Polyurethane foam and interior components for vehicles

Abstract

The present invention improves the ventilation properties of a polyurethane foam by reducing or not using 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 a carbon number of 5-50, inclusive.

Description

Technical Field

[0001] The present disclosure relates to polyurethane foam and interior members of a vehicle. This application is based on Japanese Patent Application No. 2023-35388 filed on March 8, 2023, claims the benefit of their priority, and all the contents of those patent applications are incorporated herein by reference.

Background Art

[0002] A technique of adding a cyclic siloxane to improve the air permeability of polyurethane foam is disclosed in Patent Document 1.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, cyclic siloxanes are subject to various regulations. In addition, the 19th SVHC (Substances of Very High Concern) list of the European REACH Regulation includes decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and octamethylcyclotetrasiloxane. The present disclosure has been made in view of the above circumstances, and aims to improve the air permeability of polyurethane foam by reducing cyclic siloxanes or without using cyclic siloxanes. The present disclosure can be realized in the following forms.

Means for Solving the Problems

[0005] [1]<! A polyol, a polyisocyanate, a tin catalyst, A polyurethane foam obtained from a mixed composition, The composition comprises a polyurethane foam containing a hydrocarbon having 5 to 50 carbon atoms. [Effects of the Invention]

[0006] According to this disclosure, the permeability of polyurethane foam can be improved by reducing or eliminating the use of cyclic siloxanes. [Brief explanation of the drawing]

[0007] [Figure 1] This is a diagram of an interior component for a vehicle equipped with polyurethane foam according to one embodiment. [Modes for carrying out the invention]

[0008] Herein lies a preferred example of this disclosure. [2] The polyurethane foam according to [1], wherein the polyol is a polyester polyol. [3] The polyurethane foam according to [1] or [2], wherein the composition comprises a flame retardant. [4] A polyurethane foam as described in any one of the following items [1] to [3], having an air permeability of 25 L / min or more according to JIS K6400-7 Method A:2012. [5] The polyurethane foam according to any one of [1] to [4], wherein the composition contains 5.0 parts by mass or less of the hydrocarbon per 100 parts by mass of the polyol. [6] A vehicle interior component comprising the polyurethane foam described in any one of items [1] to [5].

[0009] The following will describe the present disclosure in detail. In this specification, for a description using "-" for a numerical range, unless otherwise specified, it includes the lower limit value and the upper limit value. For example, for the description "10 - 20", it includes both the lower limit value "10" and the upper limit value "20". That is, "10 - 20" has the same meaning as "10 or more and 20 or less". Also, in this specification, the upper limit value and the lower limit value of each numerical range can be arbitrarily combined.

[0010] 1. Polyurethane foam The polyurethane foam is obtained from a composition (hereinafter also 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 to 50 carbon atoms.

[0011] (1) Polyol The polyol is not particularly limited. Various polyols may be used alone or in combination of two or more. Examples of the polyol include polyether polyol, polyester polyol, polyether ester polyol, polycarbonate diol, and a polyol having a carbon-carbon bond main chain. Examples of the polyether polyol include polyoxypropylene·polyoxyethylene polyol, polymer polyol, and polyoxytetramethylene glycol. Examples of the polyester polyol include aliphatic or aromatic polycondensation polyester polyol and polycaprolactone polyol. Examples of the polyol having a carbon-carbon bond main chain include polyolefin polyols such as polybutadiene polyol and isoprene polyol, and acrylic polyol.

[0012] (1.1) Polyether polyol Examples of polyether polyols include those obtained by adding one or more of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, epichlorohydrin, styrene oxide, etc. to one or more of the following initiators (compounds), or polytetramethylene ether glycol.

