Polycarbonate diol and method for producing the same

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] This invention relates to a polycarbonate diol using a specific raw material dihydroxy compound and a method for producing the same. This invention also relates to a polyurethane using this polycarbonate diol. [Background technology]

[0002] Polycarbonate diols are used as raw materials for the soft segments of polyurethanes and thermoplastic elastomers, as well as in paints and adhesives. They are widely used as raw materials that provide high durability, overcoming the shortcomings of polyether polyols and polyester polyols in terms of weather resistance, heat resistance, hydrolysis resistance, and humid heat resistance.

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

[0004] For example, to improve flexibility, there are examples of using long-chain dihydroxy compounds such as 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol (Patent Documents 1, 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 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] Patent documents 1 and 2, and non-patent document 1 describe polycarbonate diols using long-chain dihydroxy compounds. However, the influence of impurity content in the dihydroxy compound on the resulting polycarbonate diol and the properties of polyurethane when this polycarbonate diol is used to produce polyurethane has not been investigated. As a result, problems remain regarding the color of the resulting polycarbonate diol and the properties of the polyurethane obtained using the polycarbonate diol, particularly flexibility (elongation) and heat and humidity resistance.

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

[0009] As a result of diligent research to solve the aforementioned problems, the present inventors have discovered that when producing polycarbonate diols using a specific long-chain dihydroxy compound as the dihydroxy compound, by using a long-chain dihydroxy compound with an acid value within a specific range, it is possible to provide a polycarbonate diol that has good color tone and, when used as a raw material compound (raw material monomer) for polyurethane, imparts excellent flexibility (elongation) and moisture and heat resistance to the resulting polyurethane, thus leading to the present invention. In other words, the gist of this invention is as follows:

[0010] [1] In 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 consists of 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 mgKOH / g or more and 15.00 mgKOH / g or less. A method for producing a polycarbonate diol, characterized by the above. 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 mgKOH / g or more and 250 mgKOH / 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 hydroxy terminals.

[0015] [6] In the polycarbonate diol obtained by subjecting a dihydroxy compound and a carbonate compound to a transesterification reaction in the presence of a transesterification catalyst, the dihydroxy compound consists of 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 mgKOH / g or more and 15.00 mgKOH / g or less. A polycarbonate diol characterized by the above. 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 mgKOH / g or more and 250 mgKOH / 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 remaining 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 hydroxy 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 according to

[11] .

[0022]

[13] A paint or coating agent using the polyurethane according to

[11] .

[0023]

[14]

[11] Elastic fiber made of polyurethane as described above.

[0024]

[15]

[11] A water-based polyurethane paint using the polyurethane described above.

[0025]

[16]

[11] Adhesives or adhesives using polyurethane as described in polyurethane.

[0026]

[17] Aqueous polyurethane dispersion using a polycarbonate diol as described in any of [6] to

[10] .

[0027]

[18] An active energy ray curable polymer composition using a polycarbonate diol as described in any of [6] to

[10] . [Effects of the Invention]

[0028] The polycarbonate diol provided by the present invention has good color tone and, when used as a raw material compound (raw material monomer) for polyurethane, can impart excellent flexibility (elongation) and moisture and 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 in elastic fibers, synthetic or artificial leather, paints, and high-performance elastomers, and are extremely useful in industry. [Modes for carrying out the invention]

[0029] The embodiments of the present invention will be described in detail below, but the present invention is not limited to the embodiments described below and can be implemented in various ways within the scope of its gist.

[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, 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. 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 and 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 (This indicates a divalent hydrocarbon group with 10 to 12 carbon atoms.)

[0031] Furthermore, as described later, the polycarbonate diol of the present invention may contain impurities such as those that do not have a hydroxyl terminus, or by-products such as raw material compounds (dihydroxy compound (1) and carbonate compounds) remaining after the transesterification reaction in the production process of polycarbonate diol, transesterification catalysts, and phenols produced during the reaction. From this perspective, it may also be referred to as a "polycarbonate diol composition" rather than a "polycarbonate diol." However, it is generally difficult for compounds obtained through chemical reactions to consist of 100% of the target substance, and it is common knowledge among those skilled in the art that the final product will contain some amount of impurities. Therefore, in this invention, a polycarbonate diol containing impurities such as residues after the reaction is referred to as "polycarbonate diol" rather than "polycarbonate diol composition." The amount of impurities, such as residual raw material compounds, in the polycarbonate diol of the present invention is determined by the value measured when the polycarbonate diol is subjected to the respective impurity content measurement method.

