WO2010013710A1 - ポリエステルポリオール、ポリウレタン用組成物、ポリウレタンフォーム用組成物、ポリウレタン樹脂およびポリウレタンフォーム - Google Patents
ポリエステルポリオール、ポリウレタン用組成物、ポリウレタンフォーム用組成物、ポリウレタン樹脂およびポリウレタンフォーム Download PDFInfo
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- WO2010013710A1 WO2010013710A1 PCT/JP2009/063423 JP2009063423W WO2010013710A1 WO 2010013710 A1 WO2010013710 A1 WO 2010013710A1 JP 2009063423 W JP2009063423 W JP 2009063423W WO 2010013710 A1 WO2010013710 A1 WO 2010013710A1
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- fatty acid
- hydroxyl group
- polyol
- containing fatty
- polyurethane
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
Definitions
- the present invention relates to a polyester polyol, a polyurethane composition, a polyurethane foam composition, a polyurethane resin, and a polyurethane foam.
- polyurethane foam derived from castor oil which can be applied to uses such as cushioning materials for vehicle seat cushions, etc., and can provide polyurethane foam that achieves excellent balance of high resilience, moderate hardness, and excellent durability.
- the present invention relates to a polyester polyol derived from castor oil, a polyurethane resin, a polyurethane foam, and a use thereof suitable for the composition.
- Polyurethane foam one of the resin parts, is widely used for vehicle seat cushions such as automobiles due to its excellent cushioning properties.
- a cushion having high rebound resilience can obtain ideal body pressure dispersion and has a very good seating comfort, so that its needs are extremely high.
- the seat cushion is also required to have an appropriate hardness that is not too hard and not too soft, and excellent durability such as a small change in elasticity, hardness, and thickness of the seat cushion even when used for a long period of time.
- plant-derived resins obtained from plant resources are required instead of petroleum-derived resins made from petroleum resources.
- the plant-derived resins are made from raw materials obtained from plants which grow by photosynthesis while taking in CO 2 in air, the CO 2 is also consequently the atmosphere is discharged into the atmosphere by combustion treatment after use
- carbon neutral in which the amount of CO 2 does not increase, it has been attracting attention as a material that contributes to reducing environmental burden.
- polyurethane foams In response to the demand for plant-derived resins, polyurethane foams also use plant-derived castor oil-based polyols as the polyol component, which is a raw material, to reduce the environmental burden (for example, Patent Documents 1 to 4).
- Patent Documents 1 to 4 plant-derived castor oil-based polyols
- these foams cannot achieve the physical properties required by the market as described above, that is, moderate hardness and impact resilience, and excellent durability in a well-balanced manner.
- Patent Document 5 discloses a foam using a polyester polyol obtained by condensing 12-hydroxystearic acid derived from castor oil.
- the foam in the document 5 has only about 50% rebound resilience, and as a cushion material for vehicle seat cushions and the like, polyurethane foam imparted with high rebound resilience cannot be provided.
- Patent Document 6 using a plant-derived polyurethane foam composition in which a plant-derived polyol and a low monool polyol are combined, as a cushioning material for a vehicle seat cushion or the like, moderate hardness and impact resilience, and durability It is disclosed to provide a polyurethane foam having a good balance of properties.
- the present invention seeks to solve the problems associated with the prior art as described above, contributes to reducing the environmental burden, and as a cushioning material such as a vehicle seat cushion, has high resilience, moderate hardness, And a composition for obtaining a polyurethane foam or polyurethane resin that achieves excellent durability in a well-balanced manner, preferably a plant-derived composition, and a (plant-derived) polyurethane resin and polyurethane foam having such physical properties There is.
- a polyurethane foam obtained from a polyurethane foam composition containing a specific polyester polyol (A) contributes to a reduction in environmental burden and is used for vehicles.
- a cushioning material such as a seat cushion
- the inventors have found that excellent high rebound resilience, appropriate hardness, and excellent durability can be achieved in a well-balanced manner, and the present invention has been completed.
- the present invention is specified by, for example, the following items [1] to [12].
- the polyester polyol (A) of the present invention comprises a raw material containing at least one selected from the group consisting of a hydroxyl group-containing fatty acid and a hydroxyl group-containing fatty acid ester, and an average functional group number exceeding 3 and not more than 8.
- the polyester polyol (A) of the present invention comprises a raw material containing at least one selected from the group consisting of a hydroxyl group-containing fatty acid and a hydroxyl group-containing fatty acid ester, and an average functional group number of more than 3 and 8 or less.
- At least one selected from the group consisting of the hydroxyl group-containing fatty acid and the hydroxyl group-containing fatty acid ester has a carbon-carbon double bond in the molecule.
- At least one selected from the group consisting of the hydroxyl group-containing fatty acid and the hydroxyl group-containing fatty acid ester is obtained from castor oil.
- the (I), (II) or (III) is preferably obtained from castor oil.
- the hydroxyl group-containing fatty acid is ricinoleic acid and the hydroxyl group-containing fatty acid ester is ricinoleic acid ester.
- a mass ratio of the polyhydric alcohol and the total amount of the hydroxyl group-containing fatty acid and the hydroxyl group-containing fatty acid ester is 1: 1 to 1: 100. It is also preferred that the mass ratio of the polyhydric alcohol and the (I), (II) or (III) is 1: 1 to 1: 100.
- the polyurethane composition of the present invention contains at least a polyol (P) containing the polyester polyol (A), a catalyst, and a polyisocyanate, and the polyester polyol (A) is contained in the polyol (P). It is contained in the range of 10 to 95% by mass.
- the polyurethane foam composition of the present invention is characterized in that the polyurethane composition further comprises a foam stabilizer and a foaming agent.
- the polyurethane composition preferably further contains a low monool polyol (B) having a total unsaturation value of 0.035 meq / g or less in addition to the polyol (P).
- the polyurethane foam composition preferably further contains a low monool polyol (B) having a total unsaturation of 0.035 meq / g or less in addition to the polyol (P).
- the polyurethane resin of the present invention is obtained by reacting the polyurethane composition.
- the polyurethane foam of the present invention is characterized by reacting the polyurethane foam composition.
- a composition capable of obtaining a polyurethane foam or polyurethane resin that achieves excellent high rebound resilience, moderate hardness, and excellent durability in a balanced manner preferably a plant-derived composition, and such It is possible to provide a polyurethane foam or a polyurethane resin having a physical property (derived from a plant).
- the obtained polyurethane foam or polyurethane resin can contribute to the reduction of environmental burden in response to the recent social trend toward global environmental conservation.
- the polyurethane composition of the present invention contains at least a polyol (P) containing a specific polyester polyol (A), a catalyst, a polyisocyanate, and the specific polyester polyol (A) is contained in the polyol (A). It is contained in the range of 10 to 95% by mass. Further, the composition preferably contains a foam stabilizer, a foaming agent, a crosslinking agent, other auxiliary agents, and the like, if necessary, and the total unsaturation is 0 in the polyol (P). It is preferable to contain other polyols, such as a low monool polyol (B) of 0.035 meq / g or less. In addition, the polyurethane foam composition of the present invention further includes a foam stabilizer and a foaming agent and, if necessary, a low monool polyol (B) in the polyurethane composition of the present invention.
- the polyol (P) used in the present invention contains at least a specific polyester polyol (A) and, if necessary, other polyols such as a low monool polyol (B) and a polymer-dispersed polyol.
- the polyester polyol (A) of the present invention is 10 to 95% by mass, preferably 20 to 95% by mass, more preferably 25% with respect to 100% by mass of all the components of the polyol (P). ⁇ 90% by mass, most preferably 51 to 90% by mass.
- the polyester polyol (A) is less than 10% by mass, the advantage of using a polyester polyol synthesized using a high-purity product is higher than that of a polyester polyol using normal purity castor oil fatty acid. It is not preferable in that it is not shown, and if it exceeds 95% by mass, it is not preferable in terms of poor moldability.
- the polyurethane foam or polyurethane resin in consideration of the environment can be manufactured by containing 51 mass% or more of polyester polyols (A).
- the polyester polyol (A) having a hydroxyl value of 15 to 100 mgKOH / g of the present invention has a raw material containing at least one selected from the group consisting of a hydroxyl group-containing fatty acid and a hydroxyl group-containing fatty acid ester, and an average functional group number exceeding 3.
- the total of the hydroxyl group-containing fatty acid and the hydroxyl group-containing fatty acid ester is 90 to 100% by mass, preferably 95 to 100% by mass, and more preferably, in the raw material. 97 to 100% by mass.
- the obtained polyurethane resin or polyurethane foam can achieve high rebound resilience, moderate hardness, and excellent durability in a balanced manner.
- the raw material is contained at a higher concentration, a polyurethane resin or polyurethane foam having higher resilience can be obtained.
- the polyester polyol (A) having a hydroxyl value of 15 to 100 mgKOH / g has a raw material containing at least one selected from the group consisting of a hydroxyl group-containing fatty acid and a hydroxyl group-containing fatty acid ester, and an average functional group number. It is obtained by condensation with a polyhydric alcohol that is more than 3 and 8 or less, and the raw material contains 90 to 100% by mass of the following (I), (II) or (III).
- one kind of hydroxyl group-containing fatty acid (I) (in the present invention, “one kind” may also be referred to as “single component”) means an optical isomer of the fatty acid, cis-trans isomerism. The isomers are collectively referred to as “one kind of hydroxyl group-containing fatty acid (I)” as a single component fatty acid without distinguishing the body.
- the “one kind of hydroxyl group-containing fatty acid ester (II)” means, in addition to the optical isomer and cis-trans isomer of the fatty acid ester, the functional group derived from alcohol in the ester is polyol (A). These compounds are collectively referred to as “one kind of hydroxyl group-containing fatty acid ester (II)” as a single component fatty acid ester. That is, as “one kind of hydroxyl group-containing fatty acid ester (II)", for example, in the case of a mixture of methyl ricinoleate and ethyl ricinoleate, these are combined into one kind of ricinoleic acid ester (containing one kind of hydroxyl group). Fatty acid ester (II)).
- one hydroxyl group-containing fatty acid (i) and an ester obtained from the one hydroxyl group-containing fatty acid (i) are, for example, one hydroxyl group-containing fatty acid (i) is ricinoleic acid. If present, the ester obtained from the one hydroxy group-containing fatty acid (i) is a ricinoleic acid ester. In the embodiment (III), it means that 90 to 100% by mass of the mixture (for example, ricinoleic acid and ricinoleic acid ester) is contained in the raw material. In addition, about (III) 1 type in the mixture of 1 type of hydroxyl group containing fatty acid (i) and ester obtained from this 1 type of hydroxy group containing fatty acid (i), it is the same as that of the above-mentioned.
- hydroxyl group-containing fatty acid examples include ricinoleic acid, 12-hydroxystearic acid, cerebronic acid, hydroxyundecanoic acid, etc.
- ricinoleic acid derived from castor oil and 12-hydroxystearic acid can contribute to reducing environmental burden. desirable.
- the hydroxyl group-containing fatty acid ester is, for example, an esterified product of the fatty acid, that is, ricinoleic acid ester such as methyl ricinoleate, ethyl ricinoleate, propyl ricinoleate, butyl ricinoleate, methyl 12-hydroxystearate, 12 12-hydroxystearic acid esters such as ethyl-hydroxystearate, 12-hydroxypropyl stearate, butyl 12-hydroxystearate, cerebronates such as methyl cerebronate, ethyl cerebronate, propyl cerebronate, butyl cerebronate, hydroxy Hydroxyundecanoic acid esters such as methyl undecanoate, ethyl hydroxyundecanoate, propyl hydroxyundecanoate, and butyl hydroxyundecanoate.
- ricinoleic acid ester such as methyl ricinoleate, ethyl ricino
- ricinoleic acid esters such as methyl ricinoleate, ethyl ricinoleate, propyl ricinoleate and butyl ricinoleate derived from castor oil, methyl 12-hydroxystearate, ethyl 12-hydroxystearate, and 12-hydroxystearic acid 12-hydroxystearic acid esters such as propyl acid and butyl 12-hydroxystearate are preferable because they can contribute to reducing the environmental burden.
- the viscosity of the polyester polyol is lowered, and the handling at the time of producing the polyurethane resin and polyurethane foam is good.
- Such fatty acid and fatty acid ester are not particularly limited, but ricinoleic acid and ricinoleic acid ester are preferable in that the use of a hydroxyl group-containing fatty acid having a large number of carbon atoms lowers the viscosity of the polyester polyol.
- the viscosity of the polyol is lowered during production.
- the proportion of carbon-carbon double bonds contained in at least one molecule selected from the group consisting of hydroxyl group-containing fatty acids and hydroxyl group-containing fatty acid esters is determined by 1 H-NMR measurement. It can be determined by calculating 3E / 2D using the peak area E of the protons bonded to and the peak area D of the protons of the alkyl terminal methyl group.
