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

Abstract

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

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 Art

[0002] As an unsaturated dibasic acid composition, dimer acid mainly composed of a dibasic acid obtained by dimerization of an unsaturated fatty acid having 10 to 22 carbon atoms is known. As the dimer acid, for example, dimer acids obtained from natural or plant-derived fatty acids such as rice bran fatty acid, soybean oil fatty acid, tall oil fatty acid, rapeseed oil fatty acid, and oleic acid, linoleic acid, linolenic acid, erucic acid, etc. obtained by purifying these are known.

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

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0005] Resins having a dimer acid skeleton have a wide variety of uses and are used, for example, in applications that are used in high-temperature environments. Therefore, the dimer acid used as the raw material is also required to have thermal stability.

[0006] In Patent Documents 1 to 4, nothing has been studied regarding the thermal stability of dimer acid or hydrogenated products of dimer acid. Naturally, nothing has been studied regarding the relationship between the iodine value, the ratio of olefin protons to aromatic protons, and 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 Problems

[0008] As a result of intensive studies, the inventors of the present invention have newly found that a hydrogenated unsaturated dibasic acid composition exhibits surprisingly excellent thermal stability when it satisfies specific conditions, and have completed the present invention.

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

[0010] It is preferable that the hydrogenated unsaturated dibasic acid composition is a partial hydrogenated product of a raw material composition containing a dimerization product of oleic acid, linoleic acid, and / or linolenic acid.

[0011] The hydrogenated unsaturated dibasic acid composition contains a monobasic acid, It is preferable that the content of the monobasic acid is 10% or less based on 100% of the hydrogenated unsaturated dibasic acid composition in terms of the area ratio of gas chromatography.

[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 includes 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] It is preferable that the acid is citric acid.

[0016] It is preferable that the hydrogenation catalyst is a nickel catalyst.

Advantages of the Invention

[0017] The hydrogenated unsaturated dibasic acid composition of the present invention has a specific iodine value and, 1 due to the ratio (Olefin Hα / ArHα) of the integral value (Olefin Hα) of the peak corresponding to the olefin proton to the integral value (ArHα) of the peak corresponding to the aromatic proton in 1H-NMR measurement being within a specific range, it has excellent thermal stability. Since the hydrogenated unsaturated dibasic acid composition of the present invention has excellent thermal stability, it can be used in a wide range of applications such as lubricant additives, fuel oil additives, rust inhibitors, ink compositions, and flux compositions. Further, the polyester composition and polyamide composition 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 oil agents, adhesives, resin compositions, hot melt compositions, primer compositions, and polyurethane compositions.

Embodiments for Carrying Out 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 more. (B) 1 In 1H-NMR measurement, the ratio (Olefin Hα / ArHα) of the integral value (Olefin Hα) of the peak corresponding to olefin protons to the integral value (ArHα) of the peak corresponding to aromatic protons 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 of (A) and (B) above. In order to distinguish the unsaturated dibasic acid composition obtained by hydrogenating an unsaturated dibasic acid composition of a raw material such as dimer acid, which is one of the production methods of the hydrogenated unsaturated dibasic acid composition of the present invention, from the unsaturated dibasic acid composition of the raw material, the unsaturated dibasic acid composition of the present invention is labeled with "hydrogenated", which represents a state in which a part of the unsaturated bonds of the unsaturated dibasic acid composition of the raw material is returned 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. Among these, it is preferable to contain a dimerization product of oleic acid, linoleic acid, and / or linolenic acid.

[0021] Since many commercially available dimer acids use unsaturated fatty acids having 18 carbon atoms as raw materials, the main component is a dibasic acid having 36 carbon atoms. Examples of the structure of dimer acid include, but are not limited to, the following.

Chemical formula

[0022] As the dimer acid, either a synthetic product or a commercially available product can be used. Commercially available products can be provided as compositions of various mixtures. Specifically, they contain monobasic acids (unreacted substances and isomer components, etc.), dibasic acids (main components), tribasic acids, etc. (by-products), and there are various specifications depending on their content ratios, etc.

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

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

[0025] Examples of commercially available dimer acids include Tsunodyme 228, Tsunodyme 205, Tsunodyme 216, Tsunodyme 395, Tsunodyme 398 (hereinafter abbreviated as Td228, Td205, Td216, Td395, Td398, respectively. All are manufactured by Tsukuno Oleochemicals Co., Ltd.), Halidimer 200 (manufactured by Halma Kasei Co., Ltd.), etc. Among these, Td228, Td395, and Td398 are preferred.