[0032] <Dihydroxy compound> The dihydroxy compound used as a 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 mgKOH / g or more and 15.00 mgKOH / 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. Specific examples of such dihydroxy compound (1) include the following. Terminal dihydroxy compounds of linear hydrocarbons such as 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol; Dihydroxy compounds having a branched chain 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, 1,10-dodecanediol, etc.;

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

[0035] These dihydroxy compounds (1) are produced by one or more reactions, including the reduction of carbonyl compounds such as aldehydes, ketones, carboxylic acids, and carboxylic acid derivatives, and the hydration reaction of alkenyl compounds. Among these, dihydroxy compounds produced by one or more reactions, including the reduction reaction of carboxylic acids or carboxylic acid derivatives, are preferred because it is easier to control the acid value within the range defined in the present invention, and the effect of the present invention in controlling the acid value is effectively exhibited. Examples of the carboxylic acid derivatives include ester compounds, amide compounds, acid anhydrides, acid halides, and nitrile compounds.

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

[0037] The acid value of the dihydroxy compound (1), which is a raw material for the polycarbonate diol of the present invention, has an upper limit of 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, and more preferably 0.08 mgKOH / g or more.

[0038] If the acid value of dihydroxy compound (1) exceeds the upper limit, the chemical resistance and heat and humidity resistance of the resulting polycarbonate diol urethane will decrease. On the other hand, if it is below the lower limit, the color tone and thermal stability of the resulting polycarbonate diol will deteriorate. Furthermore, if the acid value of dihydroxy compound (1) is below the lower limit, the cost of the dihydroxy compound (1) purification process will increase, making it economically disadvantageous.

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

[0040] To set the acid value of dihydroxy compound (1) within the above range, the conversion rate to dihydroxy compound (1) in the reduction reaction of the raw materials used to obtain dihydroxy compound (1), such as carboxylic acids or carboxylic acid derivatives, can be reduced, or the degree of purification of the dihydroxy compound (1) obtained by the above reaction can be reduced. Alternatively, before using dihydroxy compound (1) as a raw material in the method for producing polycarbonate diol of the present invention, an acidic compound that does not inhibit the transesterification reaction may be added to the dihydroxy compound (1) to adjust its acid value within the above range.

[0041] In addition, in the present invention, dihydroxy compounds other than dihydroxy compound (1) may be used as the raw material dihydroxy compound, as long as the objective of the present invention is not impaired. When using dihydroxy compounds other than dihydroxy compound (1), it is preferable that their proportion be 9 mol% or less, more preferably 5 mol% or less, particularly 2 mol% or less, and especially 1 mol% or less, of the total raw material dihydroxy compounds.

[0042] <Carbonate compounds> The carbonate compound used in the production of the polycarbonate diol of the present invention (hereinafter sometimes referred to as "carbonate diester") is not limited as long as the effects of the present invention are not lost, but examples include dialkyl carbonates, diaryl carbonates, or alkylene carbonates. Of these, diaryl carbonates have the advantage of allowing the reaction to proceed rapidly. However, on the other hand, when diaryl carbonates are used as raw materials, high-boiling-point phenols are produced as by-products. Since phenols are monofunctional compounds, they can act as polymerization inhibitors during polyurethane formation and are also irritating substances, so it is preferable to have a lower content of phenols in the polycarbonate diol.

[0043] Specific examples of dialkyl carbonates, diaryl carbonates, and alkylene carbonates of diester carbonates 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, dityl 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, neopentyl carbonate, etc., with ethylene carbonate being preferred.

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

[0048] Among these, diaryl carbonates are preferred because they are highly reactive and efficient for industrial production, and diphenyl carbonates are even more preferred because they are readily and inexpensively available as industrial raw materials.

[0049] <Ratio of raw material usage> In the production of the polycarbonate diol of the present invention, the amount of carbonate compound used is not particularly limited, but is usually expressed in molar ratio to 1 mole of the raw material dihydroxy compound, with a lower limit of preferably 0.35, more preferably 0.50, and even more preferably 0.60, and an upper limit of preferably 1.00, more preferably 0.98, and even more preferably 0.97. If the amount of carbonate compound used exceeds the above upper limit, the proportion of polycarbonate diols whose terminal groups are not hydroxyl groups may increase, or the molecular weight may not be within the predetermined range, and if it is below the above lower limit, polymerization may not proceed to the predetermined molecular weight.

