Polyurethane foam, battery or electrical device, and method for producing polyurethane foam

Abstract

Provided is a polyurethane foam having high density and excellent flame retardancy. In the present technology, first, a polyurethane foam is provided which contains an inorganic phosphoric acid compound and expanded graphite and has a density of 150 kg / m3 or more. The thickness of the polyurethane foam according to the present technology can be 10 mm or less. The polyurethane foam related to the technology can be used for batteries or electrical equipment. A polyurethane foam according to the present technology can be produced by a method for producing a polyurethane foam having a step of mixing a polyol, an isocyanate, an inorganic phosphoric acid compound, expanded graphite, and a gas.

Description

Technical Field

[0001] The present technology relates to polyurethane foam, and more specifically, to a polyurethane foam having flame retardancy, a battery or an electric device using the polyurethane foam, and a method for producing the polyurethane foam. Background Art

[0002] Polyurethane foam is widely used in various fields such as furniture such as sofas and chairs, bedding such as mattresses and pillows, clothing such as underwear, daily necessities such as tableware and cleaning sponges, vehicle and aircraft interior products such as car seats, electronic devices such as mobile phones, cameras, and televisions, electrical appliances such as home appliances, toys, and sundries. In addition, various developments are being carried out to improve quality or add new functions according to each field and purpose.

[0003] For example, Patent Document 1 discloses a flame-retardant polyurethane foam having excellent tensile strength, tear strength and low compression residual strain by using the following materials as polyols to improve flame retardancy, wherein the first polyol is 50 to 80 parts by mass of a polymer polyol having a number average molecular weight of 1500 to 4500 and a functional group number of 3, based on 100 parts by mass of the polyols as a whole; (B) a second polyol having a number average molecular weight of 300 to 900 and a functional group number of 3, based on 100 parts by mass of the polyols as a whole, and 5 to 16 parts by mass of a polyether polyol; and (C) a third polyol having a functional group number of 2 or 3, based on 100 parts by mass of the polyols as a whole, and 1 to 6 parts by mass of a polyester polyol.

[0004] For example, Patent Document 2 discloses a polyurethane foam having excellent heat resistance, moisture heat resistance and flame retardancy by using any one or two powder flame retardants of expanded graphite or phosphorus-based powder flame retardants. In addition, Patent Document 3 discloses a polyurethane foam having significantly excellent flame retardancy that satisfies the V-0 standard of the UL-94 vertical combustion test by using a non-halogen flame retardant as a flame retardant with a smaller amount of flame retardant. Further, Patent Document 4 discloses a polyurethane foam that uses a non-reactive phosphorus compound that is present in an amount ranging from 1 to 20 mass percent relative to the total mass of the polyurethane foam and has a cumulative reduction of less than 2% at 200°C when measured by thermogravimetric analysis, thereby having a UL94 vertical combustion grade of V-0.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2012-082273

[0008] Patent Document 2: Japanese Patent Application Publication No. 2016-176049

[0009] Patent Document 3: Japanese Patent Application Publication No. 2011-252111

[0010] Patent Document 4: Japanese Patent Application No. 2016-510837 Summary of the invention

[0011] Problem that the invention aims to solve

[0012] In recent years, the demand for polyurethane foams that can be used for vibration or impact buffering of electronic devices such as mobile phones, cameras, televisions, or electrical appliances such as household appliances, the sealing materials of various batteries, the battery periphery of electric vehicles, or the sealing materials of the electronic control unit periphery, etc., has gradually increased. In order to be used for these purposes, flame retardancy and high density are required. As mentioned above, the technology of imparting flame retardancy to polyurethane foam is being developed, but the flame retardancy of high-density polyurethane foam is still in the development stage.

[0013] Therefore, the main object of the present technology is to provide a polyurethane foam having high density and excellent flame retardancy.

[0014] Means for solving problems

[0015] In the present technology, first, a composite material containing an inorganic phosphoric acid compound and expanded graphite having a density of 150 kg / m 3 Polyurethane foam above.

[0016] The thickness of the polyurethane foam according to the present technique can be 10 mm or less.

[0017] The polyurethane foam according to the present technology can be used in batteries or electrical devices.

[0018] The polyurethane foam according to the present technique can be produced by a method for producing a polyurethane foam including a step of mixing a polyol, an isocyanate, an inorganic phosphoric acid compound, expanded graphite, and a gas. DETAILED DESCRIPTION

[0019] The preferred mode for implementing the present technology is described below. The embodiment described below is an example of a representative embodiment of the present technology, and any embodiment can be combined. In addition, the scope of the present technology should not be interpreted narrowly.

