Composition for manufacturing polyurethane foam, and foam

Abstract

To provide a composition for manufacturing a polyurethane foam that provides a foam (polyurethane foam) having excellent rebound resilience.SOLUTION: The present invention is a composition for manufacturing a polyurethane foam containing a polyol component, a blowing agent, a catalyst and a polyisocyanate. The polyol component is obtained by subjecting to an esterification reaction a polyalkylene ether glycol containing polytrimethylene ether glycol, a dibasic acid composed of an aliphatic dicarboxylic acid, and at least one selected from an aliphatic hydrocarbon having two or more hydroxy groups and castor oil. The hydroxyl value of the polyol component is preferably 25 to 130 mgKOH / g.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition for producing polyurethane foam, which is used to produce a foam (polyurethane foam) having excellent impact resilience. [Background technology]

[0002] Polyurethane resin foams are widely used as elastic materials, buffer materials, sound-absorbing materials, etc. For example, Patent Document 1 discloses, as a technology for use as a cushioning material, a polyurethane foam composition containing at least: a) 10 to 100 mass% of the total polyol components of a polyester polyol (A) having a structure obtained by condensing 6 to 28 moles of a hydroxycarboxylic acid having 15 or more carbon atoms with 1 mole of a polyhydric alcohol adjusted to have 2 to 4 hydroxyl groups per molecule; b) 0 to 90 mass% of the total polyol components of a polyol; c) a polyisocyanate in an amount such that the NCO index is 0.70 to 1.30; d) a catalyst; e) a foam stabilizer; and f) water; and a foam obtained using this composition. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2006-2145 Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, a technology has been discovered that enables polytriethylene ether glycol and polytetramethylene ether glycol to be produced from plant-derived raw materials, and these polyols are said to be useful for reducing the burden on the global environment. An object of the present invention is to provide a composition for producing polyurethane foam that can be produced using plant-derived raw materials and that can give foams (polyurethane foams) with excellent impact resilience, from the viewpoint of reducing the burden on the global environment. [Means for solving the problem]

[0005] The present inventors have discovered that, in a composition for producing polyurethane foam containing a polyol component, a blowing agent, a catalyst, and a polyisocyanate, foams with excellent rebound resilience can be obtained by using, as the polyol component, a polyalkylene ether glycol obtained by an esterification reaction of a polyalkylene ether glycol including polytrimethylene ether glycol, a dibasic acid consisting of an aliphatic dicarboxylic acid, and at least one selected from aliphatic hydrocarbons having two or more hydroxy groups and castor oil.

[0006] The present invention is as follows. 1. A composition for producing polyurethane foam, comprising a polyol component, a blowing agent, a catalyst, and a polyisocyanate, The polyol component is a composition for producing polyurethane foam, characterized in that it is obtained by an esterification reaction of a polyalkylene ether glycol including polytrimethylene ether glycol, a dibasic acid consisting of an aliphatic dicarboxylic acid, and at least one selected from an aliphatic hydrocarbon having two or more hydroxy groups and castor oil. 2. The composition for producing polyurethane foam according to item 1, wherein the aliphatic dicarboxylic acid includes succinic acid or sebacic acid. 3. The composition for producing a polyurethane foam according to item 1, wherein the aliphatic hydrocarbon having two or more hydroxy groups comprises an aliphatic triol. 4. The composition for producing a polyurethane foam according to item 1, wherein the polyol component has a hydroxyl value of 25 to 130 mgKOH / g. 5. A foam obtained by using the composition for producing a polyurethane foam according to item 1 above. [Effects of the Invention]