[0013] (1.1.1) Initiator (1.1.1.1) Polyhydric alcohols, and alkylene oxide adducts of polyhydric alcohols Examples of polyhydric alcohols: [Difunctional alcohol] Ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, trimethylene glycol [Trifunctional alcohol] Glycerol, trimethylolpropane [Tetrafunctional alcohol] Pentaerythritol [Hexafunctional alcohol] Sorbitol [Octafunctional alcohol] Sucrose (1.1.1.2) Alkylene oxide adducts of polyhydric phenols Examples of alkylene oxide adducts of polyhydric phenols: Alkylene oxide adduct of bisphenol A (1.1.1.3) Polyhydric hydroxy compounds Examples of polyhydric hydroxy compounds: Phosphoric acid, benzene phosphoric acid, polyphosphoric acid (such as tripolyphosphoric acid and tetrapolyphosphoric acid), etc. (1.1.1.4) Phenol - aniline - formaldehyde ternary condensation product (1.1.1.5) Aniline - formaldehyde condensation product (1.1.1.6) Polyamines Examples of polyamines: Ethylenediamine, diethylenetriamine, triethylenetetramine, methylenebis orthochloroaniline, 4,4 - and 2,4’ - diphenylmethanediamine, 2, for example, 4 - tolylenediamine, 2,6 - tolylenediamine, etc. (1.1.1.7) Alkanolamines Examples of alkanolamines: triethanolamine, diethanolamine, etc.

[0014] (1.1.2) Polymer polyols Polymer polyols are polyols obtained by graft polymerization of ethylenically unsaturated compounds such as acrylonitrile, styrene, and alkyl methacrylate onto the polyether polyols described above.

[0015] (1.2) Polyester polyol Polyester polyols are obtained by condensation of one or more compounds having at least two hydroxyl groups with one or more compounds having at least two carboxyl groups, or are ring-opening polymers of cyclic esters such as caprolactone and methylvalerolactone.

[0016] (1.2.1) Examples of compounds 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, methylpentanediol, butylethylpropanediol, hexamethylene glycol, decamethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol

[0017] (1.2.2) Examples of compounds 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, hemeltic acid

[0018] (1.3) Polycarbonate polyol Examples of polycarbonate polyols include those obtained by transesterification reactions between low molecular weight polyols such as butanediol and hexanediol and low molecular weight carbonates such as propylene carbonate and diethyl carbonate.

[0019] (1.4) Polyolefin-based polyols Examples of polyolefin-based polyols include polybutadiene polyols, polyisoprene polyols, hydrogenated polybutadiene polyols, and hydrogenated polyisoprene polyols.

[0020] (1.5) Plant-derived polyols In addition to the polyols mentioned above, plant-derived polyols may also be included as polyols. Examples of plant-derived polyols include castor oil polyols, soybean oil polyols, palm oil polyols, palm kernel oil polyols, coconut oil polyols, cashew oil polyols, olive oil polyols, cottonseed oil polyols, safflower oil polyols, sesame oil polyols, sunflower oil polyols, and linseed oil polyols. Plant-derived polyols typically have 2-3 hydroxyl functional groups per molecule. Examples of castor oil-based polyols include castor oil, reaction products of castor oil and polyols, and esterification reaction products of castor oil fatty acids and polyols. Examples of polyols to be reacted with castor oil or castor oil fatty acids include divalent polyols such as ethylene glycol, diethylene glycol, and propylene glycol, or trivalent or higher polyols such as glycerin, trimethylolpropane, hexanetriol, and sorbitol. Examples of soybean oil-based polyols include polyols derived from soybean oil, such as reaction products of soybean oil and polyols, and esterification reaction products of soybean oil fatty acids and polyols. The polyols used to react with soybean oil or soybean oil fatty acids can be the same as those used for castor oil. The same applies to palm oil-based polyols, cashew oil-based polyols, etc., as to soybean oil-based polyols. The various polyols exemplified as plant-derived polyols may be used individually or in combination of two or more.

[0021] (1.6) Application to the frame lamination method When polyurethane foam is used in the frame lamination method, it is preferable that the polyol included is polyester polyol. The flame lamination method is a technique for bonding other materials, such as surface materials, to polyurethane foam. In this method, a flame is applied to the surface of the polyurethane foam to melt it, and the melted areas become tacky, thereby bonding the other materials to the polyurethane foam. When polyester polyol is included, the polyurethane foam becomes more easily melted by the flame, allowing for sufficient adhesion. Note that the use of polyester polyol is not limited to the flame lamination method. For example, polyester polyol may be used for purposes such as adjusting the various physical properties of the polyurethane foam.