[0050] <Transesterification catalyst> Any metal that is generally considered to have transesterification ability can be used as a transesterification catalyst (hereinafter sometimes simply referred to as "catalyst").

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

[0052] These metals can be used as elemental metals or as metal compounds such as hydroxides and salts. Examples of salts used 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; and acetylacetonate salts. Catalyst metals can also be used as alkoxides such as methoxides and ethoxides.

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

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

[0055] Specific examples of compounds using Group 1 metals of the periodic table as transesterification catalysts 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 phenyl phosphate; disodium, dipotassium, ducesium, and dilithium salts of bisphenol A; sodium, potassium, cesium, and lithium salts of phenol; and others.

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

[0057] Examples of compounds using Group 4, Group 12, and Group 14 metals 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 such that it does not affect the performance even if it remains in the resulting polycarbonate diol. The upper limit of the weight ratio of the metal to the weight of the dihydroxy compound used as a raw material is preferably 500 ppm, more preferably 100 ppm, and even more preferably 50 ppm. On the other hand, the lower limit is preferably 0.01 ppm, more preferably 0.1 ppm, and even more preferably 1 ppm, as this is the amount at which sufficient polymerization activity can be obtained.

[0059] <Reaction conditions> The reaction temperature for the transesterification reaction can be any temperature at which a practical reaction rate can be obtained. While the temperature is not particularly limited, 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 falls below the lower limit, the transesterification reaction may not proceed at a practical rate. Furthermore, exceeding the upper limit may result in quality problems such as discoloration of the resulting polycarbonate diol or the formation of ether structures.

[0060] The reaction can be carried out at atmospheric pressure, but since transesterification is an equilibrium reaction, the reaction can be biased towards the product by distilling off the resulting monodihydroxy compound. Therefore, it is generally preferable to use reduced pressure conditions in the latter half of the reaction to distill off the monodihydroxy compound. Alternatively, it is also possible to gradually reduce the pressure from the middle of the reaction to distill off the resulting monodihydroxy compound.

[0061] In particular, increasing the degree of reduced pressure towards the end of the reaction is preferable because it allows for the distillation removal of by-products such as monodihydroxy compounds and dihydroxy compounds, as well as residual monomers such as diester carbonates. The reaction pressure at the end of the reaction is not particularly limited, but is usually capped at 10 kPa, preferably 5 kPa, and more preferably 1 kPa. In order to effectively distill off these light boiling components, the reaction can also be carried out while passing a small amount of inert gas such as nitrogen, argon, or helium through the reaction system.

[0062] When using diester carbonates or dihydroxy compounds with low boiling points in a transesterification reaction, it is possible to carry out the reaction at or near the boiling point of the diester carbonate or dihydroxy compound in the initial stages, and then gradually increase the temperature as the reaction progresses to further advance the reaction. This is preferable because it prevents the removal of unreacted diester carbonates or dihydroxy compounds in the initial stages of the reaction. Furthermore, to prevent the removal of these starting materials in the initial stages of the reaction, it is also possible to attach a reflux condenser to the reactor and carry out the transesterification reaction while refluxing the diester carbonates and dihydroxy compounds and removing the monodihydroxy compounds by distillation. This is preferable because the charged starting monomers are not lost and the ratio of reagents can be accurately adjusted.

[0063] The time required for a transesterification reaction varies greatly depending on the type and amount of dihydroxy compound, diester carbonate, and catalyst used, so it cannot be specified in general terms. However, 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 usually 3 hours or more, preferably 5 hours or more.

[0064] <Catalyst deactivation> When a catalyst is used in a transesterification reaction, the resulting polycarbonate diol usually retains some of the catalyst, and this residual metal catalyst can make it difficult to control the polyurethaneization reaction. To suppress the effect of this residual catalyst, a catalyst deactivator, such as a phosphorus-based or sulfur-based compound that is acidic or decomposes into an acidic compound, may be added in approximately equimolar amounts to the catalyst used. Furthermore, if the deactivator is heat-treated after addition, as described later, the transesterification catalyst can be efficiently deactivated.