[0007] The polyurethane foam-producing composition of the present invention allows for the efficient production of foams (polyurethane foams) with excellent impact resilience. These foams are typically flexible foams. Furthermore, the polyalkylene ether glycol used in the production of the polyol component contains polytrimethylene ether glycol. Since this polytrimethylene ether glycol can be produced from plant-derived raw materials, the biomass content (biomass content of the raw materials) of the polyurethane foam-producing composition of the present invention can be increased. While the biomass content can be increased by using polytetramethylene ether glycol, the impact resilience of a polyurethane foam-producing composition containing a polyol component produced using a polyalkylene ether glycol containing polytetramethylene ether glycol but not polytrimethylene ether glycol is slightly reduced. Furthermore, the biomass content can be increased by using castor oil in the production of the polyol component. DETAILED DESCRIPTION OF THE INVENTION

[0008] The composition for producing polyurethane foam of the present invention is a composition containing a polyol component obtained by a specific preparation method, a blowing agent, a catalyst, and a polyisocyanate.

[0009] The polyol component is a composition comprising a reaction product obtained by an esterification reaction between a polyalkylene ether glycol including polytrimethylene ether glycol, a dibasic acid consisting of an aliphatic dicarboxylic acid, and at least one selected from an aliphatic hydrocarbon having two or more hydroxy groups and castor oil.

[0010] The polyalkylene ether glycol is a compound represented by the following general formula (1). HO-[C m H 2m -O] n -H (1) (In the formula, m is an integer of 1 or more, and n is an integer of 2 or more.)

[0011] In the above general formula (1), m is an integer of 1 or more, preferably 3 to 4. Furthermore, n is an integer of 2 or more, preferably 8 to 60, more preferably 10 to 50, and even more preferably 10 to 35.

[0012] The polyalkylene ether glycol according to the present invention includes polytrimethylene ether glycol represented by the following general formula (2). HO-[(CH2)3-O] n -H (2) (In the formula, n is an integer of 2 or more, preferably 12 to 40, and more preferably 16 to 35.)

[0013] The polytrimethylene ether glycol can be produced from plant-derived raw materials, which contributes to reducing the burden on the global environment and increases the biomass content of the raw materials.

[0014] The polyalkylene ether glycol according to the present invention may consist solely of polytrimethylene ether glycol, or may further contain other polyalkylene ether glycols such as polytetramethylene ether glycol and polypropylene ether glycol. The lower limit of the content of polytrimethylene ether glycol in the polyalkylene ether glycol is preferably 20% by mass, more preferably 50% by mass.

[0015] A polyol component obtained using a polyalkylene ether glycol containing polytrimethylene ether glycol has a viscosity that is easy to handle for efficiently producing a composition for producing polyurethane foam, compared to a polyol component obtained using a polyalkylene ether glycol containing polytetramethylene ether glycol but not containing polytrimethylene ether glycol. Specifically, a polyol component having a viscosity of preferably less than 6000 mPa s as measured in accordance with JIS Z 8803 can be prepared.

[0016] The dibasic acid used in preparing the polyol component is an aliphatic dicarboxylic acid, and is a compound represented by the following general formula (3). HOOC-R 1 -COOH (3) (In the formula, R 1 is an aliphatic hydrocarbon group)

[0017] R in the above general formula (3) 1 is an aliphatic hydrocarbon group, which may be either a straight-chain hydrocarbon group or a branched hydrocarbon group.

[0018] Examples of the aliphatic dicarboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, 1,12-dodecanedioic acid, undecanedicarboxylic acid, and dimer acid. 1 The number of carbon atoms is preferably 2 to 10, more preferably 2 to 8, and particularly preferably 6. The aliphatic dicarboxylic acid is preferably succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, or sebacic acid, and particularly preferably sebacic acid. This sebacic acid can be obtained by cleaving castor oil with caustic alkali, and therefore, using the sebacic acid obtained by this process contributes to reducing the burden on the global environment and increases the biomass content of the raw material, similar to polytrimethylene ether glycol.

[0019] In the present invention, the dibasic acid to be subjected to the esterification reaction may be one kind or two or more kinds.

