Polycarbonate diol

Abstract

To provide a polycarbonate diol and the like excellent in colorless transparency comparable to that of one derived from petroleum, even when derived from a plant.SOLUTION: A polycarbonate diol has a repeating unit expressed by the following formula (1), and a terminal hydroxy group, where the integral value of a signal of 2.50-2.70 ppm is 0.01-1.0 when an integral value of a signal of 3.90-4.45 ppm is 1,000 in a 1H-NMR spectrum measured using chloroform-d as a solvent and tetramethylsilane as a reference material. In the formula, R1 expresses a divalent 2-20C aliphatic hydrocarbon.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate diol using a bio-based raw material. [Background technology]

[0002] Conventionally, petroleum-derived polycarbonate diols have been used as raw materials for polyurethane resins in a wide range of applications, such as synthetic leather, artificial leather, adhesives, furniture paints, and automotive paints, and have superior properties compared to polyethers and polyesters, such as heat resistance, weather resistance, hydrolysis resistance, and oil resistance. Similar demands are also becoming more stringent for bio-derived polycarbonate diols.

[0003] For example, there is a growing need for plant-derived polycarbonate polyols from the perspective of reducing environmental impact, and plant-derived polycarbonate polyols synthesized using a plant-derived polyol, a plant-derived ester, and a carbonate ester have been proposed (Patent Documents 1 and 2).Furthermore, biopolyester polyols synthesized using a plant-derived short-chain diol component having 2 to 4 carbon atoms and a plant-derived carboxylic acid component, and biopolyether polyols synthesized using a plant-derived short-chain diol component having 2 to 4 carbon atoms have also been proposed (Patent Document 3). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-14427 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-1475 [Patent Document 3] Patent No. 5826814 Summary of the Invention [Problem to be solved by the invention]

[0005] On the other hand, since the polycarbonate polyols described in Patent Documents 1 and 2 contain cyclic ester compounds such as valerolactone, caprolactone, and butyrolactone, which are plant-derived diol raw materials, as impurities in the raw materials, polyurethane compositions obtained from these raw materials have the problem of being inferior in durability to polyurethane compositions synthesized from petroleum-derived diol raw materials due to the heat resistance and chemical resistance, which are weaknesses of ester compounds.Furthermore, there has been a problem of coloration, which impairs quality, due to the poor weather resistance of the ether bond added to the cyclic ether compound.

[0006] Furthermore, the bio-polyurethane resin described in Patent Document 3, which uses a plant-derived short-chain diol as a raw material, has a high carbonate bond density, making it difficult to handle due to its high viscosity, and its glass transition temperature is high, making it prone to hardening, and it lacks the flexibility that polycarbonate diol copolymers inherently possess.

[0007] An object of the present invention is to provide a plant-derived polycarbonate diol that is equivalent to a petroleum-derived polycarbonate diol in appearance and colorless and transparent, as well as a urethane coating film that is excellent in flexibility and chemical resistance. [Means for solving the problem]

[0008] The present inventors have conducted extensive research to solve the above problems, and as a result have found that a polycarbonate diol capable of solving the above problems can be obtained, which has led to the completion of the present invention.

[0009] That is, the present invention includes the following aspects. [1] A polycarbonate diol having a repeating unit represented by the following formula (1) and a terminal hydroxyl group: Measurements were performed using chloroform-d as the solvent and tetramethylsilane as the standard. 1A polycarbonate diol characterized in that, in a H-NMR spectrum, when the integral value of a signal from 3.90 to 4.45 ppm is taken as 1000, the integral value of a signal from 2.50 to 2.70 ppm is 0.01 to 1.0. [ka] (In the formula, R1 represents a divalent aliphatic hydrocarbon having 2 to 20 carbon atoms.) [2] The polycarbonate diol according to [1], wherein the repeating unit represented by the formula (1) includes a repeating unit represented by the following formula (2): [ka] [3] The polycarbonate diol according to [1] or [2], wherein the repeating unit represented by the formula (1) includes a repeating unit represented by the following formula (3): [ka] [4] The polycarbonate diol according to any one of [1] to [3], wherein the repeating unit represented by the formula (1) includes a repeating unit represented by the following formula (4): [ka] [5] The polycarbonate diol according to any one of [1] to [4], which has a hydroxyl value of 32 to 280 mg-KOH / g as measured by the neutralization titration method of JIS K 0070 (1992). [6] The repeating unit represented by the formula (1) is 10 to 95 mol % of a repeating unit represented by the following formula (2), 5 to 90 mol % of repeating units represented by the following formula (3) and / or the following formula (4), The polycarbonate diol according to any one of [1] to [5], comprising: [ka] [ka] [ka] [7] The polycarbonate diol according to any one of [1] to [6], an organic polyisocyanate; A chain extender; Polyurethane resin is a reaction product of [8] The polycarbonate diol according to any one of [1] to [6], an organic polyisocyanate; 1. A coating composition comprising the reaction product of: [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a polycarbonate diol having excellent colorless and transparent appearance, and a urethane coating film having excellent flexibility and chemical resistance. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, an embodiment of the present invention (hereinafter abbreviated as "the present embodiment") will be described in detail. Note that the present invention is not limited to the following embodiment, and various modifications can be made within the scope of the gist of the present invention.

