Polycarbonate diol and its manufacturing method

Abstract

To provide polycarbonate diol having excellent color tone, and, when used as a raw material compound (raw material monomer) of polyurethane, capable of imparting excellent flexibility (elongation) and moisture and heat resistance to obtained polyurethane.SOLUTION: In a method for manufacturing polycarbonate diol by performing ester interchange reaction of a dihydroxy compound and a carbonate compound under the presence of an ester exchange catalyst, the hydroxy compound is made of a compound (hereinafter, referred to as "dihydroxy compound (1)") represented by the following formula (1), an acid value of the hydroxy compound (1) is 0.04 mgKOH / g or more and 15.00 mgKOH / g or less. HO-R1-OH (1) (In a formula (1), R1 represents a divalent hydrocarbon group of 10 to 12 carbon atoms.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate diol using a specific starting dihydroxy compound and a method for producing the same. The present invention also relates to a polyurethane using the polycarbonate diol. [Background technology]

[0002] Polycarbonate diols are used as raw materials for soft segment parts of polyurethanes and thermoplastic elastomers, as well as in paints, adhesives, etc., and are widely used as raw materials that impart high durability, such as excellent weather resistance, heat resistance, hydrolysis resistance, and moist heat resistance, which are considered to be drawbacks of polyether polyols and polyester polyols.

[0003] Conventionally, polyurethanes made from polycarbonate diols obtained using lower alkyl diols such as 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol have been generally known, but these do not fully satisfy the required performance in terms of moist heat resistance and elongation. Therefore, in order to solve this problem, polycarbonate diols with various structures have been proposed.

[0004] For example, there are examples in which long-chain dihydroxy compounds such as 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol are used to improve flexibility (Patent Documents 1 and 2, Non-Patent Document 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 2802657 [Patent Document 2] Patent No. 3240194 [Non-patent literature]

[0006] [Non-Patent Document 1] Magdalena M. Mazureka, Polym. Adv. Technol. 2015, 26 57-67 Summary of the Invention [Problem to be solved by the invention]

[0007] Patent Documents 1 and 2 and Non-Patent Document 1 describe polycarbonate diols using long-chain dihydroxy compounds, but no study has been conducted on the influence of the impurity content in the dihydroxy compound on the resulting polycarbonate diol and on the physical properties of polyurethane when this polycarbonate diol is used to produce polyurethane, and problems remain with the color tone of the resulting polycarbonate diol and the physical properties of polyurethane obtained using the polycarbonate diol, particularly flexibility (elongation) and moist heat resistance.

[0008] The present invention aims to provide a polycarbonate diol using a long-chain dihydroxy compound, which has not been achieved by conventional techniques, i.e., a polycarbonate diol that has a good color tone and, when used as a raw material compound (raw material monomer) for polyurethane, can impart excellent flexibility (elongation) and moist heat resistance to the resulting polyurethane. [Means for solving the problem]

[0009] As a result of intensive research to solve the above problems, the present inventors have found that when a polycarbonate diol is produced using a specific long-chain dihydroxy compound as a dihydroxy compound, by using a long-chain dihydroxy compound having an acid value within a specific range, it is possible to provide a polycarbonate diol that has a good color tone and, when used as a raw material compound (raw material monomer) for polyurethane, can impart excellent flexibility (elongation) and moist heat resistance to the resulting polyurethane, and have arrived at the present invention. That is, the gist of the present invention is as follows.

[0010] [1] A method for producing a polycarbonate diol by transesterification of a dihydroxy compound and a carbonate compound in the presence of a transesterification catalyst, characterized in that the dihydroxy compound is a compound represented by the following formula (1) (hereinafter referred to as "dihydroxy compound (1)"), and the acid value of the dihydroxy compound (1) is 0.04 mg KOH / g or more and 15.00 mg KOH / g or less. HO-R 1 -OH …(1) (In the above formula (1), R 1 represents a divalent hydrocarbon group having 10 to 12 carbon atoms.

[0011] [2] The method for producing a polycarbonate diol according to [1], wherein the hydroxyl value of the obtained polycarbonate diol is 20 mg KOH / g or more and 250 mg KOH / g or less.

[0012] [3] The method for producing a polycarbonate diol according to [1] or [2], wherein the dihydroxy compound (1) is one or more selected from the group consisting of 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol.

[0013] [4] The method for producing a polycarbonate diol according to any one of [1] to [3], wherein the dihydroxy compound (1) remaining in the obtained polycarbonate diol is less than 0.5% by weight based on the polycarbonate diol.

[0014] [5] The method for producing a polycarbonate diol according to any one of [1] to [4], wherein 98.5 mol % or more of the terminals of the obtained polycarbonate diol are hydroxyl terminals.

[0015] [6] A polycarbonate diol obtained by subjecting a dihydroxy compound and a carbonate compound to a transesterification reaction in the presence of a transesterification catalyst, wherein the dihydroxy compound is a compound represented by the following formula (1) (hereinafter referred to as "dihydroxy compound (1)"), and the acid value of the dihydroxy compound (1) is 0.04 mg KOH / g or more and 15.00 mg KOH / g or less. HO-R 1 -OH …(1) (In the above formula (1), R 1 represents a divalent hydrocarbon group having 10 to 12 carbon atoms.

[0016] [7] The polycarbonate diol according to [6], having a hydroxyl value of 20 mg KOH / g or more and 250 mg KOH / g or less.

[0017] [8] The polycarbonate diol according to [6] or [7], wherein the dihydroxy compound (1) is one or more selected from the group consisting of 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol.

[0018] [9] The polycarbonate diol according to any one of [6] to [8], wherein the residual amount of the dihydroxy compound (1) is less than 0.5% by weight.

[0019]

[10] The polycarbonate diol according to any one of [6] to [9], wherein 98.5 mol % or more of the terminals are hydroxyl terminals.

[0020]

[11] A polyurethane using the polycarbonate diol according to any one of [6] to

[10] .

[0021]

[12] Artificial leather or synthetic leather using the polyurethane described in

[11] .

[0022]

[13] A paint or coating agent using the polyurethane described in

[11] .

[0023]

[14] Elastic fiber using polyurethane as described in

[11] .

[0024]

[15] A water-based polyurethane paint using the polyurethane described in

[11] .

[0025]

[16] A pressure-sensitive adhesive or adhesive using the polyurethane described in

[11] .

[0026]

[17] A water-based polyurethane dispersion using the polycarbonate diol according to any one of [6] to

[10] .

[0027]

[18] An active-energy radiation-curable polymer composition using the polycarbonate diol according to any one of [6] to

[10] . [Effects of the Invention]

[0028] The polycarbonate diol provided by the present invention has a good color tone, and when used as a raw material compound (raw material monomer) for polyurethane, can impart excellent flexibility (elongation) and moist heat resistance to the resulting polyurethane. Therefore, the polycarbonate diol of the present invention and the polyurethane obtained using the polycarbonate diol of the present invention are suitable for applications such as elastic fibers, synthetic or artificial leather, paints, and high-performance elastomers, and are extremely useful industrially. DETAILED DESCRIPTION OF THE INVENTION

[0029] Hereinafter, the embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments and can be practiced in various modified forms within the scope of the gist thereof.

[0030] [Polycarbonate diol] The polycarbonate diol of the present invention is a polycarbonate diol obtained by transesterifying a dihydroxy compound and a carbonate compound in the presence of a transesterification catalyst, characterized in that the dihydroxy compound is a compound represented by the following formula (1) (hereinafter referred to as "dihydroxy compound (1)") and the acid value of the dihydroxy compound (1) is 0.04 mg KOH / g or more and 15.00 mg KOH / g or less. This polycarbonate diol is produced by transesterifying a dihydroxy compound (1) having an acid value of 0.04 mg KOH / g or more and 15.00 mg KOH / g or less with a carbonate compound in the presence of a transesterification catalyst according to the method for producing a polycarbonate diol of the present invention. HO-R 1 -OH …(1) (In the above formula (1), R 1 represents a divalent hydrocarbon group having 10 to 12 carbon atoms.

[0031] As will be described later, the polycarbonate diol of the present invention may not be hydroxy-terminated, and may contain impurities such as raw material compounds (dihydroxy compound (1) and carbonate compound) remaining after the transesterification reaction in the production process of the polycarbonate diol, transesterification catalysts, and by-products such as phenols produced during the reaction. From this perspective, the polycarbonate diol may be called a "polycarbonate diol composition" rather than a "polycarbonate diol." However, it is generally difficult to obtain a compound obtained by a chemical reaction that is 100% of the target substance, and it is common knowledge among those skilled in the art that the product will contain a small amount of impurities. Therefore, in the present invention, a polycarbonate diol containing impurities such as residues after the reaction is called a "polycarbonate diol" rather than a "polycarbonate diol composition." The amount of impurities such as residual raw material compounds in the polycarbonate diol of the present invention can be determined as a value measured when the polycarbonate diol is subjected to a method for measuring the content of each impurity.

[0032] <Dihydroxy compounds> The dihydroxy compound that is the raw material for the polycarbonate diol of the present invention is represented by the following formula (1) and has an acid value of 0.04 mg KOH / g or more and 15.00 mg KOH / g or less. HO-R 1 -OH …(1) (In the above formula (1), R 1 represents a divalent hydrocarbon group having 10 to 12 carbon atoms.

[0033] R in formula (1) 1 The hydrocarbon group may be linear or branched, and specific examples of such dihydroxy compounds (1) include the following: Terminal dihydroxy compounds of straight-chain hydrocarbons such as 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol; branched-chain dihydroxy compounds such as 2-heptyl-1,3-propanediol, 2-pentyl-1,5-pentanediol, 2,2-dibutyl-1,3-propanediol, 1,10-undecanediol, 2-heptyl-1,4-butanediol, 2,11-dodecanediol, and 1,10-dodecanediol;

[0034] Among them, R in Eq. (1) 1 is an unsubstituted alkylene group, particularly a linear alkylene group, which is preferable in that the polyurethane produced using the resulting polycarbonate diol has good chemical resistance, low-temperature properties, and heat resistance. Therefore, as the dihydroxy compound (1), 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol are preferred, 1,10-decanediol and 1,12-dodecanediol are more preferred, and 1,10-decanediol is most preferred.

[0035] These dihydroxy compounds (1) are produced through one or more reactions, including reduction of carbonyl compounds such as aldehydes, ketones, carboxylic acids, and carboxylic acid derivatives, and hydration of alkenyl compounds. Among these, dihydroxy compounds produced through one or more reactions, including reduction of carboxylic acids and carboxylic acid derivatives, are preferred in that the acid value can be easily controlled within the range specified in the present invention and the effect of the present invention in controlling the acid value can be effectively exhibited. Examples of the carboxylic acid derivatives include ester compounds, amide compounds, acid anhydrides, acid halides, and nitrile compounds.

[0036] In addition, it is preferable that the dihydroxy compound (1) is derived from a plant, from the viewpoint of reducing the environmental load. Examples of the dihydroxy compound (1) that can be derived from a plant include 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol.

[0037] The upper limit of the acid value of the dihydroxy compound (1) used as the raw material for the polycarbonate diol of the present invention is 15.00 mgKOH / g, preferably 10.00 mgKOH / g or less, more preferably 6.00 mgKOH / g or less, particularly preferably 4.00 mgKOH / g or less, and most preferably 3.00 mgKOH / g or less. On the other hand, the lower limit is 0.04 mgKOH / g, preferably 0.06 mgKOH / g or more, more preferably 0.08 mgKOH / g or more.

[0038] If the acid value of the dihydroxy compound (1) exceeds the upper limit, the chemical resistance and moist heat resistance of the urethane using the obtained polycarbonate diol will be reduced. On the other hand, if it is below the lower limit, the color tone and thermal stability of the obtained polycarbonate diol will be deteriorated. In addition, if the acid value of the dihydroxy compound (1) is below the lower limit, the cost of the purification process of the dihydroxy compound (1) will increase, which will be economically disadvantageous.

[0039] In the present invention, the acid value of the dihydroxy compound (1) is determined by a measurement method in accordance with JIS K1557-5 (2007).

[0040] The acid value of dihydroxy compound (1) can be adjusted to the above range by lowering the conversion rate to dihydroxy compound (1) in the reduction reaction of, for example, carboxylic acid or carboxylic acid derivative, which is a raw material for obtaining dihydroxy compound (1), or by lowering the degree of purification of dihydroxy compound (1) obtained by the above reaction. Also, the acid value may be adjusted to the above range by adding an acidic compound that does not inhibit the transesterification reaction to dihydroxy compound (1) before using it as a raw material for the method for producing polycarbonate diol of the present invention.

[0041] In the present invention, a dihydroxy compound other than dihydroxy compound (1) may be used as the starting dihydroxy compound as long as the object of the present invention is not impaired. When a dihydroxy compound other than dihydroxy compound (1) is used, the proportion of the dihydroxy compound other than dihydroxy compound (1) is preferably 9 mol % or less, more preferably 5 mol % or less, particularly preferably 2 mol % or less, and even more preferably 1 mol % or less of the total starting dihydroxy compounds.

[0042] <Carbonate compounds> The carbonate compound (hereinafter sometimes referred to as "carbonate diester") used in the production of the polycarbonate diol of the present invention is not limited as long as it does not impair the effects of the present invention, and examples thereof include dialkyl carbonate, diaryl carbonate, and alkylene carbonate. Among these, the use of diaryl carbonate has the advantage that the reaction proceeds quickly. However, on the other hand, when diaryl carbonate is used as a raw material, there is a problem in that phenols with high boiling points are by-produced. Since phenols are monofunctional compounds, they can be polymerization inhibitors during polyurethane formation and are also irritating substances, so the content of phenols in the polycarbonate diol is preferably as low as possible.