[0020] The aliphatic hydrocarbon having two or more hydroxy groups (hereinafter referred to as "polyhydroxy compound") used in preparing the polyol component can be a diol, triol, tetraol, pentaol, hexaol, or the like.

[0021] Examples of polyhydroxy compounds include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 2-methyl-1,8-octanediol, glycerin, trimethylolethane, trimethylolpropane, tributyrolpropane, hexanetriol, pentaerythritol, and sorbitol.

[0022] In the present invention, the polyhydroxy compound to be subjected to the esterification reaction may be one kind or two or more kinds. Preferably, the polyhydroxy compound according to the present invention comprises a triol, i.e., an aliphatic triol.

[0023] As the castor oil used in preparing the polyol component, oil extracted from castor (ricinus) seeds or a purified product thereof can be used.

[0024] When polyalkylene ether glycol, dibasic acid, and at least one selected from aliphatic hydrocarbons having two or more hydroxy groups and castor oil are subjected to an esterification reaction to prepare the polyol component of the present invention, they are used in the following proportions, which ensure the production of a polyurethane foam that provides a foam with excellent rebound resilience.

[0025] When the polyalkylene ether glycol, dibasic acid, and polyhydroxy compound are subjected to the esterification reaction, the proportions of their amounts used are 70 to 95 mass%, 3 to 20 mass%, and 2 to 20 mass%, preferably 72 to 93 mass%, 4 to 18 mass%, and 3 to 18 mass%, and more preferably 76 to 92 mass%, 5 to 16 mass%, and 3 to 15 mass%, respectively. When the polyalkylene ether glycol, dibasic acid, and castor oil are subjected to the esterification reaction, the proportions of the amounts used are 40 to 70 mass%, 5 to 15 mass%, and 25 to 45 mass%, preferably 41 to 68 mass%, 6 to 14 mass%, and 26 to 44 mass%, and more preferably 43 to 65 mass%, 7 to 14 mass%, and 27 to 44 mass%, respectively.

[0026] The esterification reaction can be carried out without a solvent, but may also be carried out in the presence of a reaction solvent, such as xylene, methyl ethyl ketone, or cyclohexane.

[0027] The esterification reaction is preferably carried out while heating a mixture of all raw materials. The lower limit of the reaction temperature is preferably 150°C, more preferably 160°C, and the upper limit is preferably 250°C, more preferably 200°C. The atmosphere of the reaction system is not particularly limited and may be either air or an inert gas. When an inert gas is used, nitrogen gas, argon gas, helium gas, etc. can be used.

[0028] When an esterification reaction is carried out to prepare the above-mentioned polyol component, the reaction system usually contains a polyol component consisting of multiple reaction products and by-produced water. Therefore, by removing the water, a polyol component suitable as a raw material for the composition for producing polyurethane foam of the present invention can be obtained.

[0029] The polyol component obtained by the esterification reaction is usually liquid, and its viscosity (measured at 25°C using a B-type viscometer in accordance with JIS Z 8803) is preferably less than 6000 mPa s. When a polyol component having such a viscosity is used in combination with a catalyst, polyisocyanate, etc., a composition for producing polyurethane foam, which is used to produce polyurethane foams with excellent rebound resilience, can be efficiently produced. The hydroxyl value of the polyol component is preferably 25 to 130 mgKOH / g, more preferably 30 to 125 mgKOH / g.

[0030] The composition for producing polyurethane foam of the present invention may contain, in addition to the above polyol component, other polyol components, such as the above polyalkylene ether glycol, polyols other than the above polyhydroxy compounds, compounds having hydroxy groups and carboxy groups, soybean oil-based polyols, etc. The hydroxyl value of the other polyol components is not particularly limited, but is preferably 25 to 130 mgKOH / g.

[0031] When the composition for producing polyurethane foam of the present invention contains another polyol component, the upper limit of its content is preferably 50 parts by mass, more preferably 20 parts by mass, based on 100 parts by mass of the content of the above-mentioned polyol component.

