate (TCEP), and a condensation product of tris-1,3-dichloro-2-propyl phosphate (TDCP) is preferred. Among them, from the viewpoints of safety, flame retardancy, and anti-fogging property, the condensate of TCPP is more preferred.

[0057] The blending amount of the flame retardant is not particularly limited. From the viewpoint of ensuring sufficient flame retardancy, the blending amount of the flame retardant is preferably 3 parts by mass or more, more preferably 8 parts by mass or more, and further preferably 13 parts by mass or more, with respect to 100 parts by mass of the polyol. On the other hand, from the viewpoints of maintaining various physical properties of the polyurethane foam and the viewpoint of manufacturing cost, it is preferably 28 parts by mass or less, more preferably 25 parts by mass or less, and further preferably 22 parts by mass or less. From these viewpoints, the blending amount of the flame retardant is preferably 3 parts by mass or more and 28 parts by mass or less, more preferably 8 parts by mass or more and 25 parts by mass or less, and further preferably 13 parts by mass or more and 22 parts by mass or less, with respect to 100 parts by mass of the polyol.

[0058] (4) Foam stabilizer The polyurethane resin composition can contain a foam stabilizer. The foam stabilizer is not particularly limited.

[0059] Specifically, the foam stabilizer can use: silicone-based compounds, organopolysiloxane, organopolysiloxane-polyoxyalkylene copolymer, polyalkenyl siloxane having a polyoxyalkylene side chain, silicone fatty acid copolymer, and the like; anionic surfactants, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, and the like; polyether siloxane; and phenolic compounds, and the like. These foam stabilizers can be used alone or two or more in combination.

[0060] The blending amount of the foam stabilizer is not particularly limited. The blending amount of the foam stabilizer is preferably 0.03 parts by mass or more and 5.0 parts by mass or less, with respect to 100 parts by mass of the polyol.

[0061] (5) Foaming agent The polyurethane resin composition can contain a foaming agent. The foaming agent is not particularly limited. As the foaming agent, water, pentane, cyclopentane, hexane, cyclohexane, dichloromethane, carbon dioxide, and the like are suitable. In the case where the foaming agent is water, the addition amount is determined in a range in which a target density and a good foaming state can be obtained in the polyurethane foam, and is generally preferably 1 part by mass or more and 10 parts by mass or less, with respect to 100 parts by mass of the polyol.

[0062] (6) Polyisocyanate The polyisocyanate is not particularly limited. As the polyisocyanate, at least one or more selected from the group consisting of aromatic isocyanates, alicyclic isocyanates, and aliphatic isocyanates is suitably used. One or more of aliphatic isocyanates and one or more of aromatic isocyanates can also be used in combination.

[0063] In addition, the polyisocyanate can be any one of a difunctional polyisocyanate having two isocyanate groups in one molecule and a trifunctional or higher polyisocyanate having three or more isocyanate groups in one molecule, and can be used alone or in combination.

[0064] For example, as the difunctional polyisocyanate, aromatic isocyanates, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, xylene diisocyanate, 3,3'-dimethyl-4,4'-diphenyl diisocyanate, 3,3'-dimethoxy-4,4'-diphenyl diisocyanate, and the like; alicyclic isocyanates, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexane diisocyanate, and the like; aliphatic isocyanates, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropyl glycol diisocyanate, methylene diisocyanate, lysine isocyanate, and the like can be given.

[0065] In addition, as the trifunctional or higher polyisocyanate, 1-methylbenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene-2,4,6-triisocyanate, biphenyl-2,4,4'-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, methyldiphenylmethane-4,6,4'-triisocyanate, 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate, triphenylmethane-4,4',4'-triisocyanate, polymeric MDI, and the like can be given.

[0066] In addition, in addition to these, polyurethane prepolymer, carbodiimide-modified isocyanate, isocyanurate-modified isocyanate, biuret-modified isocyanate can also be used.

[0067] The mixing ratio of the polyisocyanate to the polyol is not particularly limited. The isocyanate index is preferably 80 or more and 120 or less. The isocyanate index (INDEX) is a value of 100 times the number of moles of isocyanate groups contained in the polyurethane resin composition with respect to 1 mole of active hydrogen groups, and is calculated by [(isocyanate equivalent in the composition / active hydrogen equivalent in the composition) x 100].