[0043] Specific examples of dialkyl carbonates, diaryl carbonates, and alkylene carbonates of carbonic acid diesters that can be used in the production of the polycarbonate diol of the present invention are as follows:

[0044] Examples of dialkyl carbonates include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diisobutyl carbonate, ethyl-n-butyl carbonate, and ethyl isobutyl carbonate, with dimethyl carbonate and diethyl carbonate being preferred.

[0045] Examples of diaryl carbonates include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, and di-m-cresyl carbonate, with diphenyl carbonate being preferred.

[0046] Examples of alkylene carbonates include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 1,3-pentylene carbonate, 1,4-pentylene carbonate, 1,5-pentylene carbonate, 2,3-pentylene carbonate, 2,4-pentylene carbonate, and neopentyl carbonate, with ethylene carbonate being preferred.

[0047] These may be used alone or in combination of two or more.

[0048] Among these, diaryl carbonates are preferred because they are highly reactive and can be produced efficiently industrially, and among these, diphenyl carbonate is more preferred because it is readily available as an industrial raw material at low cost.

[0049] <Ratio of raw materials used> In the production of the polycarbonate diol of the present invention, the amount of the carbonate compound used is not particularly limited, but usually, in terms of the molar ratio relative to 1 mole of the raw material dihydroxy compound, the lower limit is preferably 0.35, more preferably 0.50, and even more preferably 0.60, and the upper limit is preferably 1.00, more preferably 0.98, and even more preferably 0.97. If the amount of the carbonate compound used exceeds the above upper limit, the proportion of polycarbonate diols having terminal groups other than hydroxyl groups may increase, or the molecular weight may not fall within the specified range, and if it is less than the above lower limit, polymerization may not proceed to the specified molecular weight.

[0050] <Transesterification catalyst> There are no limitations on the metal that can be used as the transesterification catalyst (hereinafter, sometimes simply referred to as "catalyst"), as long as it is a metal that is generally considered to have transesterification ability.

[0051] Examples of catalyst metals include Group 1 metals on the periodic table such as lithium, sodium, potassium, rubidium, and cesium; Group 2 metals on the periodic table such as magnesium, calcium, strontium, and barium; Group 4 metals on the periodic table such as titanium and zirconium; Group 5 metals on the periodic table such as hafnium; Group 9 metals on the periodic table such as cobalt; Group 12 metals on the periodic table such as zinc; Group 13 metals on the periodic table such as aluminum; Group 14 metals on the periodic table such as germanium, tin, and lead; Group 15 metals on the periodic table such as antimony and bismuth; and lanthanoid metals such as lanthanum, cerium, europium, and ytterbium. Among these, from the viewpoint of increasing the transesterification reaction rate, Group 1 metals on the periodic table, Group 2 metals on the periodic table, Group 4 metals on the periodic table, Group 5 metals on the periodic table, Group 9 metals on the periodic table, Group 12 metals on the periodic table, Group 13 metals on the periodic table, and Group 14 metals on the periodic table are preferred, Group 1 metals and Group 2 metals on the periodic table are more preferred, and Group 2 metals on the periodic table are even more preferred. Among the metals in Group 1 of the periodic table, lithium, potassium, and sodium are preferred, with lithium and sodium being more preferred, and sodium being even more preferred. Among the metals in Group 2 of the periodic table, magnesium, calcium, and barium are preferred, with calcium and magnesium being more preferred, and magnesium being even more preferred.

[0052] These metals may be used as simple metals or as metal compounds such as hydroxides or salts. When used as salts, examples of the salts include halide salts such as chlorides, bromides, and iodides; carbonates; carboxylates such as acetates, formates, and benzoates; sulfonates such as methanesulfonic acid, toluenesulfonic acid, and trifluoromethanesulfonic acid; phosphorus-containing salts such as phosphates, hydrogen phosphates, and dihydrogen phosphates; acetylacetonate salts; and the like. The catalyst metals can also be used as alkoxides such as methoxides and ethoxides.

[0053] Of these, preferably, acetates, nitrates, sulfates, carbonates, phosphates, hydroxides, halide salts, and alkoxides of metals in Group 1, Group 2, Group 4, Group 5, Group 9, Group 12, Group 13, and Group 14 of the periodic table are used, more preferably, acetates, carbonates, and hydroxides of metals in Group 1 or Group 2 of the periodic table are used, still more preferably, compounds of metals in Group 2 of the periodic table such as magnesium and calcium are used, and particularly preferably, acetates of the metals are used.

[0054] These metals and metal compounds may be used alone or in combination of two or more.

[0055] Specific examples of compounds using a Group 1 metal of the periodic table as a transesterification catalyst include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenylborohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenylphosphate; disodium salt, dipotassium salt, dicesium salt, dilithium salt of bisphenol A; sodium salt, potassium salt, cesium salt, lithium salt of phenol; and the like.

[0056] Examples of compounds using Group 2 metals of the periodic table include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenylphosphate, etc.

[0057] Examples of compounds using metals from Group 4, 12, and 14 of the periodic table include titanium alkoxides such as tetraethyl titanate, tetraisopropyl titanate, and tetra-n-butyl titanate; titanium halides such as titanium tetrachloride; zinc salts such as zinc acetate, zinc benzoate, and zinc 2-ethylhexanoate; tin compounds such as tin(II) chloride, tin(IV) chloride, tin(II) acetate, tin(IV) acetate, dibutyltin dilaurate, dibutyltin oxide, and dibutyltin dimethoxide; zirconium compounds such as zirconium acetylacetonate, zirconium oxyacetate, and zirconium tetrabutoxide; and lead compounds such as lead(II) acetate, lead(IV) acetate, and lead(IV) chloride.

[0058] The amount of transesterification catalyst used is preferably an amount that does not affect performance even if it remains in the resulting polycarbonate diol, and the upper limit is preferably 500 ppm, more preferably 100 ppm, and even more preferably 50 ppm, as the weight ratio of the metal to the weight of the dihydroxy compound used as a raw material. On the other hand, the lower limit is preferably 0.01 ppm, more preferably 0.1 ppm, and even more preferably 1 ppm, as an amount that provides sufficient polymerization activity.

[0059] <Reaction conditions> The reaction temperature during the transesterification reaction can be any temperature that allows a practical reaction rate to be obtained. The temperature is not particularly limited, but the lower limit is usually 70°C, preferably 100°C, and more preferably 130°C. The upper limit of the reaction temperature is usually 250°C, preferably 200°C, more preferably 190°C, even more preferably 180°C, and particularly preferably 170°C. If the reaction temperature is below the lower limit, the transesterification reaction may not proceed at a practical rate. If the reaction temperature exceeds the upper limit, the resulting polycarbonate diol may become discolored, or quality problems such as the formation of an ether structure may occur.

[0060] Although the reaction can be carried out at normal pressure, the transesterification reaction is an equilibrium reaction, and the reaction can be biased toward the product system by distilling off the produced monodihydroxy compound from the system. Therefore, it is usually preferable to carry out the reaction under reduced pressure in the latter half of the reaction while distilling off the monodihydroxy compound. Alternatively, the pressure can be gradually reduced from the middle of the reaction to carry out the reaction while distilling off the produced monodihydroxy compound.

[0061] In particular, it is preferable to carry out the reaction at a higher degree of reduced pressure towards the end of the reaction, since this allows the by-product monodihydroxy compounds such as phenols, dihydroxy compounds, and residual monomers such as carbonate diesters to be distilled off. The reaction pressure at the end of the reaction is not particularly limited, but the upper limit is usually 10 kPa, preferably 5 kPa, and more preferably 1 kPa. In order to effectively distill off these low-boiling components, the reaction can also be carried out while passing a small amount of an inert gas such as nitrogen, argon, or helium into the reaction system.

[0062] When a diester carbonate or a dihydroxy compound with a low boiling point is used in the transesterification reaction, a method can be employed in which the reaction is carried out at a temperature close to the boiling point of the diester carbonate or dihydroxy compound in the early stages of the reaction, and the temperature is gradually raised as the reaction progresses to further promote the reaction. This method is preferred because it can prevent the distillation of unreacted diester carbonate or dihydroxy compound in the early stages of the reaction. Furthermore, in order to prevent the distillation of raw materials in the early stages of the reaction, it is also possible to attach a reflux condenser to the reactor and reflux the diester carbonate and dihydroxy compound while distilling off the monodihydroxy compound to carry out the transesterification reaction. This method is preferred because the charged raw material monomers are not lost and the quantitative ratio of the reagents can be accurately adjusted.

[0063] The time required for the transesterification reaction cannot be generally defined because it varies greatly depending on the types and amounts of the dihydroxy compound, carbonate diester, and catalyst used, but the reaction time required to reach a predetermined molecular weight is usually 50 hours or less, preferably 20 hours or less, and more preferably 10 hours or less, and is usually 3 hours or more, and preferably 5 hours or more.

[0064] <Catalyst deactivation> When a catalyst is used in the transesterification reaction, the catalyst usually remains in the obtained polycarbonate diol, and the remaining metal catalyst may make it impossible to control the reaction when carrying out the polyurethane-forming reaction. In order to suppress the influence of this remaining catalyst, a catalyst deactivator may be added in an amount approximately equimolar to the catalyst used, such as an acidic compound or a phosphorus-based or sulfur-based compound that decomposes to form an acidic compound. Furthermore, after the addition, by carrying out a heat treatment as described below, the transesterification catalyst can be efficiently deactivated.

[0065] Examples of phosphorus compounds used to inactivate the transesterification catalyst include inorganic phosphoric acids such as phosphoric acid and phosphorous acid, and organic phosphoric acid esters such as dibutyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, and triphenyl phosphite. These may be used alone or in combination of two or more.

[0066] The amount of phosphorus-based compound, etc. used to inactivate the catalyst is not particularly limited, but as mentioned above, it is sufficient if it is approximately equimolar with the transesterification catalyst used. Specifically, the upper limit is preferably 5 mol, more preferably 2 mol, and the lower limit is preferably 0.8 mol, more preferably 1.0 mol, per mol of the transesterification catalyst used. If a smaller amount of phosphorus-based compound, etc. is used, the transesterification catalyst is not sufficiently deactivated, and when the obtained polycarbonate diol is used as, for example, a raw material for producing polyurethane, the reactivity of the polycarbonate diol with isocyanate groups may not be sufficiently reduced. Furthermore, if a phosphorus-based compound, etc. is used in an amount exceeding this range, the obtained polycarbonate diol may become discolored.

[0067] Inactivation of the transesterification catalyst by adding a phosphorus-based compound or the like can be carried out at room temperature, but is more efficient when heated. The temperature of this heat treatment is not particularly limited, but the upper limit is preferably 150°C, more preferably 120°C, and even more preferably 100°C, and the lower limit is preferably 50°C, more preferably 60°C, and even more preferably 70°C. At temperatures lower than these, deactivation of the transesterification catalyst takes a long time, which is inefficient, and deactivation may be insufficient. On the other hand, at temperatures exceeding 150°C, the obtained polycarbonate diol may become discolored.

[0068] The reaction time with the phosphorus-based compound is not particularly limited, but is usually 1 to 5 hours.

[0069] <Refining> The reaction product obtained by the transesterification reaction contains impurities not having a hydroxyl group at the polymer terminal, phenol, the starting dihydroxy compound, the starting carbonate compound, the low-boiling cyclic carbonate produced as a by-product, the added catalyst, and the like, and therefore can be purified in order to remove these. For purification, low-boiling compounds can be removed by distillation. Specific distillation methods include vacuum distillation, steam distillation, thin-film distillation, and the like, and any method can be used without any particular limitations. Among these, thin-film distillation is particularly effective.

[0070] Although there are no particular limitations on the conditions for thin film distillation, the upper limit of the temperature during thin film distillation is preferably 250°C, more preferably 200°C, and the lower limit is preferably 120°C, more preferably 150°C. By setting the lower limit of the temperature during thin film distillation to the above value, the effect of removing low boiling components becomes sufficient. Also, by setting the upper limit to 250°C, coloration of the polycarbonate diol obtained after thin film distillation can be prevented.

[0071] The upper limit of the pressure during thin-film distillation is preferably 500 Pa, more preferably 150 Pa, and even more preferably 50 Pa. By setting the pressure during thin-film distillation to the above upper limit or less, the effect of removing low-boiling components can be sufficiently obtained. The upper limit of the temperature at which the polycarbonate diol is kept warm immediately before thin-film distillation is preferably 250°C, more preferably 150°C. The lower limit is preferably 80°C, more preferably 120°C.

[0072] By keeping the temperature of the polycarbonate diol warm just before the thin film distillation at or above the lower limit, it is possible to prevent the fluidity of the polycarbonate diol just before the thin film distillation from decreasing, while by keeping the temperature at or below the upper limit, it is possible to prevent the polycarbonate diol obtained after the thin film distillation from being colored.

[0073] In addition, in order to remove water-soluble impurities, the polycarbonate diol may be washed with water, alkaline water, acidic water, a chelating agent solution, or the like. In that case, the compound dissolved in water can be arbitrarily selected.

[0074] [Physical properties of polycarbonate diol] <Molecular weight and molecular weight distribution> The lower limit of the number average molecular weight (Mn) of the polycarbonate diol of the present invention is usually 250, preferably 500, more preferably 700, and particularly preferably 1,000. On the other hand, the upper limit is usually 5,000, preferably 4,000, and more preferably 3,000. When the number average molecular weight of the polycarbonate diol is less than the above lower limit, sufficient hardness cannot be obtained when made into polyurethane. On the other hand, when it exceeds the above upper limit, the viscosity increases, which hinders handling during polyurethane formation.

[0075] The molecular weight distribution (Mw / Mn) of the polycarbonate diol of the present invention is not particularly limited, but the lower limit is usually 1.5, preferably 1.7, and more preferably 1.9. The upper limit is usually 3.5, preferably 3.0. When the molecular weight distribution exceeds the above upper limit, the physical properties of the polyurethane produced using this polycarbonate diol tend to deteriorate, such as becoming hard at low temperatures and having poor elongation. When trying to produce a polycarbonate diol with a molecular weight distribution less than the above lower limit, advanced purification operations such as removing oligomers may be required.