[0020] 1. Composition for producing polyurethane foam

[0021] The polyurethane foam of the present technology is produced using a composition containing an inorganic phosphoric acid compound and expanded graphite. The composition used for producing the polyurethane foam of the present technology may also contain polyol, isocyanate, catalyst, foam stabilizer, foaming agent, etc. as needed.

[0022] As described later, the polyurethane foam involved in the present technology is preferably produced using a mechanical foaming method. That is, the composition used in the production of the polyurethane foam involved in the present technology can be appropriately used as a composition for mechanical foaming. Hereinafter, each component will be described in detail.

[0023] (1) Inorganic phosphate compounds

[0024] The polyurethane foam involved in the present technology is characterized by using an inorganic phosphoric acid compound. By using an inorganic phosphoric acid compound and expanded graphite described later, even a polyurethane foam with a density of 150 kg / m 3 The above polyurethane foams can also exhibit high flame retardancy.

[0025] As long as the purpose and effect of the present technology are not impaired, the inorganic phosphate compound that can be used in the present technology can be freely selected and used from one or more inorganic phosphate compounds that can be used in the production of polyurethane foam. For example, inorganic polyphosphates such as ammonium polyphosphate, inorganic phosphates such as ammonium phosphate, etc. can be listed.

[0026] As long as the purpose and effect of the present technology are not impaired, the amount of the inorganic phosphate compound in the composition used in the manufacture of the polyurethane foam involved in the present technology can be freely set. In the present technology, the lower limit of the content of the inorganic phosphate compound in the composition is, for example, 10 parts by mass or more, preferably 15 parts by mass or more, and more preferably 20 parts by mass or more relative to 100 parts by mass of the polyol described later. By making the lower limit of the content of the inorganic phosphate compound in the composition within this range, the flame retardancy of the manufactured polyurethane foam can be further improved.

[0027] In the present technology, the upper limit of the content of the inorganic phosphate compound in the composition is, for example, 80 parts by mass or less, preferably 70 parts by mass or less, and more preferably 60 parts by mass or less relative to 100 parts by mass of the polyol described later. By setting the upper limit of the content of the inorganic phosphate compound in the composition within this range, it is possible to contribute to cost reduction and improve the mechanical properties of the manufactured polyurethane foam.

[0028] (2) Expanded graphite

[0029] The polyurethane foam involved in the present technology is characterized by using expanded graphite. By using the above-mentioned inorganic phosphoric acid compound and expanded graphite, even if the density is 150kg / m 3 The above polyurethane foams can also exhibit high flame retardancy.

[0030] As long as the purpose and effect of the present technology are not impaired, the amount of expanded graphite in the composition used in the manufacture of the polyurethane foam involved in the present technology can be freely set. In the present technology, the lower limit of the content of the expanded graphite in the composition is, for example, 10 parts by mass or more, preferably 15 parts by mass or more, and more preferably 20 parts by mass or more relative to 100 parts by mass of the polyol described later. By making the lower limit of the content of the expanded graphite in the composition within this range, the flame retardancy of the manufactured polyurethane foam can be further improved.

[0031] In the present technology, the upper limit of the content of the expanded graphite in the composition is, for example, 80 parts by mass or less, preferably 70 parts by mass or less, and more preferably 60 parts by mass or less relative to 100 parts by mass of the polyol described later. By setting the upper limit of the content of the expanded graphite in the composition within this range, it is possible to help reduce costs and improve the mechanical properties of the manufactured polyurethane foam.

[0032] As long as the purpose and effect of the present technology are not damaged, the total amount of the aforementioned inorganic phosphate compound and expanded graphite in the composition used in the manufacture of the polyurethane foam involved in the present technology can also be freely set. In the present technology, the lower limit of the total amount of the inorganic phosphate compound and expanded graphite in the composition is, for example, 20 mass parts or more relative to 100 mass parts of polyols described later, preferably 30 mass parts or more, more preferably 40 mass parts or more, further preferably 43 mass parts or more, and further preferably 50 mass parts or more. By making the lower limit of the total amount of the inorganic phosphate compound and expanded graphite in the composition within the range, the flame retardancy of the manufactured polyurethane foam can be further improved.