- the mass ratio of the polyhydric alcohol having an average functional group number described later of more than 3 to 8 or less and the total amount of the hydroxyl group-containing fatty acid and the hydroxyl group-containing fatty acid ester is usually 1: 1 to 1: 100.
- the ratio is preferably 1: 5 to 1:70, more preferably 1: 5 to 1:50.
- the total amount is less than 1 part by mass relative to 1 part by mass of the polyhydric alcohol, it becomes difficult to design a desired polyester polyol, and when it exceeds 100 parts by mass, the hydroxyl value of the polyester polyol is low. This is not preferable because the activity at the time of producing the polyurethane resin and polyurethane foam becomes low and molding becomes difficult.
- Hydroxylic group-containing fatty acid or hydroxyl group-containing fatty acid ester derived from castor oil it is preferable that one kind selected from a hydroxyl group-containing fatty acid and a hydroxyl group-containing fatty acid ester is obtained from castor oil because it can further contribute to reducing environmental burden.
- the raw material according to the present invention is a mixture containing a total of 90 to 100% by mass of hydroxyl group-containing fatty acid and / or hydroxyl group fatty acid ester obtained by hydrolysis, esterification and transesterification of castor oil in the raw material. It is preferable that In addition, about the hydrolysis of castor oil, esterification, and transesterification, the method similar to the below-mentioned can be used.
- the raw material according to the present invention includes (I) one type of hydroxyl group-containing fatty acid derived from castor oil, (II) one type of hydroxyl group-containing fatty acid ester derived from castor oil, or (III) derived from castor oil.
- the resulting polyurethane foam or polyurethane resin contains 90 to 100% by mass of a mixture of one hydroxyl group-containing fatty acid (i) and an ester obtained from the one hydroxyl group-containing fatty acid (i). High resilience, moderate hardness, and excellent durability can be achieved in a balanced manner, which is preferable.
- castor oil-derived compounds or mixtures are 50 mol% or more, preferably 70 to 100 mol%, more preferably 80 to 80 mol% with respect to a total of 100 mol% of the hydroxyl group-containing fatty acid and hydroxyl group-containing fatty acid ester contained in the raw material. 100 mol% is contained. It is desirable that the compound or mixture derived from castor oil is 50 mol% or more because it can contribute to a reduction in environmental load.
- castor oil-derived compounds or mixtures have a mass ratio of 1: 1 to 1: 100 (polyhydric alcohol: compound or A mixture), preferably 1: 5 to 1:70, more preferably 1: 5 to 1:50.
- amount of the compound or mixture derived from castor oil is less than 1 part by mass relative to 1 part by mass of the polyhydric alcohol, it becomes difficult to design a polyester polyol from which a desired flexible polyurethane foam can be obtained. If it exceeds 100 parts by mass, the hydroxyl value of the resulting polyester polyol will be too low, the reaction activity during the production of the polyurethane resin and polyurethane foam will be low, and molding will be difficult.
- the raw material containing these hydroxyl group-containing fatty acids and hydroxyl group-containing fatty acid esters derived from castor oil can be obtained by any of the following.
- a castor oil is hydrolyzed to obtain a castor oil fatty acid, which is purified to obtain a raw material containing 90 to 100% by mass of a hydroxyl group-containing fatty acid as a single component.
- the castor oil is transesterified with alcohol to obtain a castor oil fatty acid ester, which is purified to obtain a raw material containing 90 to 100% by mass of the fatty acid ester.
- hydrogenated castor oil is used instead of castor oil
- hydrogenated castor oil fatty acid is used instead of castor oil fatty acid
- 90 to 100% by mass of 12-hydroxystearic acid and 12-hydroxystearic acid ester is used.
- the raw material containing can also be obtained.
- the esterification of fatty acid is not particularly limited as long as it is a general esterification.
- esterification can be performed by a known method such as performing in the presence of an alkali catalyst.
- the raw material derived from castor oil according to the present invention includes the above-mentioned (1) and (2) if a total of 90 to 100% by mass of a single component hydroxyl group-containing fatty acid and an ester obtained from the fatty acid are contained in the raw material. ) Or a mixture of (3).
- castor oil fatty acid or castor oil fatty acid ester in (1) and (3) above known methods such as distillation, extraction and crystallization can be used.
- distillation In the distillation of castor oil fatty acid, it is preferable to perform distillation at a temperature of 180 ° C. or less using a thin film evaporator because castor oil fatty acid is thermally decomposed at about 200 ° C. and side reactions occur in the intramolecular dehydration.
- the thin film distillation apparatus to be used is not particularly limited, but a rotating thin film distillation apparatus, a falling film distillation apparatus, etc. are used, and a rotating thin film distillation apparatus under high vacuum called molecular distillation is particularly preferable from the viewpoint of evaporation efficiency.
- a general solvent extraction method is used for the extraction of castor oil fatty acid.
- Hexane etc. are used from viewpoints, such as the solubility of a castor oil fatty acid and the ease of removal after extraction.
- Castor oil fatty acid and hexane are mixed at an arbitrary ratio and separated at any temperature.
- the hexane phase and castor oil fatty acid phase are separated, and hexane partially dissolved in castor oil fatty acid is removed to remove high-purity castor oil fatty acid. Can be obtained.
- Examples of the fatty acid obtained from (1) above include ricinoleic acid and 12-hydroxystearic acid.
- the hydroxyl group-containing fatty acid ester contained in the raw material derived from castor oil is obtained by the above (2) or (3).
- Examples of the fatty acid obtained from (2) or (3) above include ricinoleic acid esters such as methyl ricinoleate, ethyl ricinoleate, propyl ricinoleate and butyl ricinoleate, methyl 12-hydroxystearate, ethyl 12-hydroxystearate, And 12-hydroxystearic acid esters such as propyl 12-hydroxystearate and butyl 12-hydroxystearate.
- fatty acids are contained as a single component in a raw material derived from castor oil in an amount of 90 to 100% by mass, preferably 95 to 100% by mass, and more preferably 97 to 100% by mass.
- a polyurethane resin or polyurethane foam using a raw material containing a single component fatty acid derived from castor oil in high purity, the resulting resin or foam can contribute to a further reduction in environmental impact, and In particular, excellent high resilience, moderate hardness, and excellent durability can be achieved in a well-balanced manner.
- the content of the fatty acid in the raw material is less than 90% by mass, there are many fatty acids that do not contain a hydroxyl group, and when a polyester polyol is obtained by condensing a polyol and the fatty acid, When the hydroxyl group is capped and reacted with an isocyanate to obtain a polyurethane resin or polyurethane foam, the non-reactive terminal forms a dangling chain, which reduces the resilience of the polyurethane resin or polyurethane foam.
- the content of fatty acid in the raw material is 95 to 100% by mass, it is excellent when molding polyurethane resin or urethane foam because there are few fatty acids that do not contain hydroxyl groups and the proportion of molecular end hydroxyl groups that are capped is low. It is most preferable because of its high resilience.
- the ratio of the hydroxyl group-containing fatty acid contained in the raw material containing at least one selected from the group consisting of a hydroxyl group-containing fatty acid and a hydroxyl group-containing fatty acid ester is a hydroxyl group-containing amount measured by the method of JIS K1557-1.
- the hydroxyl value A of the fatty acid is determined by the ratio A / B of the acid value B of the hydroxyl group-containing fatty acid measured by the method of JIS K1557-5.
- the ratio of the hydroxyl group-containing fatty acid ester contained in the raw material containing at least one selected from the group consisting of a hydroxyl group-containing fatty acid and a hydroxyl group-containing fatty acid ester is, in the case of methyl ester, the hydroxyl group adjacent by 1 H-NMR.
- the measurement result can be obtained by calculating 3C / F using the peak area C of protons bonded to carbon and the peak area F of protons bonded to carbon atoms adjacent to the oxygen atom of the ester group.
- the peak area C of protons bonded to the carbon adjacent to the hydroxyl group and the peak area of protons bonded to the carbon atom adjacent to the oxygen atom of the ester group A measurement result can be obtained by calculating 2C / G using G.
- the total amount (purity:%) of the hydroxyl group-containing fatty acid and the hydroxyl group-containing fatty acid ester contained in the raw material is determined by the peak area C of protons bonded to hydroxyl adjacent carbon and the alkyl terminal methyl group by 1 H-NMR.
- a measurement result can be obtained by calculating 3C / D using the proton peak area D.
- the ratio of the mixture of one kind of hydroxyl group-containing fatty acid (i) and the ester obtained from the one kind of hydroxy group-containing fatty acid (i) contained in the raw material is also measured by the above 1 H-NMR. It can be determined in the same way as.
- one kind of hydroxyl group-containing fatty acid can be qualitatively and quantitatively measured by gas chromatography (GC).
- GC gas chromatography
- the qualitative and quantitative determination by GC is also possible for the ester obtained from the one kind of hydroxy group-containing fatty acid (i).
- ricinoleic acid and ricinoleic acid ester are preferred in that the viscosity of the polyol becomes low during polyol production.
- the raw material containing at least one selected from the group consisting of a hydroxyl group-containing fatty acid and a hydroxyl group-containing fatty acid ester contains 0 to 10% by mass of other hydroxycarboxylic acid and / or hydroxycarboxylic acid ester, Preferably, it may be contained in an amount of 0 to 5% by mass, more preferably 0 to 3% by mass.
- these hydroxycarboxylic acids and / or hydroxycarboxylic acid esters are preferably less than 50 mol%, more preferably 0 with respect to 100 mol% in total of the hydroxyl group-containing fatty acid and the hydroxyl group-containing fatty acid ester contained in the raw material. -30 mol%, more preferably 0-20 mol%. It is desirable that the total of these hydroxycarboxylic acids and / or hydroxycarboxylic acid esters is less than 50 mol% because the viscosity of the polyester polyol can be reduced.
- hydroxycarboxylic acids examples include lactic acid, glycolic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, and ⁇ -hydroxybutyric acid.
- hydroxycarboxylic acid ester examples include lactic acid ester, glycolic acid ester, 2-hydroxybutyric acid ester, 3-hydroxybutyric acid ester, and ⁇ -hydroxybutyric acid ester.
- the esterification is not particularly limited as long as it is a general esterification as described above. For example, methanol, ethanol, n-propanol, iso-propanol, n-butanol, tert-butanol, and the like, Examples include esterification with hydroxycarboxylic acid.
- esterification can be performed by a known method such as performing in the presence of an alkali catalyst.
- the raw material when lactic acid and / or lactic acid ester is used as the hydroxycarboxylic acid, the raw material may contain 90 to 100% by mass of any of the following (IV) to (XI): it can.
- the definitions of “one type” and “ester” are the same as described above.
- polyhydric alcohol having an average functional group number exceeding 3 and 8 or less The polyhydric alcohol having an average functional group number of more than 3 and not more than 8 used for forming the polyester polyol (A) together with the raw material derived from castor oil is a desired polyhydric alcohol. If present, a polyol generally used for production of polyurethane foam can be used.
- a polyhydric alcohol (hereinafter sometimes referred to as a polyol) in order to prepare a polyester polyol (A) capable of producing a polyurethane resin or polyurethane foam having high resilience by sufficiently proceeding with crosslinking of the polyurethane resin or polyurethane foam.
- the polyhydric alcohol used preferably has an average number of hydroxyl groups (average number of functional groups) of more than 3 and 8 or less.
- the average number of hydroxyl groups is More preferably, it is 3.5 or more and 8 or less.
- the polyol viscosity is increased, which is not preferable in that it is difficult to use in a foaming machine at the time of polyurethane foam production. It is not preferable.
- the polyhydric alcohol having 3 or more and 8 or less hydroxyl groups include polyhydric alcohols having 4 to 8 hydroxyl groups per molecule, polyoxyalkylene polyols, and polyester polyols. These polyhydric alcohols can be used alone or in combination.
- a polyhydric alcohol having 2 or 3 hydroxyl groups per molecule under the condition that the average hydroxyl group of the polyhydric alcohol does not become 3 or less, a polyoxyalkylene polyol, a polyester polyol, etc. using this as a initiator Also good.
- polyhydric alcohols containing 4 to 8 hydroxyl groups per molecule examples include tetravalent alcohols such as diglycerin, pentaerythritol, and ⁇ -methylglucoside; hexavalent alcohols such as dipentaerythritol; glucose, sorbitol, dextrose, fructose, Examples thereof include saccharides such as sucrose and derivatives thereof; phenols having 7 to 8 hydroxyl groups. Also, an alkylene oxide adduct of a polyhydric alcohol obtained by adding ethylene oxide, propylene oxide or the like to the polyhydric alcohol can be used. These polyhydric alcohols can be used singly or in combination of two or more.
