Polyurethane foam and interior material

Abstract

[Problem] To provide a technology for producing a polyurethane foam which exhibits excellent physical properties despite containing a high degree of biomass. [Solution] The present technology provides a polyurethane foam obtained from a composition containing a polyol and an isocyanate, wherein said polyol contains a plant-derived polyol and a polyether polyol which has a number-average molecular weight of 3,000 or more and is obtained by the addition polymerization of only propylene oxide (PO) with an initiator.

Description

Polyurethane foam and interior materials

[0001] The present technology relates to a polyurethane foam. More specifically, the present technology relates to a polyurethane foam using a plant-derived raw material and an interior material including the polyurethane foam.

[0002] Polyurethane foams are used in a wide variety of fields, from furniture such as sofas and chairs, bedding such as mattresses and pillows, clothing such as underwear, daily necessities such as dish sponges and cleaning sponges, interior products for vehicles and aircraft such as car seats, toys, and miscellaneous goods. Various developments are underway to improve quality and add new functions according to each field and purpose.

[0003] Furthermore, in recent years, technology that utilizes biomass raw materials in polyurethane foam as a so-called carbon-neutral renewable resource has been attracting attention in order to contribute to the formation of a sustainable society.

[0004] For example, Patent Document 1 discloses a polyurethane foam using a polyester polyol derived from castor oil, which is a plant-derived polyol. Specifically, (A) polyol compounds are (i) a polyether polyol having a number average molecular weight of 4,000 to 7,000 and a hydroxyl value of 20 to 60 mgKOH / g, which is obtained by addition polymerization of EO and PO; (ii) a polyether polyol having a number average molecular weight of 300 to 1,000 and a hydroxyl value of 100 to 800 mgKOH / g, which is obtained by addition polymerization of only PO; (iii) a polyester polyol having a number average molecular weight of 560 to 3,000 and an average hydroxyl value of 50 to 200 mgKOH / g, which is derived from castor oil; and (iv) a polyhydric alcohol. The technology disclosed uses a mixed polyol (B) adjusted to have an average hydroxyl value of 250 to 350 mgKOH / g, a water-incompatible polyether-modified polysiloxane foam stabilizer (C) an isocyanate component made of crude MDI with an NCO content of 28 to 33%, and a cell count of 60 cells / 25 mm or more, thereby achieving cell miniaturization without foam shrinkage even when produced by continuous slabstock molding, and producing a polyurethane foam with excellent sound absorption and heat insulation properties and low density.

[0005] Japanese Patent Application Laid-Open No. 2015-3971

[0006] As mentioned above, various technologies for producing polyurethane foams using biomass raw materials are being developed, but polyurethane foams using biomass raw materials have problems such as poor reactivity during production compared to general polyurethane foams, which can result in reduced physical properties.

[0007] Therefore, the main object of this technology is to provide a technology for producing polyurethane foam that has excellent physical properties despite having a high biomass content.

[0008] The present technology first provides a polyurethane foam obtained from a composition containing a polyol and an isocyanate, wherein the polyol contains: a plant-derived polyol; and a polyether polyol having a number average molecular weight of 3,000 or more, obtained by addition polymerization of only propylene oxide (PO) to an initiator. The polyol may contain a polyester ether polyol containing an ester group and an oxypropylene group and / or an oxyethylene group. The polyurethane foam according to the present technology can have a biomass content of 10% or more. The density of the polyurethane foam according to the present technology is 40 kg / m ３ In this technology, the tensile elongation rate can be 12% or more, and the 30% compression hardness can be 8.0 N / cm or less. ２ or more, density is 30 kg / m ３ A polyurethane foam is provided, which is:

[0009] The present technology further provides an interior material using the polyurethane foam according to the present technology.

[0010] 1 is a micrograph showing the cell state of each polyurethane foam in the examples.

[0011] Preferred embodiments for implementing the present technology will be described below. The embodiments described below are examples of typical embodiments of the present technology, and any of the embodiments can be combined. Furthermore, the scope of the present technology is not to be interpreted narrowly by these embodiments.

[0012] 1. Composition for Producing Polyurethane Foam The polyurethane foam according to the present technology is produced using a composition containing a polyol and an isocyanate. The composition used for producing the polyurethane foam according to the present technology may also contain a blowing agent, a catalyst, etc., as necessary. Each component will be described in detail below.

[0013] (1) Polyol The composition for producing polyurethane foam according to the present technology is characterized in that it uses a plant-derived polyol as the polyol. As the plant-derived polyol that can be used in the present technology, one or more plant-derived polyols that can be used in the production of polyurethane foam can be freely selected and used, as long as the action and effect of the present technology are not impaired.

[0014] Examples of plant-derived polyols that can be used in the present technology include polyols derived from natural fats and oils. Natural fat-and-oil-derived polyols are natural fats and oils such as castor oil, soybean oil, rapeseed oil, and coconut oil, or derivatives thereof (e.g., modified natural fat and oil polyols, unmodified natural fat and oil polyols), which contain hydroxyl groups on the hydrocarbon chain and have two or more hydroxyl groups per molecule. In the present technology, two or more of these polyols may be used in combination.

[0015] Other examples of plant-derived polyols include cashew nut shell liquid-derived polyols. Commercially available plant-derived polyols may also be used.

[0016] In the present technology, castor oil having a secondary hydroxyl group and its derivatives are preferred as plant-derived polyols, and modified castor oil polyols, which are synthetic polyols derived from castor oil, are preferred as castor oil derivatives.