[0033] In the present technology, the upper limit of the total amount of the inorganic phosphate compound and the expanded graphite in the composition is, for example, less than 160 mass parts, preferably less than 120 mass parts, more preferably less than 100 mass parts relative to 100 mass parts of polyols described later. By making the upper limit of the total amount of the inorganic phosphate compound and the expanded graphite in the composition within the range, it is helpful to reduce costs, and during manufacturing, it is possible to prevent the viscosity of the mixture of raw materials from becoming too high, as a result, it is possible to improve workability. In addition, it is possible to improve the mechanical properties of the manufactured polyurethane foam.

[0034] (3) Polyols

[0035] As the polyol that can be used in the present technology, one or more polyols that can be used in the production of polyurethane foam can be freely selected and used as long as the purpose and effect of the present technology are not impaired. For example, polyester polyol, polycarbonate polyol, polyether polyol, polyester ether polyol, etc. can be listed.

[0036] Examples of the polyester polyol include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid; aliphatic carboxylic acids such as ricinoleic acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid; alicyclic dicarboxylic acids such as hexahydrophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid; or polyester polyols such as polypropylene glycol obtained by dehydration condensation reaction of acid esters or anhydrides thereof with ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, or a mixture thereof; and polylactone polyols and polycaprolactone polyols obtained by ring-opening polymerization of lactone monomers such as ε-caprolactone and methylvalerolactone. In addition to these, examples of the polyester polyol include polyols having a naturally-derived ester group.

[0037] Examples of the polycarbonate polyol include those obtained by reacting at least one of polyols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, and diethylene glycol with diethylene carbonate, dimethyl carbonate, diethyl carbonate, and the like.

[0038] As polyether polyol, for example, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol etc. obtained by polymerizing cyclic ethers such as ethylene oxide, propylene oxide, tetrahydrofuran, etc., and their copolyethers can be listed. In addition, it is also possible to use polyols such as glycerol or trimethylolethane to polymerize the above-mentioned cyclic ethers.

[0039] Examples of the polyester ether polyol include those obtained by dehydration condensation reaction of aliphatic, aromatic or alicyclic dicarboxylic acids exemplified in the polyester polyol; or acid esters or anhydrides thereof with diols such as diethylene glycol or propylene oxide adducts, or mixtures thereof.

[0040] In the present technology, considering the environment, biodegradable polyols can also be used. As biodegradable polyols that can be used in the present technology, as long as the purpose and effect of the present technology are not damaged, one or more biodegradable polyols that can be used in the manufacture of polyurethane foam can be freely selected. For example, polyglycolic acid (PGA), polylactic acid (PLA), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), polycaprolactone (PCL), polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyhydroxyalkanoic acid (PHA), cellulose, cellulose acetate, chitosan, starch, processed starch, xylitol, sorbitol, mannitol, maltitol, castor oil polyols and the like having hydroxyl groups and natural esters, etc.

[0041] (4) Isocyanate

[0042] As long as the purpose and effect of the present technology are not impaired, one or more isocyanates that can be used in the manufacture of polyurethane foam can be freely selected and used. For example, one or more of aromatic isocyanates, aliphatic isocyanates and alicyclic isocyanates can be freely used in combination.

[0043] Examples of the aromatic isocyanate that can be used in the present technology include 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, xylylene diisocyanate, 3,3′-dimethyl-4,4′-biphenyl diisocyanate, and 3,3′-dimethoxy-4,4′-biphenyl diisocyanate.

[0044] Examples of aliphatic isocyanates that can be used in the present technology include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethylhexanoate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, 1,5-pentamethylene diisocyanate (PDI), decamethylene diisocyanate, and derivatives thereof.

[0045] Examples of the alicyclic isocyanate include monocyclic alicyclic isocyanates such as 1,3-cyclopentane diisocyanate, 1,3-cyclopentane diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), dimer acid diisocyanate, trans-cyclohexane 1,4-diisocyanate, hydrogenated toluene diisocyanate (hydrogenated TDI), and hydrogenated tetramethylxylylene diisocyanate (hydrogenated TMXDI); crosslinked cyclic alicyclic isocyanates such as norbornene diisocyanate, norbornene diisocyanate methyl, dicycloheptane triisocyanate, isocyanate methyl dicycloheptane, and di(diisocyanatomethyl)tricyclodecane; and derivatives thereof.

[0046] The amount of isocyanate used in the present technology can be freely set as long as it does not damage the purpose and effect of the present technology. In the present technology, the lower limit of the isocyanate in the composition is, for example, 20 mass parts or more relative to 100 mass parts of polyols, preferably 40 mass parts or more, and more preferably 60 mass parts or more. In addition, even if the amount of isocyanate is small, there is no problem as long as the amount of isocyanate and polyol is consistent, but when the isocyanate index is less than 80, it sometimes causes the mechanical strength (tensile elongation) of the manufactured polyurethane foam to be insufficient or the hardness is insufficient. Therefore, in the present technology, the isocyanate index is preferably 80 or more, more preferably 85 or more, and further preferably 90 or more. By setting the lower limit of the isocyanate index within this range, the mechanical strength (tensile elongation) and hardness of the manufactured polyurethane foam can be improved.