[0065] Examples of phosphorus compounds used to deactivate transesterification catalysts 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 individually or in combination of two or more types.

[0066] The amount of phosphorus-based compounds used to deactivate the catalyst is not particularly limited, but as mentioned above, it should be approximately equimolar to the transesterification catalyst used. Specifically, the upper limit is preferably 5 moles, more preferably 2 moles, and the lower limit is preferably 0.8 moles, more preferably 1.0 mole, per mole of transesterification catalyst used. If a smaller amount of phosphorus-based compounds is used, the deactivation of the transesterification catalyst may not be sufficient, and when the resulting polycarbonate diol is used as a raw material for polyurethane production, for example, the reactivity of the polycarbonate diol to the isocyanate group may not be sufficiently reduced. Furthermore, if phosphorus-based compounds exceeding this range are used, the resulting polycarbonate diol may become discolored.

[0067] The deactivation of the transesterification catalyst by adding phosphorus compounds, etc., can be carried out at room temperature, but it is more efficient with heating. 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 this, the deactivation of the transesterification catalyst takes a long time and is inefficient, and deactivation may be insufficient. On the other hand, at temperatures above 150°C, the obtained polycarbonate diol may become discolored.

[0068] There is no specific time limit for the reaction with phosphorus compounds, etc., but it is usually 1 to 5 hours.

[0069] <Purification> The reaction product obtained by the transesterification reaction contains impurities that do not have hydroxyl groups at the polymer ends, phenol, the starting dihydroxy compound, the starting carbonate compound, the by-product light-boiling cyclic carbonate, and the added catalyst, and can therefore be purified to remove these impurities. For purification in this process, light-boiling compounds can be removed by distillation. There are no particular restrictions on the specific distillation method, such as vacuum distillation, steam distillation, or thin-film distillation; any method can be used, but thin-film distillation is particularly effective.

[0070] There are no particular restrictions on the thin-film distillation conditions, but the temperature during thin-film distillation is preferably 250°C at the upper limit, and more preferably 200°C. The lower limit is preferably 120°C, and more preferably 150°C. By setting the lower limit of the temperature during thin-film distillation to the aforementioned value, sufficient removal of light-boiling components can be achieved. Furthermore, by setting the upper limit to 250°C, discoloration of the polycarbonate diol obtained after thin-film distillation can be prevented.

[0071] The pressure during thin-film distillation is preferably 500 Pa, more preferably 150 Pa, and even more preferably 50 Pa. By keeping the pressure during thin-film distillation below the above upper limit, a sufficient removal effect of light-boiling components can be obtained. Furthermore, the temperature at which the polycarbonate diol is kept warm immediately before thin-film distillation is preferably 250°C at the upper limit, and more preferably 150°C at the lower limit, and preferably 80°C at the lower limit, and more preferably 120°C at the lower limit.

[0072] By keeping the temperature of the polycarbonate diol being kept warm immediately before thin-film distillation above the lower limit mentioned above, it is possible to prevent a decrease in the fluidity of the polycarbonate diol immediately before thin-film distillation. On the other hand, by keeping the temperature below the upper limit mentioned above, it is possible to prevent the polycarbonate diol obtained after thin-film distillation from becoming discolored.

[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 dissolution solution, or the like. In that case, the compound to be 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. If the number average molecular weight of the polycarbonate diol is less than the above lower limit, sufficient hardness cannot be obtained when making polyurethane. On the other hand, if it exceeds the above upper limit, the viscosity increases, and it becomes difficult to handle 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 with gel permeation chromatography (GPC). When Mn is difficult to measure 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] <Percentage of terminal alkyloxy or aryloxy groups / Hydroxyl value> The polycarbonate diols of the present invention basically have hydroxyl groups, i.e., hydroxyl terminals, as the end structure of the polymer. However, in the reaction products obtained by the reaction of dihydroxy compounds with diester carbonates, there may be some polymers with structures other than hydroxyl groups at the end as impurities. Specific examples of such structures include those with alkyloxy or aryloxy groups at the end of the molecular chain, and these are mostly structures derived from diester carbonates. The ratio of hydroxyl groups (hydroxyl terminals), alkyloxy groups, and aryloxy groups is usually 1 It is calculated using H-NMR.