[0022] The polyester polyol content is not particularly limited. Preferably, the polyester polyol content is 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 even more preferably 3 parts by mass or more and 10 parts by mass or less, when the total polyol content is 100 parts by mass.

[0023] 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 to 4500, more preferably 500 to 3500, and even more preferably 800 to 2500. The weight-average molecular weight of the polyester polyol can be measured by gel permeation chromatography (GPC). If the polyol is a commercially available product, the catalog value may be used as the weight-average molecular weight. The hydroxyl value of the polyester polyol is not particularly limited. Preferably, the hydroxyl value of the polyester polyol is 80 mg KOH / g or more and 350 mg KOH / g or less, more preferably 100 mg KOH / g or more and 300 mg KOH / g or less, and even more preferably 150 mg KOH / g or more and 250 mg KOH / g or less. The number of functional groups in a polyester polyol is not particularly limited. Preferably, the number of functional groups is 2.0 or more, more preferably 2.1 or more, and even more preferably 2.2 or more. For example, the number of functional groups in a polyester polyol may be 4.0 or less.

[0024] From the viewpoint of ensuring the flexibility of the polyurethane foam, polyester polyol is preferably used in combination with polyether polyol. The polyether polyol used in combination with polyester polyol is not particularly limited. The content of the polyether polyol used in combination is 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 even more preferably 90 parts by mass or more and 97 parts by mass or less, when the total polyol is 100 parts by mass.

[0025] The weight-average molecular weight, hydroxyl value, and number of functional groups of the polyether polyol used in combination are not particularly limited. The weight-average molecular weight of the above-mentioned polyether polyol is preferably 500 to 10000, more preferably 1000 to 6000, and even more preferably 1500 to 4000. The weight-average molecular weight of the polyether polyol can be measured by gel permeation chromatography (GPC). The hydroxyl value of the above polyether polyol is preferably 40 mg KOH / g or more and 300 mg KOH / g or less, more preferably 45 mg KOH / g or more and 150 mg KOH / g or less, and even more preferably 50 mg KOH / g or more and 80 mg KOH / g or less. The number of functional groups in the above-mentioned polyether polyol is preferably 2.0 or more, more preferably 2.1 or more, and even more preferably 2.2 or more. The number of functional groups in the polyester polyol is, for example, 4.0 or less.

[0026] (2) Catalyst The polyurethane resin composition contains a tin catalyst. Based on the finding that the permeability of polyurethane foam decreases as the amount of tin catalyst increases, the inventors of this invention conducted extensive research. They then discovered that the permeability of polyurethane foam can be improved by incorporating hydrocarbons even when a tin catalyst is included, leading to the development of the technology disclosed herein.

[0027] As the tin catalyst, one or more selected from the group consisting of tin(II) octoate (2-ethylhexanoate tin, stanus dioctoate), tin(II) acetate, tin(II) octanoate, tin dioleate, tin(II) neodecanoate, stanus dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, dibutyltin dimaleate, and dioctyltin diacetate can be used.

[0028] The amount of tin catalyst in the polyurethane resin composition is not particularly limited. From the viewpoint of sufficiently promoting the polyurethane formation reaction, the amount of tin catalyst is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and even more preferably 0.06 parts by mass or more, per 100 parts by mass of polyol. On the other hand, from the viewpoint of maintaining the various physical properties of the polyurethane foam and from the viewpoint of manufacturing costs, it is preferably 1.0 part by mass or less, more preferably 0.5 parts by mass or less, and even more preferably 0.2 parts by mass or less. From these viewpoints, the amount of tin catalyst is preferably 0.01 parts by mass or more and 1.0 part by mass or less, more preferably 0.03 parts by mass or more and 0.5 parts by mass or less, and even more preferably 0.06 parts by mass or more and 0.2 parts by mass or less, per 100 parts by mass of polyol. Furthermore, the amount of tin catalyst may be 0.17 parts by mass or less, 0.15 parts by mass or less, or 0.13 parts by mass or less.