[0068] (7) a hydrocarbon having 5 or more and 50 or less carbon atoms The hydrocarbon having 5 or more and 50 or less carbon atoms is not particularly limited as long as the number of carbon atoms is within the range. The hydrocarbon can be any one of a saturated hydrocarbon and an unsaturated hydrocarbon. The hydrocarbon can be any one of a hydrocarbon having a branched structure and a cyclic hydrocarbon. As the hydrocarbon, a n-alkane having 5 or more and 50 or less carbon atoms and an iso-alkane having 5 or more and 50 or less carbon atoms are exemplified. The hydrocarbon having 5 or more and 50 or less carbon atoms can be used alone or in combination of two or more.

[0069] (7.1) a n-alkane having 5 or more and 50 or less carbon atoms As the n-alkane having 5 or more and 50 or less carbon atoms, at least one selected from the group consisting of n-nonaπe, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, n-nonadecane, and n-eicosane is exemplified.

[0070] (7.2) an iso-alkane having 5 or more and 50 or less carbon atoms As the iso-alkane having 5 or more and 50 or less carbon atoms, at least one selected from the group consisting of isodecane, isododecane, 7-methyldodecane, and 7-n-hexyltridecane is exemplified.

[0071] (7.3) blending amount of the hydrocarbon having 5 or more and 50 or less carbon atoms The blending amount of the hydrocarbon having 5 or more and 50 or less carbon atoms in the polyurethane resin composition is not particularly limited, and is only required to be blended. From the viewpoint of sufficiently ensuring the air permeability of the polyurethane foam, the blending amount of the hydrocarbon is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and further preferably 0.3 parts by mass or more, relative to 100 parts by mass of the polyol. On the other hand, from the viewpoint of maintaining various physical properties of the polyurethane foam and the viewpoint of manufacturing cost, it is preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, and further preferably 1.0 parts by mass or less. From these viewpoints, the blending amount of the hydrocarbon is preferably 0.1 parts by mass or more and 5.0 parts by mass or less, more preferably 0.2 parts by mass or more and 3.0 parts by mass or less, and further preferably 0.3 parts by mass or more and 1.0 parts by mass or less, relative to 100 parts by mass of the polyol. In addition, in the case where two or more kinds of hydrocarbons are used, the above-mentioned blending amount indicates the total amount of all the hydrocarbons.

[0072] (8) other additives Other additives such as a crosslinking agent, a plasticizer, a filler, an antioxidant, a UV absorber, an antifoaming agent, a compatibilizer, a colorant, a stabilizer, an antibacterial agent, a mildew-proof agent, a deodorant, an odor-removing agent, a fragrance, a perfume, and the like can be appropriately blended in the polyurethane resin composition. As the crosslinking agent, a crosslinking agent of a short-chain diol such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, glycerol, trimethylolpropane, and the like can be mentioned. As the colorant, pigments, dyes, colorants, and the like can be mentioned.

[0073] (9) Reason for improvement of air permeability of polyurethane foam The reason for improvement of air permeability is explained. The polyurethane resin composition contains a hydrocarbon having 5 to 50 carbon atoms, and it is presumed that a large number of cell membranes of the polyurethane foam are broken at the time of foaming molding. Therefore, high air permeability of the polyurethane foam is ensured.

[0074] (10) Physical properties of polyurethane foam The physical properties of the polyurethane foam can be appropriately set according to the use or the like. The polyurethane foam is preferably a soft polyurethane foam.

[0075] The polyurethane foam preferably has the following physical properties.

[0076] (10.1) Apparent density The apparent density (JIS K7222:2005) is preferably 8 kg / m 3 -120 kg / m 3 , more preferably 10 kg / m 3 -80 kg / m 3 , further preferably 15 kg / m 3 -45 kg / m 3 .

[0077] (10.2) Hardness The hardness (JIS K6400-2 D method:2012) is preferably 10 N-600 N, more preferably 50 N-300 N, further preferably 80 N-150 N. As long as the hardness is in the range, it is soft and is preferred as a soft polyurethane foam.

[0078] (10.3) Resilience The resilience (JIS K6400-3:2011) is preferably 1%-80%, more preferably 5%-70%, further preferably 15%-60%.

[0079] (10.4) Tensile strength, tensile rate, tear strength The tensile strength (JIS K6400-5:2012) is preferably 30 kPa or greater, more preferably 50 kPa or greater, and further preferably 70 kPa or greater. The upper limit of the tensile strength is not particularly limited, and is, for example, 500 kPa or less.

[0080] The tensile elongation (JIS K6400-5:2012) is preferably 80% to 500%. The tensile elongation is preferably 80% or greater in terms of softness as a soft polyurethane foam.

[0081] The tear strength (JIS K6400-5:2012) is preferably 2.0 N / cm or greater, more preferably 3.0 N / cm or greater, and further preferably 4.0 N / cm or greater. The upper limit of the tear strength is not particularly limited, and is, for example, 50 N / cm or less.