[0017] In this specification, "castor oil" includes unmodified castor oil, modified castor oil, dehydrated castor oil, hydrogenated castor oil, etc. Here, unmodified castor oil is an ester of a fatty acid and glycerin. Unmodified castor oil contains ricinoleic acid as the main component, and other components include unsaturated fatty acids such as oleic acid, linoleic acid, and linolenic acid, and saturated fatty acids such as palmitic acid and stearic acid.

[0018] The content of the plant-derived polyol in the polyol used in the present technology can be freely set as long as it does not impair the action and effect of the present technology. The lower limit of the content of the plant-derived polyol in 100 parts by mass of the polyol used in the present technology is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, more preferably 25 parts by mass or more, even more preferably 30 parts by mass or more, still more preferably 35 parts by mass or more, and particularly preferably 40 parts by mass or more. In the present technology, even when the content of the plant-derived polyol in the polyol is set within this range to improve the biomass degree, a polyurethane foam with excellent physical properties can be produced by using a specific foam stabilizer described below.

[0019] The upper limit of the plant-derived polyol content per 100 parts by mass of the polyol used in the present technology is, for example, 80 parts by mass or less, preferably 75 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 65 parts by mass or less. In the present technology, by setting the plant-derived polyol content in the polyol within this range, deterioration in the physical properties of the produced polyurethane foam can be suppressed.

[0020] In the present technology, polyols other than plant-derived polyols are also used in combination. Examples of polyols other than plant-derived polyols include polyester polyols, polyether polyols, polycarbonate polyols, polyester ether polyols, and polymer polyols.

[0021] Examples of polyester polyols 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 naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as hexahydrophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid; and esters or acid anhydrides of these with ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5- Examples of polyester polyols include polypropylene glycol obtained by a dehydration condensation reaction with pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, cyclohexanedimethanol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, or a mixture thereof; polylactone polyols and polycaprolactone polyols obtained by ring-opening polymerization of lactone monomers such as ε-caprolactone and methylvalerolactone; and other polyester polyols such as polyols having naturally occurring ester groups.

[0022] Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc., which are obtained by polymerizing cyclic ethers such as ethylene oxide (EO), propylene oxide (PO), and tetrahydrofuran as an initiator, and copolyethers thereof. Polyether polyols can also be obtained by polymerizing the above-mentioned cyclic ethers using polyhydric alcohols such as glycerin and trimethylolethane.

[0023] The initiator for the polyether polyol used in this technology is not particularly limited, and any compound that can be used as a general polyether polyol initiator can be freely selected and used. Examples of initiators that can be used in this technology include compounds having at least two active hydrogen groups. More specifically, examples include water; polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, pentaerythritol, tetramethylolcyclohexane, and 2,2,6,6-tetra(hydroxymethyl)cyclohexanol; amines such as ethylenediamine, tolylenediamine, diphenylmethanediamine, and diethylenetriamine; alkanolamines such as ethanolamine, diethanolamine, and triethanolamine; sugar alcohols such as sorbitol, mannitol, and dulcitol; and sugars such as sucrose and methyl glucoside, or derivatives thereof.

[0024] Among polyether polyols, this technology is characterized by using a polyether polyol with a number average molecular weight of 3,000 or more obtained by addition polymerization of only propylene oxide (PO) as an initiator. Polyether polyols obtained by addition polymerization of ethylene oxide (EO) as an initiator are hydrophilic, thereby improving miscibility with water, while polyether polyols obtained by addition polymerization of propylene oxide (PO) as an initiator are hydrophobic, thereby improving compatibility with plant-derived polyols. Therefore, in conventional technologies, when using plant-derived polyols, it has been common to use a polyether polyol obtained by addition polymerization of ethylene oxide (EO) as an initiator and a polyether polyol obtained by addition polymerization of propylene oxide (PO) as an initiator in combination. On the other hand, in this technology, a polyether polyol having a number average molecular weight of 3,000 or more, which is obtained by addition polymerization of only propylene oxide (PO), is used as the initiator. This provides an appropriate degassing effect, preventing shrinkage of the polyurethane foam produced, enabling the production of a stable polyurethane foam, while also successfully improving the tensile elongation.

[0025] The content of the polyether polyol having a number average molecular weight of 3000 or more obtained by addition polymerization of only propylene oxide (PO) to an initiator in the polyol used in the present technology can be freely set as long as it does not impair the function and effect of the present technology. The lower limit of the content of the polyether polyol having a number average molecular weight of 3000 or more obtained by addition polymerization of only propylene oxide (PO) to an initiator per 100 parts by mass of the polyol used in the present technology is, for example, 5.0 parts by mass or more, preferably 6.0 parts by mass or more, and more preferably 7.0 parts by mass or more. In the present technology, by setting the content of the polyether polyol having a number average molecular weight of 3000 or more obtained by addition polymerization of only propylene oxide (PO) to an initiator in the polyol within this range, an appropriate degassing effect is exhibited during polyurethane foam production, and the tensile elongation of the produced polyurethane foam can be further improved.

[0026] The upper limit of the content of polyether polyol having a number average molecular weight of 3000 or more obtained by addition polymerization of only propylene oxide (PO) to an initiator in 100 parts by mass of polyol used in the present technology is, for example, 40 parts by mass or less, preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less. In the present technology, by setting the content of polyether polyol having a number average molecular weight of 3000 or more obtained by addition polymerization of only propylene oxide (PO) to an initiator in the polyol within this range, deterioration in the physical properties of the produced polyurethane foam can be suppressed.