[0012] <Polycarbonate diol> The polycarbonate diol of this embodiment has a repeating unit represented by the following formula (1) ("repeating unit (1)") and a terminal hydroxyl group. [ka] In the formula, R1 represents a divalent aliphatic hydrocarbon having 2 to 20 carbon atoms.

[0013] The aliphatic hydrocarbon group of R1 may be a straight-chain aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, or a combination thereof.

[0014] The aliphatic hydrocarbon group of R1 preferably has 2 to 15 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 4 to 6 carbon atoms.

[0015] The repeating unit (1) preferably contains a repeating unit represented by the following formula (2) ("repeating unit (2)"). Preferably, 10 to 95 mol % of the repeating unit (1) is the repeating unit (2). [ka]

[0016] The repeating unit (1) preferably contains a repeating unit represented by the following formula (3) ("repeating unit (3)"). Preferably, 5 to 90 mol % of the repeating unit (1) is the repeating unit (3). [ka]

[0017] The repeating unit (1) preferably contains a repeating unit represented by the following formula (4) ("repeating unit (4)"): Preferably, 5 to 90 mol % of the repeating unit (1) is the repeating unit (4). [ka]

[0018] The repeating unit (1) preferably contains a repeating unit (2) and a repeating unit (3). The repeating unit (1) preferably contains a repeating unit (2) and a repeating unit (4). The repeating unit (1) preferably contains the repeating unit (2), the repeating unit (3) and the repeating unit (4).

[0019] The repeating unit (1) preferably contains 10 to 95 mol % of the repeating unit (2) and 5 to 90 mol % of the repeating unit (3) and / or the repeating unit (4). When the repeating unit (1) contains the repeating unit (3) and the repeating unit (4), the above-mentioned "5 to 90 mol %" refers to the total amount of the repeating unit (3) and the repeating unit (4).

[0020] The total amount of the repeating unit (2) and the repeating unit (3), the total amount of the repeating unit (2) and the repeating unit (4), or the total amount of the repeating unit (2), the repeating unit (3) and the repeating unit (4) is preferably 70 mol % or more, more preferably 80 mol % or more, even more preferably 90 mol % or more, and particularly preferably 95 mol % or more, of the repeating unit (1).

[0021] When the repeating unit (2) accounts for 10 to 95 mol % of the repeating unit (1), chemical resistance tends to be excellent, and it is more preferable that the repeating unit (2) accounts for 30 to 70 mol %.

[0022] When the repeating unit (3) and / or the repeating unit (4) accounts for 5 to 90 mol % of the repeating unit (1), flexibility tends to be excellent, and it is more preferable that the amount is 30 to 70 mol %.

[0023] The polycarbonate diol of one embodiment of the present invention is produced from a diol (preferably of plant origin) as a raw material, which may be a diol having no side chain, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, or 1,14-tetradecanediol, 2-methyl-1,8-octanediol, or 2-ethyl- One or more diols can be used as raw materials: diols with side chains such as 1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, and 2,2-dimethyl-1,3-propanediol; and cyclic diols such as 1,4-cyclohexanedimethanol and 2-bis(4-hydroxycyclohexyl)-propane.

[0024] It is also possible to use a small amount of a compound having three or more hydroxyl groups in one molecule, such as trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, etc. From the viewpoint of suppressing gelation during synthesis of polycarbonate diol, the amount of the compound having three or more hydroxyl groups in one molecule is preferably 0.01 to 5 wt %, more preferably 0.01 to 1 wt %, based on the total amount of diol.

[0025] A particularly preferred polycarbonate diol according to one embodiment of the present invention is a polycarbonate diol made from 1,4-butanediol and 1,6-hexanediol as raw materials, and specifically, the polycarbonate diol is one in which 10 to 95 mol % of the repeating units (1) in the polycarbonate polyol are repeating units (2) derived from 1,4-butanediol, and 5 to 90 mol % of the repeating units (1) are repeating units (3) derived from 1,6-hexanediol.

[0026] <Method for producing polycarbonate diol> One known production method involves mixing a carbonate raw material (described later) with the diol raw material described above, reacting them at 100 to 200°C under normal or reduced pressure in the presence of a transesterification catalyst, removing the resulting alcohol derived from the carbonate raw material, and then heating the mixture at 160 to 250°C under reduced pressure to remove unreacted carbonate raw material and diol, and condensing the low-molecular-weight polycarbonate diol to obtain a polycarbonate diol of a predetermined molecular weight.

[0027] The reaction temperature for removing impurities from the bio-based 1,4-butanediol is, for example, 130 to 200°C, preferably 150 to 180°C, and more preferably 130 to 160°C.

[0028] In this case, the degree of reduced pressure is, for example, 2.0 to 9.0 kPa, preferably 3.0 to 7.0 kPa, and more preferably 3.5 to 5.0 kPa.

[0029] Examples of carbonate raw materials used in the synthesis of the polycarbonate diol of one embodiment of the present invention include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate, diaryl carbonates such as diphenyl carbonate, and alkylene carbonates such as ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, and 1,2-pentylene carbonate. One or more carbonates from these can be used as raw materials. From the viewpoints of availability and ease of setting polymerization reaction conditions, it is more preferable to use dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, and dibutyl carbonate.