[0032] Examples of blowing agents contained in the composition for producing polyurethane foam of the present invention include water, organic acids or esters thereof (formic acid, methyl formate, etc.) that generate carbon dioxide when reacted with isocyanates, hydrocarbons (isobutane, normal pentane, isopentane, cyclopentane, etc.), halogenated hydrocarbons (pentafluorobutane, pentafluoropropane, hexafluoropropane, heptafluoropropane, trans-1,2-dichloroethylene, 1-chloro-1,2,2,2-tetrafluoroethane, 1,1-dichloro-1-fluoroethane, 1,1,1,2-tetrafluoroethane, , 1,1,2,2-tetrafluoroethane, 1-chloro-1,1-difluoroethane, 1,1,1,3,3-pentafluorobutane, 1,1,1,2,3,3,3-heptafluoropropane, trichlorofluoromethane, dichlorodifluoromethane, 1,1,1,3,3,3-hexafluoropropane, 1,1,1,2,3,3-hexafluoropropane, difluoromethane, difluoroethane, 1,1,1,3,3-pentafluoropropane, 1,1-difluoroethane, etc.), ethers, halogenated ethers, etc., can be used.

[0033] The content of the blowing agent in the composition for producing polyurethane foam of the present invention is preferably 0.3 to 5.0 parts by mass, more preferably 0.5 to 3.5 parts by mass, per 100 parts by mass of all polyols, including those containing other polyol components.

[0034] The catalyst contained in the composition for producing polyurethane foam of the present invention can be one or more selected from amine compounds, transition metal compounds, and the like.

[0035] Examples of the amine compound include tertiary amines, imidazole compounds, ammonium salts, etc. Among these, tertiary amines are preferred, such as triethylenediamine, 1,8-diazabicycloundec-7-ene, tris(dimethylaminopropyl)amine, dimethylaminocyclohexylamine, bis(dimethylaminopropyl)-N-methylamine, N,N,N',N'-tetramethylethylenediamine, 1,1,4,7,7-pentamethyldiethylenetriamine, N,N-dimethylaminoethanol, N,N-dimethylaminoethoxyethanol, 2-[2-(2-dimethylaminoethoxy)ethoxy]ethanol, 1-(dimethylamino)-2-propanol, N,N-dimethylaminoethoxyisopropanol, N,N-dimethylaminoethoxyethoxyisopropanol, N,N,N'-trimethylaminoethoxyisopropanol, and N,N,N'-trimethylaminoethoxyisopropanol. trimethylaminoethylethanolamine, N,N-dimethylaminoethyl-N'-methylaminoisopropanol, bis[2-(dimethylamino)ethyl]ether, N,N,N'-trimethyl-N'-(2-hydroxyethyl)bis(2-aminoethyl)ether, N,N,N'-trimethyl-N'-hydroxyisopropylbis(2-aminoethyl)ether, N,N,N'-trimethyl-N'-(3-aminopropyl)bis(2-aminoethyl)ether, hexamethyltriethylenetetramine, N,N-dimethylaminoethyl-N'-methylaminoethyl-N''-methylaminoisopropanol, N,N-dimethylaminoethyl-N'-methylaminoethyl-N''-methylaminoethanol, and the like.

[0036] Examples of transition metal compounds include tin compounds, bismuth compounds, lead compounds, iron compounds, zinc compounds, cobalt compounds, nickel compounds, etc. Among these, tin compounds are preferred, and examples thereof include dibutyltin dilaurate, dimethyltin dilaurate, dioctyltin dilaurate, dimethyltin diacetate, dibutyltin diacetate, dimethyltin dilauryl mercaptide, dibutyltin dilauryl mercaptide, dimethyltin diisooctyl maleate, dibutyltin diisooctyl maleate, dimethyltin bi(2-ethylhexyl mercaptoacetate), dibutyltin bi(2-ethylhexyl mercaptoacetate), tin octoate, tin oleate, tin laurate, etc.