[0027] As the polyether polyol having a number average molecular weight of 3,000 or more obtained by addition polymerization of only propylene oxide (PO) to an initiator, either a bifunctional polyether polyol or a trifunctional polyether polyol can be used, but it is preferable to use a combination of a bifunctional polyether polyol and a trifunctional polyether polyol.

[0028] In this technology, it is also possible to use a polyether polyol having a number average molecular weight of less than 3,000, which is obtained by addition polymerization of only propylene oxide (PO) as an initiator. In this technology, it is particularly preferable to use a polyether polyol having a number average molecular weight of less than 3,000, which is obtained by addition polymerization of only propylene oxide (PO) as an initiator, and which has a number average molecular weight of 2,000 or less, preferably a number average molecular weight of 1,500 or less, and more preferably a number average molecular weight of 1,000 or less. The aforementioned degassing effect can be further improved by using in combination a polyether polyol having a number average molecular weight of 3,000 or more, which is obtained by addition polymerization of only propylene oxide (PO) as an initiator, and a polyether polyol having a number average molecular weight of 2,000 or less, which is obtained by addition polymerization of only propylene oxide (PO) as an initiator.

[0029] The content of the polyether polyol having a number average molecular weight of 2000 or less, obtained by addition polymerization of only propylene oxide (PO) to an initiator in the polyol used in the present technology, can be freely set as long as it does not impair the function and effect of the present technology. The lower limit of the content of the polyether polyol having a number average molecular weight of 2000 or less, obtained by addition polymerization of only propylene oxide (PO) to an initiator, per 100 parts by mass of the polyol used in the present technology is, for example, 5.0 parts by mass or more, preferably 6.0 parts by mass or more, and more preferably 7.0 parts by mass or more. In the present technology, by setting the content of the polyether polyol having a number average molecular weight of 2000 or less, obtained by addition polymerization of only propylene oxide (PO) to an initiator in the polyol, within this range, an appropriate degassing effect is exhibited during polyurethane foam production, and the tensile elongation of the produced polyurethane foam can be further improved.

[0030] The upper limit of the content of polyether polyol having a number average molecular weight of 2000 or less, obtained by addition polymerization of only propylene oxide (PO) to an initiator, per 100 parts by mass of the polyol used in the present technology is, for example, 50 parts by mass or less, preferably 45 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 35 parts by mass or less. In the present technology, by setting the content of polyether polyol having a number average molecular weight of 2000 or less, obtained by addition polymerization of only propylene oxide (PO) to an initiator in the polyol, within this range, deterioration in the physical properties of the produced polyurethane foam can be suppressed.

[0031] As the polyether polyol having a number average molecular weight of 2000 or less obtained by addition polymerization of only propylene oxide (PO) to an initiator, either a bifunctional polyether polyol or a trifunctional polyether polyol can be used, but it is preferable to use a trifunctional polyether polyol.

[0032] The polyether polyol having a number average molecular weight of 2,000 or less, obtained by addition polymerization of only propylene oxide (PO) to an initiator, preferably has a secondary OH group. Use of a polyether polyol having a secondary OH group provides an appropriate degassing effect during the production of polyurethane foam, further improving the tensile elongation of the produced polyurethane foam.

[0033] In this technology, it is also possible to use a polyether polyol other than the polyether polyol obtained by addition polymerization of only propylene oxide (PO) as an initiator in combination.

[0034] Examples of polyester ether polyols include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; and dibasic acids such as alicyclic dicarboxylic acids such as hexahydrophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid; or acid esters or acid anhydrides of these acids with diethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, and the like. Examples of the olefin copolymer include glycols such as cyclohexanedimethanol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, and cyclohexanedimethanol, glycols such as propylene oxide adducts, and polyhydric alcohols such as glycerin, trimethylolpropane, trimethylolethane, and pentaerythritol, as well as those obtained by a dehydration condensation reaction with a mixture of these.

[0035] Among polyester ether polyols, the present technology preferably uses a polyester ether polyol containing an ester group and an oxypropylene group and / or an oxyethylene group. The use of a polyester ether polyol containing an ester group and an oxypropylene group and / or an oxyethylene group can improve the foamability when a polyurethane foam is produced using the polyester ether polyol, and can also improve the hardness of the produced polyurethane foam at the initial compression stage.

[0036] Examples of polyester ether polyols containing an ester group and an oxypropylene group and / or an oxyethylene group include polyester ether polyols obtained by addition polymerization of propylene oxide (PO) and / or ethylene oxide (EO) to the dibasic acid; polyester ether polyols obtained by addition polymerization of propylene oxide (PO) and / or ethylene oxide (EO) to an ester polyol obtained by dehydration condensation of the dibasic acid and the polyhydric alcohol or the like; and polyester ether polyols obtained by dehydration condensation of the dibasic acid and an ether polyol obtained by adding propylene oxide (PO) and / or ethylene oxide (EO) to the initiator described above.

[0037] The content of the polyester ether polyol containing an ester group and an oxypropylene group and / or an oxyethylene group can be freely set as long as it does not impair the function and effect of the present technology. The lower limit of the content of the polyester ether polyol containing an ester group and an oxypropylene group and / or an oxyethylene group per 100 parts by mass of the polyol used in the present technology is, for example, 1.0 part by mass or more, preferably 2.0 parts by mass or more, more preferably 3.0 parts by mass or more, even more preferably 4.0 parts by mass or more, and particularly preferably 5.0 parts by mass or more. In the present technology, by setting the content of the polyester ether polyol containing an ester group and an oxypropylene group and / or an oxyethylene group within this range, the foamability during polyurethane foam production can be further improved, and the initial compression hardness of the produced polyurethane foam can be further improved.

