Hydrogenated unsaturated dibasic acid composition, method for producing hydrogenated unsaturated dibasic acid composition, polyester composition, and polyamide composition

Abstract

To provide a hydrogenated unsaturated dibasic acid composition exhibiting superior thermal stability, a production method thereof, and a polyester composition and a polyamide composition obtained by reaction of the hydrogenated unsaturated dibasic acid composition.SOLUTION: The present invention provides a hydrogenated unsaturated dibasic acid composition satisfying the following (A) and (B). (A) An iodine value is 55 or more. (B) In a 1H-NMR measurement, a ratio (Olefin Hα / ArHα) of an integral value (Olefin Hα) of a peak corresponding to olefin protons to an integral value (ArHα) of a peak corresponding to aromatic protons is 0.10 or more and 0.80 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel hydrogenated unsaturated dibasic acid composition, a method for producing the same, a polyester composition, and a polyamide composition. [Background technology]

[0002] Known unsaturated dibasic acid compositions include dimer acids whose main component is a dibasic acid obtained by dimerizing unsaturated fatty acids having 10 to 22 carbon atoms. Examples of dimer acids include natural or plant-derived fatty acids such as rice bran fatty acids, soybean oil fatty acids, tall oil fatty acids, and rapeseed oil fatty acids, as well as dimer acids obtained from raw materials such as oleic acid, linoleic acid, linolenic acid, and erucic acid, which are obtained by refining these fatty acids.

[0003] Dimer acids are widely used in various applications, for example, as polyamide resins, polyester resins, etc., having a dimer acid-derived skeleton. Various types of such dimer acids are known, and hydrogenated dimer acids are also known (see, for example, Patent Documents 1 to 4). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-002085 [Patent Document 2] Japanese Patent Application Publication No. 08-113549 [Patent Document 3] Special Publication No. 08-503453 [Patent Document 4] Japanese Patent Application Publication No. 63-258830 Summary of the Invention [Problem to be solved by the invention]

[0005] Resins having a dimer acid skeleton are used in a wide range of applications, including applications requiring use in high-temperature environments, and therefore the dimer acids used as raw materials are also required to have thermal stability.

[0006] Patent Documents 1 to 4 do not consider the thermal stability of dimer acids or hydrogenated dimer acids, and naturally do not consider the relationship between the iodine value, the ratio of olefin protons to aromatic protons, and the thermal stability.

[0007] Therefore, an object of the present invention is to provide a hydrogenated unsaturated dibasic acid composition having excellent thermal stability, a method for producing the same, and a polyester composition and a polyamide composition obtained by reacting the hydrogenated unsaturated dibasic acid composition. [Means for solving the problem]

[0008] As a result of extensive research, the present inventors have surprisingly discovered that a hydrogenated unsaturated dibasic acid composition exhibits excellent thermal stability when certain conditions are satisfied, and have thus completed the present invention.

[0009] That is, the present invention relates to a hydrogenated unsaturated dibasic acid composition that satisfies the following (A) and (B): (A) The iodine value is 55 or higher. (B) 1 In H-NMR measurement, the ratio (Olefin Hα / ArHα) of the integral value of the peak corresponding to the olefin proton (Olefin Hα) to the integral value of the peak corresponding to the aromatic proton (ArHα) is 0.10 or more and 0.80 or less.

[0010] The hydrogenated unsaturated dibasic acid composition is preferably a partially hydrogenated product of a feedstock composition comprising the dimerization products of oleic acid, linoleic acid, and / or linolenic acid.

[0011] the hydrogenated unsaturated dibasic acid composition comprises a monobasic acid; The content of the monobasic acid is preferably 10% or less in terms of area ratio in gas chromatography relative to 100% of the hydrogenated unsaturated dibasic acid composition.

[0012] The present invention also relates to a polyester composition obtained by reacting the hydrogenated unsaturated dibasic acid composition with a polyol component, and a polyamide composition obtained by reacting the hydrogenated unsaturated dibasic acid composition with a polyamine component.