[0078] For example, when diphenyl carbonate is used as the diester carbonate, 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 as the terminal group; and when ethylene carbonate is used, a hydroxyethoxy group (HOCH2CH2O-) 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 chains in the polycarbonate diol that have 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, in terms of the number of terminal groups. There is no particular upper limit to the proportion of molecular chains whose ends are hydroxyl terminals, and it is usually 99.9 mol%, preferably 99.999 mol%, and most preferably 100 mol%. A larger proportion of hydroxyl terminals allows the degree of polymerization to increase sufficiently during the polyurethaneization reaction, enabling the reaction to proceed smoothly.

[0080] As described above, the polycarbonate diol of the present invention typically has a molecular chain with an alkyloxy group or aryloxy group at the end in 5 mol% or less, and both terminal groups of the molecular chain are basically hydroxyl groups (hydroxyl terminus). In the polyurethaneization reaction, these hydroxyl groups are structured to react with isocyanates.

[0081] The lower limit of the hydroxyl value of the polycarbonate diol of the present invention is typically 20 mg KOH / g, preferably 25 mg KOH / g, and more preferably 35 mg KOH / g. The upper limit is typically 250 mg KOH / g, preferably 200 mg KOH / g, and more preferably 100 mg KOH / g. If the hydroxyl value is below the lower limit, the viscosity may become too high, making handling difficult during polyurethane formation. If it exceeds the upper limit, the resulting polyurethane may lack sufficient strength and hardness.

[0082] The hydroxyl value can be measured by commonly known methods, but 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 typically exhibits a waxy solid state at or near room temperature, but its viscosity can be reduced by heating, making it easier to handle. Furthermore, it can 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 facilitate transport and reaction.

[0084] <Hazen color values> The color of the polycarbonate diol of the present invention is preferably within a range that does not affect the color of the resulting polyurethane. The degree of coloring is expressed in Hazen color numbers (according to JIS K0071-1 (1998)) and the value (hereinafter referred to as "Hazen color number") is not particularly limited, but it is preferably 50 or less, more preferably 40 or less, even more preferably 30 or less, and most preferably 20 or less.

[0085] <Residual catalyst amount> While some of the transesterification catalyst used in the production of the polycarbonate diol of the present invention may remain in the polycarbonate diol of the present invention, if an excessive amount of catalyst remains, it becomes difficult to control the reaction during the polyurethaneization reaction, which may accelerate the polyurethaneization reaction more than intended, causing gelation and potentially preventing the acquisition of a uniform polyurethane. Therefore, it is preferable that no transesterification catalyst remains.

[0086] The upper limit of the amount of catalyst remaining in the polycarbonate diol is not particularly limited, but from the viewpoint of obtaining 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. Examples of the type of metal remaining include the metals of the catalytic active components having transesterification ability as described above.

[0087] Furthermore, 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 ppm by weight, preferably 0.1 ppm by weight, more preferably 1 ppm by weight, and particularly preferably 5 ppm by weight, as the content in terms of catalyst metal. Normally, it is difficult to remove the catalyst used when producing the polycarbonate diol after production, and it is often difficult to reduce the amount of remaining catalyst to below the lower limit of the amount used, as described later.

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

[0089] <Impurity content> (Phenols) Phenols are monofunctional compounds that can act as polymerization inhibitors during polyurethane formation and are also irritants; therefore, it is preferable that the residual amount of phenols in the polycarbonate diol of the present invention be as low as possible. Specifically, the weight ratio of phenols to 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. To reduce the amount of phenols in polycarbonate diol, it is effective to use a high vacuum of 1 kPa or less as an absolute pressure during the polymerization reaction of the polycarbonate diol, or to perform thin-film distillation after the synthesis of the polycarbonate diol, as described above.

[0090] (Diester carbonate) The polycarbonate diol of the present invention may contain residual diester carbonate used as a raw material during production. The amount of residual diester carbonate in the polycarbonate diol of the present invention is not limited, but a small amount is preferable, and the upper limit is usually 5% by weight, preferably 3% by weight, and more preferably 1% by weight. If the diester carbonate content of the polycarbonate diol is too high, it may inhibit the reaction during polyurethane formation. On the other hand, there is no particular lower limit, but it 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 is preferably low, 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 high, the molecular length of the soft segment portion when it is made into polyurethane may be insufficient, and the desired physical properties may not be obtained. The residual amount of dihydroxy compound (1) in the polycarbonate diol is 1This can be determined by 1H-NMR measurement, gas chromatography (GC), and liquid chromatography (LC).