[0038] The upper limit of the content of polyester ether polyol containing ester groups and oxypropylene groups and / or oxyethylene groups per 100 parts by mass of the polyol used in the present technology is, for example, 30 parts by mass or less, preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 16 parts by mass or less. In the present technology, by setting the content of polyester ether polyol containing ester groups and oxypropylene groups and / or oxyethylene groups in the polyol within this range, deterioration in the physical properties of the produced polyurethane foam can be suppressed.

[0039] The number-average molecular weight of the polyester ether polyol containing an ester group and an oxypropylene group and / or an oxyethylene group used in the present technology is not limited as long as it does not impair the function and effect of the present technology. The lower limit of the number-average molecular weight of the polyester ether polyol containing an ester group and an oxypropylene group and / or an oxyethylene group is, for example, 300 or more, preferably 400 or more, and more preferably 500 or more. Setting the lower limit of the number-average molecular weight within this range can prevent foam shrinkage and an excessive increase in the density of the polyurethane foam produced.

[0040] The upper limit of the number average molecular weight of the polyester ether polyol containing an ester group and an oxypropylene group and / or an oxyethylene group is, for example, not more than 1,000, preferably not more than 900, and more preferably not more than 800. By setting the upper limit of the number average molecular weight within this range, the compression hardness of the polyurethane foam produced can be improved, and the expansion ratio can be increased, allowing a polyurethane foam with a suitable density to be produced.

[0041] In the present technology, it is preferable to use a polyester ether polyol produced using a phthalate ester as the polyester ether polyol containing an ester group and an oxypropylene group and / or an oxyethylene group. The use of a polyester ether polyol produced using a phthalate ester can improve foamability during polyurethane foam production.

[0042] Examples of polycarbonate polyols include those obtained by reacting at least one polyhydric alcohol such as ethylene glycol, 1,2-propylene glycol, 1,3-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 diethylene glycol with diethylene carbonate, dimethyl carbonate, diethyl carbonate, or the like.

[0043] The polymer polyol is a polyol obtained by polymerizing an ethylenically unsaturated monomer in a polyol, or a polyol obtained by emulsifying and dispersing a polymer of an ethylenically unsaturated monomer in a polyol, etc. Specific examples include polyols obtained by graft polymerizing acrylonitrile, styrene, etc. onto a polyol, and polystyrene or polyacrylonitrile dispersed in a polyol.

[0044] In this technology, biodegradable polyols can also be used in consideration of the environment. As the biodegradable polyol that can be used in this technology, one or more biodegradable polyols that can be used in the production of polyurethane foams can be freely selected and used, as long as the purpose and effects of the technology are not impaired. Examples of biodegradable polyols that can be used in this technology include 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), and polyhydroxyalkanoic acid (PHA).

[0045] (2) Isocyanate The isocyanate that can be used in the present technology can be freely selected from one or more isocyanates that can be used in the production of polyurethane foam, as long as it does not impair the purpose and effects of the present technology. For example, one or more aromatic isocyanates, aliphatic isocyanates, and modified polyisocyanates obtained by modifying these can be freely combined and used.

[0046] Examples of aromatic isocyanates that can be used in the present technology include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate, xylylene diisocyanate, polymeric MDI (crude MDI), and phenylene diisocyanate.

[0047] Examples of the aliphatic isocyanate include hexamethylene diisocyanate (HDI), isophorone diisocyanate, and dicyclohexamethane diisocyanate.

[0048] In the present technology, the isocyanate index can be freely set as long as it does not impair the function and effect of the present technology. In the present technology, the lower limit of the isocyanate index is, for example, 80 or more, preferably 90 or more, and more preferably 95 or more. By setting the lower limit of the isocyanate index of the polyurethane foam within this range, the strength of the polyurethane foam to be produced can be improved.

[0049] In the present technology, the upper limit of the isocyanate index is, for example, not more than 130, preferably not more than 125, and more preferably not more than 120. By setting the upper limit of the isocyanate index of the polyurethane foam within this range, it is possible to prevent the polyurethane foam from becoming too hard, making it brittle and losing its flexibility, and to improve the elasticity of the polyurethane foam.

[0050] In the present technology, the isocyanate index is a value calculated by [(isocyanate equivalent in the composition for producing polyurethane foam / active hydrogen equivalent in the composition for producing polyurethane foam)×100].

[0051] (3) Foam stabilizer A foam stabilizer can be used in the production of polyurethane foam according to the present technology. 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 polyurethane foam can be freely selected and used, as long as the action and effect of the present technology are not impaired.

[0052] Examples of foam stabilizers include silicone-based foam stabilizers, fluorine-containing compound-based foam stabilizers, surfactants, etc. Silicone-based foam stabilizers include those mainly composed of siloxane chains, those in which siloxane chains and polyether chains have a linear structure, those that are branched, and those in which polyether chains are modified to have a pendant structure on the siloxane chain. Surfactants may also be used as compatibilizers, which will be described later.

[0053] The amount of foam stabilizer in the composition used to produce the polyurethane foam according to the present technology can be freely set as long as it does not impair the purpose and effects of the present technology. 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 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.