[0026] The compositions of the above commercially available products are as follows. Each composition can be measured by liquid chromatography, gas chromatography, etc., but in the present disclosure, it is the value measured using gas chromatography. The analysis conditions of 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. As one production method, for example, an unsaturated dibasic acid composition such as the above-described synthetic product or commercially available dimer acid (raw material that has not been hydrogenated) is not fully hydrogenated, but hydrogenated under mild conditions (for example, a hydrogen pressure of 1.0 MPaG or less), and a part of it is hydrogenated (partially hydrogenated) to satisfy the above conditions (A) and (B). That is, by satisfying both of the above conditions (A) and (B), the thermal stability of the hydrogenated unsaturated dibasic acid composition is improved. On the other hand, if either one is not satisfied, the thermal stability is inferior. Incidentally, the non-hydrogenated dimer acid of the above-described synthetic product or commercially available product does not satisfy either one 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. Further, the iodine value is preferably 200 or less, and more preferably 150 or less. Here, the iodine value is represented by 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 larger the iodine value. By the iodine value being within the above range, excellent thermal stability can be obtained.

[0030] The hydrogenated unsaturated dibasic acid composition of the present invention 1 In the 1H-NMR measurement, excellent thermal stability can be obtained when 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. The ratio is preferably 0.12 or more, more preferably 0.15 or more, preferably 0.75 or less, and 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 the raw material, and its isomers), 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 the area ratio of gas chromatography based on 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 the raw material, and its isomers), the content of the tribasic acid is preferably 10% or less in terms of the area ratio of gas chromatography based on 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 such as an adhesive, a coating agent, or a paint.

[0034] As the polyol component, those commonly used in the production of polyesters can be used. For example, 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; aromatic diols such as 4,4'-methylenediphenol, etc. These polyols may be used alone or in combination of two or more.

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

[0036] As the diamine, ordinary ones used in the production of polyamides can be used. For example, aliphatic diamines such as 1,2-ethanediamine, 1,3-propanediamine, and 1,4-butanediamine; alicyclic diamines such as cyclohexanediamine; aromatic diamines such as xylylenediamine and benzenediamine, etc. can be mentioned. 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 an unsaturated dibasic acid before hydrogenation, which is a raw material, using a hydrogenation catalyst is preferable.

[0038] As the hydrogenation catalyst, a homogeneous catalyst or a heterogeneous catalyst may be used. From the viewpoint of facilitating the post-treatment after the reaction, a heterogeneous catalyst is preferable.

[0039] The hydrogenation catalyst is not particularly limited, and examples thereof include iridium catalysts, nickel catalysts, palladium catalysts, platinum catalysts, rhodium catalysts, ruthenium catalysts, etc. Among these, a nickel catalyst is preferable from the viewpoint of economy.

[0040] As the nickel catalyst, it may be any of a metal powder of nickel metal, an alloy with other metals, an oxide, a hydroxide, an inorganic salt, an organic salt, a Raney catalyst, etc., and a supported type on a carrier thereof. Examples of such catalysts include metallic nickel, reduced nickel, stabilized nickel, nickel - diatomaceous earth, Raney type nickel, modified Raney type nickel, nickel formate, Urushibara nickel, nickel boride, nickel oxide, nickel complex, 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, etc.

[0041] Among these, a stabilized nickel catalyst using diatomaceous earth or the like as a carrier is preferable because it exhibits appropriate catalytic activity for the hydrogenation reaction. Specifically, commercially available stabilized nickel catalysts such as SN-110, SN-150, SN-250, SN-300, SN-750 (manufactured by Sakai Chemical Industry Co., Ltd.), Ni-5123P, Ni-5136P, Ni-5256P, Ni-0104T, Ni-3266, Ni-3288E, Ni-3737T, Ni-5256E (manufactured by N.E. Chemcat Corporation) can be mentioned. Among these, SN-750 is preferable.

[0042] The amount of the nickel catalyst used may be any amount that can form a hydrogenated unsaturated dibasic acid composition satisfying the conditions of (A) and (B) above, and is not particularly limited. For example, 0.1 to 20% by weight is preferable, and 0.5 to 10% by weight is more preferable with respect to the raw material composition (100% by weight) containing the unsaturated dibasic acid. By setting the amount within the above range, a hydrogenated unsaturated dibasic acid composition satisfying the conditions of (A) and (B) above can be formed, which is preferable.

[0043] Examples of the raw material composition containing the unsaturated dibasic acid before hydrogenation, which is the raw material, include the dimer acid. Among the dimer acids, dimer acids of oleic acid, linoleic acid, and / or linolenic acid are preferable.

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

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

[0046] 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. Also, the upper limit of the hydrogen pressure is determined by the pressure-resistant container used, etc. For example, it is 1.0 MPaG or less. If the hydrogen pressure exceeds 1.0 MPaG, it is likely to be completely hydrogenated, which is not preferable.