[0047] In the present technology, the upper limit of the content of the isocyanate in the composition is, for example, 300 mass parts or less relative to 100 mass parts of polyols, preferably 200 mass parts or less, and more preferably 150 mass parts or less. By making the upper limit of the content of the isocyanate in the composition within this range, there is an advantage of reducing costs. In addition, as mentioned above, even if the amount of isocyanate is large, there is no problem as long as the amount of isocyanate and polyol is consistent, but if the isocyanate index exceeds 150, the mechanical strength (tensile elongation) or hardness of the manufactured polyurethane foam becomes too large, and sometimes the flexibility is impaired. Therefore, in the present technology, the isocyanate index is preferably 150 or less, more preferably 140 or less, and further preferably 130 or less. By setting the lower limit of the isocyanate index within this range, the mechanical strength (tensile elongation) and hardness of the manufactured polyurethane foam can be prevented from becoming too large, and a soft polyurethane foam with improved flexibility can be made.

[0048] (5) Foam stabilizer

[0049] In the production of the polyurethane foam involved in the present technology, a foam stabilizer can be used. As the foam stabilizer that can be used in the present technology, one or more foam stabilizers that can be used in the production of the polyurethane foam can be freely selected and used as long as the purpose and effect of the present technology are not impaired.

[0050] Examples of the foam stabilizer include silicone foam stabilizers, fluorine-containing compound foam stabilizers, surfactants, etc. Examples of the silicone foam stabilizer include silicone foam stabilizers mainly composed of siloxane chains, silicone foam stabilizers in which siloxane chains and polyether chains adopt a linear structure, branched and forked silicone foam stabilizers, silicone foam stabilizers in which polyether chains are modified into pendant shapes on siloxane chains, etc.

[0051] As long as the purpose and effect of the present technology are not impaired, the amount of the foam stabilizer in the composition used in the manufacture of the polyurethane foam involved in the present technology can be freely set. In the present technology, the lower limit of the content of the foam stabilizer in the composition is, for example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more, and more preferably 0.5 parts by mass or more relative to 100 parts by mass of the polyol. By setting the lower limit of the content of the foam stabilizer in the composition within this range, the foaming reaction can be stabilized, and as a result, a polyurethane foam with excellent mechanical properties and appearance can be obtained.

[0052] In the present technology, the upper limit of the content of the foam stabilizer in the composition is, for example, 10 parts by mass or less, preferably 7 parts by mass or less, and more preferably 5 parts by mass or less, relative to 100 parts by mass of the polyol. By setting the upper limit of the content of the foam stabilizer in the composition within this range, it can contribute to cost reduction.

[0053] (6) Catalyst

[0054] A catalyst can be used in the production of the polyurethane foam according to the present technology. As the catalyst that can be used in the present technology, one or two or more catalysts that can be used in the production of the polyurethane foam can be freely selected and used as long as the purpose and effect of the present technology are not impaired.

[0055] Examples of the catalyst include metal catalysts (organometallic catalysts) such as organic iron compounds, organic nickel compounds, organic tin compounds, organic bismuth compounds, organic lead compounds, organic cobalt compounds, organic zirconium compounds, and organic zinc compounds; triethylamine, triethylenediamine (TEDA), tetramethylguanidine, diethanolamine, bis(2-dimethylaminoethyl) ether, N,N,N',N",N"-pentamethyldiethylenetriamine, imidazole compounds, dimethylpiperazine, N-methyl-N'-(2-dimethylaminoethyl) ether, and the like. ) piperazine amines such as ethylpiperazine, N-methyl-N'-(2-hydroxyethyl)piperazine, morpholine amines such as N-methylmorpholine, N-ethylmorpholine, 1,8-diazabicyclo-[5,4,0]-undecene-7 (DBU), 1,5-diazabicyclo-[4,3,0]-nonene-5 (DBN), 1,8-diazabicyclo-[5.3.0]-decene-7 (DBD), 1,4-diazabicyclo-[3,3,0]octene-4 (DBO) and other amines known as DBU homologues.