[0054] In this technology, the upper limit of the content of the foam stabilizer in the composition is, for example, 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 3 parts by mass or less, relative to 100 parts by mass of the polyol. Setting the upper limit of the content of the foam stabilizer in the composition within this range can contribute to cost reduction.

[0055] (4) Compatibilizer A compatibilizer can be used in the production of polyurethane foam according to the present technology. The use of a compatibilizer improves the compatibility of various components in the composition for producing polyurethane foam, improves the uniformity of the composition for producing polyurethane foam, and further improves the physical properties of the produced polyurethane foam. As the compatibilizer that can be used in the present technology, one or more compatibilizers that can be used in the production of polyurethane foam can be freely selected and used, as long as the action and effect of the present technology are not impaired.

[0056] Examples of the compatibilizer include castor oil fatty acid polyoxyethylene glycol esters, polyoxyethylene adducts of castor oil, polyoxyethylene adducts of hardened castor oil, sorbitan fatty acid esters such as sorbitan castor oil fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and other nonionic surfactants; and anionic surfactants such as fatty acid alkali metal salts, alkyl sulfonic acid alkali metal salts, and alkyl benzene sulfonic acid alkali metal salts. Among these, in the present technology, it is preferable to use a nonionic surfactant as the compatibilizer, and among nonionic surfactants, it is preferable to use castor oil fatty acid polyoxyethylene glycol esters or castor oil polyoxyethylene adducts.

[0057] The amount of compatibilizer in the composition used to produce a polyurethane foam according to the present technology can be freely set as long as it does not impair the purpose and effects of the present technology. In the present technology, the lower limit of the content of the compatibilizer in the composition is, for example, 0.3 parts by mass or more, preferably 0.5 parts by mass or more, and more preferably 1.0 parts by mass or more, per 100 parts by mass of polyol. By setting the lower limit of the content of the compatibilizer in the composition within this range, the compatibility of the various components in the composition for producing a polyurethane foam is further improved, and the uniformity of the composition for producing a polyurethane foam is further improved. As a result, a polyurethane foam with excellent mechanical properties and appearance can be obtained.

[0058] In this technology, the upper limit of the content of the compatibilizer in the composition is, for example, 20 parts by mass or less, preferably 15 parts by mass or less, and more preferably 10 parts by mass or less, relative to 100 parts by mass of the polyol. By setting the upper limit of the content of the compatibilizer in the composition within this range, it is possible to prevent a decrease in reactivity and foamability during production of a polyurethane foam, and to prevent the density from becoming too high.

[0059] (5) Blowing Agent A blowing agent can be used in the production of the polyurethane foam according to the present technology. As the blowing agent that can be used in the present technology, one or more blowing agents that can be used in the production of polyurethane foam can be freely selected and used, as long as the purpose and effects of the present technology are not impaired.

[0060] Examples of the blowing agent include water, hydrocarbons, and halogenated compounds. Examples of hydrocarbons include cyclopentane, isopentane, and normal pentane. Examples of the halogenated compounds include methylene chloride, trichlorofluoromethane, dichlorodifluoromethane, nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, pentafluoroethyl methyl ether, and heptafluoroisopropyl methyl ether. In the present technology, it is preferable to use water as the blowing agent. The water may be ion-exchanged water, tap water, distilled water, or the like.

[0061] The amount of blowing agent used in producing the polyurethane foam according to the present technology can be freely set as long as it does not impair the function and effect of the present technology. In the present technology, the lower limit of the content of the blowing agent in the composition is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more, relative to 100 parts by mass of polyol. By setting the lower limit of the content of the blowing agent in the composition within this range, it is possible to improve foamability, and as a result, it is possible to obtain a polyurethane foam with excellent mechanical properties and appearance.

[0062] In this technology, the upper limit of the content of the blowing agent in the composition is, for example, 20 parts by mass or less, preferably 15 parts by mass or less, and more preferably 10 parts by mass or less, relative to 100 parts by mass of the polyol. By setting the upper limit of the content of the blowing agent in the composition within this range, it is possible to suppress formation defects due to excessive foaming and also to contribute to cost reduction.

[0063] (6) Catalyst A catalyst can be used in the production of polyurethane foam according to the present technology. As the catalyst that can be used in the present technology, one or more catalysts that can be used in the production of polyurethane foam can be freely selected and used, as long as the purpose and effects of the present technology are not impaired.

[0064] Examples of the catalyst include tin catalysts such as dibutyltin dilaurate and stannous octoate, and metal catalysts (organometallic catalysts) such as phenylmercury propionate and lead octenate. Further examples include tertiary amine catalysts such as N,N-dimethylaminohexanol, triethylenediamine, triethylamine, tripropylamine, triisopropanolamine, tributylamine, trioctylamine, hexadecyldimethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N,N-dimethylethanolamine, N,N-dimethylaminoethoxyethoxyethanol, and N,N-dimethylaminoethoxyethanol; formate and other salts of triethylenediamine; oxyalkylene adducts of amino groups of primary and secondary amines; azacyclic compounds such as N-N-dialkylpiperazines; various N,N',N'-trialkylaminoalkylhexahydrotriazines; and amine catalysts having an amino group as a functional group such as N,N,N",N"-tetramethyldiethylenetriamine.

[0065] The amount of catalyst used in producing the polyurethane foam according to the present technology can be freely set as long as it does not impair the function and effect of the present technology. In the present technology, the lower limit of the catalyst content in the composition is, for example, 0.05 parts by mass or more, preferably 0.1 parts by mass or more, and more preferably 0.3 parts by mass or more, relative to 100 parts by mass of polyol. By setting the lower limit of the catalyst content in the composition within this range, the resinification reaction and the foaming reaction can be promoted, and as a result, a polyurethane foam with excellent mechanical properties and appearance can be obtained.