[0092] [Polyurethane] Polyurethanes and polyurethane aqueous dispersions can be produced using the polycarbonate diol of the present invention. The produced polyurethane is another embodiment of the present invention.

[0093] The method for producing polyurethane using the polycarbonate diol of the present invention employs known polyurethaneization reaction conditions that are typically used for producing polyurethane. For example, polyurethane can be produced by reacting polycarbonate diol, polyisocyanate, and a chain extender at a temperature ranging from room temperature to 200°C. Alternatively, a prepolymer having isocyanate groups at the ends can be produced by first reacting a polycarbonate diol with an excess of polyisocyanate, and then increasing the degree of polymerization using a chain extender to produce polyurethane.

[0094] <Polyisocyanate> Polyisocyanates used in the production of polyurethane using polycarbonate diols include various known polyisocyanate compounds of aliphatic, alicyclic, or aromatic types. 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 obtained by converting the carboxyl group of a dimer acid to an isocyanate group; 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, and 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, etc. Examples of cyanates include xylylene diisocyanate, 4,4'-diphenyl diisocyanate, 2,4-tollylene diisocyanate, 2,6-tollylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyle diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate, and aromatic diisocyanates such as m-tetramethylxylylene diisocyanate. These may be used individually 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 offer a favorable balance of the physical properties of the resulting polyurethane and are readily available in large quantities at low cost for industrial use.

[0096] <Chain extender> The chain extenders used in the production of polyurethanes are low molecular weight compounds having at least two active hydrogen atoms that react with the isocyanate group when producing a prepolymer having an isocyanate group, as described later. Examples include polyols and polyamines.

[0097] Specific examples 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; and 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 dimergol; diols having ether groups such as diethylene glycol and propylene glycol; 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 1,4-dihydroxyethyl hydroxy Diols with alicyclic structures such as chlorohexane, 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 include polyamines such as '-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, N,N'-diaminopiperazine, and water. These chain extenders may be used individually 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 offer a favorable balance of the physical properties of the resulting polyurethane and are readily available in large quantities at low cost for industrial use.

[0099] Furthermore, the chain extender used when producing prepolymers having hydroxyl groups, as described later, is a low molecular weight compound having at least two isocyanate groups, and specifically includes compounds such as those described under <polyisocyanates>.

[0100] <Chain inhibitors> When manufacturing polyurethane, a chain arrestor containing one active hydrogen group may be used as needed to control the molecular weight of the resulting polyurethane. Examples of these chain-stopping agents 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 individually or in combination of two or more types.

[0101] <Catalyst> In the polyurethane formation reaction during the production of polyurethane, known urethane polymerization catalysts such as amine-based catalysts like triethylamine, N-ethylmorpholine, and triethylenediamine; acid-based catalysts like acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, and sulfonic acid; tin-based compounds such as trimethyltin laurate, dibutyltin dilaurate, dioctyltin dilaurate, and dioctyltin dineodecanate; and organometallic salts such as titanium-based compounds can also be used. One type of urethane polymerization catalyst may be used alone, or two or more types may be used in combination.

[0102] <Polyols other than polycarbonate diols of the present invention> In the polyurethane formation reaction when producing polyurethane, the polycarbonate diol of the present invention may be used in combination with, if necessary, other polyols other than the polycarbonate diol of the present invention (hereinafter also referred to as "other polyols"). Here, "other polyols" are not particularly limited as long as they are used in the normal production of polyurethane, and include, for example, 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 produced that further improves the flexibility, which is a characteristic 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, and more preferably 90% or more. If the weight ratio of the polycarbonate diol of the present invention is low, the flexibility and moisture and heat resistance of the polyurethane, which are characteristics of the present invention, may be lost.

[0104] When other polyols are used in combination during the production of polyurethane, the polycarbonate diol of the present invention, the other polyols, and the other raw materials must be sufficiently miscible. If the miscibility is insufficient, the urethane reaction will proceed unevenly, potentially leading to a broadened molecular weight distribution or a decrease in molecular weight of the resulting polyurethane. This can result in gelation of the polyurethane solution, deterioration of storage stability, and a decrease in the strength, solvent resistance, weather resistance, and heat resistance of the polyurethane.