- the polyoxyalkylene polyol is an oligomer or polymer obtained by ring-opening polymerization of alkylene oxide, and is usually obtained by ring-opening polymerization of alkylene oxide using an active hydrogen compound as an initiator in the presence of a catalyst.
- alkylene oxide compound used for producing the polyoxyalkylene polyol include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, cyclohexene oxide, and epichlorohydrin. , Epibromohydrin, methyl glycidyl ether, allyl glycidyl ether, or phenyl glycidyl ether.
- the polyoxyalkylene polyol is sometimes referred to as a polyoxyalkylene polyether polyol.
- the polyoxyalkylene polyol preferably has a hydroxyl value of 100 to 1800 mgKOH / g, more preferably 200 to 1200 mgKOH / g.
- Polyoxyalkylene polyols can be used alone or in combination of two or more.
- a polyhydric alcohol having 2 to 3 hydroxyl groups per molecule is used in combination with a polyol having 4 to 8 hydroxyl groups per molecule as long as the average number of functional groups of the polyhydric alcohol is not less than 3. it can.
- polyhydric alcohol having 2 to 3 hydroxyl groups per molecule examples include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4- Divalent alcohols having 2 to 10 carbon atoms such as butanediol, 1,5-pentanediol, 1,6-hexanediol and 1,4-cyclohexanediol; Trivalent compounds having 2 to 10 carbon atoms such as trimethylolpropane and glycerin
- the alcohol include phenols having two or more hydroxyl groups such as bisphenol A.
- an alkylene oxide adduct of a polyhydric alcohol obtained by adding ethylene oxide, propylene oxide or the like to the polyhydric alcohol can be used. These polyhydric alcohols can be used singly or in combination of two or more.
- polyester polyol (A) The polyester polyol (A) having a hydroxyl value of 15 to 100 mgKOH / g according to the present invention contains a hydroxyl group-containing fatty acid, a hydroxyl group-containing fatty acid ester, particularly derived from castor oil, and the average number of functional groups exceeds 3. It is obtained by condensing with a polyhydric alcohol that is 8 or less.
- the resulting condensate may be condensed with a polyhydric alcohol, or the polyhydric alcohol and the hydroxyl group-containing fatty acid and / or Alternatively, after condensing with a hydroxyl group-containing fatty acid ester, a hydroxyl group-containing fatty acid and / or a hydroxyl group-containing fatty acid ester may be further condensed.
- the apparatus for synthesizing the polyester polyol only needs to have a device for distilling the produced water or alcohol out of the system. These condensations can be carried out, for example, under an inert gas such as nitrogen gas, without solvent-free high temperature condensation. Alternatively, other known methods such as solution polymerization may be used.
- the temperature at the time of high-temperature condensation in the absence of a solvent may be any number of times as long as dehydration condensation occurs, but considering that ricinoleic acid and 12-hydroxystearic acid decompose at about 200 ° C. and cause intramolecular dehydration, It is preferably carried out between 140 ° C and 200 ° C, more preferably between 160 ° C and 180 ° C.
- the pressure during the reaction may be normal pressure, increased pressure, or reduced pressure, but it is preferable from the viewpoint of reaction efficiency to advance the reaction under normal pressure or reduced pressure.
- a tin catalyst such as tin octylate or dibutyltin dilaurate may be used, and another catalyst such as a titanium catalyst may be used.
- the acid value of the polyester polyol (A) of the present invention is 0 to 5 mgKOH / g, preferably 0 to 3 mgKOH / g, more preferably 0 to 2 mgKOH / g.
- the acid value exceeds 5 mgKOH / g, the reactivity is delayed in performing the urethanization reaction, which is not preferable.
- it is preferably 3 mgKOH / g or less, and preferably 2 mgKOH / g or less. Further preferred.
- the hydroxyl value of the polyester polyol (A) of the present invention is 15 to 100 mgKOH / g, preferably 20 to 80 mgKOH / g, more preferably 25 to 60 mgKOH / g. If the hydroxyl value is 15 mgKOH / g or more, curing during foam production proceeds in a short time, and if it is 100 mgKOH / g or less, it is preferable because it exhibits appropriate resilience and hardness as a high resilience flexible polyurethane foam. .
- the polyester polyol (A) of the present invention has a viscosity at 25 ° C. of 20000 mPa ⁇ s or less, preferably 15000 mPa ⁇ s or less, more preferably 10,000 mPa ⁇ s or less.
- the polyurethane foam obtained using the polyester polyol (A) of the present invention is derived from the plant in the foam. Since the content of the component can be made very high, it can contribute to the reduction of the environmental load. When the concept of carbon neutral is used, carbon dioxide emissions when burning polyol and polyurethane foam prepared using plant-derived crude glycerin can be reduced.
- the fact that the polymer uses a biomass raw material means that the content of carbon having a mass number of 14 and the content of carbon having a mass number of 12 and a mass number of 13 are measured as defined in ASTM D6866. This can be determined by determining the carbon content ratio (14C concentration).
- ASTM American Standard tests
- D6866 Standard Test Method for Determining the Biobased Content of Natural Range Materials Using Radiocarbon and Isotope Ratio Mass Spectrometry Analysis
- AMS Accelerated Mass Spectrometry
- the value of the 14C concentration in the polyurethane foam may be 10 pMC (Percent Modern Carbon) or more, preferably 20 pMC or more, more preferably 30 pMC.
- the polyurethane foam obtained using the polyester polyol (A) of the present invention can achieve particularly excellent high resilience, moderate hardness, and excellent durability in a well-balanced manner. Therefore, it can be suitably used as a cushion material such as a vehicle seat cushion that is environmentally friendly.
- polyester polyol (A) of the present invention can also be used as a polyol further added with propylene oxide and / or ethylene oxide.
- the polyester polyol (A) of the present invention can also be used as a polyol further added with a lactone.
- lactones include ⁇ -lactones such as ⁇ -propiolactone, ⁇ -lactones such as ⁇ -butyrolactone, ⁇ -lactones such as ⁇ -valerolactone, ⁇ -lactones such as ⁇ -caprolactone, and the like. Piolactone and ⁇ -caprolactone are preferred.
- the polyester polyol (A) of the present invention can also be used as a prepolymer derived from castor oil having a hydroxyl group terminal obtained by reaction of the polyester polyol (A) with a polyisocyanate.
- the polyisocyanate used in the present prepolymer is not particularly limited, and the conventionally known tolylene diisocyanate (the isomer ratio such as 2,4-isomer or 2,6-isomer is not particularly limited, and 2,4-isomer / 2, A 6-isomer having a ratio of 80/20 is preferably used), diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, a mixture of tolylene diisocyanate and polymethylene polyphenyl polyisocyanate, and the like can be preferably used.
- urethane-modified products and carbodiimide-modified products of these polyisocyanates, or a mixture of these and tolylene diisocyanate can be preferably used
- Low monool polyol> In the present invention, it is a polyol generally used for the production of polyurethane foam, and the total unsaturation is 0.035 meq / g or less, preferably 0.030 meq / g or less, more preferably 0.025 meq / g or less.
- the low monool polyol (B) may be used.
- the lower limit of the total degree of unsaturation is not particularly limited, but is, for example, 0.001 meq / g.
- the modified body of the said low monool polyol (B) can also be used. These low monool polyols (B) can be used alone or in combination of two or more.
- the low monool polyol (B) is 5 to 95% by mass, preferably 5 to 90% by mass, and more preferably 10 to 80% by mass with respect to 100% by mass of all the components of the polyol (P) in the polyol (P). %, Most preferably 10 to less than 50% by mass.
- the low monool polyol (B) is less than 5% by mass, it is not preferable in terms of moldability, and when it exceeds 80% by mass, it is not preferable in that it cannot contribute to reduction of the environmental load.
- low monool polyol (B) examples include polyether polyols having a total unsaturation in the above range (hereinafter also referred to as “polyether polyol (B1)”), modified products thereof, and the like. These low monool polyols may be used alone or in combination of two or more.
- the polyether polyol (B1) is an oligomer or polymer obtained by subjecting an active hydrogen compound as an initiator to ring-opening polymerization of an alkylene oxide in the presence of a catalyst, and having a total unsaturation in the above range. Is mentioned.
- a monool having an unsaturated group at one molecular end may be generated as a by-product with an increase in the molecular weight of the polyether polyol.
- the monool content is usually expressed as the total degree of unsaturation of the polyether polyol, and the smaller the value, the lower the monool content.
- Monool in the polyether polyol has a low molecular weight as compared with the polyether polyol, which is the main component, and therefore greatly broadens the molecular weight distribution of the polyether polyol and lowers the average number of functional groups.
- the resulting urethane foam has an increased hysteresis loss, decreased hardness, decreased extensibility, decreased durability, and decreased curing properties. This causes a decrease in various physical properties of the polyurethane foam.
- the durability mentioned here specifically refers to wet heat compression set or the like, which is an index of the degree of thickness reduction during long-term use as a cushion. Similarly, in the case of a polyurethane resin, there is a possibility that the extensibility and durability may be lowered.
- the monool content causing the deterioration of various physical properties of the polyurethane foam or polyurethane resin as described above is smaller.
- the polyether polyol (B1) having a low total unsaturation as described above, that is, a low monool content is selected from, for example, at least a compound having a nitrogen-phosphorus double bond, cesium hydroxide and rubidium hydroxide.
- the amount of monool produced as a by-product can be reduced as compared with the case where a conventionally known alkali metal hydroxide such as potassium hydroxide is used as a catalyst, and the resulting polyurethane Various physical properties of the foam or polyurethane resin can be improved.
- an alkali metal hydroxide when used as a catalyst, it has been difficult to achieve an appropriate hardness and impact resilience and excellent durability in a balanced manner, but it is achieved well by using the above compound as a catalyst. be able to.
- the excellent effect of the low monool polyol is noticeable when it is used in combination with a plant-derived polyol, which generally contains impurities and is often inferior in performance to petroleum-derived polyols.
- the compound having a nitrogen-phosphorus double bond is not particularly limited, but includes compounds described in JP-A-11-106500, JP-A-2000-297131 and JP-A-2001-106780, Of these, phosphazenium compounds are preferred.
- active hydrogen compound examples include an active hydrogen compound having an active hydrogen atom on an oxygen atom and an active hydrogen compound having an active hydrogen atom on a nitrogen atom, and an active hydrogen compound having 2 to 8 functional groups is preferable.
- Examples of the active hydrogen compound having an active hydrogen atom on an oxygen atom include water, a carboxylic acid having 1 to 20 carbon atoms, a polyvalent carboxylic acid having 2 to 20 carbon atoms having 2 to 6 carboxyl groups in one molecule, and carbamine. Acids, alcohols having 1 to 20 carbon atoms, polyhydric alcohols having 2 to 20 carbon atoms having 2 to 8 hydroxyl groups in one molecule, saccharides or derivatives thereof, and carbon numbers having 1 to 3 hydroxyl groups in one molecule Examples thereof include 6 to 20 aromatic compounds, polyalkylene oxides having 2 to 8 terminals per molecule, and having a hydroxyl group at at least one of the terminals.
- Examples of the active hydrogen compound having an active hydrogen atom on the nitrogen atom include aliphatic or aromatic primary amines having 1 to 20 carbon atoms, aliphatic or aromatic secondary amines having 2 to 20 carbon atoms, and 2 per molecule.
- C2-C20 polyvalent amines having 3 primary or secondary amino groups C4-C20 saturated cyclic secondary amines, C4-C20 unsaturated cyclic secondary amines, Cyclic polyamines having 4 to 20 carbon atoms containing 2 to 3 secondary amino groups in one molecule, unsubstituted or N-monosubstituted acid amides having 2 to 20 carbon atoms, and 5 to 7-membered ring
- Examples thereof include cyclic amides and imides of dicarboxylic acids having 4 to 10 carbon atoms.
- active hydrogen compounds can be used singly or in combination of two or more.
- polyhydric alcohols having 2 to 20 carbon atoms and having 2 to 8 hydroxyl groups in one molecule are preferable.
- Ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, diester Glycerin and pentaerythritol are more preferable.
- the alkylene oxide is preferably an alkylene oxide having 2 to 12 carbon atoms. Specifically, ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl Examples thereof include ethers, and more preferred are ethylene oxide, propylene oxide, 1,2-butylene oxide, and styrene oxide, and particularly preferred are ethylene oxide and propylene oxide.
- alkylene oxides may be used alone or in combination of two or more.
- a method in which a plurality of alkylene oxides are subjected to addition polymerization at the same time, a method in which addition polymerization is sequentially performed, a method in which sequential addition polymerization is repeated, or the like can be employed.
- the polyether polyol (B1) can be produced by the reaction conditions and production methods described in JP-A Nos. 2000-297131 and 2001-106780.
- the polyether polyol (B1) a polyether polyol obtained by addition polymerization of an alkylene oxide containing ethylene oxide is preferable.