[0030] The production of a polycarbonate diol according to one embodiment of the present invention is usually carried out by adding a catalyst. The catalyst used in one embodiment of the present invention can be freely selected from ordinary transesterification catalysts. For example, metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, and cerium, as well as their salts, alkoxides, and organic compounds, are used. Compounds of titanium, tin, and lead are particularly preferred. The amount of catalyst used is usually 0.00001 to 0.1% of the weight of the polycarbonate diol.

[0031] In the production of the polycarbonate diol used in this embodiment, when 1,4-butanediol and 1,6-hexanediol or 1,5-pentanediol are used as raw materials, the ratio of these raw materials is not particularly limited, but it is preferable to set the ratio of the raw materials used so that the resulting polycarbonate diol is liquid at room temperature. When two types of diols are used as raw materials, it is preferable to set the charging amounts between 30 / 70 and 70 / 30 in molar ratio. Within this range, the resulting polycarbonate diol tends to be liquid at room temperature. A ratio of 40 / 60 to 60 / 40 is more preferable because it tends to be liquid even at temperatures below 0°C.

[0032] <Integral value ratio> The polycarbonate diol of this embodiment was measured using chloroform-d as a solvent and tetramethylsilane (TMS) as a standard substance. 1 In the H-NMR spectrum, when the integral value of the signals from 3.90 to 4.45 ppm is taken as 1000, the integral value of the signals from 2.50 to 2.70 ppm (hereinafter also abbreviated as "integral value ratio") is 0.01 to 1.0. 1 In the H-NMR spectrum, the signals at 3.90 to 4.45 ppm are those of methylene bonded to carbonate, and the signals at 2.50 to 2.70 ppm are presumed to be signals derived from impurities in the biomaterial.

[0033] These impurities are presumed to be, but are not limited to, ether compounds with furan rings that are generated as impurities when fumaric acid and fumaric acid derivatives, which are used to make butanediol, are produced by oxidation of furfural, which is obtained from inedible plant waste such as corn. This is expected to contribute to the flexibility characteristic of ether compounds.

[0034] In the polycarbonate diol of this embodiment, the integral value ratio is an index representing the amount of impurities derived from biomaterials contained in a certain repeating unit. When the polycarbonate diol of this embodiment has an integral value ratio of 0.01 or more, it has excellent flexibility, and the integral value ratio is preferably 0.05 or more, and more preferably 0.1 or more. When the integral value ratio is 0.01 or more, flexibility can be maintained when a conventional polycarbonate diol is made into a urethane film. Conversely, when the integral value ratio exceeds 1.0, the polycarbonate diol suffers from reduced chemical resistance and coloration, adversely affecting quality. Therefore, the integral value ratio is preferably 0.5 or less, and more preferably 0.2 or less. Specifically, the integral value ratio is preferably 0.05 to 0.5, and more preferably 0.1 to 0.2.

[0035] A method for obtaining a polycarbonate diol having the integral ratio of this embodiment can include, for example, mixing a carbonate raw material and a diol raw material, reacting them at 100 to 160°C under normal pressure or reduced pressure in the presence of a transesterification catalyst, removing the resulting alcohol derived from the carbonate raw material to obtain a low-molecular-weight polycarbonate diol, and then heating the mixture at 140 to 180°C under reduced pressure to remove unreacted carbonate raw material and diol, and condensing the low-molecular-weight polycarbonate diol to obtain a polycarbonate diol of a predetermined molecular weight. In this case, if the reaction temperature is too high, the ether compound having a furan ring will decompose, and the ether bond will be easily incorporated into the polycarbonate, so it is necessary to set the temperature lower than the general reaction temperature.

[0036] Polyurethanes using polyether polyols are known to have inferior chemical resistance compared to those using polycarbonate diols.

[0037] The integral value ratio in the polycarbonate diol can be measured by the method described in the examples below.

[0038] <Hydroxyl value> The polycarbonate diol of this embodiment preferably has a hydroxyl value of 32 to 280 mg-KOH / g as measured by the neutralization titration method of JIS K 0070 (1992). If the hydroxyl value of the polycarbonate diol of this embodiment is 280 mg-KOH / g or less, the flexibility of the resulting polyurethane will be good. If the hydroxyl value of the polycarbonate diol of this embodiment is 32 mg-KOH / g or more, there will be no restrictions on the solids concentration of the coating agent, which is preferable. The hydroxyl value of the polycarbonate diol of this embodiment is more preferably 37 to 140 mg-KOH / g, and even more preferably 37 to 125 mg-KOH / g. The hydroxyl value of the polycarbonate diol of this embodiment is preferably 32 mg-KOH / g or more, since the molecular weight decreases and the density of carbonate bonds increases, resulting in excellent chemical resistance. The hydroxyl value of the polycarbonate diol of this embodiment is preferably 280 mg-KOH / g or less, since the methylene chain in the urethane bond becomes longer, resulting in improved flexibility. The hydroxyl value of the polycarbonate diol of this embodiment is particularly preferably 45 to 75 mg-KOH / g.

[0039] In this embodiment, the hydroxyl value of the polycarbonate diol can be measured by the method described in the examples below.