[0013] The present invention also relates to a method for producing the hydrogenated unsaturated dibasic acid composition, which comprises a hydrogenation step of hydrogenating a raw material composition containing an unsaturated dibasic acid using a hydrogenation catalyst.

[0014] It is preferable to include a step of treating the composition after the hydrogenation step with an acid and clay.

[0015] Preferably, the acid is citric acid.

[0016] The hydrogenation catalyst is preferably a nickel catalyst. [Effects of the Invention]

[0017] The hydrogenated unsaturated dibasic acid composition of the present invention has a specific iodine value and 1 The ratio (Olefin Hα / ArHα) of the integral value of the peak corresponding to the olefin proton (Olefin Hα) to the integral value of the peak corresponding to the aromatic proton (ArHα) in H-NMR measurement is within a specific range, thereby providing excellent thermal stability. The hydrogenated unsaturated dibasic acid composition of the present invention has excellent thermal stability and can be used in a wide range of applications, such as lubricating oil additives, fuel oil additives, rust inhibitors, ink compositions, and flux compositions. In addition, polyester compositions and polyamide compositions obtained by reacting the hydrogenated unsaturated dibasic acid composition of the present invention also have excellent thermal stability and can be used in a wide range of applications, such as drilling fluids, pressure-sensitive adhesives, resin compositions, hot-melt compositions, primer compositions, and polyurethane compositions. DETAILED DESCRIPTION OF THE INVENTION

[0018] 1. Hydrogenated unsaturated dibasic acid composition The hydrogenated unsaturated dibasic acid composition of the present invention satisfies the following (A) and (B). (A) The iodine value is 55 or higher. (B) 1 In H-NMR measurement, the ratio (Olefin Hα / ArHα) of the integral value of the peak corresponding to the olefin proton (Olefin Hα) to the integral value of the peak corresponding to the aromatic proton (ArHα) is 0.10 or more and 0.80 or less.

[0019] The hydrogenated unsaturated dibasic acid composition of the present invention may be any unsaturated dibasic acid composition that satisfies the requirements (A) and (B) above. In order to distinguish the unsaturated dibasic acid composition obtained by a method for producing the hydrogenated unsaturated dibasic acid composition of the present invention, in which a raw material unsaturated dibasic acid composition such as a dimer acid is hydrogenated, from the raw material unsaturated dibasic acid composition, the term "hydrogenated" is used to indicate a state in which some of the unsaturated bonds in the raw material unsaturated dibasic acid composition have been converted back to saturated bonds.

[0020] The dimer acid preferably contains a dibasic acid obtained by dimerizing a monobasic unsaturated fatty acid having 10 to 22 carbon atoms. Representative raw materials include unsaturated fatty acids such as linolenic acid, linoleic acid, oleic acid, elaidic acid, and erucic acid, and among these, it is preferable to contain a dimerization product of oleic acid, linoleic acid, and / or linolenic acid.

[0021] Most commercially available dimer acids are made from unsaturated fatty acids with 18 carbon atoms, and therefore the main component is a dibasic acid with 36 carbon atoms. Examples of the structure of dimer acids include, but are not limited to, the following: [ka]

[0022] The dimer acid may be either a synthetic product or a commercially available product. Commercially available products are available as various mixture compositions, specifically containing monobasic acids (unreacted substances, isomer components, etc.), dibasic acids (main components), tribasic acids (by-products), etc., and are classified into various standards depending on the content ratios of these components.

[0023] When the dimer acid contains a monobasic acid, the content thereof is not particularly limited, but is preferably 10% or less in terms of area ratio in gas chromatography relative to 100% of the dimer acid.

[0024] When the dimer acid contains a tribasic acid, the content thereof is not particularly limited, but is preferably 10% or less relative to 100% of the dimer acid in terms of area ratio in gas chromatography.