[0029] The tin catalyst may be used alone or in combination with other catalysts. Other catalysts that can be used include amine catalysts and quaternary ammonium salt catalysts. Specific examples of these catalysts are shown below. Tertiary amine catalysts such as triethylenediamine, triethylamine, tripropylamine, triisopropanolamine, tributylamine, trioctylamine, hexadecyldimethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N,N-dimethylethanolamine, N,N-dimethylaminohexanol, N,N-dimethylaminoethoxyethoxyethanol, and N,N-dimethylaminoethoxyethanol can be used, as well as formate and other salts of triethylenediamine, oxyalkylene adducts of amino groups of primary and secondary amines, aza ring compounds such as NN-dialkylpiperazines, various N,N',N'-trialkylaminoalkylhexahydrotriazines, and amine catalysts having an amino group as a functional group such as N,N,N",N"-tetramethyldiethylenetriamine can be employed. Furthermore, quaternary ammonium salt catalysts such as tetraalkylammonium halides including tetramethylammonium chloride, tetraalkylammonium hydroxides including tetramethylammonium hydroxide, and tetraalkylammonium organic acid salts such as tetramethylammonium 2-ethylhexanoate, 2-hydroxypropyltrimethylammonium forate, and 2-hydroxypropyltrimethylammonium 2-ethylhexanoate can also be used.

[0030] The amount of one or more catalysts selected from the group consisting of amine catalysts and quaternary ammonium salt catalysts in the polyurethane resin composition is not particularly limited. From the viewpoint of sufficiently promoting the polyurethane formation reaction, the amount of these catalysts is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.09 parts by mass or more, per 100 parts by mass of polyol. On the other hand, from the viewpoint of maintaining the various physical properties of the polyurethane foam and from the viewpoint of manufacturing costs, it is preferably 3.0 parts by mass or less, more preferably 2.0 parts by mass or less, and even more preferably 1.0 part by mass or less. From these viewpoints, the amount of one or more catalysts selected from the group consisting of amine catalysts and quaternary ammonium salt catalysts is preferably 0.01 parts by mass or more and 3.0 parts by mass or less, more preferably 0.05 parts by mass or more and 2.0 parts by mass or less, and even more preferably 0.01 parts by mass or more and 1.0 part by mass or less, per 100 parts by mass of polyol.

[0031] The polyurethane resin composition may contain a metal catalyst other than a tin catalyst. Any conventionally known metal catalyst can be used as the metal catalyst other than a tin catalyst without any particular limitations. As metal catalysts other than tin catalysts, for example, metal salts of Pb (lead), Bi (bismuth), Ni (nickel), Co (cobalt), Fe (iron), Zr (zirconium), Cu (copper), Zn (zinc), etc., and metal salts of organic acids can be used. More specifically, the following metal catalysts can be used. Pb catalysts: Lead octanoate, lead naphthenate, etc. Bi catalysts: Bismuth octylate, bismuth naphthenate, bismuth neodecanoate, bismuth rosinate, etc. Fe catalyst: Iron acetylacetonate, etc. Zr catalyst: Zirconium acetylacetonate, etc. Ni catalysts: Nickel acetylacetonate, nickel octylate, nickel naphthenate, etc. Co catalysts: Cobalt acetylacetonate, cobalt octylate, cobalt naphthenate, etc.

[0032] (3) Flame retardants The polyurethane resin composition preferably contains a flame retardant. The flame retardant is not particularly limited. Examples of flame retardants include one or more selected from the group consisting of phosphate ester flame retardants, phosphate-containing flame retardants, red phosphorus, bromine-containing flame retardants, boric acid-containing flame retardants, antimony-containing flame retardants, and metal hydroxides.

[0033] From the viewpoint of improving flame retardancy, a phosphate ester-based flame retardant is preferred. The phosphate ester-based flame retardant may be a halogenated phosphate ester-based flame retardant or a non-halogenated phosphate ester-based flame retardant. As for halogenated phosphate ester-based flame retardants, one or more selected from the group consisting of tris-1-chloro-2-propyl phosphate (TCPP) condensate, tris-2-chloroethyl phosphate (TCEP) condensate, and tris-1,3-dichloro-2-propyl phosphate (TDCP) condensate are preferred. Among these, TCPP condensates are more preferred from the viewpoint of safety, flame retardancy, and fogging resistance.