- the hydroxyl value of this polyether polyol (B1) is preferably 10 to 40 mgKOH / g, more preferably 20 to 38 mgKOH / g.
- the content of the structural units derived from ethylene oxide is preferably 5% by mass with respect to 100% by mass of the total amount of structural units derived from the alkylene oxide constituting the polyether polyol (B1). It is 30 mass% or less, More preferably, it is 10 mass% or more and 20 mass% or less.
- polyester polyol or (B) low monool polyol may be used as they are, but polymer fine particles obtained by radical polymerization of a compound having an unsaturated bond in these polyols, You may use as a polymer dispersion
- These polyols and polymer-dispersed polyols may be used in combination.
- the polymer-dispersed polyol is contained in the polyol (P) in an amount of 0 to 80% by mass, preferably 0 to 50% by mass, more preferably 0 to 30% by mass with respect to 100% by mass of all the components of the polyol (P).
- the polymer-dispersed polyol exceeds 80% by mass, it is not preferable in that it cannot contribute to the reduction of environmental load.
- the polymer-dispersed polyol is preferably a polymer polyol obtained from the low monool polyol (B) (hereinafter also referred to as “polymer polyol (PB)”), and a polymer polyol obtained from the polyether polyol (B1) (hereinafter referred to as “polymer”).
- Polyol (PB1) ”) is more preferable, and a polymer polyol obtained from a polyether polyol (B1) having a hydroxyl value of 15 mgKOH / g or more and 60 mgKOH / g or less is particularly preferable.
- the polymer-dispersed polyol is obtained by dispersing and polymerizing a compound having an unsaturated bond in the (A) polyester polyol or (B) low monool polyol using a radical initiator such as azobisisobutyronitrile. These can be obtained as a dispersion in which vinyl polymer particles are dispersed in these polyols.
- the vinyl polymer particles may be vinyl polymer particles made of a polymer of a compound having an unsaturated bond, but at the time of dispersion polymerization, at least a part of the compound having an unsaturated bond is grafted to these polyols as a dispersion medium. Polymer particles are preferred.
- the compound having an unsaturated bond is a compound having an unsaturated bond in the molecule, and examples thereof include acrylonitrile, styrene, and acrylamide. These compounds having an unsaturated bond can be used singly or in combination of two or more.
- a dispersion stabilizer or a chain transfer agent may be added in addition to the compound having an unsaturated bond.
- polyester polyol (A) a polyester polyol (A) together with a low monool polyol (B) and a polymer polyol (PB), It is more preferable to use the polyether polyol (B1) and the polymer polyol (PB1) in combination with the polyester polyol (A).
- Polyols other than low monool polyol (B) and polymer-dispersed polyol In addition to the polyester polyol (A), the low monool polyol (B), and the polymer-dispersed polyol, other polyols generally used for producing polyurethane foam may be added to the polyurethane foam composition of the present invention.
- examples of such polyols include polyether polyols having a total unsaturation level exceeding 0.035 meq / g, polymer polyols obtained from the polyether polyols, and polyester polyols.
- Such a polyol is contained in the polyol (P) in an amount of 5 to 95% by mass, preferably 10 to 80% by mass, and more preferably 10 to 70% by mass with respect to 100% by mass of all the components of the polyol (P). .
- the polyol is less than 5% by mass, it is not preferable in terms of moldability, and when it exceeds 95% by mass, it is not preferable in that it cannot contribute to a reduction in environmental load.
- Polyether polyol (C) A polyether polyol having a total degree of unsaturation exceeding 0.035 meq / g (hereinafter also referred to as “polyether polyol (C)”) is obtained by ring-opening polymerization of an alkylene oxide and has a total degree of unsaturation of 0. And oligomers or polymers exceeding 0.035 meq / g.
- Such a polyether polyol (C) is usually obtained by ring-opening polymerization of an alkylene oxide with an active hydrogen compound as an initiator in the presence of a catalyst such as an alkali metal hydroxide such as potassium hydroxide.
- active hydrogen compound As the active hydrogen compound, the active hydrogen compounds exemplified in the polyether polyol (B1) can be used. These active hydrogen compounds can be used individually by 1 type or in mixture of 2 or more types. Among these active hydrogen compounds, polyhydric alcohols having 2 to 20 carbon atoms and having 2 to 8 hydroxyl groups in one molecule are preferable. Ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, diester Glycerin and pentaerythritol are more preferable.
- alkylene oxide examples include the alkylene oxides exemplified in the polyether polyol (B1), more preferably ethylene oxide, propylene oxide, 1,2-butylene oxide, and styrene oxide, and particularly preferably ethylene oxide and propylene oxide. is there.
- alkylene oxides may be used alone or in combination of two or more.
- a method in which a plurality of alkylene oxides are subjected to addition polymerization at the same time, a method in which addition polymerization is sequentially performed, a method in which sequential addition polymerization is repeated, or the like can be employed.
- the above polyether polyol (C) is written by Takayuki Otsu, “Revised Polymer Synthesis Chemistry”, 2nd edition, 1st printing chemistry (1989), pages 172-180, Nobutaka Matsudaira and Tetsuro Maeda, “Polyurethane” 8th printing bookstore. (1964) It can be produced by the catalyst, reaction conditions, production method and the like described in pages 41 to 45.
- a polyether polyol obtained by addition polymerization of an alkylene oxide containing ethylene oxide is preferable.
- the content of the structural units derived from ethylene oxide is preferably 5% by mass with respect to 100% by mass of the total amount of structural units derived from the alkylene oxide constituting the polyether polyol (C). It is 30 mass% or less, More preferably, it is 10 mass% or more and 20 mass% or less.
- Polymer polyol (PC) examples of the polymer polyol used as the other polyol include a polymer polyol obtained from the polyether polyol (C) (hereinafter also referred to as “polymer polyol (PC)”), preferably a hydroxyl value of 15 mgKOH / g or more and 60 mgKOH. It is a polymer polyol obtained from a polyether polyol (C) of / g or less.
- This polymer polyol (PC) is obtained by dispersing and polymerizing a compound having an unsaturated bond in the polyether polyol (C) using a radical initiator such as azobisisobutyronitrile. It can be obtained as a dispersion in which vinyl polymer particles are dispersed in C).
- This vinyl polymer particle may be a vinyl polymer particle made of a polymer of a compound having an unsaturated bond, but at the time of dispersion polymerization, at least a part of the compound having an unsaturated bond is added to the polyether polyol (C) as a dispersion medium. Grafted polymer particles are preferred.
- Examples of the compound having an unsaturated bond include the compounds having an unsaturated bond exemplified in the specific polymer polyol. These compounds having an unsaturated bond can be used singly or in combination of two or more.
- a dispersion stabilizer or a chain transfer agent may be used in combination.
- polyester polyol examples include condensates of low molecular weight polyols and carboxylic acids; lactone-based polyols such as ⁇ -caprolactone ring-opening polymer and ⁇ -methyl- ⁇ -valerolactone ring-opening polymer.
- low molecular polyol examples include dihydric alcohols having 2 to 10 carbon atoms such as ethylene glycol and propylene glycol, trihydric alcohols having 2 to 10 carbon atoms such as glycerin, trimethylolpropane and trimethylolethane, pentaerythritol, and diglycerin. And saccharides such as tetrahydric alcohol such as sorbitol and sucrose.
- carboxylic acid examples include dicarboxylic acids having 2 to 10 carbon atoms such as succinic acid, adipic acid, maleic acid, fumaric acid, phthalic acid, and isophthalic acid, and carbon numbers of 2 such as succinic anhydride, maleic anhydride, and phthalic anhydride. ⁇ 10 acid anhydrides and the like.
- a physical foaming agent such as liquefied carbon dioxide can be used, but it is most desirable to use water.
- water When water is used as the foaming agent, it is preferably 1.3 to 6.0 parts by weight, more preferably 1.8 to 5.0 parts by weight, especially 100 parts by weight of all the components of the polyol (P).
- the amount is preferably 2.0 to 4.0 parts by mass.
- the catalyst used in the present invention is used for the reaction of the polyol (P) and polyisocyanate, and any conventionally known catalyst can be used without any particular limitation.
- any conventionally known catalyst can be used without any particular limitation.
- aliphatic amines such as triethylenediamine, bis (2-dimethylaminoethyl) ether, 1-isobutyl-2-methylimidazole and morpholines; organotin compounds such as tin octoate and dibutyltin dilaurate are preferably used. be able to.
- the amount of the catalyst used is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of all the components of the polyol (P).
- Foam stabilizer As the foam stabilizer used in the present invention, a conventionally known foam stabilizer can be used, and there is no particular limitation, but it is usually preferable to use an organosilicon surfactant.
- FV-1013-16, SRX-274C, SF-2969, SF-2961, SF-2962, L-5309, L-3601, L-5307, L-3600 manufactured by Toray Dow Corning Silicone Co., Ltd. L-5366, SZ-1325, SZ-1328, Y-10366 and the like can be preferably used.
- the amount of the foam stabilizer used is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of all the components of the polyol (P).
- the polyisocyanate used in the present invention is not particularly limited, and examples thereof include conventionally known polyisocyanates shown in Keiji Iwata, “Polyurethane Resin Handbook”, 1st Nikkan Kogyo Shimbun (1987), pages 71 to 98. Can be mentioned.
- toluylene diisocyanate (the ratio of isomers such as 2,4-isomer and 2,6-isomer is not particularly limited, but 2,4-isomer / 2,6-isomer is 80/20 ratio is preferable), polymethylene polyphenyl polyisocyanate (for example, Cosmonate M-200 manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) or a urethane modified product thereof, or a mixture thereof can be preferably used.
- toluylene diisocyanate is preferably used in an amount of 50 to 99% by mass with respect to the total amount of polyisocyanate from the viewpoint of balance between durability of the foam and mechanical strength. More preferably, it is contained in an amount of 70 to 90% by mass, particularly preferably 75 to 85% by mass.
- toluylene diisocyanate (the ratio of isomers such as 2,4-isomer and 2,6-isomer is not particularly limited, but 2,4-isomer / 2,6-isomer) Is preferably a ratio of 80/20), diphenylmethane diisocyanate (for example, Cosmonate PH manufactured by Mitsui Chemicals, Inc.), xylylene diisocyanate, norbornene diisocyanate, naphthalene diisocyanate, bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, etc. Can be used.
- diphenylmethane diisocyanate for example, Cosmonate PH manufactured by Mitsui Chemicals, Inc.
- xylylene diisocyanate norbornene diisocyanate
- naphthalene diisocyanate bis (isocyanatomethyl) cyclohexane, hexamethylene di
- the NCO index is preferably 0.70 to 1.30, more preferably 0.80 to 1.20.
- the NCO index means a value obtained by dividing the total number of isocyanate groups in the polyisocyanate by the total number of active hydrogens reacting with an isocyanate group such as an amino group such as a hydroxyl group and a crosslinking agent of polyol and water, and water. . That is, when the number of active hydrogens reacting with an isocyanate group and the isocyanate group in the polyisocyanate are stoichiometrically equal, the NCO index is 1.0.
- the polyurethane composition of the present invention includes a chain extender, a crosslinking agent, a communication agent, an antifoaming agent, and other auxiliary agents such as flame retardants, pigments, ultraviolet absorbers, antioxidants, etc.
- Additives generally used in producing a polyurethane foam or a polyurethane resin can be used as long as the object of the present invention is not impaired.
- additives include No. 1 Matsuhira and Tetsuro Maeda, “Polyurethane” 8th Printing Bookstore (1964), 134-137, Hitoshi Matsuo, Nobuaki Kunii, Kiyoshi Tanabe “Functional Polyurethane” 1st Printing Co., Ltd. Additives described in MC (1989) pages 54-68 and the like can be mentioned.
- Crosslinking agent Since it is also possible to use a crosslinking agent in the polyurethane foam or polyurethane resin of the present invention, which will be described later, the crosslinking agent can be added to the polyurethane composition of the present invention.
- a crosslinking agent a compound having a hydroxyl value of 200 to 1800 mgKOH / g is preferably used as the crosslinking agent.
- crosslinking agents examples include aliphatic polyhydric alcohols such as glycerin; alkanolamines such as diethanolamine and triethanolamine.
- a polyoxyalkylene polyol having a hydroxyl value of 200 to 1800 mgKOH / g can also be used as a crosslinking agent, and a conventionally known crosslinking agent can also be used.
- a crosslinking agent it is preferable to use an amount of 0.5 to 10 parts by mass with respect to 100 parts by mass of all the components of the polyol (P).
- the method for producing the polyurethane resin according to the present invention is not particularly limited, and a conventionally known production method can be appropriately employed. Specifically, a polyol (P) containing a polyester polyol (A) is mixed with a catalyst, an antifoaming agent, another polyol such as a low monool polyol (B), other auxiliary agents, a crosslinking agent, and the like in advance. After preparing the premix, the resin premix and polyisocyanate are mixed and cured to obtain a polyurethane resin.