[0076] Here, Mw is the weight average molecular weight and Mn is the number average molecular weight, and it can usually be determined by measurement using gel permeation chromatography (GPC). When it is difficult to measure Mn by gel permeation chromatography (GPC), it can also be calculated from the OH value of the polyol as follows. Also, 1 It is also possible to measure by 1H-NMR. <Calculation of the number average molecular weight of polyol from OH value> It is calculated by the acetylation method described in JIS K1557-1 (2007).

[0077] <Ratio of terminal alkyloxy or aryloxy groups, hydroxyl value> The polycarbonate diol of the present invention basically has a terminal structure of the polymer as a hydroxyl group, i.e., a hydroxyl terminal. However, in the reaction product obtained by the reaction of a dihydroxy compound with a carbonic acid diester, some polymers may have a structure in which the terminal is not a hydroxyl group as an impurity. Specific examples of such structures include those in which the molecular chain terminal is an alkyloxy group or an aryloxy group, and most of these are structures derived from a carbonic acid diester. The ratio of the hydroxyl group (hydroxyl terminal), alkyloxy group, and aryloxy group is usually 1 Calculated by H-NMR.

[0078] For example, when diphenyl carbonate is used as the carbonic acid diester, a phenoxy group (PhO-) may remain as the aryloxy group; when dimethyl carbonate is used, a methoxy group (MeO-) may remain as the alkyloxy group; when diethyl carbonate is used, an ethoxy group (EtO-) may remain; and when ethylene carbonate is used, a hydroxyethoxy group (HOCH2CHO-) may remain as the terminal group (where Ph represents a phenyl group, Me represents a methyl group, and Et represents an ethyl group).

[0079] In the present invention, the proportion of molecular chain terminals contained in the polycarbonate diol that are hydroxyl terminals rather than alkyloxy or aryloxy groups is usually 95 mol % or more, preferably 98.5 mol % or more, and more preferably 99 mol % or more of the total number of terminals in terms of the number of terminal groups. There is no particular upper limit to the proportion of hydroxyl terminals at the molecular chain terminals, and it is usually 99.9 mol %, preferably 99.999 mol %, and most preferably 100 mol %. If the proportion of hydroxyl terminals is high, the degree of polymerization increases sufficiently during the polyurethane-forming reaction, allowing the reaction to proceed smoothly.

[0080] As described above, the polycarbonate diol of the present invention has a molecular chain terminal with an alkyloxy group or aryloxy group ratio of usually 5 mol % or less, and both terminal groups of the molecular chain are basically hydroxyl groups (hydroxyl terminals), and has a structure in which these hydroxyl groups can react with isocyanate during the polyurethane reaction.

[0081] The lower limit of the hydroxyl value of the polycarbonate diol of the present invention is usually 20 mgKOH / g, preferably 25 mgKOH / g, more preferably 35 mgKOH / g. The upper limit is usually 250 mgKOH / g, preferably 200 mgKOH / g, more preferably 100 mgKOH / g. If the hydroxyl value is below the lower limit, the viscosity may become too high, making handling difficult during polyurethane formation. If the hydroxyl value is above the upper limit, the strength and hardness of the polyurethane may be insufficient.

[0082] The hydroxyl value may be measured by a commonly known method, and for example, it can be measured and calculated by the acetylation method described in JIS K1557-1 (2007).

[0083] <Solvent solubility> The polycarbonate diol of the present invention is usually in the form of a wax-like solid at around room temperature, but the viscosity can be reduced by heating, making it easier to handle. It can also be dissolved in amide solvents such as dimethylformamide and dimethylacetamide, ester solvents such as γ-butyrolactone, and sulfoxide solvents such as dimethyl sulfoxide, which may make it easier to transport or react.

[0084] <Hazen color number> The color of the polycarbonate diol of the present invention is preferably in a range that does not affect the color tone of the resulting polyurethane, and the value (hereinafter referred to as "Hazen color number") when the degree of coloration is expressed by the Hazen color number (based on JIS K0071-1 (1998)) is not particularly limited, but is preferably 50 or less, more preferably 40 or less, even more preferably 30 or less, and of these, 20 or less is suitable.

[0085] <Residual catalyst amount> The transesterification catalyst used in producing the polycarbonate diol of the present invention may remain in the polycarbonate diol of the present invention. However, if an excessive amount of catalyst remains, it becomes difficult to control the polyurethane-forming reaction, and the polyurethane-forming reaction may be accelerated more than expected, resulting in gelation, and a uniform polyurethane may not be obtained, so it is preferable that the transesterification catalyst does not remain.

[0086] The upper limit of the amount of catalyst remaining in the polycarbonate diol is not particularly limited, but from the viewpoint of obtaining a homogeneous polyurethane from this polycarbonate diol, the content in terms of catalyst metal is usually 100 ppm by weight, preferably 50 ppm by weight, more preferably 30 ppm by weight, and particularly preferably 10 ppm by weight. The type of remaining metal includes the metal of the catalytic active component having the transesterification ability described above.

[0087] The lower limit of the amount of catalyst remaining in the polycarbonate diol of the present invention is not particularly limited, but is usually 0.01 weight ppm, preferably 0.1 weight ppm, more preferably 1 weight ppm, and particularly preferably 5 weight ppm, in terms of the content in terms of catalyst metal. Usually, it is difficult to remove the catalyst used in producing the polycarbonate diol after production, and it is often difficult to reduce the amount of remaining catalyst to less than the lower limit of the amount used, which will be described later.

[0088] The amount of catalyst remaining in the polycarbonate diol can be measured by inductively coupled plasma (ICP) emission spectrometry. The amount of catalyst remaining in the polycarbonate diol can be adjusted by adjusting the amount of catalyst used during production, isolating the catalyst by filtering the product, or extracting the catalyst using a solvent such as water.

[0089] <Impurity content> (phenols) Phenols are monofunctional compounds that can inhibit polymerization during polyurethane formation and are also irritating substances, so the residual amount of phenols in the polycarbonate diol of the present invention is preferably as low as possible. Specifically, the weight ratio of phenols to the polycarbonate diol is usually 1000 ppm or less, preferably 500 ppm or less, more preferably 300 ppm or less, and most preferably 100 ppm or less. In order to reduce the amount of phenols in the polycarbonate diol, it is effective to create a high vacuum of 1 kPa or less in absolute pressure during the polymerization reaction of the polycarbonate diol, as described above, or to perform thin-film distillation after the synthesis of the polycarbonate diol.

[0090] (carbonate diester) The polycarbonate diol of the present invention may contain residual carbonate diesters used as raw materials during production. While there are no limitations on the amount of residual carbonate diesters in the polycarbonate diol of the present invention, a lower amount is preferable, with the upper limit usually being 5% by weight, preferably 3% by weight, and more preferably 1% by weight. If the carbonate diester content in the polycarbonate diol is too high, it may inhibit the polyurethane-forming reaction. Meanwhile, the lower limit is not particularly limited, and is 0.1% by weight, preferably 0.01% by weight, and more preferably 0% by weight.

[0091] (Dihydroxy compounds) The polycarbonate diol of the present invention may contain residual dihydroxy compound (1) used during production. The amount of residual dihydroxy compound (1) in the polycarbonate diol of the present invention is not limited, but a smaller amount is preferable, and is usually less than 5% by weight, preferably less than 1% by weight, more preferably less than 0.5% by weight, and even more preferably less than 0.05% by weight. If the amount of residual dihydroxy compound (1) in the polycarbonate diol is large, the molecular length of the soft segment moiety when made into polyurethane may be insufficient, and desired physical properties may not be obtained. The residual amount of dihydroxy compound (1) in the polycarbonate diol is 1It can be determined by H-NMR measurement, gas chromatography (GC), and liquid chromatography (LC).

[0092] [Polyurethane] The polycarbonate diol of the present invention can be used to produce polyurethanes and polyurethane water dispersions. The produced polyurethanes are another embodiment of the present invention.

[0093] In the method for producing polyurethane using the polycarbonate diol of the present invention, known polyurethane reaction conditions for producing ordinary polyurethane are used. For example, polyurethane can be produced by reacting polycarbonate diol with polyisocyanate and a chain extender at a temperature ranging from room temperature to 200°C. Alternatively, a polycarbonate diol may be reacted with an excess amount of polyisocyanate to produce a prepolymer having an isocyanate group at its terminal, and then a chain extender may be used to increase the degree of polymerization to produce polyurethane.

[0094] <Polyisocyanate> Examples of polyisocyanates that can be used when producing polyurethane using polycarbonate diol include various known aliphatic, alicyclic, and aromatic polyisocyanate compounds. For example, aliphatic diisocyanates such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and dimer diisocyanate in which the carboxyl groups of dimer acids are converted to isocyanate groups; alicyclic diisocyanates such as 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and 1,4-bis(isocyanatomethyl)cyclohexane. Cyanates: aromatic diisocyanates such as xylylene diisocyanate, 4,4'-diphenyl diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate, and m-tetramethylxylylene diisocyanate. These may be used alone or in combination of two or more.

[0095] Among these, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and isophorone diisocyanate are preferred because they provide a good balance of physical properties for the polyurethane obtained and are available industrially in large quantities at low cost.

[0096] <Chain extender> The chain extender used in producing polyurethane is a low molecular weight compound having at least two active hydrogens that react with isocyanate groups when producing a prepolymer having an isocyanate group, which will be described later. Typical examples of such a compound include polyols and polyamines.

[0097] Specific examples thereof include linear diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol; 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, and 2-methyl-1,4-butanediol. branched chain diols such as 1,2-butanediol, 2,4-heptanediol, 1,4-dimethylolhexane, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, and dimer diol; diols having an ether group such as diethylene glycol and propylene glycol; 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethyl silyl Diols with alicyclic structures such as cyclohexane, diols with aromatic groups such as xylylene glycol, 1,4-dihydroxyethylbenzene, and 4,4'-methylenebis(hydroxyethylbenzene); polyols such as glycerin, trimethylolpropane, and pentaerythritol; hydroxyamines such as N-methylethanolamine and N-ethylethanolamine; ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, 4,4 Examples of the polyamines include N,N'-diaminodicyclohexylmethane, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, 4,4'-diphenylmethanediamine, methylenebis(o-chloroaniline), xylylenediamine, diphenyldiamine, tolylenediamine, hydrazine, piperazine, and N,N'-diaminopiperazine; and water. These chain extenders may be used alone or in combination of two or more.

[0098] Among these, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane, ethylenediamine, 1,3-diaminopropane, isophoronediamine, and 4,4′-diaminodicyclohexylmethane are preferred because they result in a favorable balance of physical properties in the resulting polyurethane and are available industrially in large quantities at low cost.

[0099] Furthermore, the chain extender used in producing a prepolymer having a hydroxyl group, which will be described later, is a low-molecular-weight compound having at least two isocyanate groups, and specific examples thereof include the compounds described in the <Polyisocyanate> section.

[0100] <Chain terminator> When producing polyurethane, a chain terminator having one active hydrogen group can be used as needed to control the molecular weight of the resulting polyurethane. Examples of these chain terminators include aliphatic monools having one hydroxyl group, such as methanol, ethanol, propanol, butanol, and hexanol, and aliphatic monoamines having one amino group, such as diethylamine, dibutylamine, n-butylamine, monoethanolamine, diethanolamine, and morpholine. These may be used alone or in combination of two or more.

[0101] <Catalyst> In the polyurethane-forming reaction when producing polyurethane, known urethane polymerization catalysts can be used, such as amine catalysts such as triethylamine, N-ethylmorpholine, and triethylenediamine; acid catalysts such as acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, and sulfonic acid; tin compounds such as trimethyltin laurate, dibutyltin dilaurate, dioctyltin dilaurate, and dioctyltin dineodecanoate; and organometallic salts such as titanium compounds. One urethane polymerization catalyst may be used alone, or two or more may be used in combination.

[0102] <Polyols other than the polycarbonate diol of the present invention> In the polyurethane-forming reaction when producing polyurethane, the polycarbonate diol of the present invention may be used in combination with a polyol other than the polycarbonate diol of the present invention (hereinafter also referred to as "other polyol"), if necessary. Here, the other polyol is not particularly limited as long as it is one that is normally used in producing polyurethane, and examples thereof include polyether polyols, polycarbonate polyols, polyester polyols, polycaprolactone polyols, and polycarbonate diols other than the polycarbonate diol of the present invention. For example, when used in combination with a polyether polyol, a polyurethane can be obtained that has further improved flexibility, which is a feature of the polycarbonate diol of the present invention.

[0103] When other polyols are used in combination, the weight ratio of the polycarbonate diol of the present invention to the combined weight of the polycarbonate diol of the present invention and the other polyols is preferably 70% or more, more preferably 90% or more. If the weight ratio of the polycarbonate diol of the present invention is low, the flexibility and moist heat resistance of the polyurethane, which are the characteristics of the present invention, may be lost.

[0104] When other polyols are used in combination during polyurethane production, the polycarbonate diol of the present invention, the other polyols, and other raw materials must be sufficiently compatible with each other. If the compatibility is insufficient, the urethanization reaction may proceed unevenly, broadening the molecular weight distribution of the resulting polyurethane or decreasing the molecular weight, which may result in gelation of the polyurethane solution, deterioration of storage stability, and reduction in the strength, solvent resistance, weather resistance, and heat resistance of the polyurethane.