[0040] <Thermoplastic polyurethane> The method for producing the thermoplastic polyurethane of this embodiment is not particularly limited, and any polyurethane reaction technology known in the polyurethane industry can be used. For example, a method in which three types of polyisocyanate compound (preferably an organic polyisocyanate) (a), polycarbonate diol (b), and chain extender (c) are simultaneously mixed and reacted, or a method in which the polyisocyanate compound (a) and the polycarbonate diol (b) are reacted in advance to form a prepolymer, and then the chain extender (c) is added to extend the chain, can be used. In addition to the above components (a) to (c), other components, such as carboxyl group- and / or sulfonic group-containing polyols or salts thereof, and known polyols, may also be used as synthetic raw materials for the polyurethane resin of this embodiment, as long as they do not impair the effects of the present invention.

[0041] <Coating composition> The coating composition of the present embodiment contains a urethane prepolymer obtained by reacting the above-mentioned polycarbonate diol with an organic polyisocyanate, and the urethane prepolymer preferably has a terminal isocyanate group.

[0042] Furthermore, the coating composition of the present embodiment more preferably contains a polyurethane resin obtained by reacting the above-mentioned polycarbonate diol, organic polyisocyanate, and chain extender, and is even more preferably an aqueous coating composition containing a polyurethane resin obtained by reacting the above-mentioned polycarbonate diol, organic polyisocyanate, and chain extender.

[0043] The organic polyisocyanate to be used is not particularly limited, but examples thereof include known organic polyisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and mixtures thereof (TDI), crude TDI, diphenylmethane-4,4'-diisocyanate (MDI), crude MDI, naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-4-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, xylylene diisocyanate (XDI), and phenylene diisocyanate. Examples of suitable organic polyisocyanates include aromatic diisocyanates such as 4,4'-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPD), and cyclohexane diisocyanate (hydrogenated XDI), as well as isocyanurate-modified products, carbodiimide-modified products, and biuret-modified products of these isocyanates. These organic polyisocyanates may be used alone or in combination of two or more.

[0044] The coating composition of this embodiment can be produced by a known production method in the art. For example, a two-component solvent-based coating composition can be produced by mixing the base paint obtained from the above-mentioned polycarbonate diol with a curing agent made of organic polyisocyanate just before coating; a one-component solvent-based coating composition can be produced by reacting the above-mentioned polycarbonate diol with an organic polyisocyanate to form a urethane prepolymer having terminal isocyanate groups; a one-component solvent-based coating composition can be produced by reacting the above-mentioned polycarbonate diol, organic polyisocyanate, and a chain extender to form a polyurethane resin; or a one-component water-based coating composition can be produced.

[0045] To the coating composition of the present embodiment, for example, curing accelerators (catalysts), fillers, dispersants, flame retardants, dyes, organic or inorganic pigments, release agents, flowability modifiers, plasticizers, antioxidants, ultraviolet absorbers, light stabilizers, antifoaming agents, leveling agents, colorants, solvents, etc. may be added depending on various applications. [Example]

[0046] The present embodiment will be described in more detail below using examples, but the present embodiment is not limited to these examples. The test methods in the following examples were carried out according to the following test methods.

[0047] <Evaluation method for polycarbonate diol> 1) Hydroxyl value of polycarbonate diol (average hydroxyl value) Measurement was carried out in accordance with JIS K 0070 (1992).

[0048] 2) Number average molecular weight (Mn) of polycarbonate diol converted into hydroxyl value The hydroxyl value of the polycarbonate diol was measured by a method using an acetylation reagent in accordance with JIS K 0070 (1992), and the molecular weight (Mn) was calculated from the value using the following formula. Mn = 56.1 x 2 x 1000 ÷ hydroxyl value

[0049] 3) Polycarbonate diol composition (copolymerization ratio) A 1g sample of polycarbonate diol was placed in a 100ml recovery flask, and 30g of ethanol and 4g of potassium hydroxide were added. The mixture was allowed to react at 100°C for 1 hour. After cooling to room temperature, 2-3 drops of phenolphthalein were added as an indicator and the mixture was neutralized with hydrochloric acid. The neutralized mixture was cooled in a refrigerator for 1 hour, after which the precipitated salt was removed by filtration, and the filtrate was analyzed by GC (gas chromatography). GC analysis was performed using a gas chromatograph GC-2014 (Shimadzu Corporation) equipped with a DB-WAX (J&W) column. The GC analysis was performed using a flame ionization detector (FID) as a detector, with diethylene glycol diethyl ester as the internal standard, to quantitatively analyze each component. The column temperature profile was maintained at 130°C for 5 minutes, then increased to 200°C at 10°C / min. The composition (copolymerization ratio) of the polycarbonate diol was determined from the molar ratio of each alcohol component detected from the above analysis results.

[0050] 4) Calculation method for integral ratio of polycarbonate diol (1 H-NMR) The integral value ratio in the polycarbonate diol was determined as follows. First, 50 mg of a sample was dissolved in 0.75 mL of chloroform-d (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). Tetramethylsilane (TMS) was added to the solution as a chemical shift standard, and the resulting solution was analyzed using an ECZ500 (SC) manufactured by JEOL Ltd. 1 H-NMR was measured. In the measurement, the resonance frequency was 500 MHz, the pulse width was 45°, the waiting time was 5 seconds, the number of accumulations was 500, and the TMS signal was set at 0 ppm. 1 The integral value ratio of the polycarbonate diol was measured as described above. 1 The integral value of the signal from 3.90 to 4.45 ppm and the integral value of the signal from 2.50 to 2.70 ppm obtained by H-NMR were used to calculate the integral value ratio according to the following formula: integral value ratio=D / C×1000 C: Integrated value of the signal from 3.90 to 4.45 ppm D: Integrated value of the signal from 2.50 to 2.70 ppm

[0051] 5) Color index of polycarbonate diol <apha> Measured according to JIS K1557-5(2007) <apha> Less than 20: 〇 Almost no coloring is observed. 20 or more but less than 50: △ Slight discoloration is observed. 50 or above: × Discoloration is observed.