[0025] Commercially available dimer acids include, for example, Tsunodyme 228, Tsunodyme 205, Tsunodyme 216, Tsunodyme 395, and Tsunodyme 398 (hereinafter abbreviated as Td228, Td205, Td216, Td395, and Td398, respectively, all manufactured by Tsuno Oleochemicals Co., Ltd.), and Haridimer 200 (manufactured by Harima Chemicals Co., Ltd.). Among these, Td228, Td395, and Td398 are preferred.

[0026] The compositions of the commercially available products are as follows. Each composition can be measured by liquid chromatography, gas chromatography, etc., but in this disclosure, the values ​​were measured using gas chromatography. The analytical conditions for gas chromatography are as described in the Examples.

[0027] [Table 1]

[0028] The method for producing the hydrogenated unsaturated dibasic acid composition of the present invention is not particularly limited. One production method, for example, involves hydrogenating an unsaturated dibasic acid composition (raw material) such as the above-mentioned synthesized or commercially available dimer acid under mild conditions (e.g., a hydrogen pressure of 1.0 MPaG or less) without completely hydrogenating it, thereby partially hydrogenating it (partially hydrogenating), thereby satisfying the above conditions (A) and (B). That is, satisfying both the above conditions (A) and (B) improves the thermal stability of the hydrogenated unsaturated dibasic acid composition, while failing to satisfy either one of them results in poor thermal stability. Note that the above-mentioned synthesized or commercially available unhydrogenated dimer acid does not satisfy either or both of the above conditions (A) and (B).

[0029] The iodine value of the hydrogenated unsaturated dibasic acid composition of the present invention is 55 or more, preferably 58 or more, and more preferably 60 or more. The iodine value is preferably 200 or less, and more preferably 150 or less. Here, the iodine value is expressed as the number of grams of iodine added to 100 g of the hydrogenated unsaturated dibasic acid composition, and the higher the degree of unsaturation of the hydrogenated unsaturated dibasic acid composition, the higher the iodine value. Having an iodine value within the above range ensures excellent thermal stability.

[0030] The hydrogenated unsaturated dibasic acid composition of the present invention 1 In H-NMR measurement, excellent thermal stability can be obtained by having the ratio (Olefin Hα / ArHα) of the integral value of the peak corresponding to the olefin proton (Olefin Hα) to the integral value of the peak corresponding to the aromatic proton (ArHα) be 0.10 or more and 0.80 or less. The ratio is preferably 0.12 or more, more preferably 0.15 or more, and preferably 0.75 or less, more preferably 0.70 or less.

[0031] When the hydrogenated unsaturated dibasic acid composition of the present invention contains a monobasic acid (including a partially or fully hydrogenated monobasic acid, a monobasic acid contained in a raw material, and an isomer thereof), the content of the monobasic acid is preferably 10% or less, more preferably 5% or less, and even more preferably 3% or less, in terms of area ratio by gas chromatography, relative to 100% of the hydrogenated unsaturated dibasic acid composition.

[0032] When the hydrogenated unsaturated dibasic acid composition of the present invention contains a tribasic acid (including a partially or fully hydrogenated tribasic acid, a tribasic acid contained in a raw material, and an isomer thereof), the content of the tribasic acid is preferably 10% or less in terms of area ratio by gas chromatography relative to 100% of the hydrogenated unsaturated dibasic acid composition.

[0033] The hydrogenated unsaturated dibasic acid composition of the present invention can be reacted with a polyol component to obtain a polyester composition (including a polyester polyol composition). The polyester composition can be used as a urethane resin for adhesives, coating agents, paints, etc.

[0034] The polyol component can be any of those commonly used in polyester production, including aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and neopentyl glycol; aliphatic triols such as 1,2,3-propanetriol, 1,2,4-butanetriol, and trimethylolpropane; alicyclic diols such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol; and aromatic diols such as 4,4'-methylenediphenol. These polyols can be used alone or in combination of two or more.