[0066] In this technology, the upper limit of the catalyst content in the composition is, for example, 20 parts by mass or less, preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, per 100 parts by mass of polyol. By setting the upper limit of the catalyst content in the composition within this range, destabilization of the resinification reaction and the foaming reaction can be prevented, and a good balance between the resinification reaction and the foaming reaction can be maintained. As a result, a polyurethane foam with excellent mechanical properties and appearance can be obtained.

[0067] (7) Others In the production of polyurethane foam according to the present technology, one or more of various components that can be used in the production of polyurethane foam can be freely selected and used as other components depending on the purpose, as long as the action and effect of the present technology are not impaired.

[0068] Examples of components that can be used in producing polyurethane foams according to the present technology include flame retardants, stabilizers, plasticizers, colorants, pigments, degassing agents, antioxidants, crosslinking agents, antibacterial agents, compatibilizers, and ultraviolet absorbers.

[0069] 2. Polyurethane Foam The polyurethane foam according to the present technology is produced using the composition for producing polyurethane foam described above. The polyurethane foam according to the present technology may be any of flexible polyurethane foam, rigid polyurethane foam, and semi-rigid polyurethane foam. The physical properties of the polyurethane foam according to the present technology are described below.

[0070] (1) Biomass Degree The biomass degree of the polyurethane foam according to the present technology can be freely set as long as it does not impair the functions and effects of the present technology. The lower limit of the biomass degree of the polyurethane foam according to the present technology is, for example, 5 or more, preferably 8 or more, more preferably 10 or more, and even more preferably 12 or more. The higher the biomass degree of the polyurethane foam according to the present technology, the more it contributes to the environment, so there is no upper limit on the biomass degree.

[0071] In this technology, the "biomass ratio" is a value calculated using the following formula: Biomass ratio (%) = {(weight of biomass material × biomass ratio of biomass material / 100) / total weight of raw materials}

[0072] (2) Density The density of the polyurethane foam according to the present technology can be freely set as long as it does not impair the function and effect of the present technology. The lower limit of the density of the polyurethane foam according to the present technology is, for example, 10 kg / m ３ or more, preferably 11 kg / m ３ More preferably, 12 kg / m ３ More preferably, 15 kg / m ３ The upper limit of the density of the polyurethane foam according to the present technology is, for example, 50 kg / m ３ Preferably 40 kg / m or less ３ or less, more preferably 35 kg / m ３ More preferably 30 kg / m or less ３ The following is the result.

[0073] In the present technology, the "density" is a value measured in accordance with a method based on JIS K7222:2005 / ISO 845:1988.

[0074] (3) Tensile elongation The tensile elongation of the polyurethane foam according to the present technology can be freely set as long as it does not impair the functions and effects of the present technology. The lower limit of the tensile elongation of the polyurethane foam according to the present technology is, for example, 10% or more, preferably 11% or more, more preferably 12% or more, and even more preferably 13% or more. The upper limit of the tensile elongation of the polyurethane foam according to the present technology is not particularly limited, and is, for example, 30% or less, 25% or less.

[0075] In this technology, the "tensile elongation" is a value measured at a speed of 100 mm / min in accordance with the method based on JIS K 6251 and calculated based on the following formula: Tensile elongation (%) = (gauge length after test (mm) - gauge length before test (mm)) ÷ gauge length before test (mm) × 100

[0076] (4) 10% Compression Hardness The 10% compression hardness of the polyurethane foam according to the present technology can be freely set as long as it does not impair the function and effect of the present technology. The lower limit of the 10% compression hardness of the polyurethane foam according to the present technology is, for example, 6.0 N or more, preferably 6.5 N or more, and more preferably 7.0 N or more. The upper limit of the 10% compression hardness of the polyurethane foam according to the present technology is not particularly limited, and is, for example, 20 N or less, 15 N or less.

[0077] In this technology, the "10% compression hardness" is a value calculated based on the following formula, obtained by compressing three stacked samples, each 40 mm square and 10 mm thick, to a thickness of 60% at a speed of 50 mm / min, measuring the stroke amount using an "Autograph AGS-J (MAX500N)" manufactured by Shimadzu Corporation: 10% compression hardness (N) = {stroke amount (N) / (sample width (mm) x thickness (mm))} x 100

[0078] (5) 30% Compression Hardness The 30% compression hardness of the polyurethane foam according to the present technology can be freely set as long as it does not impair the function and effect of the present technology. The lower limit of the 30% compression hardness of the polyurethane foam according to the present technology is, for example, 7.0 N or more, preferably 7.5 N or more, more preferably 8.0 N or more, even more preferably 8.1 N or more, still more preferably 8.2 N or more, even more preferably 8.3 N or more, and particularly preferably 8.4 N or more. The upper limit of the 30% compression hardness of the polyurethane foam according to the present technology is not particularly limited, and is, for example, 25 N or less, 20 N or less.

[0079] In the present technology, the "30% compression hardness" is a value measured and calculated using the same method as the "10% compression hardness" described above.