- a polyol (P) containing a polyester polyol (A) is mixed with a catalyst, an antifoaming agent, another polyol such as a low monool polyol (B), other auxiliary agents, a crosslinking agent, and the like in advance.
- the resin premix and polyisocyanate are mixed and cured to obtain a polyurethane resin.
- a polyol (P) containing a polyester polyol (A) is reacted with an excess of isocyanate to synthesize a prepolymer having an isocyanate group at the end, and then a catalyst or a necessary crosslinking agent is mixed with the prepolymer.
- a polyurethane resin can also be obtained.
- the polyurethane resin of the present invention can achieve a high balance of high resilience, moderate hardness, and excellent durability, and can contribute to reducing the environmental burden by using a raw material derived from castor oil.
- Polyurethane resins are preferably used for applications such as adhesives and sealants that require particularly high impact resilience.
- the Shore A hardness is usually in the range of 30 to 90, preferably in the range of 35 to 90, more preferably in the range of 40 to 70 under the conditions in accordance with JIS K6253, and the impact resilience (%) Is usually 50% or more, preferably 60 to 80%, more preferably 65 to 80% under the conditions according to JIS K6255, and the maximum point stress (MPa) is usually 0.5 MPa under the conditions according to JIS K6251. As mentioned above, it is preferably 0.8 MPa or more, and the maximum elongation (%) is 50 to 400%, preferably 60 to 200% under the conditions according to JIS K6251.
- the method for producing the polyurethane foam according to the present invention is not particularly limited, and a conventionally known production method can be appropriately employed. Specifically, any of a slab foam method, a hot cure mold foam method, and a cold cure mold foam method can be adopted. When manufacturing a vehicle seat pad such as an automobile, the cold cure mold foam method is preferable.
- a known cold cure mold foam method can be adopted.
- a polyol (P) containing a polyester polyol (A), a foaming agent, a catalyst, a foam stabilizer, other polyols such as a low monool polyol (B), other auxiliaries, a crosslinking agent, and the like are mixed in advance.
- the resin premix and polyisocyanate are usually mixed using a high-pressure foaming machine or low-pressure foaming machine so as to have a predetermined NCO index, and this mixture is poured into a mold.
- a polyurethane foam having a certain shape can be obtained by reaction, foaming and curing.
- the curing time is usually from 30 seconds to 30 minutes
- the mold temperature is usually from room temperature to about 80 ° C
- the curing temperature is preferably from room temperature to about 150 ° C.
- the cured product may be heated in the range of 80 to 180 ° C. so long as it does not impair the temperature.
- the resin premix is usually mixed with polyisocyanate in a high-pressure foaming machine or low-pressure foaming machine, but when a hydrolyzable compound such as an organotin catalyst is used as the catalyst, the foaming agent is water. In order to avoid contact with water, it is preferable that the water component and the organotin catalyst component are injected into the foaming machine through different paths and mixed by the mixing head of the foaming machine. It is preferable that the viscosity of the resin premix to be used is 2500 mPa ⁇ s or less from the viewpoint of the mixing property in the foaming machine and the moldability of the foam.
- the polyurethane foam of the present invention is a seat cushion for vehicles such as automobiles that requires high impact resilience. It is preferably used for applications such as seat backs.
- the appropriate hardness range is 25% ILD, preferably 140 to 280 N / 314 cm 2 , more preferably 200. ⁇ 260 N / 314 cm 2 .
- the appropriate impact resilience range is preferably 45 to 75%, more preferably 55 to 70%, and most preferably 60 to 70%.
- the excellent durability range is wet heat compression set, preferably 14% or less, more preferably 12% or less.
- the elongation of the polyurethane foam of the present invention is 50 to 200%, preferably 60 to 150%.
- the polyurethane foam of the present invention can be suitably used as a cushioning material.
- it can be suitably used as a seat cushion for a vehicle such as an automobile or a seat pad for a seat back.
- Core density in the table of Examples, the core density is abbreviated as “Dco”)
- the measurement was performed in accordance with the apparent density measuring method described in JIS K-6400.
- the skin was removed from the polyurethane foam sample, a cuboid foam sample was prepared, and the core density was measured.
- Foam hardness (abbreviated as “25% ILD” in the tables of the examples) Measurement was carried out in accordance with method A described in JIS K-6400. However, measurement was performed on a polyurethane foam having a thickness of 100 mm.
- Humid heat compression set (abbreviated as “WS” in the tables of the examples) Measurement was carried out by the method described in JIS K-6400. At the time of measurement, the core portion of the molded polyurethane foam was cut out to 50 mm ⁇ 50 mm ⁇ 25 mm and used as a test piece. The test piece was compressed to a thickness of 50%, sandwiched between parallel flat plates, and allowed to stand for 22 hours at 50 ° C. and a relative humidity of 95%. 30 minutes after taking out a test piece, the thickness was measured and the distortion rate was measured compared with the thickness before a test.
- Acid value was measured by the method described in JIS K-1557-5.
- Hydroxyl value (OHV) Measurement was performed by the method described in JIS K-1557-1.
- Viscosity (mPa ⁇ s / 25 ° C) Using a conical plate type rotational viscometer (E type viscometer), the viscosity at 25 ° C. was measured.
- the ratio of the hydroxyl group-containing fatty acid contained in the raw material containing at least one selected from the group consisting of a hydroxyl group-containing fatty acid and a hydroxyl group-containing fatty acid ester is determined according to JIS K1557-1.
- the hydroxyl value A of the hydroxyl group-containing fatty acid measured by the method, and the ratio A / B of the acid value B of the hydroxyl group-containing fatty acid measured by the method of JIS K1557-5 were determined.
- the ratio of the hydroxyl group-containing fatty acid ester was determined by subtracting the ratio of the hydroxyl group-containing fatty acid determined by the above method.
- the ratio of the total amount of the mixture of one kind of hydroxyl group-containing fatty acid (i) contained in the raw material and the ester obtained from the one kind of hydroxy group-containing fatty acid (i) is also the above 1 H-NMR.
- the ratio of the ester obtained from the one kind of hydroxy group-containing fatty acid (i) is reduced by subtracting the ratio of the hydroxyl group-containing fatty acid determined by the above method to obtain the hydroxyl group-containing fatty acid ester.
- the ratio was calculated.
- the total amount (purity:%) of the hydroxyl group-containing fatty acid and the hydroxyl group-containing fatty acid ester contained in the raw material was calculated using the measurement methods (11) and (12) above.
- Rebound resilience (%) Using a sample for rebound resilience measurement obtained by the method described in the resin preparation method, the sample was measured with a rebound resilience apparatus manufactured by Ueshima Seisakusho in accordance with the Dupke method (Dupke method) described in JIS K6255.
- a castor oil fatty acid obtained by hydrolyzing the castor oil (manufactured by Ito Oil Co., Ltd .: trade name CO-FA, purity: 86%) and a molecular distillation apparatus (Shibata Kagaku) having an evaporation surface area of 0.03 m 2 was used to remove the hydroxyl-free component, which is a low boiling component, to obtain a high purity castor oil fatty acid.
- the evaporation conditions at this time were a charging speed of 200 g / h, an evaporation surface temperature of 160 ° C., a pressure of 15 Pa, and a wiper rotation speed of 300 rpm.
- the acid value of the high purity castor oil fatty acid obtained at that time was 180.7 mgKOH / g, and the hydroxyl value was 172.9 mgKOH / g.
- the purity of the high purity castor oil fatty acid (1) determined from these was 95.7%. .
- the high purity castor oil fatty acid (1) is ricinoleic acid.
- Purification Example 2 The same operation as in Purification Example 1 was performed except that the charging was performed at a charging rate of 220 g / h and an evaporation surface temperature of 170 ° C.
- the acid value of the high purity castor oil fatty acid obtained at that time was 176.3 mg KOH / g, and the hydroxyl value was 173.5 mg KOH / g.
- the high purity castor oil fatty acid (2) is ricinoleic acid.
- the solid content was dried in a vacuum dryer at 25 ° C. for 24 hours to obtain high purity 12-HSA.
- the purity of the high purity 12-HSA was determined by 1 H-NMR to be 92.0%.
- Polyester polyol A-1 A high-purity castor oil fatty acid (1) obtained in Purification Example 1 and castor oil fatty acid (manufactured by Ito Oil Co., Ltd .: trade name CO-FA, purity: 86%) previously mixed to a purity of 95.0% Purified castor oil fatty acid 1944 g, SOR-400 (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., polyol obtained by adding propylene oxide to sorbitol, hydroxyl value 400 mgKOH / g), 78 g PE-450 (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., pentaerythritol) 2 liters equipped with 97 g of polyol having a propylene oxide added thereto, a hydroxyl value of 450 mgKOH / g) (more than the average functional group number of polyhydric alcohol
- Table 1 shows the hydroxyl value (OHV), average number of functional groups (calculated value), and viscosity of the obtained polyester polyols A-2 to A-8 (polyols A-2 to A-8).
- Tables 2 and 3 show the hydroxyl value (OHV), average number of functional groups (calculated value), and viscosity of the obtained polyester polyols A-9 to A-20 (polyols A-9 to A-20).
- This polyol (B1-1) had a total unsaturation of 0.025 meq / g, a hydroxyl value of 24 mgKOH / g, and a terminal oxyethylene group content of 15% by mass.
- Synthesis Example 24 Polymer polyol (PB1-1) A polyether polyol (B1-1) having a hydroxyl value of 24 mgKOH / g obtained in Synthesis Example 21 is filled in a 1-liter pressure-resistant autoclave equipped with a thermometer, a stirring device, a pressure gauge, and a liquid feeding device. The temperature was raised to 120 ° C. while stirring. The mixture was continuously charged with a mixture of polyether polyol (B1-1), radical polymerization initiator, acrylonitrile and dispersion stabilizer, and the reaction temperature was 120 ° C., the reaction pressure was 400 kPa, and the residence time was 50 minutes. After the initial polymerization was removed from the outlet, a reaction solution was continuously obtained. In addition, the usage-amount of a raw material is as follows.
- Radical polymerization initiator 2,2′-azobis (2-isobutyronitrile)
- the obtained reaction liquid was subjected to a heating and decompression treatment for 3 hours under the conditions of 120 ° C. and 655 Pa or less to remove unreacted acrylonitrile and a decomposition product of a radical polymerization initiator, and a polymer polyol having a hydroxyl value of 19 mgKOH / g ( PB1-1) was obtained.
- This polymer polyol (PB1-1) has a vinyl polymer content of 20% by mass (the total amount of acrylonitrile used is 20% by mass relative to the total amount of polyether polyol (B1-1) and acrylonitrile used of 100% by mass). there were.
- Synthesis Example 25 Polymer polyol (PC1-1) A polyether polyol (C1-2) having a hydroxyl value of 34 mg KOH / g obtained in Synthesis Example 23 is filled in a 1-liter pressure-resistant autoclave equipped with a thermometer, a stirring device, a pressure gauge, and a liquid feeding device. The temperature was raised to 120 ° C. while stirring. The mixture was continuously charged with a mixture of polyether polyol (C1-2), radical polymerization initiator, acrylonitrile and dispersion stabilizer, and the reaction temperature was 120 ° C., the reaction pressure was 400 kPa, and the residence time was 50 minutes. After the initial polymerization was removed from the outlet, a reaction solution was continuously obtained. In addition, the usage-amount of a raw material is as follows.
- Radical polymerization initiator 2,2′-azobis (2-isobutyronitrile)
- the obtained reaction solution was subjected to a heating and decompression treatment for 3 hours under the conditions of 120 ° C. and 655 Pa or less to remove unreacted acrylonitrile, decomposition products of the radical polymerization initiator, etc., and a polymer polyol having a hydroxyl value of 23 mgKOH / g ( PC1-1) was obtained.
- the vinyl polymer content of this polymer polyol (PC1-1) is 30% by mass (the total amount of acrylonitrile used is 30% by mass with respect to 100% by mass of the total amount of polyether polyol (C1-2) and acrylonitrile). there were.
- Example 1 58 parts of the polyester polyol (A-1) obtained in Synthesis Example 1, 30 parts of the low monool polyol (B-1) synthesized in Synthesis Example 21, and the polymer polyol (PB1-1) synthesized in Synthesis Example 24 ) 12 parts, cross-linking agent: 2.0 parts by Actol KL-210 (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.), communication agent: 2.5 parts by Actcol EP-505S (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.), Foam stabilizer: 0.7 part of FV-1013-16 (manufactured by Toray Dow Corning Co., Ltd.), water: 2.3 parts, catalyst: R-9000 (manufactured by Active Materials Chemical Co., Ltd.) 1.2 parts Were mixed to prepare a resin premix.