[0105] <Solvent> A solvent may be used in the polyurethane-forming reaction when producing the polyurethane. Preferred solvents include amide solvents such as dimethylformamide, diethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; ketone solvents such as methyl ethyl ketone, cyclohexanone, and methyl isobutyl ketone; ether solvents such as tetrahydrofuran and dioxane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; and aromatic hydrocarbon solvents such as toluene and xylene. These solvents may be used alone or as a mixed solvent of two or more. Among these, preferred organic solvents are dimethylformamide, dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide, methyl ethyl ketone, ethyl acetate, toluene, and the like. Furthermore, a polyurethane in the form of a water dispersion can also be produced from a polyurethane composition containing the polycarbonate diol of the present invention, polydiisocyanate, and the chain extender.

[0106] <Polyurethane manufacturing method> As a method for producing polyurethane using the above-mentioned reactants, a production method generally used in experiments or industrially can be used. Examples of such methods include a method in which the polycarbonate diol of the present invention, other polyols used as needed, polyisocyanate, and a chain extender are mixed together and reacted (hereinafter, this may be referred to as a "one-step method"), and a method in which the polycarbonate diol of the present invention, other polyols, and polyisocyanate are first reacted to prepare a prepolymer having isocyanate groups at both ends, and then the prepolymer is reacted with a chain extender (hereinafter, this may be referred to as a "two-step method").

[0107] The two-stage method involves a step of preparing an intermediate having isocyanates at both ends of the portion corresponding to the soft segment of polyurethane by previously reacting the polycarbonate diol of the present invention and other polyols used as needed with one equivalent or more of polyisocyanate. In this way, if a prepolymer is prepared and then reacted with a chain extender, it may be easy to adjust the molecular weight of the soft segment portion, and this is useful when it is necessary to ensure phase separation between the soft segment and the hard segment.

[0108] <One step method> The one-stage method, also called a one-shot method, is a method in which the polycarbonate diol of the present invention, other polyol, polyisocyanate, and chain extender are charged all at once to carry out the reaction. The amount of polyisocyanate used in the one-stage method is not particularly limited, but when the total number of hydroxyl groups in the polycarbonate diol of the present invention and other polyols and the sum of the number of hydroxyl groups and the number of amino groups in the chain extender is taken as 1 equivalent, the lower limit is preferably 0.7 equivalents, more preferably 0.8 equivalents, even more preferably 0.9 equivalents, and particularly preferably 0.95 equivalents, and the upper limit is preferably 3.0 equivalents, more preferably 2.0 equivalents, even more preferably 1.5 equivalents, and particularly preferably 1.1 equivalents.

[0109] If the amount of polyisocyanate used is too large, unreacted isocyanate groups will undergo side reactions, and the viscosity of the resulting polyurethane will become too high, making it difficult to handle and reducing its flexibility. If the amount is too small, the molecular weight of the polyurethane will not be large enough, and sufficient polyurethane strength will not be obtained. The amount of chain extender used is not particularly limited, but when the total number of hydroxyl groups in the polycarbonate diol of the present invention and other polyols minus the number of isocyanate groups in the polyisocyanate is taken as 1 equivalent, the lower limit is preferably 0.7 equivalents, more preferably 0.8 equivalents, even more preferably 0.9 equivalents, and particularly preferably 0.95 equivalents, and the upper limit is preferably 3.0 equivalents, more preferably 2.0 equivalents, even more preferably 1.5 equivalents, and particularly preferably 1.1 equivalents. If the amount of chain extender used is too large, the resulting polyurethane tends to be difficult to dissolve in a solvent and to be difficult to process, whereas if the amount is too small, the resulting polyurethane may be too soft and may not have sufficient strength, hardness, elastic recovery performance, or elastic retention performance, or may have poor heat resistance.

[0110] <Two step method> The two-stage method is also called the prepolymer method, and there are mainly the following methods. (a) A method of producing a polyurethane by first reacting the polycarbonate diol of the present invention and other polyol with an excess amount of polyisocyanate at a reaction equivalent ratio of polyisocyanate / (polycarbonate diol of the present invention and other polyol) of more than 1 to 10.0 or less to produce a prepolymer having an isocyanate group at the molecular chain terminal, and then adding a chain extender to the prepolymer. (b) A method in which a polyisocyanate is reacted in advance with an excess of the polycarbonate diol of the present invention and other polyol at a reaction equivalent ratio of polyisocyanate / (polycarbonate diol of the present invention and other polyol) of 0.1 or more and less than 1.0 to produce a prepolymer having hydroxyl groups at the molecular chain terminals, and then a polyisocyanate having isocyanate groups at the terminals as a chain extender is reacted with this to produce polyurethane.

[0111] The two-stage process can be carried out in the absence of a solvent or in the presence of a solvent. The two-stage polyurethane production can be carried out by any of the following methods (1) to (3). (1) First, without using a solvent, polyisocyanate is directly reacted with the polycarbonate diol of the present invention and other polyols to synthesize a prepolymer, which is then used as is in the chain extension reaction. (2) A prepolymer is synthesized by the method described in (1), then dissolved in a solvent and used in the subsequent chain extension reaction. (3) A solvent is used from the beginning, and polyisocyanate is reacted with the polycarbonate diol of the present invention and other polyols, followed by a chain extension reaction.

[0112] In the case of method (1), it is important to obtain polyurethane in the presence of a solvent during the chain extension reaction by, for example, dissolving the chain extender in the solvent or dissolving the prepolymer and chain extender in the solvent simultaneously. The amount of polyisocyanate used in the two-stage method (a) is not particularly limited, but when the total number of hydroxyl groups in the polycarbonate diol of the present invention and the other polyol is taken as 1 equivalent, the lower limit of the number of isocyanate groups is preferably more than 1.0 equivalent, more preferably 1.2 equivalents, and even more preferably 1.5 equivalents, and the upper limit is preferably 10.0 equivalents, more preferably 5.0 equivalents, and even more preferably 3.0 equivalents.

[0113] If the amount of isocyanate used is too large, the excess isocyanate groups will cause side reactions, making it difficult to achieve the desired physical properties of the polyurethane; for example, the viscosity will become too high, which will tend to reduce the flexibility of the resulting polyurethane, make it difficult to handle, and reduce productivity. If the amount is too small, the molecular weight of the resulting polyurethane will not increase sufficiently, which may result in reduced strength and thermal stability. The amount of chain extender used is not particularly limited, but the lower limit is preferably 0.1 equivalents, more preferably 0.5 equivalents, and even more preferably 0.8 equivalents, and the upper limit is preferably 5.0 equivalents, more preferably 3.0 equivalents, and even more preferably 2.0 equivalents, relative to 1 equivalent of the number of isocyanate groups contained in the prepolymer.

[0114] When the chain extension reaction is carried out, monofunctional organic amines or alcohols may be present in order to adjust the molecular weight.

[0115] Furthermore, the amount of polyisocyanate used when preparing a hydroxyl-terminated prepolymer in the two-step method (b) is not particularly limited, but when the total number of hydroxyl groups in the polycarbonate diol of the present invention and the other polyol is taken as 1 equivalent, the lower limit in terms of the number of isocyanate groups is preferably 0.1 equivalent, more preferably 0.5 equivalent, and even more preferably 0.7 equivalent, and the upper limit is preferably 0.99 equivalent, more preferably 0.98 equivalent, and even more preferably 0.97 equivalent.

[0116] If the amount of isocyanate used is too small, the process of obtaining the desired molecular weight in the subsequent chain extension reaction will be long, and production efficiency will tend to decrease. If the amount is too large, the viscosity will be too high, and the flexibility of the resulting polyurethane will decrease, or the handling will be poor, resulting in poor productivity.

[0117] The amount of chain extender used is not particularly limited, but when the total number of hydroxyl groups in the polycarbonate diol of the present invention and other polyols used in the prepolymer is taken as 1 equivalent, the lower limit of the total equivalent including the equivalent of the isocyanate groups used in the prepolymer is preferably 0.7 equivalents, more preferably 0.8 equivalents, and even more preferably 0.9 equivalents, and the upper limit is preferably less than 1.0 equivalent, more preferably 0.99 equivalents, and even more preferably 0.98 equivalents.

[0118] When the chain extension reaction is carried out, monofunctional organic amines or alcohols may be present in order to adjust the molecular weight.

[0119] The chain extension reaction is usually carried out at 0°C to 250°C, but this temperature varies depending on the amount of solvent, the reactivity of the raw materials used, the reaction equipment, etc., and is not particularly limited. If the temperature is too low, the reaction will proceed slowly, or the production time may be long due to the low solubility of the raw materials and polymers. If the temperature is too high, side reactions or decomposition of the resulting polyurethane may occur. The chain extension reaction may be carried out under reduced pressure while degassing.

[0120] In addition, a catalyst, a stabilizer, etc. may be added to the chain extension reaction, if necessary. Examples of catalysts include compounds such as triethylamine, tributylamine, dibutyltin dilaurate, stannous octoate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, and sulfonic acid, and one type may be used alone or two or more types may be used in combination. Examples of stabilizers include compounds such as 2,6-dibutyl-4-methylphenol, distearyl thiodipropionate, N,N'-di-2-naphthyl-1,4-phenylenediamine, and tris(dinonylphenyl)phosphite, and these may be used alone or in combination. When the chain extender is a highly reactive one such as a short-chain aliphatic amine, the process may be carried out without adding a catalyst.

[0121] <Water-based polyurethane dispersion> The polycarbonate diol of the present invention can be used to produce an aqueous polyurethane dispersion, which has higher dispersibility than conventional polycarbonate diols. In addition, the aqueous polyurethane dispersion is less likely to aggregate during storage, and therefore has excellent storage stability. In this case, when a polyol containing the polycarbonate diol of the present invention is reacted with an excess polyisocyanate to produce a prepolymer, a compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups is mixed to form a prepolymer, which is then subjected to a neutralization salt process of the hydrophilic functional group, an emulsification process by adding water, and a chain extension reaction process to produce an aqueous polyurethane dispersion. The raw materials, additives, catalysts, solvents, etc. used in the prepolymer formation and chain extension reaction processes can be the same as those used in the polyurethane production described above.

[0122] The hydrophilic functional group in the compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups used herein is, for example, a carboxyl group or a sulfonic acid group, which can be neutralized with an alkaline group. The isocyanate-reactive group is a group such as a hydroxyl group, a primary amino group, or a secondary amino group that generally reacts with isocyanate to form a urethane bond or a urea bond, and these groups may be present together in the same molecule.

[0123] Specific examples of compounds having at least one hydrophilic functional group and at least two isocyanate-reactive groups include 2,2'-dimethylolpropionic acid, 2,2-methylolbutyric acid, and 2,2'-dimethylolvaleric acid. Other examples include diaminocarboxylic acids such as lysine, cystine, and 3,5-diaminocarboxylic acid. These may be used alone or in combination. When actually using these compounds, they can be neutralized with amines such as trimethylamine, triethylamine, tri-n-propylamine, tributylamine, and triethanolamine, or alkaline compounds such as sodium hydroxide, potassium hydroxide, and ammonia.

[0124] When producing an aqueous polyurethane dispersion, the amount of the compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups used is preferably 1% by weight, more preferably 5% by weight, and even more preferably 10% by weight, based on the total weight of the polycarbonate diol of the present invention and other polyols, in order to improve dispersibility in water. On the other hand, if too much is added, the properties of the polycarbonate diol of the present invention may not be maintained, so the upper limit is preferably 50% by weight, more preferably 40% by weight, and even more preferably 30% by weight.

[0125] When producing an aqueous polyurethane dispersion, the reaction may be carried out in the presence of a solvent such as methyl ethyl ketone, acetone, or N-methyl-2-pyrrolidone in the prepolymerization step, or may be carried out without a solvent. When a solvent is used, it is preferable to remove the solvent by distillation after producing the aqueous dispersion.

[0126] When producing a solventless aqueous polyurethane dispersion using the polycarbonate diol of the present invention as a raw material, the upper limit of the number average molecular weight calculated from the hydroxyl value of the polycarbonate diol of the present invention is preferably 5,000, more preferably 4,000, even more preferably 3,000, and particularly preferably 2,000. The lower limit of the number average molecular weight is preferably 300, more preferably 500, and even more preferably 800. If the number average molecular weight calculated from the hydroxyl value exceeds the upper limit or is smaller than the lower limit, it may be difficult to form a dispersion.

[0127] When producing the aqueous polyurethane dispersion, the polycarbonate diol of the present invention may be used in combination with other polyols as required. Here, the other polyol is not particularly limited as long as it is one that is normally used in producing polyurethane, and examples thereof include polyether polyols, polycarbonate polyols, polyester polyols, polycaprolactone polyols, and polycarbonate diols other than the polycarbonate diol of the present invention. For example, when used in combination with a polyether polyol, a polyurethane can be obtained that has further improved flexibility, which is a feature of the polycarbonate diol of the present invention.

[0128] When other polyols are used in combination, the weight ratio of the polycarbonate diol of the present invention to the combined weight of the polycarbonate diol of the present invention and the other polyols is preferably 70% or more, more preferably 90% or more. If the weight ratio of the polycarbonate diol of the present invention is low, the polyurethane properties and handleability that are characteristic of the present invention may be lost.

[0129] When other polyols are used in combination during the production of an aqueous polyurethane dispersion, the polycarbonate diol of the present invention, the other polyols used as needed, and other raw materials must be sufficiently dispersed or dissolved in the aqueous solvent. If the dispersibility is insufficient, the urethanization reaction will proceed unevenly, broadening the molecular weight distribution of the resulting aqueous polyurethane dispersion or reducing the molecular weight, resulting in aggregation of the aqueous polyurethane dispersion and poor storage stability. Furthermore, the strength, solvent resistance, weather resistance, heat resistance, etc. of the polyurethane obtained from the aqueous polyurethane dispersion may be deteriorated.

[0130] Furthermore, during synthesis or storage of the aqueous polyurethane dispersion, emulsion stability may be maintained by using in combination an anionic surfactant typified by higher fatty acids, resin acids, acidic fatty alcohols, sulfates, higher alkyl sulfonates, alkylaryl sulfonates, sulfonated castor oil, sulfosuccinates, etc.; a cationic surfactant such as a primary amine salt, a secondary amine salt, a tertiary amine salt, a quaternary amine salt, or a pyridinium salt; or a nonionic surfactant typified by a known reaction product of ethylene oxide with a long-chain fatty alcohol or a phenol.