[0082] (10.5) Air permeability The air permeability (JIS K6400-7 A method:2012) is preferably 25 L / min or greater, more preferably 60 L / min or greater, and further preferably 100 L / min or greater. In addition, the air permeability is usually 300 L / min or less.

[0083] 2. Production of polyurethane foam The polyurethane foam can be produced by a publicly known foaming method in which a polyurethane resin composition is mixed to react a polyol and a polyisocyanate. The foaming method is block foaming or molding foaming, and can be any molding method. The block foaming is a method in which the mixed polyurethane resin composition is sprayed onto a conveyer belt, and foamed at normal temperature under atmospheric pressure. In addition, the molding foaming is a method in which the mixed polyurethane resin composition is filled into a mold (molding die), and foamed in the mold.

[0084] 3. Use of polyurethane foam The use of the polyurethane foam is not particularly limited. The hydrocarbon used in the polyurethane foam of the present embodiment has a decomposition property, and has a small environmental burden, and is thus suitable for various uses.

[0085] The polyurethane foam of the present embodiment can reduce the cyclic siloxane, or can improve the air permeability of the polyurethane foam without using the cyclic siloxane, and is suitable as an indoor member for a vehicle. In addition, the polyurethane foam of the present embodiment is also suitable as an indoor member for a vehicle in terms of being able to contribute to reduction of volatile organic compounds (VOC) and the like.

[0086] The indoor member for a vehicle is not particularly limited. As the indoor member for a vehicle, members used for vehicle seats, members used for interior members of a vehicle, and the like can be given.

[0087] Figure 1 As one example of an indoor member of a vehicle, a skin material 10 used for a seat for a vehicle is shown. The skin material 10 has a surface material composed of, for example, leather, synthetic leather, or fabric, and a polyurethane foam bonded to the surface material. Such a skin material is suitable as a skin material of an air-conditioned seat provided with a heating unit, a cooling unit, or the like. That is, in the case where the polyurethane foam of the present embodiment is used as a skin material of an air-conditioned seat, the air permeability of the skin material can be sufficiently ensured, and the energy efficiency of the air-conditioned seat can be improved. Figure 1 The arrows schematically represent the flow of air in the air-conditioned seat. In addition, the flow of air can also be Figure 1 the reverse direction of the arrows.

[0088] Examples 1. Production of Polyurethane Foam A polyurethane resin composition prepared by blending the proportions of Table 1 was foamed by a slab method to produce the polyurethane foams of the comparative examples, the reference examples, and the examples. The reference examples are comparative examples in which the composition does not contain a hydrocarbon having 5 to 50 carbon atoms.

[0089] Details of each raw material are described below.

[0090] • Polyol 1: polyether polyol, number of functional groups 3, weight average molecular weight 3000, hydroxyl value 56 mgKOH / g • Polyol 2: polyester polyol, weight average molecular weight 2400, hydroxyl value 205 mgKOH / g, DG196AX, manufactured by COIM • Foaming agent: water • Amine catalyst: N,N-dimethylaminohexanol • Foam stabilizer: silicone-based foam stabilizer, product code: SZ-1136, manufactured by DOW CORNING TORAY CO., LTD. • Flame retardant: condensate of tris (1-chloro-2-propyl) phosphate (TCPP), CR-504L, manufactured by OHTA CHEMICAL INDUSTRIES CO., LTD. • Antioxidant 1: phenolic antioxidant, Songox 1135, manufactured by Songwon • Antioxidant 2: CS-25LF, manufactured by Momentive • Pigment: black 4114TT • Isocyanate: toluene diisocyanate (80% by mass of a mixture of 2,4-toluene diisocyanate and 20% by mass of 2,6-toluene diisocyanate) • Tin catalyst: tin (II) octoate • Cyclic siloxane: cyclopentasiloxane, SH245, manufactured by DOW CORNING TORAY CO., LTD. • Hydrocarbon: n-dodecane, C12H26 The polyurethane foam is manufactured in the following order.

[0091] The raw materials other than the polyisocyanate are measured in a cup container and stirred to make a mixed solution.

[0092] The polyisocyanate is added to the mixed solution and stirred to make a polyurethane resin composition.

[0093] [Table 1]

[0094] 2. Evaluation method (1) Apparent density (density) The apparent density was measured based on JIS K 7222:2005.

[0095] (2) Hardness (25% ILD hardness) The hardness was measured based on JIS K6400-2 D method:2012.

[0096] (3) Resilience The resilience was measured based on JIS K6400-3:2011.