[0056] As long as the purpose and effect of the present technology are not impaired, the amount of the catalyst in the composition used in the manufacture of the polyurethane foam involved in the present technology can be freely set. In the present technology, the lower limit of the content of the catalyst in the composition is, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more, and more preferably 0.1 parts by mass or more relative to 100 parts by mass of the polyol. By setting the lower limit of the catalyst content in the composition within this range, various reactions during manufacture can be promoted, and as a result, a polyurethane foam with excellent mechanical properties and appearance can be obtained.

[0057] In the present technology, the upper limit of the content of the catalyst in the composition is, for example, 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 2 parts by mass or less relative to 100 parts by mass of the polyol. By setting the upper limit of the content of the catalyst in the composition within this range, it is possible to prevent various reactions from becoming unstable during production. As a result, a polyurethane foam having excellent mechanical properties and appearance can be obtained.

[0058] (7) Gas for bubble generation

[0059] In the production of polyurethane foam involved in the present technology, a foaming gas can be used. As the foaming gas that can be used in the present technology, one or more foaming gases that can be used in the production of polyurethane foam can be freely selected and used as long as the purpose and effect of the present technology are not impaired.

[0060] As the gas for foaming, for example, inert gases such as dry air and nitrogen can be cited. As long as the purpose and effect of the present technology are not impaired, the mixing ratio of the gas for foaming and other raw materials can be freely set according to the purpose of the manufactured polyurethane foam, etc. In the present technology, the mixing ratio of the gas for foaming and other raw materials can be set to, for example, 10% by volume or more, preferably 15% by volume or more, and more preferably 20% by volume or more in 100% by volume of the total of the gas for foaming and other raw materials.

[0061] In the present technology, the upper limit of the mixing ratio of the bubble forming gas and other raw materials can be set to, for example, 100 volume % or less, preferably 95 volume % or less, and more preferably 90 volume % or less, based on 100 volume % of the total of the bubble forming gas and other raw materials.

[0062] (8) Foaming agent

[0063] As described later, the polyurethane foam involved in the present technology can be produced by a mechanical foaming method, so in this case, the polyurethane foam involved in the present technology can be produced even without a foaming agent, but a foaming agent can also be used in the present technology. As the foaming agent that can be used in the present technology, one or more foaming agents that can be used in the production of the polyurethane foam can be freely selected and used as long as the purpose and effect of the present technology are not impaired.

[0064] As a foaming agent that can be used in the present technology, any of a chemical foaming agent and a physical foaming agent can be used. As a chemical foaming agent, for example, a reactive foaming agent that generates carbon dioxide by reacting with the aforementioned isocyanates such as water, formic acid, acetic acid, and other carboxylic acids to cause foaming, and an organic or inorganic thermal decomposition type chemical foaming agent can be listed. As an organic foaming agent, azodicarbonamide (ADCA), azodicarboxylic acid metal salts (barium azodicarboxylate, etc.), azobisisobutyronitrile (AIBN) and other azo compounds, N, N'-dinitrosopentamethylenetetramine (DPT) and other nitroso compounds, hydrazine dicarbonamide, 4, 4'-oxybis (benzenesulfonyl hydrazide), toluenesulfonyl hydrazide (TSH) and other hydrazine derivatives, toluenesulfonyl semicarbazide and other semicarbazide compounds, etc. As an inorganic foaming agent, ammonium carbonate, sodium carbonate, ammonium bicarbonate, sodium bicarbonate, ammonium nitrite, sodium borohydride, anhydrous monosodium citrate, etc. can be listed.

[0065] Examples of the physical blowing agent include freons such as hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs), halogen-containing hydrocarbons such as hydrofluoroolefins (HFOs) and methylene chloride, volatile hydrocarbons such as heptane, hexane, pentane, and cyclopentane, carbon dioxide, nitrogen, and air.

[0066] As long as the purpose and effect of the present technology are not impaired, the amount of the blowing agent in the composition used in the manufacture of the polyurethane foam involved in the present technology can be freely set. In the present technology, the content of the blowing agent in the composition is, for example, 10 parts by mass or less, preferably 7 parts by mass or less, and more preferably 5 parts by mass or less relative to 100 parts by mass of the polyol. By making the upper limit of the content of the blowing agent in the composition within this range, it is possible to suppress poor formation caused by excessive foaming, and it can also help to reduce costs.

[0067] (9) Antioxidants

[0068] The present technology is characterized in that an antioxidant is used. As the antioxidant that can be used in the present technology, one or more antioxidants that can be used in the production of polyurethane foam can be freely selected and used as long as the effect of the present technology is not impaired. For example, one or more of naphthylamine, diphenylamine, p-phenylenediamine, quinoline, hydroquinone derivatives, monophenol, thiobisphenol, hindered phenol, phosphite, etc. can be freely used in combination.