- cross-linking agent 2.0 parts by Actol KL-210 (manufactured by Mitsui Chemicals Polyurethanes Co
- Example 2 to 4 Comparative Examples 1 to 4
- a flexible polyurethane foam Examples 2 to 4 and Comparative Examples 1 to 4) was obtained in the same manner as in Example 1, except that the amount of charging was changed according to Table 4. Table 4 shows the physical properties of the obtained flexible polyurethane foam.
- Polyester polyols (A-9 to A-14, A-16, A-18), low monool polyol (B-1), low monool polyol (C—) obtained in Synthesis Examples 9 to 14, 16, and 18 1), polymer polyol (PB1-1), polymer polyol (PC1-1), cross-linking agent (Actol KL-210), cross-linking agent (glycerin, manufactured by Wako Pure Chemical Industries, Ltd.), communication agent (Actco- EP-505S), foam stabilizer (FV-1013-16), water, catalyst (R-9000), catalyst (dibutyltin dilaurate: DBTDL (Neostam U-100, manufactured by Nitto Kasei Co., Ltd.), catalyst ( 70% dipropylene glycol solution of bis (2-dimethylaminoethyl) ether: NIAX A-1, manufactured by Momentive Co., Ltd.) and the amount of foam stabilizer (Y-10366) Soft polyurethan
- Example 13 A polyol (A-19) adjusted to 40 ° C. and Cosmonate PH (MDI-PH: manufactured by Mitsui Chemicals) adjusted to 50 ° C. with an NCO index of 1.00 for 1 minute with stirring blades. After mixing in the apparatus, degassed under reduced pressure for 1 minute, and 80 with a mold for measuring physical properties (sheet mold; thickness 2 mm ⁇ 12 mm ⁇ 32 mm, hardness measurement and impact resilience measurement button; thickness 11 mm ⁇ diameter 28 mm). C. for 24 hours. It was confirmed by IR measurement of the sample after curing that there was no unreacted NCO. Table 6 shows the physical properties of the obtained polyurethane resin.
- Example 14 and 15 Comparative Examples 8 and 9 Except that the polyols (A-2, A-4, A-7 and A-20) obtained in Synthesis Example 2, Synthesis Example 4, Synthesis Example 7 and Synthesis Example 20 were used as shown in Table 6. It carried out similarly to Example 13 and obtained the sample after hardening. Each cured sample was confirmed to have no unreacted NCO by IR measurement. Table 6 shows the physical properties of the obtained polyurethane resin.
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Abstract
Description
(II)1種のヒドロキシル基含有脂肪酸エステル、
(III)1種のヒドロキシル基含有脂肪酸(i)と、該1種のヒドロキシ基含有脂肪酸(i)から得られるエステルとの混合物。
本発明のポリウレタン用組成物は、少なくとも、特定のポリエステルポリオール(A)を含むポリオール(P)、触媒、ポリイソシアネートを含み、かつ、特定のポリエステルポリオール(A)が、ポリオール(A)中に、10~95質量%の範囲で含まれる。また、該組成物には、必要に応じて、整泡剤、発泡剤、架橋剤、その他の助剤などを含むことが好ましく、さらに、該ポリオール(P)中に、総不飽和度が0.035meq/g以下の低モノオールポリオール(B)などのその他のポリオールを含有することが好ましい。また、本発明のポリウレタンフォーム用組成物は、本発明のポリウレタン用組成物に、さらに、整泡剤および発泡剤と、必要に応じて、低モノオールポリオール(B)を含む。
本発明で用いられるポリオール(P)は、少なくとも、特定のポリエステルポリオール(A)と、必要に応じて、低モノオールポリオール(B)、ポリマー分散ポリオールなどのその他のポリオールを含有する。
本発明の水酸基価が15~100mgKOH/gのポリエステルポリオール(A)は、ヒドロキシル基含有脂肪酸およびヒドロキシル基含有脂肪酸エステルからなる群から選ばれる少なくとも1種を含む原料と、平均官能基数が3を超えて8以下である多価アルコールとの縮合により得られ、該原料中に、ヒドロキシル基含有脂肪酸およびヒドロキシル基含有脂肪酸エステルを合計で90~100質量%、好ましくは95~100質量%、さらに好ましくは、97~100質量%含むことを特徴とする。ヒドロキシル基含有脂肪酸およびヒドロキシル基含有脂肪酸エステルが、90質量%以上含まれると、得られるポリウレタン樹脂またはポリウレタンフォームは、高反発弾性、適度な硬度、優れた耐久性をバランス良く達成することができる。特に、該原料中に、より高濃度で含まれると、より高反発弾性のポリウレタン樹脂またはポリウレタンフォームを得ることができる。
(II)1種のヒドロキシル基含有脂肪酸エステル、
(III)1種のヒドロキシル基含有脂肪酸(i)と、該1種のヒドロキシ基含有脂肪酸(i)から得られるエステルとの混合物。
本発明において、ヒドロキシル基含有脂肪酸およびヒドロキシル基含有脂肪酸エステルから選ばれる1種が、ひまし油から得られることが、より環境負荷低減に寄与できるため好ましい。
本発明において、ヒドロキシル基含有脂肪酸およびヒドロキシル基含有脂肪酸エステルからなる群から選ばれる少なくとも1種を含む原料中には、その他のヒドロキシカルボン酸および/またはヒドロキシカルボン酸エステルが、0~10質量%、好ましくは0~5質量%、さらに好ましくは0~3質量%含まれていても良い。
(V)1種のヒドロキシル基含有脂肪酸と乳酸エステルとの混合物、
(VI)1種のヒドロキシル基含有脂肪酸エステルと乳酸との混合物、
(VII)1種のヒドロキシル基含有脂肪酸エステルと乳酸エステルとの混合物、
(VIII)1種のヒドロキシル基含有脂肪酸(i)と、該1種のヒドロキシ基含有脂肪酸(i)から得られるエステル、および乳酸との混合物、
(IX)1種のヒドロキシル基含有脂肪酸(i)と、該1種のヒドロキシ基含有脂肪酸(i)から得られるエステル、および乳酸エステルとの混合物、
(X)1種のヒドロキシル基含有脂肪酸(i)、該1種のヒドロキシ基含有脂肪酸(i)から得られるエステル、乳酸および乳酸エステルから選ばれる少なくとも1種以上の混合物、
(XI)ヒドロキシル基含有脂肪酸、ヒドロキシル基含有脂肪酸エステル、乳酸および乳酸エステルから選ばれる少なくとも1種以上を含む混合物。
前記原料、特にひまし油由来の原料と共に、ポリエステルポリオール(A)の形成のために用いられる、本発明に係る平均官能基数が3を超えて8以下である多価アルコールは、所望の多価アルコールであれば、ポリウレタンフォームの製造用に一般的に使用されるポリオールを用いることができる。
本発明の水酸基価が15~100mgKOH/gであるポリエステルポリオール(A)は、上記原料中に、特にひまし油由来の、ヒドロキシル基含有脂肪酸、ヒドロキシル基含有脂肪酸エステルと、上記平均官能基数が3を超えて8以下である多価アルコールとを縮合させて得られる。この場合、ヒドロキシル基含有脂肪酸および/またはヒドロキシル基含有脂肪酸エステルを縮合させた後、得られた縮合物を多価アルコールと縮合させてもよいし、あるいは多価アルコールと、ヒドロキシル基含有脂肪酸および/またはヒドロキシル基含有脂肪酸エステルとを縮合させた後、さらに、ヒドロキシル基含有脂肪酸および/またはヒドロキシル基含有脂肪酸エステルを縮合させてもよい。
<(B)低モノオールポリオール>
本発明では、ポリウレタンフォームの製造用に一般に使用されるポリオールであり、かつ、総不飽和度が0.035meq/g以下、好ましくは0.030meq/g以下、より好ましくは0.025meq/g以下の低モノオールポリオール(B)を用いてもよい。なお、総不飽和度の下限値は特に限定されないが、たとえば0.001meq/gである。また、前記低モノオールポリオール(B)の変性体も用いることができる。これらの低モノオールポリオール(B)は1種単独でまたは2種以上を混合して使用することができる。
上記ポリエーテルポリオール(B1)としては、開始剤である活性水素化合物にアルキレンオキシドを、通常、触媒存在下で開環重合させることにより得られ、かつ総不飽和度が上記範囲のオリゴマーまたは重合物が挙げられる。
上記のような総不飽和度が小さい、すなわち低モノオール含有量のポリエーテルポリオール(B1)は、たとえば、少なくとも、窒素-リン2重結合を有する化合物、水酸化セシウムおよび水酸化ルビジウムから選択される少なくとも1種の化合物を触媒として使用することによって製造することができる。上記化合物を触媒として用いることによって、水酸化カリウムなどの従来公知のアルカリ金属水酸化物を触媒として使用した場合に比較して副生するモノオール量を低減させることができ、結果として得られるポリウレタンフォームまたはポリウレタン樹脂の諸物性を向上させることができる。たとえば、アルカリ金属水酸化物を触媒として使用すると、適度な硬度および反発弾性、ならびに優れた耐久性をバランス良く達成することは困難であったが、上記化合物を触媒として用いることによって良好に達成することができる。特に、この低モノオールポリオールの優れた効果は、一般的に不純物が含まれ、石油由来ポリオールに比べて性能が劣ることが多い植物由来ポリオールと併用した場合に顕著に現れる。
上記活性水素化合物としては、酸素原子上に活性水素原子を有する活性水素化合物や窒素原子上に活性水素原子を有する活性水素化合物が挙げられ、官能基数が2~8の活性水素化合物が好ましい。
上記アルキレンオキシドとしては、炭素数2~12のアルキレンオキシドが好ましい。具体的には、エチレンオキシド、プロピレンオキシド、1,2-ブチレンオキシド、2,3-ブチレンオキシド、スチレンオキシド、シクロヘキセンオキシド、エピクロロヒドリン、エピブロモヒドリン、メチルグリシジルエーテル、アリルグリシジルエーテル、フェニルグリシジルエーテル等が挙げられ、より好ましくはエチレンオキシド、プロピレンオキシド、1,2-ブチレンオキシド、スチレンオキシドであり、特に好ましくはエチレンオキシド、プロピレンオキシドである。
本発明では、(A)ポリエステルポリオール、あるいは(B)低モノオールポリオールをそのまま使用してもよいが、これらのポリオール中で不飽和結合を有する化合物をラジカル重合させて得られたポリマー微粒子が、これらのポリオール中に分散したポリマー分散ポリオールとして使用してもよい。また、これらのポリオールと、ポリマー分散ポリオールとを併用してもよい。
本発明のポリウレタンフォーム用組成物には、ポリエステルポリオール(A)、低モノオールポリオール(B)、ポリマー分散ポリオール以外に、ポリウレタンフォームの製造用に一般に使用されるその他のポリオールを添加してもよい。このようなポリオールとしては、たとえば、総不飽和度が0.035meq/gを超えるポリエーテルポリオール、このポリエーテルポリオールから得られるポリマーポリオール、ポリエステルポリオールなどが挙げられる。このようなポリオールは、ポリオール(P)中に、ポリオール(P)全成分100質量%に対して、5~95質量%、好ましくは10~80質量%、さらに好ましくは10~70質量%含まれる。ポリオールが、5質量%未満であるとき、成形性の点で好ましくなく、95質量%を超えると、環境負荷の低減に寄与できないという点で好ましくない。