[0037] The catalyst content in the composition for producing polyurethane foam of the present invention is preferably 0.2 to 2.0 parts by mass, more preferably 0.3 to 1.3 parts by mass, per 100 parts by mass of all polyols including those containing other polyol components.

[0038] The polyisocyanate contained in the composition for producing polyurethane foam of the present invention can be one or more selected from aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, modified products thereof, and the like.

[0039] Examples of aromatic polyisocyanates include diphenylmethane diisocyanates (MDI) such as 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 2,2'-diphenylmethane diisocyanate; crude diphenylmethane diisocyanate; polynuclear polyphenylene polymethyl polyisocyanate (polymeric MDI); tolylene diisocyanate (TDI) such as 2,4-toluene diisocyanate and 2,6-toluene diisocyanate; naphthalene diisocyanate (NDI) such as 1,4-naphthalene diisocyanate and 1,5-naphthalene diisocyanate; 1,5-tetrahydronaphthalene diisocyanate; 1,2-phenylene diisocyanate and 1,3-phenyl Examples of suitable diisocyanates include phenylene diisocyanates (PDI) such as diisocyanate and 1,4-phenylene diisocyanate; xylene diisocyanate (XDI); tetramethylxylylene diisocyanate (TMXDI); tolidine diisocyanate (TODI); 2,4,6-trimethylphenyl-1,3-diisocyanate, 2,4,6-triisopropylphenyl-1,3-diisocyanate, chlorophenylene-2,4-diisocyanate, 4,4'-diphenylether diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3,3'-dimethoxy-4,4'-diphenylene diisocyanate, and 3,3'-dichloro-4,4'-biphenylene diisocyanate.

[0040] Examples of aliphatic polyisocyanates include ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, 1,2-butylene diisocyanate, 1,3-butylene diisocyanate, 2,3-butylene diisocyanate, pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, lysine diisocyanate (LDI), and lysine triisocyanate (LTI), as well as biuret, isocyanurate, or adduct forms of these compounds.

[0041] Examples of alicyclic polyisocyanates include isophorone diisocyanate (IPDI), cyclohexylene diisocyanate (CHDI), 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate, hydrogenated XDI (H6XDI), hydrogenated MDI (H12MDI), 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, norbornene diisocyanate (NBDI), and biuret, isocyanurate, or adduct forms of these compounds.

[0042] In the present invention, the polyisocyanate preferably includes an aromatic polyisocyanate, and particularly preferably includes tolylene diisocyanate (TDI).

[0043] In the composition for producing polyurethane foam of the present invention, the polyisocyanate is contained so that the equivalent ratio (NCO / OH) of the total amount of hydroxy groups contained in all polyols, including those containing other polyol components, to the total amount of isocyanate groups in the polyisocyanate, i.e., the isocyanate index, is preferably 0.7 to 1.3, more preferably 0.9 to 1.1, in order to obtain a foam with excellent impact resilience.

[0044] The composition for producing a polyurethane foam of the present invention may further contain, as optional components, a foam stabilizer, a viscosity modifier, a formaldehyde scavenger, a plasticizer, an antioxidant, an ultraviolet absorber, an antibacterial agent, a flame retardant, a colorant, etc.

[0045] As the foam stabilizer, a nonionic surfactant, an anionic surfactant, a cationic surfactant, or the like can be used.

[0046] When the composition for producing a polyurethane foam of the present invention contains a foam stabilizer, the content thereof is preferably 0.1 to 3.0 parts by mass per 100 parts by mass of all polyols, including those containing other polyol components.