[0035] The hydrogenated unsaturated dibasic acid composition of the present invention can also be reacted with a polyamine component such as a diamine to obtain a polyamide composition, which can be used, for example, as an epoxy curing agent, an ink binder, or a hot-melt adhesive.

[0036] The diamine may be any of those commonly used in the production of polyamides, including, for example, aliphatic diamines such as 1,2-ethanediamine, 1,3-propanediamine, and 1,4-butanediamine; alicyclic diamines such as cyclohexanediamine; and aromatic diamines such as xylylenediamine and benzenediamine. These diamines may be used alone or in combination of two or more.

[0037] 2. Method for producing hydrogenated unsaturated dibasic acid composition The method for producing the hydrogenated unsaturated dibasic acid composition of the present invention is not particularly limited. For example, a production method including a step of hydrogenating a raw material composition containing a raw material unhydrogenated unsaturated dibasic acid using a hydrogenation catalyst is preferred.

[0038] The hydrogenation catalyst may be a homogeneous catalyst or a heterogeneous catalyst, with the heterogeneous catalyst being preferred from the viewpoint of ease of post-treatment after the reaction.

[0039] The hydrogenation catalyst is not particularly limited, but examples thereof include iridium catalysts, nickel catalysts, palladium catalysts, platinum catalysts, rhodium catalysts, and ruthenium catalysts. Of these, nickel catalysts are preferred from the viewpoint of economy.

[0040] The nickel catalyst may be any of nickel metal powder, alloys with other metals, oxides, hydroxides, inorganic salts, organic salts, Raney catalysts, etc., and carrier-supported forms thereof. Examples of such catalysts include metallic nickel, reduced nickel, stabilized nickel, nickel-diatomaceous earth, Raney-type nickel, modified Raney-type nickel, nickel formate, Urushihara nickel, nickel boride, nickel oxide, nickel complexes, nickel-copper-diatomaceous earth, nickel-zirconia-diatomaceous earth, nickel-alumina, nickel-silica-alumina, nickel-cobalt, nickel-copper-cobalt, nickel-iron, nickel-iron-cobalt, nickel-iron-phosphorus, nickel oxide-silica, nickel oxide-magnesium oxide-alumina, and nickel oxide-molybdenum trioxide-alumina.

[0041] Among these, stabilized nickel catalysts using diatomaceous earth or the like as a support are preferred because they exhibit catalytic activity suitable for hydrogenation reactions. Specific examples include commercially available stabilized nickel catalysts SN-110, SN-150, SN-250, SN-300, and SN-750 (manufactured by Sakai Chemical Industry Co., Ltd.), Ni-5123P, Ni-5136P, Ni-5256P, Ni-0104T, Ni-3266, Ni-3288E, Ni-3737T, and Ni-5256E (manufactured by N.E. Chemcat Corporation), with SN-750 being preferred.

[0042] The amount of the nickel catalyst used is not particularly limited as long as it is an amount that can form a hydrogenated unsaturated dibasic acid composition that satisfies the above conditions (A) and (B), but for example, it is preferably 0.1 to 20 wt %, more preferably 0.5 to 10 wt %, relative to the raw material composition (100 wt %) containing the unsaturated dibasic acid. By setting it in this range, a hydrogenated unsaturated dibasic acid composition that satisfies the above conditions (A) and (B) can be formed, which is preferable.

[0043] The raw material composition containing the unsaturated dibasic acid before hydrogenation as the raw material can include the dimer acids. Among the dimer acids, dimer acids of oleic acid, linoleic acid, and / or linolenic acid are preferred.

[0044] The hydrogenation time is, for example, preferably 1 to 50 hours, more preferably 3 to 48 hours, which is preferable because a hydrogenated unsaturated dibasic acid composition that satisfies the above conditions (A) and (B) can be formed by setting the time within the above range.