[0097] (4) Tensile strength, tensile elongation, tear strength The tensile strength, tensile elongation, and tear strength were measured based on JIS K6400-5:2012.

[0098] (5) Compression set The compression set was measured based on JIS K6400-4 A method:2004, 50% compression, 70°C, 22 hours.

[0099] (6) Airflow The airflow was measured based on JIS K6400-7 A method.

[0100] (7) VOC value For the measurement of the VOC value, a 7-mg test piece was prepared from each sample, the test piece was placed in a glass tube, and a thermal desorption device was used to thereby perform the VOC measurement method prescribed in “Deutsche Gesellschaft fur Galerietechnik VDA 278”. Specifically, each test piece was heated under conditions of a temperature of 90°C and a time of 30 minutes, the gas generated upon heating was analyzed by a gas chromatograph mass spectrometer, and the VOC value was calculated.

[0101] (8) Combustibility The flame retardancy was measured according to the U.S. automobile safety standard (FMVSS-302). In the case where any one of the following conditions is satisfied, it is regarded as “pass”.

[0102] ・Self-extinguishment before the marker line ・Combustion distance is 51 mm or less (60 seconds or less) ・Combustion speed is 102 mm / min or less 3. Results The results are described in Table 1.

[0103] Comparative Examples 1-3 show the results of polyurethane foams to which 0.11 parts by mass, 0.13 parts by mass, 0.18 parts by mass of tin catalyst, respectively, and no additive (cyclic siloxane or hydrocarbon) is added. The ventilation amounts of Comparative Examples 1-3 are 120 L / min, 82 L / min, 27 L / min, respectively. It is known that if the amount of tin catalyst is increased, the ventilation amount decreases.

[0104] Reference Examples 1-4 show the results of polyurethane foams to which 0.11 parts by mass, 0.13 parts by mass, 0.18 parts by mass, 0.23 parts by mass of tin catalyst, respectively, and 0.5 parts by mass of cyclic siloxane is added. The gas permeability of Reference Examples 1-4 is improved compared to Comparative Examples 1-3 to which the same amount of tin catalyst is added.

[0105] Examples 1-4 show the results of polyurethane foams to which 0.11 parts by mass, 0.13 parts by mass, 0.18 parts by mass, 0.23 parts by mass of tin catalyst, respectively, and 0.5 parts by mass of n-dodecane is added. The gas permeability of Examples 1-4 is improved compared to Comparative Examples 1-3 to which the same amount of tin catalyst is added. In addition, the gas permeability of Examples 1-4 is substantially the same as that of Reference Examples 1-4 to which the same amount of tin catalyst is added.

[0106] It is thereby confirmed that Examples 1-4 can improve the gas permeability even if no cyclic siloxane is added.

[0107] In addition, the total VOC of Example 1 is 445.6 ppm. It is confirmed that Example 1 has a practical VOC value. In addition, the total VOC of Comparative Example 1 is 439.5 ppm. The total VOC of Reference Example 1 is 527.0 ppm.

[0108] Furthermore, dodecane is detected in the polyurethane foam of Example 1. That is, it is known that the polyurethane foam of the present disclosure can be understood as a polyurethane foam containing a hydrocarbon having 5 or more and 50 or less carbon atoms and a tin catalyst.

[0109] Furthermore, the combustibility of Example 1 is “Pass”. It is confirmed that Example 1 has a practical combustibility. In addition, the combustibility of Comparative Example 1 and Reference Example 1 is also “Pass”.

[0110] According to the above embodiment, the air permeability of the polyurethane foam can be improved without using the cyclic siloxane. In addition, on the basis of the improvement in the air permeability of the polyurethane foam, it can be confirmed that the hydrocarbon can be a substitute for the cyclic siloxane.

[0111] The present disclosure is not limited to the above-described embodiments, and various modifications or changes can be made within the scope of the present disclosure.

Claims

1. A polyurethane foam obtained from a composition in which a polyol, a polyisocyanate, and a tin catalyst are mixed, wherein the composition contains a hydrocarbon having 5 or more and 50 or less carbon atoms.

2. The polyurethane foam according to claim 1, wherein as the polyol, a polyester polyol is contained.

3. The polyurethane foam according to claim 1, wherein the composition contains a flame retardant.

4. The polyurethane foam according to claim 1, wherein the polyurethane foam has a ventilation rate of 25 L / min or more based on JIS K6400-7 A method:2012.

5. The polyurethane foam according to claim 1, wherein in the composition, 5.0 parts by mass or less of the hydrocarbon is contained with respect to 100 parts by mass of the polyol.

6. A member for use in an interior of a vehicle, wherein a polyurethane foam according to any one of claims 1 to 5.

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