[0047] While the method for producing the polyurethane foam-producing composition of the present invention is not particularly limited, the polyol component and polyisocyanate are preferably blended as close to each other as possible, since the urethane reaction begins when the polyol component, catalyst, and polyisocyanate come into contact. A specific method for producing the polyurethane foam-producing composition in this manner involves mixing the polyol component with the raw material components (catalyst, blowing agent, foam stabilizer, etc.) excluding the polyisocyanate, and then mixing the resulting mixture (hereinafter referred to as the "first mixture") with the polyisocyanate. In this production method, the first mixture is first prepared using, for example, a mixing vessel equipped with a stirring means and piping connected to the mixing vessel for supplying the various raw materials, such as the polyol component, and then mixed with the polyisocyanate. In this production method, the polyol component used has a manageable viscosity, as described above. Therefore, the polyol component does not flow or stagnate in the piping, and can be suitably supplied to the mixing vessel in the desired amount, resulting in efficient production of the first mixture. Subsequently, the first mixture and the polyisocyanate can be smoothly mixed. Furthermore, mixing the resulting polyol component with a catalyst, a blowing agent, a foam stabilizer, etc. does not require large power consumption, making it economical.

[0048] The polyurethane foam-producing composition of the present invention can generally be used to produce a soft foam (polyurethane foam). The method for producing such a foam is not particularly limited, but examples of the method that can be used include feeding the polyurethane foam-producing composition into a mold or container and then foaming, or spraying the composition onto a substrate or the like to form a coating film and then foaming. The polyurethane foam production temperature is not particularly limited, but is preferably 10°C to 50°C, more preferably 20°C to 40°C, and even more preferably 25°C to 40°C.

[0049] When the foam of the present invention is subjected to a test in accordance with JIS K6400-3 to measure the impact resilience, it can be preferably 22% or more, more preferably 25% or more.

[0050] The foam of the present invention can be used in a wide range of fields, such as vehicle parts, construction and civil engineering parts, housing equipment, daily necessities, sporting goods, leisure goods, agricultural and forestry materials, and fishing materials, but is particularly useful in bedding, which is a type of daily necessities, because it takes advantage of its excellent rebound resilience. [Example]

[0051] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, "parts" are by mass unless otherwise specified.

[0052] 1. Synthesis of polyol components The raw materials used in the synthesis of the polyol component are as follows:

[0053] 1-1. Polyalkylene ether glycol (hereinafter also referred to as "raw material (A)") (1) Polytrimethylene ether glycol The polymers used were "H-1000" and "H-2000" (both trade names) manufactured by SK Chemicals Co., Ltd. The average molecular weights were 1000 and 2000, respectively. (2) Polytetramethylene ether glycol Mitsubishi Chemical Corporation's "bioPTMG650" and "bioPTMG1000" (both trade names) were used. The average molecular weights were 650 and 1000, respectively. (3) Polypropylene ether glycol The polymers used were "P1000" and "P2000" (both trade names) manufactured by ADEKA Corporation. The average molecular weights were 1000 and 2000, respectively.

[0054] 1-2. Dibasic acid (hereinafter referred to as "raw material (B)") (1) Sebacic acid We used "Sebacic Acid TA" (trade name) manufactured by Ito Oil Mills, Ltd. This product is sebacic acid obtained by cleaving castor oil with caustic alkali. (2) Succinic acid "Biosuccinium" (trade name) manufactured by Rocket was used.

[0055] 1-3. Castor oil and polyhydroxy compounds (hereinafter referred to as "raw material (C)") (1) Castor oil "URIC H-30" (trade name) manufactured by Ito Oil Mills was used. (2) Trimethylolpropane "Trimethylolpropane" (trade name) manufactured by Nantong Hyakuchuan Co., Ltd. was used.