[0045] The hydrogenation temperature is, for example, preferably 100 to 250° C., more preferably 150 to 200° C. By setting the temperature within this range, a hydrogenated unsaturated dibasic acid composition that satisfies the above conditions (A) and (B) can be formed, which is preferable.

[0046] The hydrogenation is preferably carried out under hydrogen pressure. The hydrogen pressure is preferably 0.1 MPaG or more, more preferably 0.5 MPaG or more. The upper limit of the hydrogen pressure is determined depending on the pressure vessel used, etc., but is, for example, 1.0 MPaG or less. A hydrogen pressure exceeding 1.0 MPaG is undesirable because complete hydrogenation is likely to occur.

[0047] After the hydrogenation step, a step of treating the composition after the hydrogenation step with an acid and clay may be included.

[0048] Examples of the acid include citric acid, phytic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etidronic acid, lactic acid, succinic acid, malic acid, fumaric acid, phosphoric acid, and boric acid. Among these, citric acid is preferred from the viewpoints of economy and the small impact it has on products when it remains.

[0049] The amount of the acid used is not particularly limited, but is preferably 0.05 to 5% by weight, more preferably 0.1 to 3% by weight, based on the total weight of the unsaturated dibasic acid composition after hydrogenation to be treated.

[0050] The acid can be added as an aqueous solution, and the concentration of the aqueous solution is not particularly limited, but is preferably 0.1 to 50% by weight, and more preferably about 0.1 to 30% by weight.

[0051] Examples of the white clay include activated white clay obtained by activating white clay or acid white clay with an acid such as a mineral acid. Examples of activated white clay include commercially available products such as Galleon Earth V2, Galleon Earth V2R, Galleon Earth NV, Galleon Earth NVZ, Galleonite #251, Galleonite #212, Galleonite #136, Galleonite #336, and Galleonite #436 (manufactured by Mizusawa Industrial Chemicals, Ltd.), Activated White Clay SA85 and Activated White Clay SA1 (manufactured by Toshin Chemical Industry Co., Ltd.), and Tonsil SUPREME 134 FF, Tonsil OPTIMUM 231S, and Tonsil OPTIMUM 230 FF (manufactured by Clariant).

[0052] The amount of the clay used is not particularly limited, but is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, based on the total weight of the unsaturated dibasic acid composition to be treated.

[0053] The treatment with the acid and clay is preferable because it makes it possible to remove the fatty acid salt formed by the hydrogenation catalyst.

[0054] The hydrogenation step and the step of treating with acid and clay can be repeated two or more times.

[0055] The reduction rate of the iodine value due to the hydrogenation (iodine value after hydrogenation / iodine value of raw material before hydrogenation) is preferably 0.3 to 0.9, more preferably 0.4 to 0.85. The above range is preferable because excellent thermal stability is achieved.

[0056] By the hydrogenation 1 The reduction rate of the peak integral ratio (Olefin Hα / ArHα) in H-NMR (integral ratio after hydrogenation / integral ratio of raw material before hydrogenation) is preferably 0.05 or more and 0.6 or less, more preferably 0.1 or more and 0.5 or less. This range is preferable because it provides excellent thermal stability.

[0057] The production method of the present invention makes it possible to form a hydrogenated unsaturated dibasic acid composition that satisfies the above conditions (A) and (B), and the obtained hydrogenated unsaturated dibasic acid composition has excellent thermal stability. [Example]

[0058] EXAMPLES The present invention will be explained in more detail below by showing examples and comparative examples, but the present invention is not limited to the following examples.