[0052] 6) Low-temperature storage stability of polycarbonate diol The appearance of the polycarbonate diol was evaluated after it was stored in a refrigerator at 0°C for one month. The evaluation results were expressed as follows: ○: Transparent liquid △: Cloudy waxy ×: Solidification

[0053] <Evaluation method for polyurethane films> 1) Room temperature tensile test Using the polyurethane film prepared by the method described in Example 1, rectangular test pieces measuring 10 mm in width, 100 mm in length, and approximately 0.5 mm in thickness were obtained in accordance with JIS K6251 (2017). The obtained test pieces were subjected to a tensile test using a tensile tester (manufactured by Orientec Co., Ltd., product name "Tensilon, Model RTE-1210") at a chuck distance of 20 mm, a tensile speed of 100 mm / min, and a temperature of 23°C (relative humidity of 55%) to measure the strength at break and the elongation at break.

[0054] 1. Breaking strength 50MPa or more: ◎ Good. 40MPa or more but less than 50MPa: 〇 Generally good. 20 MPa or more but less than 40 MPa: △ Somewhat insufficient. Less than 20MPa: × Insufficient.

[0055] 2. Elongation at break Over 600%: ◎ Good. 500% or more but less than 600%: 〇 Generally good. 400% or more but less than 500%: △ Somewhat insufficient. Less than 400%: × Insufficient.

[0056] 2) Evaluation of humidity and heat resistance Using the polyurethane film thus produced, strip-shaped samples measuring 10 mm in width, 100 mm in length, and approximately 50 μm in thickness were prepared. These were heated in a gear oven at a temperature of 80°C and a humidity of 85% for one month. After heating, the samples were measured for breaking strength in the same manner as in the above-mentioned <Room Temperature Tensile Test>, and the breaking strength retention (%) was calculated using the following formula: Breaking strength retention rate (%) = Breaking strength after heating / Breaking strength before heating × 100 90% or more: Good 80% or more but less than 90%: △ Fairly good. Less than 80%: × Poor.

[0057] 3) Evaluation of oleic acid resistance The prepared polyurethane film was used to create a strip-shaped sample measuring 10 mm wide, 50 mm long, and approximately 50 μm thick. First, the mass of the coating film was weighed before testing. This coating film was placed in a 250 ml glass bottle containing 50 ml of oleic acid as a test solvent and allowed to stand in a thermostatic chamber at 23°C for two weeks. After testing, the coating film was removed and lightly wiped on both sides with a paper wiper. The mass was then measured using a precision balance, and the mass change rate (swelling rate) was calculated using the following formula: Swelling rate (%) = [(mass after test - mass before test) / mass before test] x 100 Less than 10%: ◎ No swelling of the coating film is observed. 10% or more but less than 20%: 〇 Slight swelling of the coating is observed. 20% or more: △ Swelling of the coating film is observed.

[0058] <Coating film evaluation method> 1) Chemical resistance A cotton ball with a diameter of 10 mm soaked in various solvents (ethanol, methyl ethyl ketone, xylene) was placed on the coating film obtained by the method of Example 9 for 1 minute, and the state of the coating film after removing the solvent remaining on the surface was observed. The evaluation method was as follows. ○: Transparent, no dents △: Slightly cloudy or slightly dented ×: Cloudy or dented

[0059] 2) Weather resistance test 1. Preparation of coating film for weather resistance test To the coating solutions prepared in the Examples and Comparative Examples, 0.2% by mass of IRGANOX 1076 and 0.2% by mass of TINUVIN 765 were added and stirred to prepare coating solutions for weather resistance tests. These were applied to a white acrylonitrile-butadiene-styrene (ABS) resin plate using an applicator, and then heat-cured at 80°C for 2 hours to obtain a coating film with a thickness of 40 μm for weather resistance tests.

[0060] 2. Weather resistance test method The obtained coating film for weather resistance test was subjected to a DPWL-5R test using a Suga Test Instruments Co., Ltd. (black panel temperature 60°C, irradiance 30 w / m 2 A weather resistance test was carried out for one month using a UV fluorescent lamp (SUGA-FS-40) under cycle conditions: 4 hours of irradiation at 60°C, 4 hours of humidification at 40°C.

[0061] 3. Color difference measurement Using SM-P45 manufactured by Suga Test Instruments Co., Ltd., the L value, a value, and b value of the coating film were measured before and after the weather resistance test, and the color difference was calculated using the ΔE calculation method described below. ΔE={(L1-L2)2+(a1-a2)2+(b1-b2)2}1 / 2 In the above formula, L1, a1, and b1 represent the L value, a value, and b value of the coating film before the weather resistance test, and L2, a2, and b2 represent the L value, a value, and b value of the coating film after the weather resistance test.