[0080] The polyurethane foam according to the present technology can be used for a wide variety of purposes in a wide range of fields, taking advantage of its high quality. For example, it can be suitably used for furniture such as sofas and chairs, bedding such as mattresses and pillows, clothing such as underwear, daily necessities such as dish sponges and cleaning sponges, vehicle and aircraft interior products such as car seats, construction joint materials, construction cushioning materials, construction sealants, home appliance sealants, sound absorbing materials, soundproofing materials, packaging materials, vehicle insulation materials, condensation prevention materials, interior materials, home appliance insulation materials, pipe insulation materials, various covers, cushioning materials, toys, miscellaneous goods, etc.

[0081] Taking advantage of its excellent physical properties, the polyurethane foam according to the present technology can be suitably used for vehicle and aircraft interior products, building interior materials, and the like.

[0082] 4. Method for Producing Polyurethane Foam The polyurethane foam according to the present technology can be produced by preparing a composition by mixing the components of the composition for producing the polyurethane foam described above, and then proceeding with a resinification reaction and a foaming reaction. As the methods for the resinification reaction and the foaming reaction, any general method can be freely combined and used as long as it does not impair the functions and effects of the present technology.

[0083] The foaming method for producing polyurethane foam according to the present technology can employ any of slab foaming, batch foaming, and mold foaming. Slab foaming is a method in which a polyurethane foam-producing composition (a raw material for polyurethane foam) is mixed and discharged onto a moving conveyor, and foamed at atmospheric pressure and room temperature. Batch foaming is a method in which a polyurethane foam-producing composition (a raw material for polyurethane foam) is mixed and discharged into a foaming box, and foamed at atmospheric pressure and room temperature. Mold foaming is a method in which a polyurethane foam-producing composition (a raw material for polyurethane foam) is mixed and injected into the cavity of a mold (forming die), and foamed to the shape of the cavity.

[0084] In the production of polyurethane foam according to the present technology, when the components are mixed to prepare the polyurethane foam-producing composition according to the present technology, the inner diameter and length of the mixing head of a low-pressure injection machine typically used in slab foaming or batch foaming, and the shape and number of impeller blades can be set as desired, and the impeller rotation speed can also be freely set depending on the type and purpose of the components of the polyurethane foam-producing composition used in the present technology. The lower limit of the rotation speed when the components are mixed to prepare the polyurethane foam-producing composition is, for example, 1,000 rpm or more, preferably 1,500 rpm or more, more preferably 2,000 rpm or more, and even more preferably 2,500 rpm or more. Setting the lower limit of the rotation speed within this range can promote the resinification reaction and the foaming reaction, resulting in a polyurethane foam with excellent mechanical properties and appearance.

[0085] The upper limit of the rotation speed when mixing the components to prepare the polyurethane foam-producing composition is, for example, 6,000 rpm or less, preferably 5,000 rpm or less, more preferably 4,500 rpm or less, and even more preferably 4,000 rpm or less. By setting the upper limit of the rotation speed within this range, destabilization of the resinification reaction and the foaming reaction can be prevented, and a good balance between the resinification reaction and the foaming reaction can be maintained. As a result, a polyurethane foam with excellent mechanical properties and appearance can be obtained.

[0086] The discharge rate of the prepared polyurethane foam-producing composition when it is discharged onto a belt conveyor or into a mold can also be freely set depending on the types of components of the polyurethane foam-producing composition used in the present technology, the rotation speed, etc. The lower limit of the discharge rate is, for example, 90 kg / min or more, preferably 100 kg / min or more, more preferably 105 kg / min or more, and even more preferably 110 kg / min or more. Setting the lower limit of the discharge rate within this range can prevent a decrease in production speed, thereby improving production efficiency.

[0087] The upper limit of the discharge rate is, for example, 300 kg / min or less, preferably 250 kg / min or less, more preferably 240 kg / min or less, and even more preferably 230 kg / min or less. By setting the upper limit of the discharge rate within this range, the resinification reaction and the foaming reaction can be promoted, and as a result, a polyurethane foam excellent in mechanical properties and appearance can be obtained.

[0088] The present technology will be described in more detail below based on examples. Note that the examples described below are examples of typical examples of the present technology, and the scope of the present technology should not be construed as being narrow.

[0089] (1) Production of Polyurethane Foams Each of the polyurethane foams was produced by mixing and stirring the raw materials shown in Table 1 below to prepare a composition, discharging the prepared composition into a foaming box and foaming it at atmospheric pressure and room temperature (batch foaming).

[0090] (2) Evaluation The produced polyurethane foams were evaluated for various physical properties using the following methods.

[0091] [Biomass Degree] The biomass degree was calculated using the following formula: Biomass degree (%) = {(Weight of biomass material × Biomass degree of biomass material / 100) / Total weight of raw materials}

[0092] [Density] The density of the produced polyurethane foam was measured in accordance with the method based on JIS K7222:2005 / ISO 845:1988.

[0093] [Tensile elongation] Measurement was performed at a speed of 100 mm / min in accordance with the method based on JIS K 6251, and calculated based on the following formula: Tensile elongation (%) = (gauge length after test (mm) - gage length before test (mm)) ÷ gage length before test (mm) × 100

[0094] [10% Compression Hardness] [30% Compression Hardness] Three stacked samples, each 40 mm square and 10 mm thick, were compressed to a thickness of 60% at a speed of 50 mm / min, and the stroke amount was measured using a measuring device, "Autograph AGS-J (MAX500N)" manufactured by Shimadzu Corporation, and the hardness was calculated based on the following formula: 10% or 30% compression hardness (N) = {stroke amount (N) / (sample width (mm) × thickness (mm))} × 100

[0095] [Air Permeability] The air permeability of the produced polyurethane foam was measured in accordance with the method based on JIS L1096 Method A (Fragile type method).