[0059] [Raw materials for hydrogenated unsaturated dibasic acid composition] The starting dimer acids used in the production of the hydrogenated unsaturated dibasic acid composition are as follows: (dimer acid) Td228: Product name, manufactured by Tsuno Oleochemicals Co., Ltd. Td395: Product name, manufactured by Tsuno Oleochemicals Co., Ltd. Td398: Product name, manufactured by Tsuno Oleochemicals Co., Ltd. Empol 1061: Product name, manufactured by Emery Empol 1062: Product name, manufactured by Emery Pripol 1013: Product name, manufactured by Cargill Pripol 1098: Trade name, manufactured by Cargill OLEON975: Product name, manufactured by Oleon (Among the above dimer acids, the compositions of Td228, Td395, and Td398 are as shown in Table 1 above. The compositions of the other dimer acids are as shown in Table 2 below. The analysis conditions for the compositions are as described below.) [Table 2]

[0060] Example 1 Dimer acid (trade name: Td395, manufactured by Tsuno Oleochemicals Co., Ltd.) and 1 wt. % Ni catalyst (trade name: SN-750, manufactured by Sakai Chemical Industry Co., Ltd.) based on the dimer acid were charged into an autoclave and heated to 180°C. Hydrogenation was carried out for 3 hours under a pressure of 0.7 MPaG with hydrogen, yielding a composition containing hydrogenated dimer acid. After hydrogenation, the Ni catalyst was removed by filtration. Then, 20 wt. % aqueous citric acid solution and Galleon Earth® V2 were added in amounts of 1.3 wt. % and 2.0 wt. % based on the hydrogenated dimer acid, respectively, and the mixture was heated to 90°C. After dehydration under reduced pressure at 0 to 5 Torr for 1 hour, filtration was carried out to yield a hydrogenated unsaturated dibasic acid composition.

[0061] The obtained hydrogenated unsaturated dibasic acid composition was subjected to gas chromatography measurement under the conditions described below. As a result, it was found that the monobasic acid content was 0.6% (relative area), the dibasic acid content was 98.9% (relative area), and the tribasic acid content was 0.5% (relative area), which were almost the same as the monobasic acid, dibasic acid, and tribasic acid contents of the starting dimer acid.

[0062] Examples 2 to 4 A hydrogenated unsaturated dibasic acid composition was obtained in the same manner as in Example 1, except that the hydrogenation time was changed to the time shown in Table 3.

[0063] Example 5 To the hydrogenated unsaturated dibasic acid composition obtained in Example 4, 1 wt. % of a Ni catalyst (product name: SN-750, manufactured by Sakai Chemical Industry Co., Ltd.) was added, and the mixture was placed in an autoclave and heated to 180°C. The mixture was pressurized with hydrogen to 0.7 MPaG and hydrogenated for an additional 24 hours, yielding a twice-hydrogenated unsaturated dibasic acid composition. After hydrogenation, the Ni catalyst was removed by filtration, and then 20 wt. % aqueous citric acid solution and Galleon Earth (registered trademark) V2 were added in amounts of 1.3 wt. % and 2.0 wt. % relative to the twice-hydrogenated unsaturated dibasic acid composition, respectively, and the mixture was heated to 90°C. After dehydration under reduced pressure at 0 to 5 Torr for 1 hour, filtration was performed to yield a hydrogenated unsaturated dibasic acid composition.

[0064] Example 6 A hydrogenated unsaturated dibasic acid composition was obtained in the same manner as in Example 4, except that the amount of Ni catalyst added was 7% by weight based on the dimer acid.

[0065] (Examples 7 to 14) Hydrogenated unsaturated dibasic acid compositions were obtained in the same manner as in Example 1, except that the type of dimer acid and the hydrogenation time were changed as shown in Table 3.

[0066] (Comparative Examples 1 to 8) The dimer acids used in the examples and commercially available dimer acids were measured for various physical properties without hydrogenation.

[0067] (Comparative Example 9) Hydrogenation was carried out in the same manner as in Example 4, except that the Ni catalyst in Example 4 was changed to a 2 wt% Pd catalyst (metal loading: 5%, palladium carbon (AD), manufactured by Kawaken Fine Chemical Co., Ltd.), and then the Pd catalyst was removed by filtration. In Comparative Example 9, the treatment with 20 wt% citric acid aqueous solution and Galleon Earth (registered trademark) V2 was not carried out.