[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, boric acid, etc. Among these, citric acid is preferable from the viewpoints of economy and less influence when remaining in the product.

[0049] The amount of the acid used is not particularly limited. For example, 0.05 to 5% by weight is preferable, and 0.1 to 3% by weight is more preferable with respect to the total weight of the unsaturated dibasic acid composition after hydrogenation to be treated.

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

[0051] Examples of the clay include clay and activated clay obtained by activating clay or acid clay with an acid such as a mineral acid. Examples of the activated 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, Galleonite #436 (manufactured by Mizusawa Chemical Industry Co., Ltd.), Activated Clay SA85, Activated Clay SA1 (manufactured by ToShin Kasei Co., Ltd.), Tonsil SUPREME134FF, Tonsil OPTIMUM231S, Tonsil OPTIMUM230FF (manufactured by Clariant).

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

[0053] Treatment with the acid and the clay is preferable because fatty acid salts formed by the hydrogenation catalyst can be removed.

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

[0055] The reduction rate of the iodine value by the hydrogenation (iodine value after hydrogenation / iodine value of the raw material before hydrogenation) is preferably 0.3 or more and 0.9 or less, and more preferably 0.4 or more and 0.85 or less. Being within the above range is preferable because it has excellent thermal stability.

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

[0057] By the production method of the present invention, a hydrogenated unsaturated dibasic acid composition satisfying the above conditions (A) and (B) can be formed, and the obtained hydrogenated unsaturated dibasic acid composition has excellent thermal stability.

Examples

[0058] Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited by the following Examples.

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

Table 2

[0060] (Example 1) Dimer acid (trade name: Td395, manufactured by Tsukino Oleochemicals Co., Ltd.) and a Ni catalyst (trade name: SN-750, manufactured by Sakai Chemical Industry Co., Ltd.) at 1% by weight based on the dimer acid were charged into an autoclave and heated to 180°C. It was pressurized with hydrogen to 0.7 MPaG and hydrogenated for 3 hours to obtain a composition containing hydrogenated dimer acid. After the hydrogenation was completed, the Ni catalyst was removed by filtration. Then, a 20% by weight aqueous citric acid solution and Gallion Earth (registered trademark) V2 were added in amounts of 1.3% and 2.0% by weight, respectively, based on the hydrogenated dimer acid, and heated to 90°C. After depressurizing and dehydrating at 0 - 5 Torr for 1 hour, filtration was performed to obtain a hydrogenated unsaturated dibasic acid composition.

[0061] The obtained hydrogenated unsaturated dibasic acid composition was measured by gas chromatography under the conditions described later. As a result, the content of monobasic acid was 0.6% (relative area), the content of dibasic acid was 98.9% (relative area), and the content of tribasic acid was 0.5% (relative area), which was found to be almost the same as the contents of monobasic acid, dibasic acid, and tribasic acid in the raw material dimer acid.

[0062] (Examples 2 - 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 described in Table 3.

[0063] (Example 5) To the hydrogenated unsaturated dibasic acid composition obtained in Example 4, 1 wt% of a Ni catalyst (trade name: SN-750, manufactured by Sakai Chemical Industry Co., Ltd.) was added, charged into an autoclave, and heated to 180°C. It was pressurized with hydrogen to 0.7 MPaG and further hydrogenated for 24 hours to obtain an unsaturated dibasic acid composition that had been hydrogenated twice. After completion of hydrogenation, the Ni catalyst was removed by filtration, and then 20 wt% aqueous citric acid solution and Gallion Earth (registered trademark) V2 were added in amounts of 1.3 wt% and 2.0 wt% respectively to the unsaturated dibasic acid composition that had been hydrogenated twice, and heated to 90°C. After dehydration under reduced pressure at 0 - 5 Torr for 1 hour, filtration was performed to obtain 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 addition amount of the Ni catalyst was changed to 7 wt% based on the dimer acid.

[0065] (Examples 7 - 14) A hydrogenated unsaturated dibasic acid composition was 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 - 8) For the dimer acid used in the examples and commercially available dimer acids, various physical properties were measured as they were without hydrogenation.

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

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

[0069] (Comparative Examples 11 and 12) An 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 following evaluations were performed on the obtained unsaturated dibasic acid composition and the non-hydrogenated dimer acid (raw material).