[0069] As long as the purpose and effect of the present technology are not impaired, the amount of the antioxidant in the composition used in the manufacture of the polyurethane foam involved in the present technology can be freely set. In the present technology, the lower limit of the content of the antioxidant in the composition is, for example, 0.01 parts by mass or more, preferably 0.03 parts by mass or more, and more preferably 0.05 parts by mass or more relative to 100 parts by mass of the polyol. By making the lower limit of the content of the antioxidant in the composition within this range, the effect of preventing discoloration caused by preventing scorching can be improved.

[0070] In the present technology, the upper limit of the content of the antioxidant in the composition is, for example, 5 parts by mass or less, preferably 4 parts by mass or less, and more preferably 3 parts by mass or less relative to 100 parts by mass of the polyol. By making the upper limit of the content of the antioxidant in the composition within this range, it can help reduce costs.

[0071] (10) Moisture adsorbent

[0072] In the manufacture of the polyurethane foam involved in the present technology, a moisture adsorbent can be used. As the moisture adsorbent that can be used in the present technology, as long as the purpose and effect of the present technology are not impaired, one or more moisture adsorbents that can be used in the polyurethane foam can be freely selected and used. In particular, when water is not used as a foaming agent, it is preferable to use a moisture adsorbent so that physical properties and density can be controlled.

[0073] Examples of the moisture adsorbent include zeolite, silica gel, calcium oxide, activated carbon, potassium hydroxide, sodium hydroxide, and lithium hydroxide.

[0074] The amount of the moisture adsorbent in the composition used for the production of the polyurethane foam according to the present technology can be freely set as long as the purpose and effect of the present technology are not impaired. In the present technology, the lower limit of the content of the moisture adsorbent in the composition is, for example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more, and more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the polyol.

[0075] In the present technique, the upper limit of the content of the moisture adsorbent in the composition is, for example, 10 parts by mass or less, preferably 7 parts by mass or less, and more preferably 5 parts by mass or less, relative to 100 parts by mass of the polyol.

[0076] (11) Others

[0077] In the production of the polyurethane foam according to the present technique, as other components, one or two or more of various components that can be used for the production of the polyurethane foam can be freely selected and used according to the purpose, unless the object and effect of the present technique are impaired.

[0078] Examples of components that can be used in the production of the polyurethane foam according to the present technique include flame retardants other than inorganic phosphate compounds and expanded graphite, pigments, stabilizers, plasticizers, colorants, crosslinking agents, antimicrobial agents, dispersants, and ultraviolet absorbers.

[0079] 2. Polyurethane foam

[0080] The polyurethane foam involved in the present technology contains an inorganic phosphoric acid compound and expanded graphite. In addition, it may also contain a gas for foaming. That is, the polyurethane foam involved in the present technology is manufactured using the aforementioned composition. The amount of the inorganic phosphoric acid compound, expanded graphite and the gas for foaming in the polyurethane foam involved in the present technology is the same as that in the aforementioned composition, so the description is omitted here.

[0081] (1) Density

[0082] The polyurethane foam involved in this technology is characterized in that its density is 150kg / m 3 Because the density of the polyurethane foam involved in this technology is 150kg / m 3 As described above, it can be applied to cushioning materials for vibration or impact cushioning of electronic devices such as mobile phones, cameras, and televisions, or electrical devices such as home appliances, sealing materials for various batteries, and sealing materials around batteries or electronic control units of electric vehicles.

[0083] If the density of the polyurethane foam involved in this technology is 150kg / m 3 Above, the effect of the present technology can be exerted, but 180 kg / m 3 More preferably, 200 kg / m3 above.

[0084] The upper limit of the density of the polyurethane foam involved in the present technology can be freely set as long as the purpose and effect of the present technology are not impaired, for example, 1200 kg / m 3 Below, preferably 1000kg / m 3 Below, more preferably 800kg / m 3 By setting the density of the polyurethane foam within this range, cushioning properties can be imparted without impairing the flexibility of the polyurethane foam (preventing hardening).

[0085] (2) Thickness

[0086] The thickness of the polyurethane foam according to the present technology can be freely set as long as the object and effect of the present technology are not impaired. However, the polyurethane foam according to the present technology has excellent flame retardancy even when the thickness is 10 mm or less.