[0068] (Comparative Example 10) A hydrogenated unsaturated dibasic acid composition was prepared in the same manner as in Comparative Example 9, and after removing the Pd catalyst by filtration, a 20 wt% aqueous citric acid solution and Galleon Earth (registered trademark) V2 were added in amounts of 1.3 wt% and 2.0 wt% relative to the hydrogenated dimer acid, respectively, and the mixture was heated to 90°C. After dehydration under reduced pressure at 0 to 5 Torr for 1 hour, filtration was carried out to obtain a hydrogenated unsaturated dibasic acid composition.

[0069] (Comparative Examples 11 and 12) A hydrogenated unsaturated dibasic acid composition was obtained in the same manner as in Comparative Example 9, except that the type of dimer acid was changed as shown in Table 4.

[0070] The resulting hydrogenated unsaturated dibasic acid composition and the non-hydrogenated dimer acid (raw material) were evaluated as follows.

[0071] [Evaluation method] <Composition analysis using gas chromatography> As a pretreatment for gas chromatography analysis, the starting dimer acid and the resulting hydrogenated unsaturated dibasic acid composition were subjected to dimethylation by a conventional method. The dimer acid and unsaturated dibasic acid compositions treated as above were subjected to gas chromatography under the following conditions. Analytical column: Non-polar capillary column chemically bonded with dimethylpolysiloxane (column length: 5 m) Heating conditions: After holding at 100°C for 1 minute, heat to 350°C at 20°C / min and hold for 20 minutes Detector and temperature: Flame ionization detector (FID), 380°C Injected sample: 1.0 μL (hexane solution) (evaluation) In the gas chromatogram obtained under the above analytical conditions, the peak with a retention time of 4.5 to 7.0 minutes was determined to be a monobasic acid, the peak with a retention time of 9.0 to 14.7 minutes was determined to be a dibasic acid, and the peak with a retention time of 14.7 to 18.8 minutes was determined to be a tribasic acid.

[0072] <Method for evaluating iodine value (IV)> Measurement was carried out in accordance with JIS K 0070.

[0073] <Calculation Method of Olefin Hα and ArHα> The 1H-NMR spectra of Olefin Hα and ArHα were measured under the following conditions. · NMR apparatus: manufactured by Bruker BioSpin · Spectrometer: Bruker BioSpin AVANCE III HD 400 · Number of data points: 64k · Number of dummy scans: 2 times · Observed nucleus: 1H · Number of integrations: 16 times · Observation frequency: 400.26 MHz · NMR sample tube: 5 mm φ · Sample amount: 5 - 20 mg · Measurement solvent: deuterated chloroform · Amount of heavy solvent: 0.6 mL · Measurement temperature: room temperature · Internal standard: TMS (Evaluation) Among the H-NMR spectra obtained under the above analysis conditions, 1 the integral value of the peak at 4.6 - 5.9 ppm was defined as Olefin Hα, and the integral value of the peak at 6.6 - 7.2 ppm was defined as ArHα.

[0074] <Heat Resistance> The obtained hydrogenated unsaturated dibasic acid composition and the non-hydrogenated dimer acid were respectively placed in containers made of borosilicate glass with an inner mouth diameter of φ21.5 mm, a body diameter of φ24 mm, and a total length of 40 mm, and the weight before measurement was measured (Ag). The container was placed in an oven at 180 °C, and the weight after 24 hours in an air atmosphere was measured (Bg). The heat resistance was evaluated by the following formula. Heat resistance (weight loss %) = (A - B) / A × 100 A lower value indicates better heat resistance.