[0034] The amount of flame retardant added is not particularly limited. From the viewpoint of ensuring sufficient flame retardancy, the amount of flame retardant added is preferably 3 parts by mass or more, more preferably 8 parts by mass or more, and even more preferably 13 parts by mass or more, per 100 parts by mass of polyol. On the other hand, from the viewpoint of maintaining the various physical properties of polyurethane foam and from the viewpoint of manufacturing costs, it is preferably 28 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 22 parts by mass or less. From these viewpoints, the amount of flame retardant added 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 even more preferably 13 parts by mass or more and 22 parts by mass or less, per 100 parts by mass of polyol.

[0035] (4) Foam stabilizer The polyurethane resin composition may contain a foam stabilizer. The foam stabilizer is not particularly limited. Specifically, foam stabilizers include silicone compounds such as organopolysiloxanes, organopolysiloxane-polyoxyalkylene copolymers, polyalkenylsiloxanes having polyoxyalkylene side chains, and silicone-grease copolymers; anionic surfactants such as sodium dodecylbenzenesulfonate and sodium lauryl sulfate; polyethersiloxanes; and phenolic compounds. These foam stabilizers may be used individually or in combination of two or more. The amount of foam stabilizer added is not particularly limited. Preferably, the amount of foam stabilizer added is 0.03 parts by mass or more and 5.0 parts by mass or less per 100 parts by mass of polyol.

[0036] (5) Foaming agent The polyurethane resin composition may contain a blowing agent. The blowing agent is not particularly limited. Suitable blowing agents include water, pentane, cyclopentane, hexane, cyclohexane, dichloromethane, and carbon dioxide. When water is used as the blowing agent, the amount added is determined to obtain the desired density and good foaming state in the polyurethane foam, and is usually preferably 1 to 10 parts by mass per 100 parts by mass of polyol.

[0037] (6) Polyisocyanates The polyisocyanate is not particularly limited. Preferably, at least one polyisocyanate selected from the group consisting of aromatic isocyanates, alicyclic isocyanates, and aliphatic isocyanates is used. A combination of one or more aliphatic isocyanates and one or more aromatic isocyanates is also possible. Furthermore, the polyisocyanate may be a bifunctional polyisocyanate having two isocyanate groups in one molecule, or a trifunctional or more polyisocyanate having three or more isocyanate groups in one molecule, and may be used alone or in combination of several. For example, difunctional polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylenediisocyanate, p-phenylenediisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, xylylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylenediisocyanate, and 3,3'-dimethoxy-4,4'-biphenylenediisocyanate. Examples include aromatic isocyanates such as phenylenediisocyanate, alicyclic isocyanates such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, and methylcyclohexane diisocyanate, and aliphatic isocyanates such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylenediisocyanate, methylene diisocyanate, and lysine isocyanate. Examples of polyisocyanates with three or more functions include 1-methylbenzol-2,4,6-triisocyanate, 1,3,5-trimethylbenzol-2,4,6-triisocyanate, biphenyl-2,4,4'-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, methyldiphenylmethane-4,6,4'-triisocyanate, 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate, triphenylmethane-4,4',4"-triisocyanate, polymeric MDI, and the like. In addition, other urethane prepolymers, carbodiimide-modified isocyanates, isocyanurate-modified isocyanates, and biuret-modified isocyanates can also be used.

[0038] The mixing ratio of polyisocyanate and polyol is not particularly limited. The isocyanate index is preferably between 80 and 120. The isocyanate index (INDEX) is the value obtained by multiplying the number of moles of isocyanate groups per mole of active hydrogen groups contained in the polyurethane resin composition by 100, and is calculated as [(Isocyanate equivalent in composition / Equivalent of active hydrogen in composition) × 100].

[0039] (7) Hydrocarbons with 5 to 50 carbon atoms Hydrocarbons having 5 to 50 carbon atoms are not particularly limited as long as the number of carbon atoms is within this range. Hydrocarbons may be saturated hydrocarbons or unsaturated hydrocarbons. Hydrocarbons may be branched hydrocarbons or cyclic hydrocarbons. Preferred examples of hydrocarbons include n-paraffins having 5 to 50 carbon atoms and isoparaffins having 5 to 50 carbon atoms. Hydrocarbons having 5 to 50 carbon atoms may be used individually or as a mixture of two or more.