[0131] Furthermore, when preparing an aqueous polyurethane dispersion, an aqueous polyurethane dispersion can also be produced by mechanically mixing water at high shear with an organic solvent solution of a prepolymer in the presence of an emulsifier, if necessary, without the neutralization / salting step.

[0132] The aqueous polyurethane dispersions produced in this way can be used for a variety of purposes. In particular, in response to the recent demand for chemical raw materials with a low environmental impact, they can be used as a replacement for conventional products that do not use organic solvents.

[0133] Specific applications of the aqueous polyurethane dispersion include, for example, coating agents, aqueous paints, adhesives, synthetic leather, and artificial leather. In particular, the aqueous polyurethane dispersion produced using the polycarbonate diol of the present invention is excellent in flexibility, moist heat resistance, etc., and can be used more effectively as a coating agent, etc., than aqueous polyurethane dispersions using conventional polycarbonate diols.

[0134] <Storage stability of polyurethane solutions and aqueous polyurethane dispersions> The storage stability of polyurethane solutions and aqueous polyurethane dispersions produced using organic solvents and / or water and the polycarbonate diol of the present invention can be determined by adjusting the polyurethane concentration in the solution or dispersion (hereinafter, sometimes referred to as "solids concentration") to 1 to 80% by weight, storing the solution or dispersion under specific temperature conditions, and then visually checking for any changes in the solution or dispersion.

[0135] For example, in the case of a polyurethane solution (N,N-dimethylformamide / toluene mixed solution, solids concentration 30% by weight) produced by the above-mentioned two-stage method using the polycarbonate diol of the present invention, 4,4'-dicyclohexylmethane diisocyanate, and isophoronediamine, the period during which no change is observed visually in the polyurethane solution when stored at -10°C is preferably 8 hours, more preferably 1 day or more, even more preferably 3 days or more, and even more preferably 7 days or more.Furthermore, the period during which no change is observed visually in the polyurethane solution or polyurethane dispersion when stored at 0°C is preferably 1 month, more preferably 3 months or more, and even more preferably 6 months or more.

[0136] Furthermore, for example, with regard to an aqueous polyurethane dispersion (dispersed in an N-methyl-2-pyrrolidone / water mixture, solids concentration: 30 wt%) produced using the polycarbonate diol of the present invention, 4,4'-dicyclohexylmethane diisocyanate, and ethylenediamine, when stored at 20°C, the period during which no changes in the polyurethane aqueous dispersion are observed visually is preferably 1 day, even 3 days, more preferably 7 days or more, even more preferably 14 days, and particularly preferably 1 month or more.

[0137] <Additives> Various additives such as heat stabilizers, light stabilizers, colorants, fillers, stabilizers, UV absorbers, antioxidants, anti-tack agents, flame retardants, antioxidants, inorganic fillers, etc. can be added or mixed into the polyurethane of the present invention produced using the polycarbonate diol of the present invention, within the range that does not impair the properties of the polyurethane.

[0138] Compounds that can be used as heat stabilizers include phosphorus compounds such as aliphatic, aromatic, or alkyl group-substituted aromatic esters of phosphorous acid and phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonates, dialkyl pentaerythritol diphosphites, and dialkyl bisphenol A diphosphites; phenol derivatives, particularly hindered phenol compounds; sulfur-containing compounds such as thioethers, dithioacid salts, mercaptobenzimidazoles, thiocarbanilides, and thiodipropionic acid esters; and tin compounds such as tin maleates and dibutyltin monoxide.

[0139] Specific examples of hindered phenol compounds include "Irganox1010" (trade name: manufactured by BASF Japan Ltd.), "Irganox1520" (trade name: manufactured by BASF Japan Ltd.), and "Irganox245" (trade name: manufactured by BASF Japan Ltd.).

[0140] Examples of phosphorus compounds include "PEP-36," "PEP-24G," and "HP-10" (all trade names: manufactured by ADEKA Corporation), and "Irgafos 168" (trade name: manufactured by BASF Japan Ltd.).

[0141] Specific examples of sulfur-containing compounds include thioether compounds such as dilauryl thiopropionate (DLTP) and distearyl thiopropionate (DSTP).

[0142] Examples of light stabilizers include benzotriazole-based and benzophenone-based compounds, and specific examples that can be used include "TINUVIN622LD" and "TINUVIN765" (both manufactured by Chiba Specialty Chemicals Co., Ltd.), "SANOL LS-2626" and "SANOL LS-765" (both manufactured by Sankyo Co., Ltd.).

[0143] Examples of ultraviolet absorbers include "TINUVIN328" and "TINUVIN234" (both manufactured by Chiba Specialty Chemicals Co., Ltd.).

[0144] Examples of colorants include dyes such as direct dyes, acid dyes, basic dyes, and metal complex dyes; inorganic pigments such as carbon black, titanium oxide, zinc oxide, iron oxide, and mica; and organic pigments such as coupling azo pigments, condensed azo pigments, anthraquinone pigments, thioindigo pigments, dioxazone pigments, and phthalocyanine pigments.

[0145] Examples of inorganic fillers include short glass fibers, carbon fibers, alumina, talc, graphite, melamine, and clay.

[0146] Examples of flame retardants include additive and reactive flame retardants such as phosphorus- and halogen-containing organic compounds, bromine- or chlorine-containing organic compounds, ammonium polyphosphate, aluminum hydroxide, and antimony oxide.

[0147] These additives may be used alone or in any combination of two or more in any ratio. The amount of these additives added, expressed as a weight ratio to the polyurethane, has a lower limit of preferably 0.01 wt%, more preferably 0.05 wt%, and even more preferably 0.1 wt%, and an upper limit of preferably 10 wt%, more preferably 5 wt%, and even more preferably 1 wt%. If the amount of additive added is too small, the effect of adding the additive cannot be fully obtained, while if the amount is too large, the additive may precipitate in the polyurethane or cause turbidity.

[0148] <Polyurethane film / polyurethane plate> When a film is produced using the polyurethane of the present invention, the lower limit of the thickness of the film is preferably 10 μm, more preferably 20 μm, and even more preferably 30 μm, and the upper limit is preferably 1000 μm, more preferably 500 μm, and even more preferably 100 μm. If the film is too thick, sufficient moisture permeability tends to be insufficient, while if it is too thin, pinholes tend to form and the film tends to be prone to blocking, making it difficult to handle.

[0149] <Molecular weight> The molecular weight of the polyurethane of the present invention is adjusted appropriately depending on the application and is not particularly limited, but is preferably 50,000 to 500,000, and more preferably 100,000 to 300,000, as a weight average molecular weight (Mw) converted into polystyrene as measured by GPC. If Mw is less than the lower limit, sufficient strength and hardness may not be obtained, while if it is greater than the upper limit, handling properties such as processability tend to be impaired.

[0150] The molecular weight distribution (Mw / Mn) of the polyurethane of the present invention is not particularly limited, but the lower limit is usually 1.5, preferably 1.7, and more preferably 1.8, and the upper limit is usually 3.5, and preferably 3.0. If the molecular weight distribution exceeds the above upper limit, moldability and handleability tend to decrease, and if an attempt is made to produce a polyurethane having a molecular weight distribution below the above lower limit, advanced purification operations may be required. In addition, by using the polycarbonate diol of the present invention produced using the dihydroxy compound (1), there is also an effect that polyurethane with a narrow molecular weight distribution can be produced.

[0151] The weight average molecular weight (Mw) and number average molecular weight (Mn) of polyurethane are usually determined in terms of standard polystyrene from measurements obtained by gel permeation chromatography (GPC).

[0152] <Tensile elongation and strength at break in room temperature tensile tests> The polyurethane of the present invention preferably has a tensile elongation at break and a breaking strength in the following ranges, as measured on a strip sample having a width of 10 mm, a length of 70 mm, and a thickness of approximately 50 to 100 μm at a chuck distance of 50 mm, a pulling rate of 500 mm / min, a temperature of 23°C, and a relative humidity of 55%. The lower limit of the breaking elongation is preferably 200%, more preferably 300%, and even more preferably 350%, and the upper limit is preferably 1000%, more preferably 800%, and even more preferably 600%. If the breaking elongation is less than the lower limit, handling properties such as processability tend to be impaired, and if it exceeds the upper limit, sufficient solvent resistance may not be obtained. The lower limit of the breaking strength is preferably 30 MPa, more preferably 40 MPa, and even more preferably 50 MPa, and the upper limit is preferably 200 MPa, more preferably 100 MPa, and even more preferably 80 MPa. If the breaking strength is below the lower limit, handling properties such as processability tend to be impaired, and if it exceeds the upper limit, flexibility may be impaired.

[0153] <Moisture and heat resistance> The polyurethane of the present invention obtained using the polycarbonate diol of the present invention has excellent moist heat resistance, and for example, in the moist heat resistance test shown in the Examples section below, it usually has an excellent moist heat resistance with a molecular weight retention of 90% or more, preferably 93% or more.

[0154] <Application> The polyurethane of the present invention has excellent solvent resistance and good flexibility and mechanical strength, and therefore can be widely used in foams, elastomers, elastic fibers, paints, fibers, pressure-sensitive adhesives, adhesives, flooring materials, sealants, medical materials, artificial leather, synthetic leather, coating agents, water-based polyurethane paints, active energy radiation-curable polymer compositions, and the like. In particular, when the polyurethane of one embodiment of the present invention is used in applications such as artificial leather, synthetic leather, water-based polyurethane, adhesives, elastic fibers, medical materials, flooring materials, paints, coating agents, etc., it has a good balance of solvent resistance, flexibility, and mechanical strength, and therefore can impart good properties such as high durability in areas that come into contact with human skin or where cosmetic agents or disinfectant alcohol are used, sufficient flexibility, and resistance to physical impact, etc. Furthermore, it can be suitably used in automotive applications such as automotive parts that require heat resistance, and outdoor applications that require weather resistance.

[0155] The polyurethane of the present invention can be used for thermosetting elastomers and cast polyurethane elastomers. Specific applications include rolls such as rolling mill rolls, papermaking rolls, office equipment rolls, and pretensioning rolls; solid tires and casters for forklifts, automobile new trams, dollies, and transport vehicles; and industrial products such as conveyor belt idlers, guide rolls, pulleys, steel pipe linings, rubber screens for ore, gears, connection rings, liners, pump impellers, cyclone cones, and cyclone liners. It can also be used for office automation equipment belts, paper feed rolls, cleaning blades for copying machines, snow plows, toothed belts, and surf rollers.

[0156] The polyurethane of the present invention is also applicable to applications as a thermoplastic elastomer. For example, it can be used in tubes and hoses, spiral tubes, fire hoses, etc., in pneumatic equipment used in the food and medical fields, painting equipment, analytical equipment, physicochemical equipment, metering pumps, water treatment equipment, industrial robots, etc. In addition, it can be used as belts such as round belts, V-belts, and flat belts in various power transmission mechanisms, spinning machines, packaging equipment, printing machines, etc. In addition, it can be used in footwear heel tops and soles, equipment parts such as couplings, packing, ball joints, bushings, gears, and rolls, sports goods, leisure goods, watch straps, etc. Furthermore, it can be used in automotive parts such as oil stoppers, gearboxes, spacers, chassis parts, interior parts, and tire chain replacements. It can also be used in films such as keyboard films and automotive films, curl cords, cable sheaths, bellows, conveyor belts, flexible containers, binders, synthetic leather, dipping products, adhesives, etc.

[0157] The polyurethane of the present invention can also be used as a solvent-based two-component paint and can be applied to wood products such as musical instruments, Buddhist altars, furniture, decorative plywood, sporting goods, etc. It can also be used as a tar epoxy urethane for automobile repair. The polyurethane of the present invention can be used as a component of moisture-curing one-component paints, blocked isocyanate-based solvent paints, alkyd resin paints, urethane-modified synthetic resin paints, ultraviolet-curing paints, water-based urethane paints, etc., and can be applied, for example, to paints for plastic bumpers, strippable paints, coating agents for magnetic tapes, overprint varnishes for floor tiles, flooring materials, paper, wood grain printed films, etc., wood varnishes, coil coats for high processing, optical fiber protective coatings, solder resists, top coats for metal printing, base coats for vapor deposition, white coats for food cans, etc.

[0158] The polyurethane of the present invention can also be used as a pressure sensitive adhesive or adhesive for food packaging, shoes, footwear, magnetic tape binders, decorative paper, wood, structural members, etc., and can also be used as a component of low temperature adhesives and hot melts. The polyurethane of the present invention can be used as a binder in magnetic recording media, inks, castings, fired bricks, graft materials, microcapsules, granular fertilizers, granular agricultural chemicals, polymer cement mortar, resin mortar, rubber chip binders, recycled foam, glass fiber sizing, and the like.

[0159] The polyurethane of the present invention can be used as a component of a fiber processing agent for shrink-proofing, wrinkle-proofing, water-repellent finishing, etc. When the polyurethane of the present invention is used as an elastic fiber, the fiberization method can be any method that allows spinning. For example, a melt spinning method can be used in which the polyurethane is first pelletized, melted, and then spun directly through a spinneret. When elastic fiber is obtained from the polyurethane of the present invention by melt spinning, the spinning temperature is preferably 250°C or less, more preferably 200°C or more and 235°C or less.

[0160] The polyurethane elastic fiber can be used as a bare yarn as it is, or can be covered with other fibers to be used as a covered yarn. Examples of other fibers include conventionally known fibers such as polyamide fibers, wool, cotton, and polyester fibers, but polyester fibers are preferred for use in the present invention. The elastic fiber using the polyurethane of the present invention may also contain a dye-disperse dye.