[0096] (3) Results The results are shown in Table 1 below. Micrographs of the cell states of Control Example 1, Example 1, Comparative Example 1, and Comparative Example 2 are shown in Figure 1. Note that measurement was impossible for Comparative Example 3 due to the occurrence of shrinkage. *1 "URIC H-30" Ito Oil Mills, Ltd. *2 "Actocol T-1000" Mitsui Chemicals, Inc. *3 "Actocol T-5000" Mitsui Chemicals, Inc. *4 "Actocol D-4000" Mitsui Chemicals, Inc. *5 "Sanix GP-400" Sanyo Chemical Industries, Ltd. *6 "Sanix GP3050NS" Sanyo Chemical Industries, Ltd. *7 "SURFRIC CO-10" Ito Oil Mills, Ltd. *8 "SURFRIC AQ-250" Ito Oil Mills, Ltd. Amine catalyst 1: "DABCO (registered trademark) 33 LSI" Evonik Japan Co., Ltd. Amine catalyst 2: "DABCO (registered trademark) BL-11" Evonik Japan Co., Ltd. Silicone-based foam stabilizer 1: "SRX-280A" Dow Corning Toray Co., Ltd. Silicone-based foam stabilizer 2: "NIAX (registered trademark) SILICONE L-626" Momentive Performance Materials Japan, LLC. Silicone foam stabilizer 3: "SRX-294A" Dow Corning Toray Co., Ltd. Organically modified polysiloxane: "TEGOSTAB B 8738 LF2" Evonik Japan Co., Ltd. Antioxidant: "PUR68" BASF Corporation

[0097] (4) Discussion As shown in Comparative Examples 1 and 2 in Table 1, the use of plant-derived raw materials generally results in a decrease in physical properties, and even with conventional technology, the best we could do was maintain the physical properties at the same level as a polyurethane foam with a biomass content of 0% (Comparative Example 1). On the other hand, even when a plant-derived polyol was used, Examples 1 to 9, which used a polyether polyol with a number-average molecular weight of 3,000 or more obtained by addition polymerization of only propylene oxide (PO) as the initiator, showed improved tensile elongation and 10% and 30% compression hardness.

[0098] Furthermore, as shown in the micrograph of FIG. 1, it was confirmed that the polyurethane foam of Example 1 was a high-quality polyurethane foam with no cell roughness and fine cell diameters.

[0099] Comparing the Examples, compared to Example 3, which used 25 parts by mass of a polyether polyol having a number average molecular weight of 3,000 or more obtained by addition polymerization of only propylene oxide (PO) as an initiator, Examples 1, 2, and 4 to 9, in which the amount of polyether polyol having a number average molecular weight of 3,000 or more obtained by addition polymerization of only propylene oxide (PO) as an initiator was 20 parts by mass or less, showed further improved 30% compression hardness. These results demonstrate that the 30% compression hardness can be further improved by setting the content of polyether polyol having a number average molecular weight of 3,000 or more obtained by addition polymerization of only propylene oxide (PO) as an initiator to 20 parts by mass or less per 100 parts by mass of the polyol used in this technology.

[0100] Furthermore, when Example 1 was compared with Examples 6 and 7, Examples 6 and 7, which used a compatibilizer, showed improved tensile elongation and 10% and 30% compression hardness compared to Example 1, which did not use a compatibilizer. These results demonstrate that the use of a compatibilizer improves the mixability of the polyol and isocyanate, accelerating the reaction and stabilizing the foam, enabling the production of higher quality polyurethane foams.

[0101] Furthermore, Examples 1, 2, and 4 to 9, which used a polyester ether polyol containing propylene oxide (PO) and ethylene oxide (EO), showed improved 30% compression hardness compared to Example 3, which did not use a polyester ether polyol containing propylene oxide (PO) and ethylene oxide (EO). These results demonstrate that the use of a polyester ether polyol containing propylene oxide (PO) and ethylene oxide (EO) in this technology can further improve 30% compression hardness.

[0102] In addition, Examples 1, 2, 4, and 6 to 9, which used a bifunctional polyether polyol obtained by addition polymerization of only propylene oxide (PO) as an initiator in combination with a trifunctional polyether polyol obtained by addition polymerization of only propylene oxide (PO) as an initiator, showed improved 10% compression hardness compared to Example 5, which did not use a bifunctional polyether polyol obtained by addition polymerization of only propylene oxide (PO) as an initiator. These results demonstrate that the 10% compression hardness can be further improved by using a bifunctional polyether polyol and a trifunctional polyether polyol in combination as a polyether polyol obtained by addition polymerization of only propylene oxide (PO) as an initiator.

Claims

1. A polyurethane foam obtained from a composition containing a polyol and an isocyanate, wherein the polyol contains: a plant-derived polyol; and a polyether polyol having a number average molecular weight of 3,000 or more, obtained by addition polymerization of only propylene oxide (PO) to an initiator.

2. The polyurethane foam according to claim 1, wherein the polyol comprises a polyester ether polyol containing an ester group and an oxypropylene group and / or an oxyethylene group.

3. The polyurethane foam according to claim 1, having a biomass content of 10% or more.

4. Density is 40 kg / m ３ 2. The polyurethane foam of claim 1, wherein:

5. Tensile elongation rate is 12% or more, 30% compression hardness is 8.0N / cm ２ or more, density is 30 kg / m ３ Below is polyurethane foam.

6. An interior material comprising the polyurethane foam according to any one of claims 1 to 5.

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