総不飽和度が0.035meq/gを超えるポリエーテルポリオール(以下、「ポリエーテルポリオール(C)」ともいう)としては、アルキレンオキシドを開環重合させて得られ、かつ総不飽和度が0.035meq/gを超えるオリゴマーまたは重合物が挙げられる。このようなポリエーテルポリオール(C)は、通常、水酸化カリウムなどのアルカリ金属水酸化物等の触媒存在下で開始剤である活性水素化合物にアルキレンオキシドを開環重合させることにより得られる。
上記活性水素化合物としては、上記ポリエーテルポリオール(B1)において例示した活性水素化合物を用いることができる。これらの活性水素化合物は、1種単独でまたは2種以上を混合して用いることができる。これらの活性水素化合物のうち、炭素原子数が2~20で、1分子中2~8個の水酸基を有する多価アルコール類が好ましく、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、グリセリン、ジグリセリン、ペンタエリスリトールがより好ましい。
上記アルキレンオキシドとしては、上記ポリエーテルポリオール(B1)において例示したアルキレンオキシドが挙げられ、より好ましくはエチレンオキシド、プロピレンオキシド、1,2-ブチレンオキシド、スチレンオキシドであり、特に好ましくはエチレンオキシド、プロピレンオキシドである。
その他のポリオールとして用いられるポリマーポリオールとしては、上記ポリエーテルポリオール(C)から得られるポリマーポリオール(以下、「ポリマーポリオール(PC)」ともいう)が挙げられ、好ましくは水酸基価が15mgKOH/g以上60mgKOH/g以下のポリエーテルポリオール(C)から得られるポリマーポリオールである。
上記ポリエステルポリオールとしては、たとえば、低分子ポリオールとカルボン酸との縮合物;ε-カプロラクトン開環重合物、β-メチル-δ-バレロラクトン開環重合物等のラクトン系ポリオール等が挙げられる。
本発明に係る発泡剤としては、液化炭酸ガス等の物理発泡剤も使用可能であるが、水を使用することが最も望ましい。
本発明において用いられる触媒は、ポリオール(P)とポリイソシアネートとの反応に用いられ、特に制限なく、従来公知の触媒が使用できる。たとえば、トリエチレンジアミン、ビス(2-ジメチルアミノエチル)エーテル、1-イソブチル-2-メチルイミダゾール、モルフォリン類等の脂肪族アミン類;オクタン酸スズ、ジブチルチンジラウレート等の有機錫化合物などを好ましく用いることができる。
本発明において用いられる整泡剤としては、従来公知の整泡剤が使用でき、特に制限は無いが、通常は有機ケイ素系界面活性剤を使用することが好ましい。
本発明において用いられるポリイソシアネートは、特に限定されず、たとえば、岩田敬治編「ポリウレタン樹脂ハンドブック」第1刷日刊工業新聞社(1987)71~98頁等に示されている従来公知のポリイソシアネートが挙げられる。この中で、発泡体を得るためには、トルイレンジイソシアネート(2,4-体や2,6-体等の異性体比率は特に限定されないが、2,4-体/2,6-体が80/20の比率のものが好ましい)、ポリメチレンポリフェニルポリイソシアネート(たとえば、三井化学ポリウレタン(株)製コスモネートM-200)もしくはそのウレタン変性体、またはこれらの混合物が好ましく使用できる。
本発明のポリウレタン用組成物には、上記成分に加えて、鎖延長剤、架橋剤、連通化剤、消泡剤、さらにその他助剤として難燃剤、顔料、紫外線吸収剤、酸化防止剤等のポリウレタンフォームまたはポリウレタン樹脂を製造する際に一般的に用いられる添加剤を、本発明の目的を損なわない範囲で用いることができる。
後述する、本発明のポリウレタンフォームまたはポリウレタン樹脂には、架橋剤を使用することも可能であるため、本発明のポリウレタン用組成物に架橋剤を添加することもできる。架橋剤を使用する場合には、好ましくは水酸基価が200~1800mgKOH/gである化合物が架橋剤として用いられる。
本発明に係るポリウレタン樹脂の製造方法は、特に限定されず、従来公知の製造方法を適宜採用することができる。具体的には、ポリエステルポリオール(A)を含むポリオール(P)を触媒、消泡剤、低モノオールポリオール(B)などのその他のポリオール、その他の助剤、架橋剤などを予め混合してレジンプレミックスを調製した後、このレジンプレミックスとポリイソシアネートを混合し、硬化させることによりポリウレタン樹脂を得ることが出来る。また、ポリエステルポリオール(A)を含むポリオール(P)を過剰のイソシアネートと反応させることにより、イソシアネート基を末端に持つプレポリマーを合成し、その後、触媒や必要な架橋剤をプレポリマーと混合することによりポリウレタン樹脂を得ることも出来る。
本発明に係るポリウレタンフォームの製造方法は、特に限定されず、従来公知の製造方法を適宜採用することができる。具体的には、スラブフォーム法、ホットキュアモールドフォーム法、コールドキュアモールドフォーム法のいずれも採用できる。自動車等の車両用シートパッドを製造する場合は、コールドキュアモールドフォーム法が好ましい。
JIS K-6400記載の見掛け密度の測定方法に準拠して測定を実施した。本発明では、ポリウレタンフォームサンプルから表皮を取り去り、直方体フォームサンプルを調製してコア密度を測定した。
JIS K-6400記載のA法に準拠して測定を実施した。ただし、厚さ100mmのポリウレタンフォームについて測定した。
JIS K-6400記載の方法により測定を実施した。
JIS K-6400記載の方法により測定を実施した。測定に際して、成形したポリウレタンフォームのコア部を50mm×50mm×25mmに切り抜き、これを試験片として使用した。試験片を50%の厚みまで圧縮し、平行平面板に挟み、50℃、相対湿度95%の条件下で22時間放置した。試験片を取り出して30分後、その厚みを測定し、試験前の厚みと比較して歪み率を測定した。
JIS K-6400記載の方法により測定を実施した。
上記で測定した、フォームの硬度、反発弾性および湿熱圧縮永久歪みにおいて、フォームの物性が、フォーム硬度:140~280N/314cm2、反発弾性:60~75%、湿熱圧縮永久歪み:14%以下の範囲にあるとき、フォームの特性バランスを○と評価して、これらの物性値が一点でも外れる場合、×と評価した。
JIS K-1557-5記載の方法により測定を実施した。
JIS K-1557-1記載の方法により測定を実施した。
JIS K-1557-3記載の方法により測定を実施した。
円錐平板型回転粘度計(E型粘度計)を用い、25℃での粘度を測定した。
ヒドロキシル基含有脂肪酸およびヒドロキシル基含有脂肪酸エステルからなる群から選ばれる少なくとも1種を含む原料中に含まれる、ヒドロキシル基含有脂肪酸の割合は、JIS K1557-1の方法により測定されるヒドロキシル基含有脂肪酸の水酸基価A、JIS K1557-5の方法により測定されるヒドロキシル基含有脂肪酸の酸価Bの比A/Bにより求めた。
ヒドロキシル基含有脂肪酸およびヒドロキシル基含有脂肪酸エステルからなる群から選ばれる少なくとも1種を含む原料を重クロロホルムに溶解し、日本電子データム(株)製 核磁気共鳴装置 AL-400により、1H-NMR測定を行なった。得られたケミカルシフトのピークを同定し、水酸基に隣接する炭素原子に結合するプロトンのピーク面積Cとアルキル末端メチル基のプロトンのピーク面積Dを比較し、3C/D×100によって、ヒドロキシル基含有脂肪酸とヒドロキシル基含有脂肪酸エステルの合計量の割合(%)を求めた。ここから、前記の方法により求められたヒドロキシル基含有脂肪酸の割合を減じて、ヒドロキシル基含有脂肪酸エステルの割合を求めた。なお、原料中に含まれる、1種のヒドロキシル基含有脂肪酸(i)と、該1種のヒドロキシ基含有脂肪酸(i)から得られるエステルとの混合物の合計量の割合も、上記1H-NMRによる測定法と同様にして行い、該1種のヒドロキシ基含有脂肪酸(i)から得られるエステルの割合は、前記の方法により求められたヒドロキシル基含有脂肪酸の割合を減じて、ヒドロキシル基含有脂肪酸エステルの割合を求めた。また、原料中に含まれる、ヒドロキシル基含有脂肪酸およびヒドロキシル基含有脂肪酸エステルの合計量(純度:%)は、上記(11)と(12)の測定法を用いて算出した。
ヒドロキシル基含有脂肪酸およびヒドロキシル基含有脂肪酸エステルからなる群から選ばれる少なくとも1種を含む原料中に含まれる、炭素-炭素二重結合を有するヒドロキシル基含有脂肪酸および/またはヒドロキシル基含有脂肪酸エステルの割合は、上記(12)の純度測定と同様にして、1H-NMR測定により求めた。すなわち、割合(%)は、1H-NMR測定による、炭素-炭素二重結合に結合するプロトンのピーク面積Eと、アルキル末端メチル基のプロトンのピーク面積Dを用いて、3E/2D×100を算出することにより求めた。
樹脂作成方法記載の方法により得られた硬度測定用サンプルを用い、高分子計器(株)製硬度計を用いてJIS K6253記載の方法により、測定を実施した。
樹脂作成方法記載の方法により得られた反発弾性測定用サンプルを用い、JIS K6255に記載のデュプケ式(デュプケ法)に準拠して上島製作所製反発弾性率装置にて測定した。
樹脂作成方法記載の方法により得られた引張強度測定用サンプルを用い、JIS K6251記載の方法により、JIS3号ダンベルにて打ち抜いたサンプルの、引張強度(最大点応力および最大点伸度)を測定した。
(精製例1)
ヒドロキシル基含有脂肪酸およびヒドロキシル基含有脂肪酸エステルからなる群から選ばれる少なくとも1種を含む原料として、ひまし油より得られる原料であるひまし油脂肪酸を用いた。
装入速度220g/h、蒸発面温度170℃で実施した以外は精製例1と同様の操作を行った。その時得られた高純度ひまし油脂肪酸の酸価は176.3mgKOH/g、水酸基価は173.5mgKOH/gであり、これらより求めた高純度ひまし油脂肪酸(2)の純度は98.4%であった。なお、高純度ひまし油脂肪酸(2)は、リシノレイン酸であることが確認された。
装入速度75g/h、蒸発面温度150℃、圧力20Paで実施した以外は精製例1と同様の操作を行い、その時得られた高純度ひまし油脂肪酸の酸価は185.3mgKOH/g、水酸基価は169.6mgKOH/gであり、これらより求めた高純度ひまし油脂肪酸(3)の純度は91.5%であった。なお、高純度ひまし油脂肪酸(3)は、リシノレイン酸であることが確認された。
ひまし油を加水分解した後にエステル交換することにより得られたひまし油脂肪酸エステル(伊藤製油(株)製:商品名CO-FAメチルエステルD)を、蒸発表面の面積が0.03m2の分子蒸留装置(柴田科学(株)製)を用いて低沸成分である水酸基不含成分を除去し、高純度ひまし油脂肪酸メチルエステルを得た。このときの蒸発条件は装入速度220g/h、蒸発表面温度120℃、圧力7Pa、ワイパー回転数300rpmであった。得られた高純度ひまし油脂肪酸メチルエステルをさらに同条件にてさらなる高純度化を行なう操作を3回繰り返し、高純度ひまし油脂肪酸メチルエステル(4)を得た。この高純度ひまし油脂肪酸メチルエステル(4)の純度を1H-NMRにより求めたところ、98.6%であった。なお、高純度ひまし油脂肪酸メチルエステル(4)は、リシノレイン酸メチルであることが確認された。
伊藤製油(株)製12-ヒドロキシステアリン酸(12-HSA)400gをブタノール600gに加え、50℃まで昇温して、完全に12-HSAに溶解させた後、25℃の室内にて、4時間放置し、12-HSAを結晶化させた。
(合成例1):ポリエステルポリオールA-1
精製例1で得られた高純度ひまし油脂肪酸(1)とひまし油脂肪酸(伊藤製油(株)製:商品名CO-FA、純度:86%)を純度95.0%になるようにあらかじめ混合した高純度ひまし油脂肪酸を1944g、SOR-400(三井化学ポリウレタン(株)製、ソルビトールにプロピレンオキシドを付加したポリオール、水酸基価400mgKOH/g)を78g、PE-450(三井化学ポリウレタン(株)製、ペンタエリスリトールにプロピレンオキシドを付加したポリオール、水酸基価450mgKOH/g)を97g(以上、多価アルコールの平均官能基数:4.6)、温度計・撹拌装置・生成する水を分離させる装置を具備した2Lのガラス製フラスコに仕込み、窒素気流下、180℃で縮合反応を実施した。酸価が10mgKOH/g以下になった時点で触媒としてオルトチタン酸テトラブチル(試薬東京化成(株)製)を0.2g添加し引き続き180℃にて縮合反応を実施し109時間縮合反応を行った。得られたポリエステルポリオールA-1(ポリオールA-1)の水酸基価(OHV)、平均官能基数(計算値)、粘度を表1に示す。
高純度ひまし油脂肪酸(1)、(3)、または高純度ひまし油脂肪酸メチルエステル(4)、SOR-400、PE-450、グリセリン(Gly:和光純薬工業(株)社製、特級)の仕込み量、縮合反応条件を、表1に従って変更した以外は、合成例1と同様に行って、ポリオールA-2~A-8を得た。なお、高純度ひまし油脂肪酸、または高純度ひまし油脂肪酸メチルエステルを用いるにあたり、合成例1と同様に、表1に記載の所望の純度となるように、あらかじめひまし油脂肪酸(伊藤製油(株)製:商品名CO-FA、純度:86%)を混合して、調製した。また、合成例A-5~A-7では、ひまし油脂肪酸(CO-FA)を用いて合成した。