[0040] (7.1) n-paraffins with 5 to 50 carbon atoms Examples of n-paraffins having 5 to 50 carbon atoms include at least one selected from the group consisting of n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, n-nonadecane, and n-eicosane.

[0041] (7.2) Isoparaffins with 5 to 50 carbon atoms Examples of isoparaffins having 5 to 50 carbon atoms include at least one selected from the group consisting of isodecane, isododecane, 7-methyldecane, and 7-n-hexyltridecane.

[0042] (7.3) Amount of hydrocarbons with 5 to 50 carbon atoms The amount of hydrocarbons having 5 to 50 carbon atoms in a polyurethane resin composition is not particularly limited and is acceptable as long as they are included. From the viewpoint of ensuring sufficient permeability of the polyurethane foam, the amount of hydrocarbons is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and even more preferably 0.3 parts by mass or more, per 100 parts by mass of polyol. On the other hand, from the viewpoint of maintaining the various physical properties of the polyurethane foam and from the viewpoint of manufacturing costs, it is preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, and even more preferably 1.0 part by mass or less. From these viewpoints, the amount of hydrocarbons 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 even more preferably 0.3 parts by mass or more and 1.0 part by mass or less, per 100 parts by mass of polyol. When two or more types of hydrocarbons are used, the above amounts refer to the total amount of all hydrocarbons.

[0043] (8) Other additives Polyurethane resin compositions may contain other additives as appropriate, such as crosslinking agents, plasticizers, fillers, antioxidants, UV absorbers, defoaming agents, compatibilizers, colorants, stabilizers, antibacterial agents, antifungal agents, deodorizers, fragrances, and scents. Examples of crosslinking agents include short-chain diol crosslinking agents such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, glycerin, and trimethylolpropane. Examples of colorants include pigments, dyes, and colorants.

[0044] (9) Why the breathability of polyurethane foam is improved Let's explain why the breathability is improved. It is presumed that the presence of hydrocarbons with 5 to 50 carbon atoms in the polyurethane resin composition causes numerous cell membranes to break during the foaming process of the polyurethane foam. Therefore, it is thought that this ensures the high breathability of the polyurethane foam.

[0045] (10) Physical properties of polyurethane foam The physical properties of the polyurethane foam can be appropriately set according to the application and other factors. Flexible polyurethane foam is preferred. The polyurethane foam preferably possesses the following physical properties. (10.1) Apparent density The apparent density (JIS K7222:2005) is 8 kg / m³. 3 -120 kg / m 3 Preferably, 10 kg / m 3 -80kg / m 3 More preferably, 15 kg / m 3 -45kg / m 3 That is even more preferable. (10.2) Hardness The hardness (JIS K6400-2 Method D:2012) is preferably between 10N and 600N, more preferably between 50N and 300N, and even more preferably between 80N and 150N. Within this range, the material is highly flexible and is suitable as a soft polyurethane foam. (10.3) Rebound elasticity The rebound elasticity (JIS K6400-3:2011) is preferably 1%-80%, more preferably 5%-70%, and even more preferably 15%-60%. (10.4) Tensile strength, elongation, tear strength The tensile strength (JIS K6400-5:2012) is preferably 30 kPa or higher, more preferably 50 kPa or higher, and even more preferably 70 kPa or higher. The upper limit of the tensile strength is not particularly limited, for example, 500 kPa or less. The elongation (JIS K6400-5:2012) is preferably between 80% and 500%. If it is 80% or higher, it is highly flexible and is preferable as a soft polyurethane foam. The tear strength (JIS K6400-5:2012) is preferably 2.0 N / cm or higher, more preferably 3.0 N / cm or higher, and even more preferably 4.0 N / cm or higher. The upper limit of the tear strength is not particularly limited, for example, 50 N / cm or less. (10.5) Air permeability The air permeability (JIS K6400-7 Method A: 2012) is preferably 25 L / min or more, more preferably 60 L / min or more, and even more preferably 100 L / min or more. However, the air permeability is usually 300 L / min or less.