[0075] <Initial Decomposition Temperature (°C)> The thermal decomposition onset temperatures of the obtained hydrogenated unsaturated dibasic acid composition and unhydrogenated dimer acid were measured using a thermal analyzer ("Thermo plus TG8120", manufactured by Rigaku) ​​under conditions of a nitrogen atmosphere, a sample weight of 10 mg, and a heating rate of 10°C / min (maximum temperature reached: 500°C). The thermal decomposition onset temperature was determined as the temperature at the point where the tangent to the TG curve at 100°C intersects with the tangent to the inflection point of the TG curve where the weight rapidly decreases on the high-temperature side.

[0076] Example 13 The hydrogenated unsaturated dibasic acid composition obtained in Example 4 and PEG400 (polyethylene glycol with a molecular weight of approximately 400 g / mol) in an amount of 96.5% by weight relative to the hydrogenated unsaturated dibasic acid composition were placed in a separable flask equipped with a stirrer, thermometer, dehydration tube, and condenser, and heated to 250°C. The reaction was carried out for 5 hours under a nitrogen stream while reducing the pressure and removing the condensed water from the system, yielding a polyester. The hydroxyl value of this polyester was measured in accordance with JIS K 0070 (neutralization titration method) and found to be 39.4 mgKOH / g.

[0077] Example 14 The hydrogenated unsaturated dibasic acid composition obtained in Example 4 and 5.6% by weight of 1,2-ethanediamine relative to the hydrogenated unsaturated dibasic acid composition were placed in a separable flask equipped with a stirrer, thermometer, and reflux condenser and heated to 240°C. Polymerization was carried out for 4 hours under a nitrogen stream at normal pressure while removing condensed water from the system, yielding a polyamide. The amine value of this polyamide was measured according to JIS K 7237 (indicator titration method) and found to be 1 mgKOH / g.

[0078] [Table 3]

[0079] [Table 4]

[0080] The above results demonstrate that the hydrogenated unsaturated dibasic acid composition of the present invention has excellent thermal stability. On the other hand, the hydrogenated unsaturated dibasic acid compositions of the comparative examples and the starting dimer acids had poor heat resistance and a lower thermal decomposition onset temperature than those of the examples, demonstrating poor thermal stability.

Claims

1. A hydrogenated unsaturated dibasic acid composition that satisfies the following (A) and (B): (A) The iodine value is 55 or more. (B) １ In H-NMR measurement, the ratio (Olefin Hα / ArHα) of the integral value of the peak corresponding to olefin protons (Olefin Hα) to the integral value of the peak corresponding to aromatic protons (ArHα) is 0.10 or more and 0.80 or less.

2. 10. The hydrogenated unsaturated dibasic acid composition of claim 1, which is a partially hydrogenated product of a feedstock composition comprising the dimerization products of oleic acid, linoleic acid, and / or linolenic acid.

3. the hydrogenated unsaturated dibasic acid composition comprises a monobasic acid; 3. The hydrogenated unsaturated dibasic acid composition according to claim 1, wherein the content of the monobasic acid is 10% or less, based on 100% of the hydrogenated unsaturated dibasic acid composition, in terms of area ratio by gas chromatography.

4. A polyester composition obtained by reacting the hydrogenated unsaturated dibasic acid composition according to claim 1 or 2 with a polyol component.

5. A polyamide composition obtained by reacting the hydrogenated unsaturated dibasic acid composition according to claim 1 or 2 with a polyamine component.

6. The method for producing a hydrogenated unsaturated dibasic acid composition according to claim 1 or 2, comprising a hydrogenation step of hydrogenating a raw material composition containing an unsaturated dibasic acid using a hydrogenation catalyst.

7. 7. The method for producing a hydrogenated unsaturated dibasic acid composition according to claim 6, further comprising a step of treating the composition after the hydrogenation step with an acid and clay.

8. The method for producing a hydrogenated unsaturated dibasic acid composition according to claim 7, wherein the acid is citric acid.

9. 7. The method for producing a hydrogenated unsaturated dibasic acid composition according to claim 6, wherein the hydrogenation catalyst is a nickel catalyst.

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