高純度ひまし油脂肪酸(1)~(3)、高純度12-HSA、SOR-400、PE-450の仕込み量、縮合反応条件を、表2または3に従って変更した以外は、合成例1と同様に行って、ポリオールA-9~A-20を得た。なお、高純度ひまし油脂肪酸を用いるにあたり、合成例1と同様に、表2または3に記載の所望の純度となるように、あらかじめひまし油脂肪酸(CO-FA、純度:86%)を混合して、調製した。また、合成例13で用いた、原料中に含まれる、ひまし油脂肪酸および12-ヒドロキシステアリン酸の合計量(純度)は、93%であった。合成例A-20では、12-ヒドロキシステアリン酸(伊藤製油(株)社製、純度:86%)を用いて合成した。
(合成例21):ポリエーテルポリオール(B1-1)
グリセリン1モルに対してテトラキス[トリス(ジメチルアミノ)ホスフォラニリデンアミノ]ホスフォニウムヒドロキシド0.01モルを加え、100℃で6時間減圧脱水した後、プロピレンオキシドを反応温度80℃、最大反応圧力3.8kg/cm2で付加重合させた。次いで、エチレンオキシドを反応温度100℃、最大反応圧力3.8kg/cm2で付加重合させてポリエーテルポリオール(B1-1)を得た。このポリオール(B1-1)の総不飽和度は0.025meq/g、水酸基価は24mgKOH/g、末端オキシエチレン基含有率は15質量%であった。
グリセリン1モルに対して水酸化カリウム0.37モルを加え、100℃で6時間減圧脱水した後、プロピレンオキシドを反応温度115℃、最大反応圧力5.0kg/cm2で付加重合させた。次いで、エチレンオキシドを反応温度115℃、最大反応圧力3.8kg/cm2で付加重合させてポリエーテルポリオール(C1-1)を得た。このポリオール(C1-1)の総不飽和度は0.062meq/g、水酸基価は28mgKOH/g、末端オキシエチレン基含有率は15質量%であった。
グリセリン1モルに対して水酸化カリウム0.37モルを加え、100℃で6時間減圧脱水した後、プロピレンオキシドを反応温度115℃、最大反応圧力5.0kg/cm2で付加重合させた。次いで、エチレンオキシドを反応温度115℃、最大反応圧力3.8kg/cm2で付加重合させてポリエーテルポリオール(C1-2)を得た。このポリオール(C1-2)の総不飽和度は0.051meq/g、水酸基価は34mgKOH/g、末端オキシエチレン基含有率は15質量%であった。
(合成例24):ポリマーポリオール(PB1-1)
温度計、撹拌装置、圧力計および送液装置を備えた1リットル容器の耐圧オートクレーブに、合成例21で得られた水酸基価24mgKOH/gのポリエーテルポリオール(B1-1)を満液状態になるまで仕込み、撹拌しながら、120℃に昇温した。これに、ポリエーテルポリオール(B1-1)、ラジカル重合開始剤、アクリロニトリルおよび分散安定化剤の混合液を連続装入し、反応温度120℃、反応圧力400kPa、滞留時間50分の条件で、アクリロニトリルをグラフト重合させ、排出口より初留を除いた後、連続的に反応液を得た。なお、原料の使用量は以下のとおりである。
ラジカル重合開始剤:50g
アクリロニトリル:1800g
また、ラジカル重合開始剤は、以下のものを使用した。
得られた反応液を120℃、655Pa以下の条件で3時間の加熱減圧処理を行なって、未反応のアクリロニトリルおよびラジカル重合開始剤の分解物等を除去し、水酸基価19mgKOH/gのポリマーポリオール(PB1-1)を得た。このポリマーポリオール(PB1-1)のビニルポリマー含量は、20質量%(アクリロニトリルの総使用量が、ポリエーテルポリオール(B1-1)、アクリロニトリルの総使用量100質量%に対して20質量%)であった。
温度計、撹拌装置、圧力計および送液装置を備えた1リットル容器の耐圧オートクレーブに、合成例23で得られた水酸基価34mgKOH/gのポリエーテルポリオール(C1-2)を満液状態になるまで仕込み、撹拌しながら、120℃に昇温した。これに、ポリエーテルポリオール(C1-2)、ラジカル重合開始剤、アクリロニトリルおよび分散安定化剤の混合液を連続装入し、反応温度120℃、反応圧力400kPa、滞留時間50分の条件で、アクリロニトリルをグラフト重合させ、排出口より初留を除いた後、連続的に反応液を得た。なお、原料の使用量は以下のとおりである。
ラジカル重合開始剤:80g
アクリロニトリル:3000g
また、ラジカル重合開始剤は、以下のものを使用した。
得られた反応液を120℃、655Pa以下の条件で3時間の加熱減圧処理を行なって、未反応のアクリロニトリルおよびラジカル重合開始剤の分解物等を除去し、水酸基価23mgKOH/gのポリマーポリオール(PC1-1)を得た。このポリマーポリオール(PC1-1)のビニルポリマー含量は、30質量%(アクリロニトリルの総使用量が、ポリエーテルポリオール(C1-2)、アクリロニトリルの総使用量100質量%に対して30質量%)であった。
(実施例1)
合成例1で得られたポリエステルポリオール(A-1)58部と、合成例21にて合成した低モノオールポリオール(B-1)30部、合成例24にて合成したポリマーポリオール(PB1-1)12部、架橋剤:アクトコールKL-210(三井化学ポリウレタン(株)製)2.0部、連通化剤:アクトコ-ルEP-505S(三井化学ポリウレタン(株)製)2.5部、整泡剤:FV-1013-16(東レ・ダウコーニング(株)社製)0.7部、水:2.3部、触媒:R-9000(活材ケミカル(株)製)1.2部を混合し、レジンプレミックスを調製した。これとポリイソシアネート(三井化学ポリウレタン(株)社製、商品名コスモネートTM-20、NCOインデックス1.00)32部を混合し、直ちにあらかじめ60℃に調整した内寸300mm×300mm×100mmの金型へ注入し、ふたを閉めて発泡させた。金型を60℃に保ったまま8分間硬化反応を進めた後、金型より軟質ポリウレタンフォームを取り出し、各種物性を測定した。得られた軟質ポリウレタンフォームの物性を表4に示す。
合成例2~8で得られたポリエステルポリオール(A-2~A-8)、低モノオールポリオール(B-1)、ポリマーポリオール(PB1-1)、架橋剤(アクトコールKL-210)、連通化剤(アクトコ-ルEP-505S)、整泡剤(FV-1013-16)、水、触媒(R-9000)、整泡剤(GE東芝シリコーン(株)社製、商品名Y-10366)の仕込み量を、表4に従って変更した以外は、実施例1と同様に行って、軟質ポリウレタンフォーム(実施例2~4、比較例1~4)を得た。得られた軟質ポリウレタンフォームの物性を表4に示す。
合成例9~14、16、18で得られたポリエステルポリオール(A-9~A-14、A-16、A-18)、低モノオールポリオール(B-1)、低モノオールポリオール(C-1)、ポリマーポリオール(PB1-1)、ポリマーポリオール(PC1-1)、架橋剤(アクトコールKL-210)、架橋剤(グリセリン、和光純薬(株)社製)、連通化剤(アクトコ-ルEP-505S)、整泡剤(FV-1013-16)、水、触媒(R-9000)、触媒(ジブチルチンジラウレート:DBTDL(Neostam U-100、日東化成(株)社製)、触媒(ビス(2-ジメチルアミノエチル)エーテルの70%ジプロピレングリコール溶液:NIAX A-1、モメンティブ(株)社製)、整泡剤(Y-10366)の仕込み量を、表5に従って変更した以外は、実施例1と同様に行って、軟質ポリウレタンフォーム(実施例5~12、比較例5~7)を得た。得られた軟質ポリウレタンフォームの物性を表5に示す。
(実施例13)
40℃に温調したポリオール(A-19)と50℃に温調したコスモネートPH(MDI-PH:三井化学(株)製)をNCOインデックス1.00で1分間、撹拌翼がついた撹拌装置にて混合後、1分間減圧脱泡し、物性測定用のモールド(シート型;厚さ2mm×12mm×32mm、硬度測定用および反発弾性測定用ボタン;厚さ11mm×直径28mm)にて80℃×24時間の硬化を行った。硬化後サンプルのIR測定にて未反応NCOがないことを確認した。得られたポリウレタン樹脂の物性を表6に示す。
合成例2、合成例4、合成例7および合成例20にて得られたポリオール(A-2、A-4、A-7およびA-20)を表6に示したように用いた以外は実施例13と同様に行って、硬化後のサンプルを得た。各々の硬化後サンプルはIR測定にて未反応NCOがないことを確認した。得られたポリウレタン樹脂の物性を表6に示す。
Claims (12)
- ヒドロキシル基含有脂肪酸およびヒドロキシル基含有脂肪酸エステルからなる群から選ばれる少なくとも1種を含む原料と、
平均官能基数が3を超えて8以下である多価アルコールとの縮合により得られる、
水酸基価が15~100mgKOH/gのポリエステルポリオール(A)であり、
該原料中に、ヒドロキシル基含有脂肪酸およびヒドロキシル基含有脂肪酸エステルを合計で90~100質量%含むことを特徴とするポリエステルポリオール(A)。 - ヒドロキシル基含有脂肪酸およびヒドロキシル基含有脂肪酸エステルからなる群から選ばれる少なくとも1種を含む原料と、
平均官能基数が3を超えて8以下である多価アルコールとの縮合により得られる、
水酸基価が15~100mgKOH/gのポリエステルポリオール(A)であって、
該原料中に、下記(I)、(II)または(III)を90~100質量%含むことを特徴とするポリエステルポリオール(A)。
(I)1種のヒドロキシル基含有脂肪酸、
(II)1種のヒドロキシル基含有脂肪酸エステル、
(III)1種のヒドロキシル基含有脂肪酸(i)と、該1種のヒドロキシ基含有脂肪酸(i)から得られるエステルとの混合物。 - 前記ヒドロキシル基含有脂肪酸およびヒドロキシル基含有脂肪酸エステルからなる群から選ばれる少なくとも1種が、分子内に炭素-炭素二重結合を有することを特徴とする請求項1または2に記載のポリエステルポリオール(A)。
- 前記ヒドロキシル基含有脂肪酸およびヒドロキシル基含有脂肪酸エステルからなる群から選ばれる少なくとも1種が、ひまし油から得られることを特徴とする請求項1~3のいずれか一項に記載のポリエステルポリオール(A)。
- 前記ヒドロキシル基含有脂肪酸がリシノレイン酸であり、
前記ヒドロキシル基含有脂肪酸エステルがリシノレイン酸エステルである、
ことを特徴とする請求項1~4のいずれか一項に記載のポリエステルポリオール(A)。 - 前記多価アルコールと、前記ヒドロキシル基含有脂肪酸およびヒドロキシル基含有脂肪酸エステルの合計量との質量比が、1:1~1:100であることを特徴とする請求項1~5のいずれか一項に記載のポリエステルポリオール(A)。
- 少なくとも、請求項1~6のいずれか一項に記載のポリエステルポリオール(A)を含むポリオール(P)、触媒、およびポリイソシアネートを含有するポリウレタン用組成物であって、
該ポリエステルポリオール(A)が、ポリオール(P)中に、10~95質量%の範囲で含まれることを特徴とするポリウレタン用組成物。 - 請求項7に記載のポリウレタン用組成物に、
さらに、整泡剤および発泡剤を含むことを特徴とするポリウレタンフォーム用組成物。 - 前記ポリオール(P)に、
さらに、総不飽和度が0.035meq/g以下の低モノオールポリール(B)を含むことを特徴とする請求項7に記載のポリウレタン用組成物。 - 前記ポリオール(P)に、
さらに、総不飽和度が0.035meq/g以下の低モノオールポリール(B)を含むことを特徴とする請求項8に記載のポリウレタンフォーム用組成物。 - 請求項7または9に記載のポリウレタン用組成物を反応させてなるポリウレタン樹脂。
- 請求項8または10に記載のポリウレタンフォーム用組成物を反応させてなるポリウレタンフォーム。
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WO2012018135A1 (ja) | 2010-08-06 | 2012-02-09 | 三井化学株式会社 | ポリオール、ポリオール組成物、及びそれを用いた軟質ポリウレタンフォーム |
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Also Published As
Publication number | Publication date |
---|---|
US9873757B2 (en) | 2018-01-23 |
TW201012842A (en) | 2010-04-01 |
EP2308913A4 (en) | 2015-01-07 |
CN102089349A (zh) | 2011-06-08 |
JP5398715B2 (ja) | 2014-01-29 |
US20110166245A1 (en) | 2011-07-07 |
EP2308913B1 (en) | 2016-04-20 |
KR20110041522A (ko) | 2011-04-21 |
CN102089349B (zh) | 2014-03-05 |
MY155117A (en) | 2015-09-15 |
US20150218301A1 (en) | 2015-08-06 |
KR101204125B1 (ko) | 2012-11-22 |
JPWO2010013710A1 (ja) | 2012-01-12 |
EP2308913A1 (en) | 2011-04-13 |
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