[0056] Synthesis Example 1 A reactor equipped with a stirrer and thermometer was charged with 32 parts of polytrimethylene ether glycol "H-1000," 6 parts of polytetramethylene ether glycol "bioPTMG650," 7 parts of polypropylene ether glycol "P1000," 12 parts of sebacic acid, and 43 parts of castor oil, and the temperature was increased. Under a nitrogen atmosphere and with stirring, the esterification reaction was carried out while maintaining the liquid temperature at 180°C to 200°C. Immediately after the start of the reaction, the produced water was distilled off. After 5 hours, the reaction system was reduced in pressure to 30 mmHg, and the reaction solution was allowed to react for an additional 3 hours while maintaining the temperature. Thereafter, the reaction system was reduced in pressure to 10 mmHg, and the reaction solution was allowed to react for an additional 7 hours while maintaining the temperature. Next, the resulting reaction liquid was cooled to 100°C, and filtered to remove impurities, and the filtrate was collected and used as a polyol component (hereinafter referred to as "polyol component (P1)"). The hydroxyl value and viscosity of this polyol component (P1) were then measured according to methods conforming to JIS K 1557-1 and JIS Z 8803. The viscosity was measured at 25°C using a B-type viscometer "TVB-10" (model name) manufactured by Toki Sangyo Co., Ltd. The biomass ratio was also calculated based on the biomass raw material ratio in the polyol. These values ​​are shown in Table 1.

[0057] Synthesis Examples 2 to 8, 11, 16 and 17 The same operation as in Synthesis Example 1 was carried out, except that the raw materials charged into the reactor were those shown in Table 1, to obtain polyol components (hereinafter referred to as "polyol components (P2) to (P8), (P11), (P16) and (P17)" (see Table 1). Viscosity measurements were not carried out on the polyol components obtained in Synthesis Examples 6, 8 and 17, and are indicated as "-" in Table 1. The same applies to the other Synthesis Examples below.

[0058] Synthesis Example 9 A reactor equipped with a stirrer and a thermometer was charged with 80 parts of polytrimethylene ether glycol "H-1000," 16 parts of sebacic acid, and 4 parts of trimethylolpropane, and the temperature was increased. Under a nitrogen atmosphere and with stirring, the esterification reaction was carried out while maintaining the liquid temperature at 180°C to 240°C. Immediately after the start of the reaction, the produced water was distilled off. After 5 hours, the pressure in the reaction system was reduced to 50 mmHg, and the reaction liquid was allowed to react for an additional 5 hours while maintaining the temperature. Thereafter, the pressure in the reaction system was reduced to 30 mmHg, and the reaction liquid was allowed to react for an additional 3 hours while maintaining the temperature. Next, the resulting reaction liquid was cooled to 100°C, and filtered to remove impurities, and the filtrate was recovered to obtain a polyol component (hereinafter referred to as "polyol component (P9)") (see Table 1).

[0059] Synthesis Examples 10 and 12-15 The same operations as in Synthesis Example 9 were carried out except that the raw materials charged into the reactor were those shown in Table 1, to obtain polyol components (hereinafter referred to as "polyol components (P10) and (P12) to (P15)") (see Table 1).

[0060] [Table 1]

[0061] 2. Composition for producing polyurethane foam and production of foam Compositions for producing polyurethane foams were produced using each of the polyol components obtained in Synthesis Examples 1 to 17, along with the blowing agent, foam stabilizer, amine catalyst, tin catalyst, and polyisocyanate shown below. Foams were then produced and evaluated.

[0062] 2-1. Foaming agent water

[0063] 2-2.Foam stabilizer (1) Foam stabilizer 1 Dow Toray "SRX280A" (product name) (2) Foam stabilizer 2 "NIAX SILICONE L-670" (product name) manufactured by Momentive Performance Materials Japan, LLC (3) Foam stabilizer 3 Dow Toray "SZ-1142" (product name)

[0064] 2-3. Catalyst (1) Amine catalyst Tosoh Corporation's triethylenediamine "TEDA L-33" (product name) (2) Tin catalyst "Neostan U-28" (product name) manufactured by Nitto Kasei Co., Ltd.