[0046] 2. Manufacturing of polyurethane foam Polyurethane foam can be produced by known foaming methods, which involve stirring and mixing a polyurethane resin composition to react a polyol with a polyisocyanate. Foaming methods include slab foaming and mold foaming, and either method may be used. Slab foaming involves extruding the mixed polyurethane resin composition onto a belt conveyor and foaming it at atmospheric pressure and room temperature. Mold foaming, on the other hand, involves filling a mold with the mixed polyurethane resin composition and foaming it within the mold.

[0047] 3. Applications of polyurethane foam The applications of polyurethane foam are not particularly limited. The hydrocarbons used in the polyurethane foam of this embodiment are easily biodegradable and have a low environmental impact, making them useful for a variety of applications.

[0048] The polyurethane foam of this embodiment is suitable as an interior component for vehicles because it can improve the breathability of the polyurethane foam by reducing or eliminating the use of cyclic silicone. Furthermore, the polyurethane foam of this embodiment is also suitable as an interior component for vehicles because it can contribute to the reduction of volatile organic compounds (VOCs) and the like.

[0049] The interior components of a vehicle are not particularly limited. Examples of interior components of a vehicle include components used in vehicle seats and components used in vehicle interior materials. Figure 1 shows an example of an interior component for a vehicle, specifically a surface material 10 used in a vehicle seat. This surface material 10 comprises a surface material made of, for example, genuine leather, synthetic leather, or fabric, and a polyurethane foam bonded to the surface material. Such a surface material is suitable as a surface material for an air-conditioned seat equipped with a heater unit, cooling unit, etc. That is, when the polyurethane foam of this embodiment is used as a surface material for an air-conditioned seat, sufficient breathability of the surface material can be ensured, and the energy efficiency of the air-conditioned seat can be improved. The arrows in Figure 1 schematically represent the airflow in the air-conditioned seat. Note that the airflow may be in the opposite direction to the arrows in Figure 1. [Examples]

[0050] 1. Manufacturing of polyurethane foam Polyurethane resin compositions were prepared using the proportions shown in Table 1, and polyurethane foams for the comparative example, reference example, and example were produced by slab foaming. The reference example is a comparative example in which the composition does not contain hydrocarbons with 5 to 50 carbon atoms. Details of each ingredient are as follows: • Polyol 1: Polyether polyol, 3 functional groups, 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 name: SZ-1136, manufactured by Toray Dow Corning. • Flame retardant: Condensate of tris-1-chloro-2-propyl phosphate (TCPP), CR-504L, manufactured by Daihachi Chemical Industry Co., Ltd. • Antioxidant 1: Phenolic antioxidant, Songox 1135, manufactured by Songwon Co., Ltd. • Antioxidant 2: CS-25LF, manufactured by Momentive Corporation Pigment: Black 4114TT • Isocyanate: Tolylene diisocyanate (a mixture of 80% by mass of 2,4-tolylene diisocyanate and 20% by mass of 2,6-tolylene diisocyanate) • Tin catalyst: Tin(II) octoate • Cyclic siloxane: Cyclopentasiloxane, SH245, manufactured by Toray Dow Corning. • Hydrocarbons: n-dodecane, C 12 H 26

[0051] The polyurethane foam was manufactured using the following procedure: The raw materials other than polyisocyanate were weighed into a cup container, stirred, and mixed to form a solution. Polyisocyanate was added to the mixed solution and stirred to obtain a polyurethane resin composition.

[0052] [Table 1]

[0053] 2. Evaluation Method (1) Apparent density (density) The apparent density was measured according to JIS K7222:2005. (2) Hardness (25% ILD hardness) Hardness was measured according to JIS K6400-2 Method D:2012. (3) Rebound elasticity The rebound elasticity was measured according to JIS K6400-3:2011. (4) Tensile strength, elongation, tear strength Tensile strength, elongation, and tear strength were measured according to JIS K6400-5:2012. (5) Compression residual strain (compression residual stress) Compression residual strain was measured according to JIS K6400-4 Method A:2004, 50% compression, 70°C, and 22 hours. (6) Air permeability Air permeability was measured according to JIS K6400-7 Method A.