[0062] ◯: ΔE is 3 or less. △: ΔE is greater than 3 and equal to or less than 5. ×: ΔE is greater than 5, or the coating film is destroyed during the weather resistance test.

[0063] 3) Softness The coating solutions prepared in the examples and comparative examples were applied to acrylonitrile-butadiene-styrene (ABS) resin plates to a thickness of 40 μm to obtain coated plates. The softness of the surfaces of the resulting coated plates was evaluated by touching them with the hand. The evaluation results were expressed as follows: ○: Good softness △: Relatively good softness ×: Does not feel soft.

[0064] [Polycarbonate diol polymerization example 1] A 1 L glass flask equipped with a rectification column filled with structured packing and a stirrer was charged with 136 g (1.5 mol) of 1,4-butanediol obtained by the bio-production method, 361 g (3.1 mol) of 1,6-hexanediol, a commonly used petroleum-derived raw material, and 403 g (4.6 mol) of ethylene carbonate. 0.09 g of titanium tetrabutoxide was added as a catalyst, and the reaction temperature was raised to 140-160°C. The pressure was reduced from 5 kPa to 3 kPa, and the resulting mixture of ethylene glycol and ethylene carbonate was distilled off for 18 hours. The reaction was then switched to simple distillation, and the pressure was gradually reduced to 0.1 kPa. The reaction was continued at 185°C for 3 hours, and the monomer was distilled off to obtain polycarbonate diol PC1. This PC1 had a hydroxyl value of 55.5 and an average molecular weight (Mn) of 2022, showing no problems with polymerization.

[0065] [Polycarbonate diol polymerization example 2] A 1 L glass flask equipped with a rectification column filled with structured packing and a stirrer was charged with 217 g (2.4 mol) of 1,4-butanediol obtained by the bio-production method, 269 g (2.3 mol) of 1,6-hexanediol, a commonly used petroleum-derived raw material, and 413 g (4.7 mol) of ethylene carbonate. 0.09g of titanium tetrabutoxide was added as a catalyst, and the reaction temperature was raised to 140-160°C. The pressure was reduced from 5kPa to 3kPa, and the reaction was carried out for 18 hours while distilling off the resulting mixture of ethylene glycol and ethylene carbonate. The reaction was then switched to simple distillation, and the pressure was gradually reduced to 0.1kPa while the reaction was carried out at 185°C for 3 hours to distill off the monomers, yielding polycarbonate diol PC2. This PC2 had a hydroxyl value of 55.8 and an average molecular weight (Mn) of 2010, so there were no problems with the polymerization.

[0066] [Polycarbonate diol polymerization example 3] A 1 L glass flask equipped with a rectification column filled with structured packing and a stirrer was charged with 314 g (3.5 mol) of 1,4-butanediol obtained by the bio-production method, 160 g (1.4 mol) of 1,6-hexanediol, a commonly used petroleum-derived raw material, and 426 g (4.8 mol) of ethylene carbonate. 0.09 g of titanium tetrabutoxide was added as a catalyst, and the reaction temperature was raised to 140-160°C. The pressure was reduced from 5 kPa to 3 kPa, and the resulting mixture of ethylene glycol and ethylene carbonate was distilled off for 18 hours. The reaction was then switched to simple distillation, and the pressure was gradually reduced to 0.1 kPa. The reaction was continued at 185°C for 3 hours, and the monomer was distilled off to obtain polycarbonate diol PC3. This PC3 had a hydroxyl value of 56.0 and an average molecular weight (Mn) of 2005, so there were no problems with polymerization.

[0067] [Polycarbonate diol polymerization example 4] A 1 L glass flask equipped with a rectification column filled with structured packing and a stirrer was charged with 213 g (2.4 mol) of 1,4-butanediol obtained by the bio-production method, 275 g (2.3 mol) of 1,6-hexanediol, a commonly used petroleum-derived raw material, and 413 g (4.7 mol) of ethylene carbonate. 0.09 g of titanium tetrabutoxide was added as a catalyst, and the reaction temperature was raised to 140-160°C. The pressure was reduced from 5 kPa to 3 kPa, and the resulting mixture of ethylene glycol and ethylene carbonate was distilled off for 18 hours. The reaction was then switched to simple distillation, and the pressure was gradually reduced to 0.1 kPa. The reaction was continued at 185°C for 2 hours, and the monomer was distilled off to obtain polycarbonate diol PC4. This PC4 had a hydroxyl value of 110.5 and an average molecular weight (Mn) of 1015, so there were no problems with the polymerization.

[0068] [Polycarbonate diol polymerization example 5] A 1 L glass flask equipped with a rectification column filled with structured packing and a stirrer was charged with 222 g (2.5 mol) of 1,4-butanediol obtained by the bio-production method, 264 g (2.2 mol) of 1,6-hexanediol, a commonly used petroleum-derived raw material, and 414 g (4.7 mol) of ethylene carbonate. 0.09 g of titanium tetrabutoxide was added as a catalyst, and the reaction temperature was raised to 140-160°C. The pressure was reduced from 5 kPa to 3 kPa, and the resulting mixture of ethylene glycol and ethylene carbonate was distilled off for 18 hours. The reaction was then switched to simple distillation, and the pressure was gradually reduced to 0.1 kPa. The reaction was continued at 185°C for 5 hours, and the monomer was distilled off to obtain polycarbonate diol PC5. This PC5 had a hydroxyl value of 37.4 and an average molecular weight (Mn) of 3,000, so there were no problems with polymerization.