[0105] <Solvent> The polyurethane formation reaction during the production of polyurethane may also use solvents. 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 individually or as a mixture of two or more solvents. Among these, preferred organic solvents include dimethylformamide, dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide, methyl ethyl ketone, ethyl acetate, and toluene. Furthermore, a polyurethane aqueous dispersion can also be produced from a polyurethane composition containing the polycarbonate diol, polydiisocyanate, and the chain extender of the present invention.

[0106] <Polyurethane Manufacturing Method> As a method for producing polyurethane using the reaction reagents described above, generally experimental or industrially used manufacturing methods can be employed. Examples include a method in which the polycarbonate diol of the present invention, other polyols used as needed, polyisocyanate, and chain extender are mixed together and reacted (hereinafter sometimes referred to as the "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 with isocyanate groups at both ends, and then the prepolymer is reacted with a chain extender (hereinafter sometimes referred to as the "two-step method").

[0107] The two-step method involves a step of preparing isocyanate intermediates for both ends of the polyurethane soft segment by reacting the polycarbonate diol of the present invention with other polyols as needed, with at least one equivalent of polyisocyanate beforehand. This method, which involves reacting the prepolymer with a chain extender after its preparation, can facilitate adjustment of the molecular weight of the soft segment and is useful when reliable phase separation between the soft and hard segments is required.

[0108] <One step method> The one-step method, also known as the one-shot method, is a method in which the reaction is carried out by charging the polycarbonate diol, other polyols, polyisocyanates, and chain extenders of the present invention all at once. The amount of polyisocyanate used in the one-step method is not particularly limited, but when the total number of hydroxyl groups of the polycarbonate diol of the present invention and other polyols, and the total number of hydroxyl groups and amino groups of the chain extender are 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 too much polyisocyanate is used, unreacted isocyanate groups tend to undergo side reactions, resulting in a polyurethane with excessively high viscosity, making it difficult to handle and impairing its flexibility. Conversely, if too little is used, the molecular weight of the polyurethane may not be sufficiently large, resulting in insufficient polyurethane strength. Furthermore, while the amount of chain extender used is not particularly limited, if the number obtained by subtracting the number of isocyanate groups of the polyisocyanate from the total number of hydroxyl groups of the polycarbonate diol of the present invention and other polyols is considered 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 too much chain extender is used, the resulting polyurethane tends to be poorly soluble in the solvent and difficult to process, and if too little is used, the resulting polyurethane may be too soft and may not have sufficient strength, hardness, elastic recovery performance, or elastic retention performance, or its heat resistance may be poor.

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

[0111] The two-step method can be performed either without a solvent or in the presence of a solvent. Polyurethane can be manufactured using a two-stage method by any of the following methods (1) to (3). (1) Without using a solvent, a prepolymer is first synthesized by directly reacting polyisocyanate with the polycarbonate diol and other polyols of the present invention, and then used directly in the chain extension reaction. (2) The prepolymer is synthesized using the method in (1), then dissolved in a solvent and used in subsequent chain extension reactions. (3) A solvent is used from the beginning to react the polyisocyanate with the polycarbonate diol and other polyols of the present invention, and then the chain extension reaction is carried out.

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

[0113] If too much isocyanate is used, the excess isocyanate groups can cause side reactions, making it difficult to achieve the desired properties of the polyurethane. For example, the viscosity may become too high, reducing the flexibility of the resulting polyurethane, or it may become difficult to handle, leading to lower productivity. If too little is used, the molecular weight of the resulting polyurethane may not increase sufficiently, resulting in low 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 relative to the number of equivalents of isocyanate groups contained in the prepolymer, and the upper limit is preferably 5.0 equivalents, more preferably 3.0 equivalents, and even more preferably 2.0 equivalents.

[0114] When carrying out the above chain extension reaction, monofunctional organic amines or alcohols may be added in the presence of the product to adjust the molecular weight.

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

[0116] If too little isocyanate is used, the subsequent chain extension reaction to obtain the desired molecular weight will take longer, which tends to reduce production efficiency. If too much is used, the viscosity will become too high, which may reduce the flexibility of the resulting polyurethane, make it difficult to handle, and lower productivity.

[0117] While there are no particular limitations on the amount of chain extender used, if the total number of hydroxyl groups of the polycarbonate diol of the present invention and other polyols used in the prepolymer is considered to be 1 equivalent, then the total equivalent including the equivalent amount of isocyanate groups used in the prepolymer is preferably 0.7 equivalents at the lower limit, more preferably 0.8 equivalents, and even more preferably 0.9 equivalents at the upper limit, preferably less than 1.0 equivalent, more preferably 0.99 equivalents, and even more preferably 0.98 equivalents.