[0161] The polyurethane of the present invention can be used as a sealant / caulking for concrete walls, induction joints, around sashes, wall-type PC (Precast Concrete) joints, ALC (Autoclaved Lightweight Concrete) joints, board joints, composite glass sealant, heat-insulating sash sealant, automotive sealant, etc.

[0162] The polyurethane of the present invention can be used as a medical material, and can be used as a blood-compatible material for tubes, catheters, artificial hearts, artificial blood vessels, artificial valves, etc., and as a disposable material for catheters, tubes, bags, surgical gloves, artificial kidney potting materials, etc. By modifying the terminals, the polyurethane of the present invention can be used as a raw material for UV-curable coating materials, electron beam-curable coating materials, photosensitive resin compositions for flexographic printing plates, photocurable optical fiber coating compositions, etc.

[0163] <Urethane (meth)acrylate oligomer> A urethane(meth)acrylate oligomer can be produced by addition reacting a polyisocyanate with a hydroxyalkyl(meth)acrylate using the polycarbonate diol of the present invention. When other raw material compounds such as a polyol and a chain extender are used in combination, the urethane(meth)acrylate oligomer can be produced by further addition reacting the polyisocyanate with these other raw material compounds.

[0164] In the present invention, when "(meth)acrylic" is used, such as (meth)acrylate or (meth)acrylic acid, it means acrylic and / or methacrylic. The ratio of the raw material compounds used in this step is substantially the same as or the same as the composition of the desired urethane (meth)acrylate oligomer. In the urethane (meth)acrylate oligomer, the amount of all isocyanate groups and the amount of all functional groups that react with isocyanate groups, such as hydroxyl groups and amino groups, are usually theoretically equimolar.

[0165] When producing a urethane (meth)acrylate oligomer, the amount of hydroxyalkyl (meth)acrylate used is typically 10 mol% or more, preferably 15 mol% or more, more preferably 25 mol% or more, and typically 70 mol% or less, preferably 50 mol% or less, based on the total amount of the hydroxyalkyl (meth)acrylate, the polycarbonate diol of the present invention, and other raw material compounds (polyols used as needed), and compounds containing functional groups reactive with isocyanates, such as chain extenders. The molecular weight of the resulting urethane (meth)acrylate oligomer can be controlled depending on this ratio. A high ratio of hydroxyalkyl (meth)acrylate tends to result in a smaller molecular weight of the urethane (meth)acrylate oligomer, while a low ratio tends to result in a larger molecular weight.

[0166] The amount of the polycarbonate diol of the present invention used is preferably 25 mol% or more, more preferably 50 mol% or more, and even more preferably 70 mol% or more, based on the total amount of the polycarbonate diol of the present invention and other polyols used. When the amount of the polycarbonate diol of the present invention used is equal to or more than the lower limit mentioned above, the elongation, hardness, weather resistance, and stain resistance of the obtained cured product tend to be good, which is preferable.

[0167] Furthermore, the amount of the polycarbonate diol of the present invention used relative to the total amount of the polycarbonate diol of the present invention and other polyols used is preferably 10% by weight or more, more preferably 30% by weight or more, even more preferably 50% by weight or more, and particularly preferably 70% by weight or more. When the amount of the polycarbonate diol of the present invention used is equal to or more than the lower limit mentioned above, the viscosity of the obtained composition decreases, improving workability, and the mechanical strength, hardness, and abrasion resistance of the obtained cured product tend to be improved, which is preferable.

[0168] Furthermore, when a chain extender is used, the amount of the polycarbonate diol of the present invention and the other polyol used 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, based on the total amount of the polycarbonate diol of the present invention, the other polyol, and the chain extender. If the amount exceeds the lower limit, the liquid stability tends to be improved, which is preferable.

[0169] During the production of urethane (meth)acrylate oligomers, a solvent can be used to adjust the viscosity. A single solvent may be used, or two or more solvents may be mixed together. Any known solvent can be used. Preferred solvents include toluene, xylene, ethyl acetate, butyl acetate, cyclohexanone, methyl ethyl ketone, and methyl isobutyl ketone. The solvent can usually be used in an amount of less than 300 parts by weight per 100 parts by weight of the solids in the reaction system.

[0170] During the production of a urethane (meth)acrylate oligomer, the total content of the urethane (meth)acrylate oligomer and its raw material compounds is preferably 20% by weight or more, more preferably 40% by weight or more, relative to the total amount of the reaction system. The upper limit of this total content is 100% by weight. When the total content of the urethane (meth)acrylate oligomer and its raw material compounds is 20% by weight or more, the reaction rate tends to be high, which is preferable, as it tends to improve production efficiency.

[0171] An addition reaction catalyst can be used when producing a urethane (meth)acrylate oligomer. Examples of this addition reaction catalyst include dibutyltin laurate, dibutyltin dioctoate, dioctyltin dilaurate, and dioctyltin dioctoate. The addition reaction catalyst may be used alone or in combination of two or more. Among these, dioctyltin dilaurate is preferred as the addition reaction catalyst from the viewpoints of environmental adaptability, catalytic activity, and storage stability.

[0172] The addition reaction catalyst is used in an amount of usually 1000 ppm by weight, preferably 500 ppm by weight, and usually 10 ppm by weight, preferably 30 ppm by weight, at the upper limit, based on the total content of the urethane (meth)acrylate oligomer produced and its raw material compounds.

[0173] Furthermore, when a (meth)acryloyl group is contained in the reaction system during the production of a urethane (meth)acrylate oligomer, a polymerization inhibitor can be used in combination. Examples of such polymerization inhibitors include phenols such as hydroquinone, methylhydroquinone, hydroquinone monoethyl ether, and dibutylhydroxytoluene, amines such as phenothiazine and diphenylamine, copper salts such as copper dibutyldithiocarbamate, manganese salts such as manganese acetate, nitro compounds, and nitroso compounds. One type of polymerization inhibitor may be used alone, or two or more types may be mixed and used. Of these, phenols are preferred as the polymerization inhibitor.

[0174] The upper limit of the polymerization inhibitor is usually 3000 ppm by weight, preferably 1000 ppm by weight, and particularly preferably 500 ppm by weight, relative to the total content of the urethane (meth)acrylate oligomer produced and its raw material compounds, and the lower limit is usually 50 ppm by weight, preferably 100 ppm by weight.

[0175] During the production of urethane (meth)acrylate oligomers, the reaction temperature is typically 20°C or higher, preferably 40°C or higher, and more preferably 60°C or higher. A reaction temperature of 20°C or higher is preferred because it increases the reaction rate and tends to improve production efficiency. Furthermore, the reaction temperature is typically 120°C or lower, preferably 100°C or lower. A reaction temperature of 120°C or lower is preferred because it reduces the occurrence of side reactions such as allophanate formation reactions. Furthermore, when a solvent is contained in the reaction system, the reaction temperature is preferably below the boiling point of the solvent, and when a (meth)acrylate is contained, it is preferably 70°C or lower to prevent reaction of the (meth)acryloyl group. The reaction time is typically about 5 to 20 hours.

[0176] The number-average molecular weight of the urethane (meth)acrylate oligomer thus obtained is preferably 500 or more, particularly preferably 1,000 or more, and 10,000 or less, particularly preferably 5,000 or less, and especially preferably 3,000 or less. When the number-average molecular weight of the urethane (meth)acrylate oligomer is above the above-mentioned lower limit, the resulting cured film tends to have good three-dimensional processing suitability and a good balance between three-dimensional processing suitability and contamination resistance, which is preferred. When the number-average molecular weight of the urethane (meth)acrylate oligomer is below the above-mentioned upper limit, the cured film obtained from the composition tends to have good contamination resistance and a good balance between three-dimensional processing suitability and contamination resistance, which is preferred. This is presumably because three-dimensional processing suitability and contamination resistance depend on the distance between crosslinking points in the network structure; a longer distance results in a flexible and extensible structure, resulting in excellent three-dimensional processing suitability, while a shorter distance results in a stronger network structure, resulting in excellent contamination resistance.

[0177] <Polyester elastomer> The polycarbonate diol of the present invention can be used as a polyester elastomer. A polyester elastomer is a copolymer composed of a hard segment primarily made of an aromatic polyester and a soft segment primarily made of an aliphatic polyether, aliphatic polyester, or aliphatic polycarbonate. When the polycarbonate diol of the present invention is used as a soft segment component, physical properties such as heat resistance and water resistance are superior to those when aliphatic polyethers or aliphatic polyesters are used. Furthermore, compared to known polycarbonate diols, the polycarbonate polyester elastomer has melt flowability, i.e., a melt flow rate suitable for blow molding and extrusion molding, and an excellent balance of mechanical strength and other physical properties. This makes it suitable for various molding materials, including fibers, films, and sheets, such as elastic yarns, boots, gears, tubes, and packings. Specifically, it can be effectively applied to applications requiring heat resistance and durability, such as joint boots for automobiles and home appliance parts, and wire coating materials.

[0178] <Active energy radiation-curable polymer composition> The active-energy radiation-curable polymer composition containing the above-mentioned urethane (meth)acrylate oligomer (hereinafter, sometimes simply referred to as "active-energy radiation-curable polymer composition") will be described. The active-energy radiation-curable polymer composition preferably has a calculated network crosslinking molecular weight of 500 to 10,000.

[0179] In this specification, the calculated network inter-crosslinking molecular weight of a composition represents the average value of the molecular weight between active energy ray reactive groups (hereinafter sometimes referred to as "crosslinking points") that form a network structure in the entire composition. This calculated network inter-crosslinking molecular weight correlates with the network area when the network structure is formed, and the larger the calculated network inter-crosslinking molecular weight, the lower the crosslinking density. In the reaction caused by active energy ray curing, when a compound having only one active energy ray reactive group (hereinafter sometimes referred to as "monofunctional compound") reacts, a linear polymer is formed, while when a compound having two or more active energy ray reactive groups (hereinafter sometimes referred to as "polyfunctional compound") reacts, a network structure is formed.

[0180] Therefore, here, the active energy ray reactive groups of the polyfunctional compound are crosslinking points, and the calculation of the calculated network molecular weight between crosslinking points is centered on the polyfunctional compound having crosslinking points, and the monofunctional compound is treated as having the effect of extending the molecular weight between crosslinking points of the polyfunctional compound, and the calculated network molecular weight between crosslinking points is calculated.Furthermore, the calculation of the calculated network molecular weight between crosslinking points is performed under the assumption that all active energy ray reactive groups have the same reactivity and all active energy ray reactive groups react by irradiation with active energy rays.

[0181] In a single-component polyfunctional compound composition in which only one type of polyfunctional compound reacts, the calculated molecular weight between crosslinking points is twice the average molecular weight per active energy ray reactive group possessed by the polyfunctional compound. For example, for a bifunctional compound with a molecular weight of 1,000, it is (1000 / 2) x 2 = 1000, and for a trifunctional compound with a molecular weight of 300, it is (300 / 3) x 2 = 200. In a polyfunctional compound mixed composition in which multiple polyfunctional compounds react, the calculated network inter-crosslinking molecular weight of the composition is the average of the calculated network inter-crosslinking molecular weights of each of the single compounds relative to the total number of active energy ray reactive groups contained in the composition. For example, in a composition consisting of a mixture of 4 moles of a bifunctional compound with a molecular weight of 1,000 and 4 moles of a trifunctional compound with a molecular weight of 300, the total number of active energy ray reactive groups in the composition is 2 × 4 + 3 × 4 = 20, and the calculated network inter-crosslinking molecular weight of the composition is {(1000 / 2) × 8 + (300 / 3) × 12} × 2 / 20 = 520.

[0182] When a composition contains a monofunctional compound, assuming that the monofunctional compound reacts with the active energy ray reactive groups (i.e., crosslinking points) of the polyfunctional compound in equimolar amounts and is located at the center of the molecular chain formed by the monofunctional compound linking to the crosslinking points, the elongation of the molecular chain due to the monofunctional compound at one crosslinking point is half the value obtained by dividing the total molecular weight of the monofunctional compound by the total number of active energy ray reactive groups of the polyfunctional compounds in the composition. Here, since the calculated network molecular weight between crosslinking points is considered to be twice the average molecular weight per crosslinking point, the elongation due to the monofunctional compound relative to the calculated network molecular weight between crosslinking points calculated for the polyfunctional compound is the value obtained by dividing the total molecular weight of the monofunctional compound by the total number of active energy ray reactive groups of the polyfunctional compounds in the composition.

[0183] For example, in a composition consisting of a mixture of 40 moles of a monofunctional compound with a molecular weight of 100 and 4 moles of a bifunctional compound with a molecular weight of 1,000, the number of active energy ray reactive groups in the polyfunctional compound is 2 × 4 = 8, so the extension due to the monofunctional compound in the calculated network inter-crosslinking molecular weight is 100 × 40 / 8 = 500. In other words, the calculated network inter-crosslinking molecular weight of the composition is 1,000 + 500 = 1,500.

[0184] From the above, the molecular weight W A Monofunctional compound M A moles and molecular weight W B f B Functional compound M B moles and molecular weight W C f C Functional compound M CIn the case of a mixture of 100% by weight and 100% by weight of terpolymer, the calculated network crosslinking molecular weight of the composition can be expressed by the following formula:

[0185]

number

[0186] The calculated network inter-crosslinking molecular weight of the active-energy radiation-curable polymer composition calculated in this manner is preferably 500 or more, more preferably 800 or more, and even more preferably 1,000 or more, and is preferably 10,000 or less, more preferably 8,000 or less, even more preferably 6,000 or less, still more preferably 4,000 or less, and particularly preferably 3,000 or less.