[0069] [Polycarbonate diol polymerization example 6] A 1-liter glass flask equipped with a rectification column filled with structured packing and a stirrer was charged with 132 g (1.5 mol) of 1,4-butanediol obtained by the bio-production method, 339 g (3.3 mol) of 1,5-pentanediol, a commonly used petroleum-derived raw material, and 429 g (4.9 mol) of ethylene carbonate. 0.09 g of titanium tetrabutoxide was added as a catalyst, and the reaction temperature was raised to 140-160°C. The pressure was reduced from 5 kPa to 3 kPa, and the resulting mixture of ethylene glycol and ethylene carbonate was distilled off for 18 hours. The reaction was then switched to simple distillation, and the pressure was gradually reduced to 0.1 kPa. The reaction was continued at 185°C for 3 hours, and the monomer was distilled off to obtain polycarbonate diol PC6. This PC6 had a hydroxyl value of 55.5 and an average molecular weight (Mn) of 2040, so there were no problems with polymerization.

[0070] [Polycarbonate diol polymerization example 7] A 1 L glass flask equipped with a rectification column filled with structured packing and a stirrer was charged with 222 g (2.5 mol) of 1,4-butanediol obtained by the bio-production method, 245 g (2.4 mol) of 1,5-pentanediol, a commonly used petroleum-derived raw material, and 434 g (4.9 mol) of ethylene carbonate. 0.09g of titanium tetrabutoxide was added as a catalyst, and the reaction temperature was raised to 140-160°C. The pressure was reduced from 5kPa to 3kPa, and the reaction was carried out for 18 hours while distilling off the resulting mixture of ethylene glycol and ethylene carbonate. The reaction was then switched to simple distillation, and the pressure was gradually reduced to 0.1kPa while the reaction was carried out at 185°C for 3 hours to distill off the monomers, yielding polycarbonate diol PC7. This PC7 had a hydroxyl value of 55.8 and an average molecular weight (Mn) of 2011, showing no problems with polymerization.

[0071] [Polycarbonate diol polymerization example 8] A 1 L glass flask equipped with a rectification column filled with structured packing and a stirrer was charged with 316 g (3.5 mol) of 1,4-butanediol obtained by the bio-production method, 146 g (1.4 mol) of 1,5-pentanediol, a commonly used petroleum-derived raw material, and 438 g (5.0 mol) of ethylene carbonate. 0.09 g of titanium tetrabutoxide was added as a catalyst, and the reaction was carried out for 18 hours at a reaction temperature of 140-160°C and a pressure reduced from 5 kPa to 3 kPa, while the resulting mixture of ethylene glycol and ethylene carbonate was distilled off. The reaction was then switched to simple distillation, and the pressure gradually reduced to 0.1 kPa while the reaction was carried out at 185°C for 3 hours to distill off the monomers, yielding polycarbonate diol PC8. This PC8 had a hydroxyl value of 54.7 and an average molecular weight (Mn) of 2050, showing no problems with polymerization.

[0072] [Polycarbonate diol polymerization example 9] A 1 L glass flask equipped with a rectification column filled with structured packing and a stirrer was charged with 128 g (1.4 mol) of petroleum-based 1,4-butanediol, 306 g (3.0 mol) of 1,6-hexanediol, a commonly used petroleum-based raw material, and 417 g (4.7 mol) of ethylene carbonate. 0.09 g of titanium tetrabutoxide was added as a catalyst, and the reaction temperature was raised to 140-160°C. The pressure was reduced from 5 kPa to 3 kPa, and the resulting mixture of ethylene glycol and ethylene carbonate was distilled off for 18 hours. The reaction was then switched to simple distillation, and the pressure was gradually reduced to 0.1 kPa. The reaction was continued at 185°C for 3 hours, and the monomer was distilled off to obtain polycarbonate diol PC9. This PC9 had a hydroxyl value of 56.0 and an average molecular weight (Mn) of 2004, so there were no problems with the polymerization.

[0073] [Polycarbonate diol polymerization example 10] A 1 L glass flask equipped with a rectification column filled with structured packing and a stirrer was charged with 430 g (4.8 mol) of petroleum-based 1,4-butanediol, 27 g (0.23 mol) of 1,6-hexanediol, a commonly used petroleum-based raw material, and 443 g (5.0 mol) of ethylene carbonate. 0.09 g of titanium tetrabutoxide was added as a catalyst, and the reaction temperature was raised to 140-160°C. The pressure was reduced from 5 kPa to 3 kPa, and the resulting mixture of ethylene glycol and ethylene carbonate was distilled off for 18 hours. The reaction was then switched to simple distillation, and the pressure was gradually reduced to 0.1 kPa. The reaction was continued at 185°C for 3 hours, and the monomer was distilled off to obtain polycarbonate diol PC10. This PC10 had a hydroxyl value of 54.5 and an average molecular weight (Mn) of 2060, so there were no problems with polymerization.