[0065] 2-4. Polyisocyanate Tosoh TDI "Coronate T-80" (product name)

[0066] Example 1 A polyurethane foam-producing composition was prepared using 100 parts of polyol component (P1), 3.5 parts of blowing agent, 1.5 parts of foam stabilizer 1, 0.1 parts of amine catalyst, 0.28 parts of tin catalyst, and 42.6 parts of polyisocyanate, with an isocyanate index of 1.00. Specifically, using a production apparatus equipped with a mixing vessel with a stirring blade and piping connected to the mixing vessel for supplying the polyol component and other raw materials, the polyol component, blowing agent, foam stabilizer, and amine catalyst were mixed and stirred for 20 seconds, and the tin catalyst was added to the resulting mixture and stirred for an additional 5 seconds. Next, the polyisocyanate was added and stirred and mixed for 6 seconds, yielding a uniform polyurethane foam-producing composition. Immediately thereafter, the composition for producing a polyurethane foam was placed in a foaming container (250 mm x 250 mm x 250 mm), and the urethane reaction and foam curing were allowed to proceed to obtain a soft foam (polyurethane foam).

[0067] The resulting foams were measured for their resilience according to JIS K6400-3, and for their compression set according to JIS K6400-4 (Method A of Compression Set Test and Humidity Heat Compression Set Test). The plant-based content of the foam was calculated based on the ratio of biomass raw materials in the polyurethane. These values ​​are shown in Table 2.

[0068] Examples 2 to 9 and 11 to 16 and Comparative Examples 1 to 2 The same procedures as in Example 1 were carried out except that the raw materials and the amounts thereof used were as shown in Table 2, to obtain compositions for producing polyurethane foams and foams (see Table 2).

[0069] Example 10 A composition for producing a polyurethane foam and a foam were obtained in the same manner as in Example 1 using 80 parts of the polyol component (P9), 20 parts of polypropylene ether triol (ADEKA Corporation's "ADEKA Polyether G-3000B" (trade name)), 3.5 parts of a blowing agent, 1.5 parts of foam stabilizer 1, 0.1 part of an amine catalyst, 0.3 parts of a tin catalyst, and 42.6 parts of a polyisocyanate, with an isocyanate index of 1.00 (see Table 2).

[0070] [Table 2]

[0071] The following is clear from Table 2: In Comparative Examples 1 and 2, compositions for producing polyurethane foams were prepared using a polyol component obtained by esterifying a polyalkylene ether glycol (i.e., polytetramethylene ether glycol) containing no polytrimethylene ether glycol, a dibasic acid, and castor oil, and the resulting foams had a rebound resilience of less than 20%. On the other hand, in Examples 1 to 16, compositions for producing polyurethane foams according to the present invention were prepared, and the resulting foams had an excellent rebound resilience of 23% or more. [Industrial Applicability]

[0072] The composition for producing polyurethane foam of the present invention is suitable for producing flexible foams having excellent resilience, and these foams can be used for vehicle parts, building and civil engineering parts, housing equipment, daily necessities, sporting goods, leisure goods, agricultural and forestry materials, fishing materials, etc., and are particularly suitable for bedding products, which are daily necessities.

Claims

1. A composition for producing a polyurethane foam, comprising a polyol component, a blowing agent, a catalyst, and a polyisocyanate, The polyol component is obtained by an esterification reaction of a polyalkylene ether glycol including polytrimethylene ether glycol, a dibasic acid consisting of an aliphatic dicarboxylic acid, and at least one selected from an aliphatic hydrocarbon having two or more hydroxy groups and castor oil.

2. 2. The polyurethane foam-producing composition according to claim 1, wherein the aliphatic dicarboxylic acid comprises succinic acid or sebacic acid.

3. 2. The polyurethane foam-making composition according to claim 1, wherein the aliphatic hydrocarbon having two or more hydroxy groups comprises an aliphatic triol.

4. 2. The composition for producing a polyurethane foam according to claim 1, wherein the polyol component has a hydroxyl value of 25 to 130 mgKOH / g.

5. A foam obtained by using the composition for producing a polyurethane foam according to claim 1.

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