[0071] [Evaluation Method] [Composition Analysis Using Gas Chromatography]< As a pretreatment for gas chromatography analysis, the raw material dimer acid and the obtained unsaturated dibasic acid composition were dimethylated by a conventional method. The gas chromatography of the dimer acid and the unsaturated dibasic acid composition subjected to the above treatment was measured under the following conditions. · Analytical column: Non-polar capillary column with chemically bonded dimethylpolysiloxane (column length: 5 m) · Temperature rising condition: After holding at 100 °C for 1 minute, the temperature was raised to 350 °C at 20 °C / min and held for 20 minutes · Detector and temperature: Flame ionization detector (FID), 380 °C · Injected sample: 1.0 μL (hexane solution) [Evaluation] Among the gas chromatograms obtained under the above analysis conditions, the peaks with retention times of 4.5 - 7.0 minutes were regarded as monobasic acids, the peaks with retention times of 9.0 - 14.7 minutes were regarded as dibasic acids, and the peaks with retention times of 14.7 - 18.8 minutes were regarded as tribasic acids.

[0072] [Evaluation Method for Iodine Value (IV)] It was measured according to 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 deuterated 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 integration value of the peak at 4.6 - 5.9 ppm was defined as Olefin Hα, and the integration 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 a container made of borosilicate glass with an inner 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 The lower the value, the better the heat resistance.

[0075] <Pyrolysis Start Temperature (°C)> The thermal decomposition start temperatures of the obtained hydrogenated unsaturated dibasic acid composition and the non-hydrogenated dimer acid were measured using a thermal analyzer ("Thermo plus TG8120", manufactured by Rigaku) under the conditions of a nitrogen atmosphere, a sample amount of 10 mg, and a heating rate of 10 °C / min (maximum reachable temperature 500 °C). For the obtained TG curve, the temperature at the point where the tangent line of the TG curve at 100 °C intersects with the tangent line of the inflection point of the TG curve with a sharp weight loss on the high-temperature side was defined as the thermal decomposition start temperature.

[0076] (Example 13) The hydrogenated unsaturated dibasic acid composition obtained in Example 4 and 96.5% by weight of PEG400 (polyethylene glycol with a molecular weight of about 400 g / mol) relative to the hydrogenated unsaturated dibasic acid composition were charged into a separable flask equipped with a stirrer, a thermometer, and a dehydration tube - condenser tube, and heated to 250 °C. While reducing the pressure and removing the condensed water outside the system, the reaction was carried out for 5 hours under a nitrogen stream to obtain a polyester. When the hydroxyl value of this polyester was measured in accordance with JIS K 0070 (neutralization titration method), the hydroxyl value was 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 charged into a separable flask equipped with a stirrer, a thermometer, and a reflux condenser, and heated to 240 °C. While removing the condensed water outside the system at normal pressure, the polymerization was carried out for 4 hours under a nitrogen stream to obtain a polyamide. When the amine value of this polyamide was measured in accordance with JIS K 7237 (indicator titration method), the amine value was 1 mgKOH / g.

[0078]

Table 3

[0079]

Table 4

[0080] From the above results, it was found that the hydrogenated unsaturated dibasic acid composition of the present invention is excellent in thermal stability. On the other hand, it was found that the hydrogenated unsaturated dibasic acid composition and the raw material dimer acid of the comparative example are inferior in heat resistance, the thermal decomposition start temperature is also lower than that of the examples, and they are inferior in thermal stability.

Claims

1. A hydrogenated unsaturated dibasic acid composition which is a partial hydride of a raw material composition containing a dimerization product of oleic acid, linoleic acid, and / or linolenic acid, wherein the raw material composition contains a monobasic acid, a dibasic acid, and a tribasic acid, and the content of the dibasic acid is 89% or more based on 100% of the total amount of the monobasic acid, dibasic acid, and tribasic acid in terms of the area ratio by gas chromatography, the hydrogenated unsaturated dibasic acid composition contains a monobasic acid, the content of the monobasic acid is 10% or less based on 100% of the hydrogenated unsaturated dibasic acid composition in terms of the area ratio by gas chromatography, and a hydrogenated unsaturated dibasic acid composition satisfying the following (A) and (B). (A)The iodine value is 55 or more. (B) 1 In the 1H-NMR measurement, the ratio (Olefin Hα / ArHα) of the integral value (Olefin Hα) of the peak corresponding to the olefin proton to the integral value (ArHα) of the peak corresponding to the aromatic proton is 0.10 or more and 0.80 or less.

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

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

4. A method for producing the 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.

5. The method for producing the hydrogenated unsaturated dibasic acid composition according to Claim 4, comprising a step of treating the composition after the hydrogenation step with an acid and clay.

6. The method for producing the hydrogenated unsaturated dibasic acid composition according to Claim 5, wherein the acid is citric acid.

7. The method for producing the hydrogenated unsaturated dibasic acid composition according to Claim 4, wherein the hydrogenation catalyst is a nickel catalyst.

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