[0187] When the calculated network inter-crosslinking molecular weight is 10,000 or less, the cured film obtained from the composition has good stain resistance and tends to have an excellent balance between three-dimensional processing suitability and stain resistance, which is preferable. Also, when the calculated network inter-crosslinking molecular weight is 500 or more, the cured film obtained has good three-dimensional processing suitability and tends to have an excellent balance between three-dimensional processing suitability and stain resistance, which is preferable. This is presumably because the three-dimensional processing suitability and stain resistance depend on the distance between crosslinking points in the network structure, and when this distance is long, the structure becomes flexible and easy to stretch, resulting in excellent three-dimensional processing suitability, while when this distance is short, the network structure becomes strong and excellent in stain resistance.

[0188] The active energy radiation-curable polymer composition may further contain other components in addition to the urethane (meth)acrylate oligomer. Examples of such other components include an active energy radiation-reactive monomer, an active energy radiation-curable oligomer, a polymerization initiator, a photosensitizer, an additive, and a solvent.

[0189] In the active energy radiation-curable polymer composition, the content of the urethane (meth)acrylate oligomer is preferably 40% by weight or more, more preferably 60% by weight or more, based on the total amount of the active energy radiation-reactive components including the urethane (meth)acrylate oligomer. The upper limit of this content is 100% by weight. When the content of the urethane (meth)acrylate oligomer is 40% by weight or more, the curability is good, and the mechanical strength of the cured product does not become too high, and three-dimensional processing suitability tends to be improved, which is preferable.

[0190] In addition, in the active-energy radiation-curable polymer composition, a high content of the urethane (meth)acrylate oligomer is preferable in terms of elongation and film-forming properties, while a low content is preferable in terms of reducing viscosity. From this perspective, the content of the urethane (meth)acrylate oligomer is preferably 50% by weight or more, more preferably 70% by weight or more, based on the total amount of all components including the active-energy radiation-reactive component and other components. The upper limit of the content of the urethane (meth)acrylate oligomer is 100% by weight, and the content is preferably less than this.

[0191] In addition, in the active-energy radiation-curable polymer composition, the total content of the active-energy radiation-reactive components including the urethane (meth)acrylate oligomer is preferably 60% by weight or more, more preferably 80% by weight or more, even more preferably 90% by weight or more, and particularly preferably 95% by weight or more, based on the total amount of the composition, in terms of excellent curing speed and surface curing properties as a composition, no tack remaining, etc. The upper limit of this content is 100% by weight.

[0192] As the active energy ray reactive monomer, any known active energy ray reactive monomer can be used. These active energy ray reactive monomers are used for the purpose of adjusting the hydrophilicity or hydrophobicity of the urethane (meth)acrylate oligomer, and the physical properties of the cured product, such as hardness and elongation, when the resulting composition is cured. The active energy ray reactive monomers may be used alone or in combination of two or more.

[0193] Examples of such active energy ray reactive monomers include vinyl ethers, (meth)acrylamides, and (meth)acrylates. Specific examples of the vinyl monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, and divinylbenzene; vinyl ester monomers such as vinyl acetate, vinyl butyrate, N-vinylformamide, N-vinylacetamide, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, and divinyl adipate; vinyl ethers such as ethyl vinyl ether and phenyl vinyl ether; allyl compounds such as diallyl phthalate, trimethylolpropane diallyl ether, and allyl glycidyl ether; (meth)acrylamide, N,N-dimethylacrylamide, N,(Meth)acrylamides such as N-dimethyl methacrylamide, N-methylol (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, Nt-butyl (meth)acrylamide, (meth)acryloylmorpholine, and methylene bis(meth)acrylamide; (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, and t-butyl (meth)acrylate; Butyl, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, morpholyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, benzyl (meth)acrylate Monofunctional (meth)acrylates such as cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, tricyclodecane (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, allyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, isobornyl (meth)acrylate, and phenyl (meth)acrylate; and ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and the like. , triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate (n=5-14), propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate (n=5-14), 1,3-butylene glycol di(meth)acrylate, 1,4-Butanediol, polybutylene glycol di(meth)acrylate (n=3-16), poly(1-methylbutylene glycol) di(meth)acrylate (n=5-20), 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, dicyclopentanediol di(meth)acrylate, tricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane Polyfunctional (meth)acrylates such as pantothenic acid trioxyethyl (meth)acrylate, trimethylolpropane trioxypropyl (meth)acrylate, trimethylolpropane polyoxyethyl (meth)acrylate, trimethylolpropane polyoxypropyl (meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, ethylene oxide-added bisphenol A di(meth)acrylate, ethylene oxide-added bisphenol F di(meth)acrylate, propylene oxide-added bisphenol A di(meth)acrylate, propylene oxide-added bisphenol F di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, bisphenol A epoxy di(meth)acrylate, and bisphenol F epoxy di(meth)acrylate are exemplified.

[0194] Among these, in particular for applications requiring coatability, monofunctional (meth)acrylates having a ring structure in the molecule, such as (meth)acryloylmorpholine, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, tricyclodecane (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, and (meth)acrylamide, are preferred. On the other hand, for applications requiring mechanical strength of the resulting cured product, polyfunctional (meth)acrylates such as 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate are preferred.

[0195] In the active-energy radiation-curable polymer composition, the content of the active-energy radiation-reactive monomer is preferably 50% by weight or less, more preferably 30% by weight or less, even more preferably 20% by weight or less, and particularly preferably 10% by weight or less, based on the total amount of the composition, from the viewpoint of adjusting the viscosity of the composition and adjusting the physical properties such as hardness and elongation of the resulting cured product.

[0196] The active energy ray-curable oligomer may be used alone or in combination of two or more thereof. Examples of the active energy ray-curable oligomer include epoxy (meth)acrylate oligomers and acrylic (meth)acrylate oligomers. In the active-energy radiation-curable polymer composition, the content of the active-energy radiation-reactive oligomer is preferably 50% by weight or less, more preferably 30% by weight or less, even more preferably 20% by weight or less, and particularly preferably 10% by weight or less, based on the total amount of the composition, from the viewpoint of adjusting the physical properties such as hardness and elongation of the obtained cured product.

[0197] The polymerization initiator is mainly used for the purpose of improving the initiation efficiency of a polymerization reaction that proceeds by irradiation with active energy rays such as ultraviolet rays and electron beams. A photoradical polymerization initiator, which is a compound that has the property of generating radicals when exposed to light, is generally used as the polymerization initiator, and any known photoradical polymerization initiator can be used. One type of polymerization initiator may be used alone, or two or more types may be used in combination. Furthermore, a photoradical polymerization initiator and a photosensitizer may be used in combination.

[0198] Examples of the photoradical polymerization initiator include benzophenone, 2,4,6-trimethylbenzophenone, 4,4-bis(diethylamino)benzophenone, 4-phenylbenzophenone, methyl orthobenzoylbenzoate, thioxanthone, diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone, 2-ethylanthraquinone, t-butylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl. ether, benzoin isobutyl ether, methyl benzoyl formate, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl]-2-methyl-propan-1-one.

[0199] Among these, benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl]-2-methyl-propan-1-one are preferred, and 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl]-2-methyl-propan-1-one are more preferred, in terms of their fast curing rate and ability to sufficiently increase crosslink density.

[0200] In addition, the active energy radiation curable polymer composition may contain a radical polymerizable group and an epoxy group or the like. When a compound having a cationic polymerizable group is contained, the above-mentioned photoradiation A cationic photopolymerization initiator may be included together with the cationic photopolymerization initiator. Any known agent can be used.

[0201] The content of these polymerization initiators in the active-energy radiation-curable polymer composition is preferably 10 parts by weight or less, and more preferably 5 parts by weight or less, relative to 100 parts by weight of the total of the active-energy radiation-reactive components. When the content of the polymerization initiator is 10 parts by weight or less, a decrease in mechanical strength due to initiator decomposition products is unlikely to occur, which is preferable.

[0202] The photosensitizer can be used for the same purpose as the polymerization initiator. The photosensitizer may be used alone or in combination of two or more. Any known photosensitizer can be used as long as the effects of the present invention can be obtained. Examples of such photosensitizers include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, and 4-dimethylaminoacetophenone.

[0203] In the active-energy radiation-curable polymer composition, the content of the photosensitizer is preferably 10 parts by weight or less, and more preferably 5 parts by weight or less, relative to 100 parts by weight of the total of the active-energy radiation-reactive components. When the content of the photosensitizer is 10 parts by weight or less, a decrease in mechanical strength due to a decrease in crosslink density is unlikely to occur, which is preferable.

[0204] The additives are optional, and various materials added to compositions used for similar purposes can be used as additives. The additives may be used alone or in combination of two or more. Examples of such additives include fillers such as glass fiber, glass beads, silica, alumina, calcium carbonate, mica, zinc oxide, titanium oxide, talc, kaolin, metal oxides, metal fibers, iron, lead, and metal powder; carbon materials such as carbon fiber, carbon black, graphite, carbon nanotubes, and fullerenes such as C60 (hereinafter, fillers and carbon materials may be collectively referred to as "inorganic components"); antioxidants, heat stabilizers, ultraviolet absorbers, Modifiers such as HALS (hindered amine light stabilizers), anti-fingerprint agents, surface hydrophilizing agents, antistatic agents, slipping agents, plasticizers, release agents, antifoaming agents, leveling agents, anti-settling agents, surfactants, thixotropy-imparting agents, lubricants, flame retardants, flame retardant assistants, polymerization inhibitors, fillers, and silane coupling agents; colorants such as pigments, dyes, and hue adjusters; and curing agents, catalysts, and curing accelerators necessary for the synthesis of monomers and / or oligomers thereof, or inorganic components.

[0205] In the active-energy radiation-curable polymer composition, the content of the additive is preferably 10 parts by weight or less, and more preferably 5 parts by weight or less, relative to 100 parts by weight of the total of the active-energy radiation-reactive components. When the content of the additive is 10 parts by weight or less, a decrease in mechanical strength due to a decrease in crosslink density is unlikely to occur, which is preferable.

[0206] The solvent can be used, for example, for the purpose of adjusting the viscosity of the active-energy radiation-curable polymer composition depending on the coating method for forming a coating film of the active-energy radiation-curable polymer composition. One solvent may be used alone, or two or more solvents may be mixed and used. Any known solvent can be used as long as the effects of the present invention can be obtained. Preferred solvents include toluene, xylene, ethyl acetate, butyl acetate, isopropanol, isobutanol, cyclohexanone, methyl ethyl ketone, and methyl isobutyl ketone. The solvent can usually be used in an amount of less than 200 parts by weight per 100 parts by weight of the solids content of the active-energy radiation-curable polymer composition.

[0207] The method for incorporating optional components such as the additives into the active-energy radiation-curable polymer composition is not particularly limited, and examples thereof include conventionally known mixing and dispersing methods. In order to more reliably disperse the optional components, it is preferable to perform a dispersion treatment using a disperser. Specific examples include methods using a two-roll mill, a three-roll mill, a bead mill, a ball mill, a sand mill, a pebble mill, a tron mill, a sand grinder, a segmented barrier triter, a planetary mixer, a high-speed impeller disperser, a high-speed stone mill, a high-speed impact mill, a kneader, a homogenizer, an ultrasonic disperser, etc.

[0208] The viscosity of the active-energy radiation-curable polymer composition can be adjusted appropriately depending on the application and mode of use of the composition, but from the viewpoints of handleability, coatability, moldability, three-dimensional formability, etc., the viscosity at 25°C as measured by an E-type viscometer (rotor 1°34' x R24) is preferably 10 mPa·s or more, more preferably 100 mPa·s or more, and is preferably 100,000 mPa·s or less, more preferably 50,000 mPa·s or less. The viscosity of the active-energy radiation-curable polymer composition can be adjusted, for example, by the content of the urethane (meth)acrylate oligomer described above, the types of the optional components described above, and the blending ratios thereof.

[0209] As a method for applying the active-energy radiation-curable polymer composition, known methods such as a bar coater method, an applicator method, a curtain flow coater method, a roll coater method, a spray method, a gravure coater method, a comma coater method, a reverse roll coater method, a lip coater method, a die coater method, a slot die coater method, an air knife coater method, and a dip coater method can be applied, and among these, the bar coater method and the gravure coater method are preferred.

[0210] The active energy radiation-curable polymer composition can be formed into a cured film by irradiating it with active energy rays. The active energy rays used to cure the composition may include infrared rays, visible light, ultraviolet rays, X-rays, electron beams, α-rays, β-rays, γ-rays, etc. From the viewpoint of equipment cost and productivity, it is preferable to use electron beams or ultraviolet rays, and suitable light sources include electron beam irradiation devices, ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low pressure mercury lamps, metal halide lamps, Ar lasers, He—Cd lasers, solid state lasers, xenon lamps, high frequency induction mercury lamps, sunlight, etc.

[0211] The dose of active energy rays can be appropriately selected depending on the type of active energy rays. For example, when curing is performed by electron beam irradiation, the dose is preferably 1 to 10 Mrad. In addition, when curing by ultraviolet irradiation, the dose is preferably 50 to 1,000 mJ / cm. 2 The atmosphere during curing may be air or an inert gas such as nitrogen or argon. Alternatively, irradiation may be carried out in a sealed space between the film or glass and the metal mold.

[0212] The thickness of the cured film is determined appropriately depending on the intended use, but the lower limit is preferably 1 μm, more preferably 3 μm, and particularly preferably 5 μm. The upper limit is preferably 200 μm, more preferably 100 μm, and particularly preferably 50 μm. A film thickness of 1 μm or more results in good design and functionality after three-dimensional processing, while a film thickness of 200 μm or less is preferable because it provides good internal curing properties and three-dimensional processing suitability. For industrial use, the lower limit of the film thickness of the cured film is preferably 1 μm, and the upper limit is preferably 100 μm, more preferably 50 μm, particularly preferably 20 μm, and most preferably 10 μm.

[0213] A laminate having a layer made of the cured film on a substrate can be obtained. This laminate is not particularly limited as long as it has a layer made of the cured film, and layers other than the substrate and the cured film may be present between the substrate and the cured film, or may be present on the outside thereof. In addition, the laminate may have multiple layers of substrates and cured films.