[0074] [Table 1]

[0075] <Evaluation of polyurethane film> [Example 1] A 500 mL separable flask equipped with a stirrer and sealed with nitrogen gas was charged with 10.5 g (0.04 mol) of 4,4'-methylenebiscyclohexyl diisocyanate (hydrogenated MDI, average number of isocyanate groups per molecule: 2.0) and 213 g of N,N-dimethylformamide (DMF), and heated to 40 °C to obtain a solution. While stirring the solution, 140 g of N,N-dimethylformamide (DMF), 0.0025 g of dibutyltin dilaurate as a catalyst, and 40 g (0.02 mol) of polycarbonate polyol PC1 were added dropwise to the flask over 30 minutes. The reaction was carried out at 50 °C with stirring for 2 hours to obtain a prepolymer with terminal isocyanate. After the temperature of the solution in the flask was lowered to room temperature, 3.4 g (0.02 mol) of isophoronediamine was added as a chain extender. The reaction was allowed to proceed at room temperature for 1 hour, and then 0.5 g of ethanol was added as a reaction terminator to obtain a DMF solution of polyurethane (solid content approximately 20% by mass). The resulting N,N-dimethylformamide (DMF) solution with a solid content of 20% by mass was applied to a glass plate and heated at 80°C for 2 hours to produce a 50 μm thick polyurethane film. After leaving it at room temperature for 24 hours, various physical properties were evaluated. The evaluation results are shown in Table 2. Regarding the physical properties of polyurethane films, the greater the elongation at break, the better the flexibility. Regarding oleic acid resistance, the lower the swelling ratio, the better the film is, with no deterioration observed.

[0076] [Examples 2 to 8] Except for using PC2 to PC8 as the polycarbonate diol, polyurethane films were obtained in the same manner as in Example 1 and subjected to evaluation of various physical properties. The evaluation results are shown in Table 2.

[0077] [Comparative Examples 1 and 2] A polyurethane film was obtained in the same manner as in Example 1, except that PC9 and PC10 were used as the polycarbonate diol, and the physical properties were evaluated. The evaluation results are shown in Table 2.

[0078] [Table 2]

[0079] <Evaluation of coating film> [Example 9] 200 g (0.1 mol) of polycarbonate diol PC1, 2.06 g of leveling agent BYK-331 (BYK Chemicals), 0.8 g of dibutyltin dilaurate (Air Products), and 356 g of butyl acetate thinner were added and stirred to obtain a coating base. 38.2 g of Duranate TPA-100 (Asahi Kasei Chemicals: hexamethylene diisocyanate-based isocyanurate curing agent, NCO content = 23.1 wt%, isocyanate groups per molecule = 3.0) was added as a curing agent and mixed to produce a coating solution (coating composition). This was applied to a glass plate using an applicator and then heated and cured at 80 °C for 2 hours to obtain a coating film. The physical properties of the coating film obtained from the coating solution (coating composition) using PC1 are shown in Table 3.

[0080] [Examples 10 to 16] Except for using PC2 to 8 as the polycarbonate diol, coating solutions (coating compositions) were prepared in the same manner as in Example 9, and the physical properties of the coating films obtained from each coating solution were evaluated. The evaluation results are shown in Table 3.

[0081] [Comparative Examples 3 and 4] Except for using PC9 and PC10 as the polycarbonate diol, coating solutions (coating compositions) were prepared in the same manner as in Example 9, and the physical properties of the coating films obtained from each coating solution were evaluated. The evaluation results are shown in Table 3.

[0082] [Table 3] < / apha> < / apha>

Claims

1. A polycarbonate diol having a repeating unit represented by the following formula (1) and a terminal hydroxyl group: Measurements were performed using chloroform-d as a solvent and tetramethylsilane as a standard substance. 1 A polycarbonate diol characterized in that, in its H-NMR spectrum, when the integral value of a signal from 3.90 to 4.45 ppm is taken as 1000, the integral value of a signal from 2.50 to 2.70 ppm is 0.01 to 1.

0. 【Chemistry 1】 (In the formula, R 1 represents a divalent aliphatic hydrocarbon having 2 to 20 carbon atoms.

2. The polycarbonate diol according to claim 1, wherein the repeating unit represented by formula (1) includes a repeating unit represented by formula (2): 【Chemistry 2】

3. The polycarbonate diol according to claim 2, wherein the repeating unit represented by formula (1) includes a repeating unit represented by formula (3): 【Transformation 3】

4. The polycarbonate diol according to claim 2, wherein the repeating unit represented by formula (1) includes a repeating unit represented by formula (4): 【Chemistry 4】

5. The polycarbonate diol according to claim 1, wherein the hydroxyl value measured by the neutralization titration method of JIS K 0070 (1992) is 32 to 280 mg-KOH / g.

6. The repeating unit represented by the formula (1) is 10 to 95 mol % of a repeating unit represented by the following formula (2), 5 to 90 mol % of repeating units represented by the following formula (3) and / or the following formula (4), The polycarbonate diol of claim 1 , comprising: 【Transformation 5】 【Transformation 6】 【Transformation 7】

7. The polycarbonate diol according to any one of claims 1 to 6, an organic polyisocyanate; A chain extender; Polyurethane resin is a reaction product of

8. The polycarbonate diol according to any one of claims 1 to 6, an organic polyisocyanate; 1. A coating composition comprising the reaction product of:

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