[0054] (7) VOC values VOC values ​​were measured by preparing 7 mg test specimens from each sample, placing them in glass tubes, and using a thermal desorption apparatus to perform the VOC measurement method specified in "German Association of the Automotive Industry VDA278". Specifically, each test specimen was heated at 90°C for 30 minutes, and the gas generated during heating was analyzed using a gas chromatograph-mass spectrometer to calculate the VOC value.

[0055] (8) Flammability Flame retardancy was measured in accordance with the U.S. Automotive Safety Standard (FMVSS-302). A "pass" rating was given if any of the following conditions were met. • Self-extinguishing before reaching the marker line • Burning distance within 51mm (within 60 seconds) • Burning rate of 102 mm / min or less

[0056] 3.Results The results are shown in Table 1. Comparative Examples 1-3 show the results for polyurethane foam with 0.11 parts by mass, 0.13 parts by mass, and 0.18 parts by mass of tin catalyst added, respectively, and without any additives (cyclic siloxane or hydrocarbon). The air permeability for Comparative Examples 1-3 was 120 L / min, 82 L / min, and 27 L / min, respectively. It was found that the air permeability decreased as the amount of tin catalyst increased. Reference Examples 1-4 show the results for polyurethane foams to which 0.11 parts by mass, 0.13 parts by mass, 0.18 parts by mass, and 0.23 parts by mass of tin catalyst were added, along with 0.5 parts by mass of cyclic siloxane. Reference Examples 1-3 showed improved air permeability compared to Comparative Examples 1-3, which had the same amount of tin catalyst added.

[0057] Examples 1-4 show the results for polyurethane foams in which 0.11 parts by mass, 0.13 parts by mass, 0.18 parts by mass, and 0.23 parts by mass of tin catalyst were added, along with 0.5 parts by mass of n-dodecane. Examples 1-4 showed improved air permeability compared to Comparative Examples 1-3, which had the same amount of tin catalyst added. Furthermore, Examples 1-4 had approximately the same air permeability as Reference Examples 1-4, which had the same amount of tin catalyst added. Therefore, it was confirmed that Examples 1-4 can improve air permeability even without the addition of cyclic siloxanes.

[0058] Furthermore, the total VOC content of Example 1 was 445.6 ppm. It was confirmed that Example 1 has a practically usable VOC value. The total VOC content of Comparative Example 1 was 439.5 ppm. The total VOC content of Reference Example 1 was 527.0 ppm. Furthermore, dodecane was detected in the polyurethane foam of Example 1. This indicates that the polyurethane foam of this disclosure can be understood as a polyurethane foam containing hydrocarbons with 5 to 50 carbon atoms and a tin catalyst.

[0059] Furthermore, the flammability of Example 1 was "acceptable." It was confirmed that Example 1 has practically usable flammability. The flammability of Comparative Example 1 and Reference Example 1 was also "acceptable."

[0060] According to the above examples, the permeability of polyurethane foam could be improved without using cyclic siloxanes. Furthermore, it was confirmed that hydrocarbons can serve as substitutes for cyclic siloxanes in improving the permeability of polyurethane foam.

[0061] This disclosure is not limited to the embodiments detailed above, and various modifications or changes are possible within the scope of this disclosure.

Claims

1. Polyols and, Polyisocyanate and, Tin catalyst and A polyurethane foam obtained from a mixed composition, The composition contains a hydrocarbon having 5 to 50 carbon atoms. Polyurethane foam with an air permeability of 25 L / min or more, based on JIS K6400-7 Method A:2012.

2. The polyurethane foam according to claim 1, wherein the composition contains a hydrocarbon having 9 to 50 carbon atoms.

3. The polyurethane foam according to claim 1, wherein the hydrocarbon is at least one selected from the group consisting of n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, n-nonadecane, and n-eicosane.

4. The polyurethane foam according to claim 1, wherein the hydrocarbon is isoparaffin.

5. The aforementioned polyol includes polyester polyol, The polyurethane foam according to claim 1, wherein the content of the polyester polyol is 20 parts by mass or less when the total polyol is 100 parts by mass.

6. The composition further contains water, The polyurethane foam according to claim 1, wherein the composition contains 1.0 part by mass or less of the hydrocarbon and 1 to 10 parts by mass of water per 100 parts by mass of the polyol.

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