[0214] As a method for obtaining a laminate having a plurality of cured films, known methods such as a method of laminating all layers in an uncured state and then curing them with active energy rays, a method of curing or semi-curing a lower layer with active energy rays and then coating an upper layer and curing it again with active energy rays, and a method of coating each layer on a release film or a base film and then laminating the layers together in an uncured or semi-cured state are applicable, but from the viewpoint of improving adhesion between layers, a method of laminating layers in an uncured state and then curing them with active energy rays is preferred. As a method for laminating layers in an uncured state, known methods such as sequential coating in which a lower layer is coated and then an upper layer is coated in layers, and simultaneous multilayer coating in which two or more layers are coated in layers simultaneously from multiple slits can be applied, but are not limited to these.

[0215] Examples of the substrate include articles of various shapes, such as plates made of polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyolefins such as polypropylene and polyethylene, various plastics such as nylon, polycarbonate, and (meth)acrylic resin, and glass or metal.

[0216] The cured film can be made into a film that has excellent stain resistance and hardness against common household stains such as ink and ethanol, and laminates using the cured film as a coating on various substrates can be made to have excellent design properties and surface protection properties.

[0217] Furthermore, when the calculated network molecular weight between crosslinking points is taken into consideration, the active-energy radiation-curable polymer composition can provide a cured film that simultaneously has flexibility capable of following deformation during three-dimensional processing, elongation at break, mechanical strength, contamination resistance, and hardness. Furthermore, it is expected that the active-energy radiation-curable polymer composition will enable the easy production of a thin-film resin sheet by single-layer coating.

[0218] The breaking elongation of the cured film is measured by cutting the cured film into 10 mm widths and conducting a tensile test using a Tensilon tensile tester (Tensilon UTM-III-100, manufactured by Orientec Co., Ltd.) at a temperature of 23°C, a tensile speed of 50 mm / min, and a chuck distance of 50 mm. The breaking elongation is preferably 50% or more, more preferably 75% or more, even more preferably 100% or more, and particularly preferably 120% or more.

[0219] The above-mentioned cured films and laminates can be used as paint replacement films and can be effectively applied to, for example, interior and exterior building materials, various components of automobiles, home appliances, and the like. [Example]

[0220] The present invention will be explained in more detail below by way of examples and comparative examples, but the present invention is not limited to these examples as long as it does not depart from the gist of the invention.

[0221] In the following, the evaluation methods for each physical property value are as follows.

[0222] [Evaluation method: dihydroxy compounds] <Acid value> The acid value of the dihydroxy compound was measured in accordance with JIS K1557-5 (2007).

[0223] [Evaluation method: Polycarbonate diol] <Number average molecular weight, quantification of phenoxy groups, and calculation of hydroxyl end group ratio> Polycarbonate diol was dissolved in CDCl3 and measured at 400 MHz. 1 H-NMR (AL-400 manufactured by JEOL Ltd.) was measured, and the phenoxy group was identified from the signal position of each component. The content of phenoxy terminals and number average molecular weight were calculated from the integrated value. The detection limit was 1000 ppm by weight as the phenoxy terminal content relative to the total weight of the sample. The hydroxyl terminal ratio was calculated as follows. Hydroxy end rate (%) = {(total number of terminals = 2) - impurity (phenoxy) terminal} / (total number of terminals = 2) × 100

[0224] <Hydroxyl value> The hydroxyl value of the polycarbonate diol was measured by automatic titration using an acetylation reagent in accordance with JIS K1557-1 (2007).

[0225] <Molecular weight distribution> The weight average molecular weight (Mw) and number average molecular weight (Mn) of polycarbonate diol in terms of polystyrene were determined by GPC measurement under the following conditions. The molecular weight distribution (Mw / Mn) was calculated. Equipment: Tosoh HLC-8320 Column: TSKgel superHZM-N (6.0mm I.D. x 15cm L x 4) Reference column: superHM-H (4.6mm I.D. x 3.5cm L x 1) Eluent: THF (tetrahydrofuran) Flow rate: 0.6mL / min Column temperature: 40℃ RI detector: RI (built-in in the device HLC-8320)

[0226] <Remaining amount of dihydroxy compounds> A solution of 250 mg of monochlorobenzene added to 500 mL of N-methylpyrrolidone was used as the internal standard solution. 0.50 g of polycarbonate diol was precisely weighed and dissolved in 5 mL of the above internal standard solution weighed with a volumetric pipette. The obtained solution was analyzed by gas chromatography (GC) under the following analytical conditions. The concentration of the dihydroxy compound was calculated in weight percent from the area ratio obtained by GC after preparing a calibration curve in advance using known dihydroxy compounds as standard substances. (Analysis conditions) Apparatus: Agilent 6850 (Agilent Technologies) Column: Agilent J&W GC column DB-WAX Inner diameter 0.25mm, length 60m, film thickness 0.25mm Detector: Flame ionization detector (FID) Temperature program: 150℃ → 190℃ (5 minutes) 190℃ → 245℃ (40 minutes)

[0227] <Hazen color number> According to JIS K0071-1 (1998), the Hazen color value was measured by comparing polycarbonate diol with a standard solution placed in a colorimetric tube. The reagent used was a chromaticity standard solution 1000 degrees (1 mg Pt / mL) (manufactured by Kishida Chemical Co., Ltd.).

[0228] [Evaluation method: Polyurethane] <Molecular weight> Polyurethane was dissolved in dimethylacetamide to a concentration of 0.14 wt%. The dimethylacetamide solution was injected into a GPC system (Tosoh Corporation, product name "HLC-8220" (column: 2 Tskgel GMH-XL columns)) to measure the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polyurethane in terms of standard polystyrene, and the molecular weight distribution (Mw / Mn) was calculated.

[0229] <Tensile test> The polyurethane solution was applied to a fluororesin sheet (Fluorine Tape Nitoflon 900, 0.1 mm thick, manufactured by Nitto Denko Corporation) using a 9.5 mil applicator and dried at 60°C for 1 hour, followed by 0.5 hours at 100°C. The film was then dried under vacuum at 100°C for 0.5 hours and at 80°C for 15 hours, after which it was left to stand at 23°C and 55% RH for at least 12 hours. 10 mm x 70 mm test pieces were cut from the resulting polyurethane film. Tensilon UTM-III-100 tensile testing was performed on these test pieces in accordance with JIS K6301 (2010) using a tensile tester (manufactured by Orientec Co., Ltd.) at a chuck distance of 50 mm, a pulling rate of 500 mm / min, a temperature of 23°C, and a relative humidity of 55%. The strength and elongation at break were measured. The greater the elongation at break, the more flexible the film.

[0230] <Heat and humidity resistance test> A 10 mm x 70 mm test piece was cut from the polyurethane film. This test piece was left to stand for 28 days in a thermo-hygrostat set at a temperature of 70°C and a relative humidity of 95%. After standing, the weight average molecular weight (Mw) of the test piece was measured using the method described above, and the ratio (molecular weight retention) to the weight average molecular weight (Mw) before the test was calculated. A higher molecular weight retention indicates higher moist heat resistance.

[0231] [Production and Evaluation of Polycarbonate Diol] [Example 1] A 5L glass separable flask equipped with a stirrer, distillate trap, and pressure regulator was charged with 1437.8g of 1,10-decanediol (1,10DD) with an acid value of 0.1mgKOH / g, 1562.2g of diphenyl carbonate, and 4.2mL of magnesium acetate tetrahydrate aqueous solution (concentration: 8.4g / L, magnesium acetate tetrahydrate: 35mg), followed by nitrogen gas replacement. With stirring, the internal temperature was raised to 160°C, and the contents were heated and dissolved. The pressure was then reduced to 24kPa over 2 minutes, and the reaction was allowed to proceed for 90 minutes while removing phenol from the system. The pressure was then reduced to 9.3kPa over 90 minutes, and further reduced to 0.7kPa over 30 minutes, and the reaction was continued. The temperature was then raised to 170°C, and the reaction was allowed to proceed for 60 minutes while removing phenol and unreacted diol from the system, yielding a polycarbonate diol-containing composition. Thereafter, 1.6 mL of a 0.85 wt % aqueous phosphoric acid solution was added to deactivate the catalyst, thereby obtaining a polycarbonate diol-containing composition.

[0232] The obtained polycarbonate diol-containing composition was sent to a thin-film distillation apparatus at a flow rate of about 20 g / min, and thin-film distillation was carried out (temperature: 180°C, pressure: 53 to 67 Pa). The thin-film distillation apparatus had a diameter of 50 mm, a height of 200 mm, and an area of 0.0314 m. 2 The molecular distillation apparatus used was a special model MS-300 manufactured by Shibata Scientific Co., Ltd., equipped with an internal condenser and a jacket. The polycarbonate diol produced in Example 1 is referred to as "PCD1." The evaluation results of the physical properties of PCD1 are shown in Table 1.

[0233] [Example 2] A polycarbonate diol was obtained by carrying out a reaction in the same manner as in Example 1, except that 1,10-decanediol (1,10DD) with an acid value of 0.4 mg KOH / g was used. The polycarbonate diol produced in Example 2 is referred to as "PCD2". Table 1 shows the evaluation results of the physical properties of PCD2.

[0234] [Example 3] A polycarbonate diol was obtained by carrying out a reaction in the same manner as in Example 1, except that 1,10-decanediol (1,10DD) with an acid value of 1.0 mgKOH / g was used. The polycarbonate diol produced in Example 3 is referred to as "PCD3". Table 1 shows the evaluation results of the physical properties of PCD3.

[0235] [Comparative Example 1] A polycarbonate diol was obtained by carrying out a reaction in the same manner as in Example 1, except that 1,10-decanediol (1,10DD) with an acid value of 17.00 mgKOH / g was used. The polycarbonate diol produced in Comparative Example 1 is referred to as "PCD4". Table 1 shows the evaluation results of the physical properties of PCD4.

[0236] Comparative Example 2 A polycarbonate diol was obtained by carrying out a reaction in the same manner as in Example 1, except that 1,10-decanediol (1,10DD) with an acid value of 0.02 mg KOH / g was used. The polycarbonate diol produced in Comparative Example 2 is referred to as "PCD5". Table 1 shows the evaluation results of the physical properties of PCD5.

[0237] [Table 1]

[0238] [Production and Evaluation of Polyurethane] [Example 4] Using PCD1 obtained in Example 1 as a raw material, polyurethane was produced by the following procedure. A separable flask equipped with a thermocouple, condenser, and stirrer was placed on a 60°C oil bath. 69.78 g of PCD1 (preheated to 80°C), 6.30 g of 1,4-butanediol, and 238.57 g of dehydrated N,N-dimethylformamide (DMF, manufactured by Wako Pure Chemical Industries, Ltd.) were added. 25.4 g of 4,4'-diphenylmethane diisocyanate (MDI) was then added. The flask was heated to 70°C over approximately 1 hour under a nitrogen atmosphere while stirring at 60 rpm. After the temperature reached 70°C, 0.019 g of Neostan U-830 (U-830, manufactured by Nitto Kasei Co., Ltd.) was added as a urethanization catalyst, and the mixture was stirred at 70°C for approximately 2 hours. Subsequently, 1.8 g of MDI was added in portions (total amount of MDI added was 27.2 g) to adjust the molecular weight, and a polyurethane with a molecular weight of approximately 156,000 was obtained. The evaluation results of the physical properties of this polyurethane are shown in Table 2.

[0239] Comparative Example 3 A polyurethane was obtained in the same manner as in Example 4, except that PCD4 obtained in Comparative Example 1 was used instead of PCD1 and the amounts were changed as shown in Table 2. The evaluation results of the physical properties of the obtained polyurethane are shown in Table 2.

[0240] [Table 2]

[0241] The following can be seen from Tables 1 and 2: Polycarbonate diol produced using 1,10-decanediol having an acid value within the range specified in the present invention has a good color tone, and when used as a raw material for polyurethane, it can provide polyurethane with excellent elongation and moist heat resistance. On the other hand, the polycarbonate diol described in Comparative Example 2, that is, the polycarbonate diol using 1,10-decanediol below the range specified in the present invention, has poor color tone. Furthermore, the polycarbonate diol described in Comparative Example 1, i.e., the polycarbonate diol synthesized using 1,10-decanediol whose acid value exceeds the range specified in the present invention, had a good color tone, but the synthesized polyurethane (Comparative Example 3) had poorer moist heat resistance compared to Example 4. Furthermore, the polyurethane of Comparative Example 3 had a wider molecular weight distribution than the polyurethane of Example 4, which may make it difficult to mold.

Claims

1. A method for producing a polycarbonate diol by subjecting a dihydroxy compound and a carbonate compound to a transesterification reaction in the presence of a transesterification catalyst, The dihydroxy compound is a compound represented by the following formula (1) (hereinafter referred to as “dihydroxy compound (1)”), The method for producing a polycarbonate diol is characterized in that the acid value of the dihydroxy compound (1) is 0.04 mg KOH / g or more and 10.00 mg KOH / g or less. HO-R １ -OH …(1) (In the above formula (1), R １ represents a divalent linear hydrocarbon group having 10 carbon atoms.

2. The method for producing a polycarbonate diol according to claim 1, wherein the dihydroxy compound (1) is 1,10-decanediol.

3. 3. The method for producing a polycarbonate diol according to claim 1, wherein the hydroxyl value of the obtained polycarbonate diol is 20 mg KOH / g or more and 250 mg KOH / g or less.

4. The method for producing a polycarbonate diol according to any one of claims 1 to 3, wherein the dihydroxy compound (1) remaining in the obtained polycarbonate diol is less than 0.5% by weight based on the weight of the polycarbonate diol.

5. The method for producing a polycarbonate diol according to any one of claims 1 to 4, wherein 98.5 mol % or more of the terminals of the obtained polycarbonate diol are hydroxyl terminals.

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