[0087] As long as the purpose and effect of the present technology are not impaired, the lower limit of the thickness of the polyurethane foam involved in the present technology can be freely set, for example, to 0.5 mm or more, preferably 0.8 mm or more, and more preferably 1 mm or more. By setting the thickness of the polyurethane foam within this range, better flame retardancy can be exerted.

[0088] The upper limit of the thickness of the polyurethane foam according to the present technique can be freely set as long as the object and effect of the present technique are not impaired, and is, for example, 10 mm or less, preferably 9.5 mm or less, and more preferably 9.0 mm or less.

[0089] (3) Purpose

[0090] The polyurethane foam involved in this technology can be used for all purposes in all fields due to its high quality. For example, it can be applied to furniture such as sofas and chairs, bedding such as mattresses and pillows, clothing such as underwear, daily necessities such as tableware and cleaning sponges, vehicle seats and other vehicle and aircraft interior products, building joint materials, building cushioning materials, building sealing materials, home appliance sealing materials, electrical equipment cushioning materials, electronic equipment cushioning materials, electrical equipment sealing materials, electronic equipment sealing materials, various battery sealing materials, sound insulation materials, packaging materials, vehicle insulation materials, vehicle battery sealing materials, vehicle electronic control unit sealing materials, anti-condensation materials, inner packaging materials, home appliance insulation materials, piping insulation materials, various covers, cushioning materials, toys, groceries, etc.

[0091] Since the polyurethane foam according to the present technology has excellent flame retardancy, it can be suitably used around heat sources in various applications.

[0092] 3. Batteries or electrical devices

[0093] The battery or electrical device involved in the present technology is a battery or electrical device using the polyurethane foam involved in the present technology. Examples of the battery or electrical device include personal computers (electronic computers), PDAs (portable information terminals), mobile phones, telephones, camcorders, digital still cameras, televisions, electronic books, electronic dictionaries, music players, radios, headphones, game consoles, navigation systems, pacemakers, hearing aids, power tools, electric shavers, refrigerators, air conditioners, stereos, water heaters, microwave ovens, dishwashers, washing machines, dryers, lighting equipment, toys, medical equipment, robots, load regulators, signal machines, etc.

[0094] 4. Method for producing polyurethane foam

[0095] The polyurethane foam of the present technology can be produced by mixing the components of the above-mentioned composition to prepare a composition, and performing a resinization reaction and a foaming reaction. The resinization reaction and the foaming reaction method can be freely combined with general methods and adopted as long as the purpose and effect of the present technology are not impaired.

[0096] In the method for producing polyurethane foam involved in the present technology, it is particularly preferred to use a mechanical foaming method. By using the mechanical foaming method, a high-density polyurethane foam can be produced compared to a chemical foaming method. In addition, a thin polyurethane foam can also be produced.

[0097] As a specific method of the mechanical foaming method, a general mechanical foaming method can be adopted as long as the purpose and effect of the present technology are not impaired. For example, the mixed raw materials other than the gas for foaming of the above-mentioned composition are put into a mixing head, and after stirring and mixing until homogeneous while mixing the gas for foaming, the polyurethane foam can be produced by heating and curing on a release paper or in a molding mold.

[0098] Example

[0099] Hereinafter, the present technology will be described in further detail based on examples. In addition, the examples described below are only examples of representative examples of the present technology, and the scope of the present technology should not be narrowly interpreted therefrom.

[0100] (1) Raw materials

[0101] Polyol 1: Polyoxyalkylene polyol (polyether polyol obtained by polymerization of ethylene oxide and propylene oxide, number of functional groups: 3, molecular weight: 3300, hydroxyl value 50 mgKOH / g)

[0102] Polyol 2: Polyoxypropylene polyether polyol (number of functional groups: 2, molecular weight: 2000, hydroxyl value 56 mgKOH / g)

[0103] Polyol 3: Polyoxypropylene polyether polyol (number of functional groups: 3, molecular weight: 600, hydroxyl value 280mgKHO / g)

[0104] Polyol 4: Castor oil-based polyol (number of functional groups: 2.5, molecular weight: 645, hydroxyl value 217 mgKOH / g)

[0105] Foam stabilizer: Siloxane foam stabilizer (Dow Toray Co., Ltd. "SZ-1952")

[0106] Catalyst 1: Nickel-based metal catalyst (Kusumoto Chemicals Co., Ltd. "K-KAT")

[0107] Catalyst 2: Iron-based metal catalyst (Nippon Chemical Industry Co., Ltd. "FIN-P1")

[0108] Pigment: Carbon black

[0109] Antioxidant: Hindered phenol antioxidant (Songwon Industrial Co., Ltd. "Songnox 1135")

[0110] Moisture adsorbent: Zeolite

[0111] Flame retardant: ammonium polyphosphate, expanded graphite or aluminum hydroxide

[0112] Isocyanate: Aromatic isocyanate (NCO% 33.5) (BASF INOAC Polyurethanes Ltd. "Lupranate M5S")

[0113] Bubble making gas: Nitrogen

[0114] (2) Production of polyurethane foam

[0115] The above components were prepared in the mixing ratios shown in Table 4 below to obtain mixed raw materials for each example and each comparative example. Next, the mixed raw materials were put into a mixing head, and a foaming gas (inert gas: nitrogen) was mixed in the mixing ratio (volume %) shown in Table 4 below while being stirred and mixed until homogeneous. Then, the mixed raw materials were supplied on a film of a predetermined thickness supplied continuously so as to have a thickness shown in Table 1 below, and then heated and cured at 120 to 200° C., thereby producing a sheet-like polyurethane foam.

[0116] (3) Evaluation

[0117] [Compressive residual strain]

[0118] The compressive residual strain was measured according to JIS K6401. A value of 10% or less was considered acceptable.

[0119] [Flame retardancy]

[0120] The flame retardancy was evaluated in accordance with the UL94 standard.

[0121] <Horizontal combustion test of foam materials: HBF, HF-1>

[0122] A test piece (50±1 mm in length×150±5 mm in width×13 mm in thickness) cut out from the polyurethane foam of each example and each comparative example was placed horizontally on a metal mesh maintained horizontally, and a flame was brought into contact with one end of the test piece for 60 seconds.

[0123] The HBF method determines that the sample is acceptable when the burning rate between the 25 mm mark and the 125 mm mark satisfies the criteria shown in Table 1 below.

[0124] [Table 1]

[0125] [Judgment criteria]

[0126]

[0127] ※If the light goes out before the marking, it is also considered a pass.

[0128] The HF method was passed when the combustion behavior and the presence or absence of ignition of the cotton placed 175±25 mm below the metal mesh satisfied the criteria shown in Table 2 below.

[0129] [Table 2]

[0130]

[0131] ※ UL94HBF judgment criteria: The burning speed is 40mm / min or less between the 100mm markings, or the burning ends at the 125mm marking.

[0132] <Vertical combustion test of foam materials: V-0, V-1>

[0133] A test piece (50±1 mm in length × 150±5 mm in width × 13 mm in thickness) cut out from the polyurethane foam of each embodiment and each comparative example was vertically mounted on a fixture and subjected to two 10-second flame contact tests with a 20 mm flame. The burning behavior and the presence or absence of ignition of the cotton placed 300±10 mm below the lower end of the test piece were considered acceptable if the criteria shown in the following Table 3 were met.

[0134] [Table 3]

[0135]

[0136] [Viscosity]

[0137] The viscosity of the mixture of raw materials other than isocyanate at 23° C. was measured using a Brookfield touch panel viscometer “DV2T”.

[0138] (4) Results

[0139] The results are shown in Table 4 below.

[0140]

[0141]

[0142] (5) Investigation

[0143] As shown in Table 4, the inorganic phosphoric acid compound and expanded graphite are contained and the density is 150 kg / m 3 All the above Examples 1 to 21 were evaluated as good. On the other hand, Comparative Example 1, which did not use a flame retardant, failed in all the combustion tests. In addition, Comparative Examples 2 to 6, which used aluminum hydroxide instead of the inorganic phosphate compound and expanded graphite, passed the horizontal combustion test: the HBF method combustion test, but failed in the HF method and the vertical combustion test.

[0144] Comparing the examples, Examples 17 to 20, which have a thickness of less than 1 mm, passed the horizontal combustion test: HF method, but failed the vertical combustion test. On the other hand, other examples with a thickness of 1 mm or more also passed the vertical combustion test. From this result, it can be seen that even if the thickness of the polyurethane foam is less than 1 mm, a sufficient flame retardant effect can be obtained, but if it is 1 mm or more, the flame retardancy is further improved.

Claims

1. A polyurethane foam containing an inorganic phosphoric acid compound and expanded graphite, with a density of 150 kg / m 3 above.

2. The polyurethane foam according to claim 1, which has a thickness of 10 mm or less.

3. A battery or an electric device comprising the polyurethane foam according to claim 1 or 2.

4. A method for producing a polyurethane foam according to claim 1 or 2, comprising the step of mixing a polyol, an isocyanate, an inorganic phosphoric acid compound, expanded graphite and a gas.

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