[0118] When carrying out the above chain extension reaction, monofunctional organic amines or alcohols may be added in the presence of the product 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 there are no particular restrictions. If the temperature is too low, the reaction may proceed slowly, or the manufacturing time may be prolonged 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 also be carried out under reduced pressure while degassing.

[0120] Furthermore, catalysts, stabilizers, and other additives can be added to the chain extension reaction as needed. Examples of catalysts include compounds such as triethylamine, tributylamine, dibutyltin dilaurate, stannous octoate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, and sulfonic acid. One catalyst may be used alone, or two or more catalysts may be used in combination. Examples of stabilizers include compounds such as 2,6-dibutyl-4-methylphenol, distearylthiodipropionate, N,N′-di-2-naphthyl-1,4-phenylenediamine, and tris(dinonylphenyl)phosphite. One of these may be used alone, or two or more may be used in combination. If the chain extender is a highly reactive compound such as a short-chain aliphatic amine, the reaction may be carried out without adding a catalyst.

[0121] <Water-based polyurethane dispersion> The polycarbonate diol of the present invention can also be used to produce aqueous polyurethane dispersions, which have higher dispersibility compared to conventional polycarbonate diols. In addition, these aqueous polyurethane dispersions have excellent storage stability because they are less prone to aggregation during storage. In this case, when producing a prepolymer by reacting a polyol containing the polycarbonate diol of the present invention with an excess of polyisocyanate, a compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups is mixed to form the prepolymer, and a water-based polyurethane dispersion is obtained through a neutralization and chlorination step of the hydrophilic functional group, an emulsification step by adding water, and a chain extension reaction step. The raw materials, additives, catalysts, solvents, etc. used in the prepolymer formation and chain extension reaction steps can be the same as those used in the polyurethane production described above.

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

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

[0124] When producing an aqueous polyurethane dispersion, the amount of compound having at least one hydrophilic functional group and at least two isocyanate-reactive groups used should, in order to improve dispersion performance in water, be preferably 1% by weight, more preferably 5% by weight, and even more preferably 10% by weight, relative to the total weight of the polycarbonate diol of the present invention and other polyols. On the other hand, adding too much may prevent the properties of the polycarbonate diol of the present invention from being maintained, so the upper limit should be preferably 50% by weight, more preferably 40% by weight, and even more preferably 30% by weight.

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

[0126] When producing an aqueous polyurethane dispersion without a solvent using the polycarbonate diol of the present invention as a raw material, the upper limit of the number average molecular weight determined 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 determined from the hydroxyl value exceeds the above upper limit or falls below the above lower limit, dispersion may become difficult.

[0127] Furthermore, when producing an aqueous polyurethane dispersion, the polycarbonate diol of the present invention may be used in combination with other polyols as needed. Here, "other polyols" are not particularly limited as long as they are used in the normal production of polyurethane, and include, for example, 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 produced that further improves the flexibility, which is a characteristic 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, and more preferably 90% or more. If the weight ratio of the polycarbonate diol of the present invention is low, the polyurethane properties and handling characteristics that are features of the present invention may be lost.

[0129] When other polyols are used in combination during the production of aqueous polyurethane dispersions, 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 urethane reaction will proceed unevenly, resulting in a broad molecular weight distribution or a decrease in molecular weight of the resulting aqueous polyurethane dispersion, which can lead to aggregation of the aqueous polyurethane dispersion and poor storage stability. Furthermore, the strength, solvent resistance, weather resistance, and heat resistance of the polyurethane obtained from the aqueous polyurethane dispersion may deteriorate.

[0130] Furthermore, in the synthesis or storage of aqueous polyurethane dispersions, emulsification stability may be maintained by using in combination anionic surfactants such as higher fatty acids, resin acids, acidic fatty alcohols, sulfate esters, higher alkyl sulfonic acids, alkylaryl sulfonic acids, sulfonated castor oil, and sulfosuccinate esters; cationic surfactants such as primary amine salts, secondary amine salts, tertiary amine salts, quaternary amine salts, and pyridinium salts; or nonionic surfactants such as known reaction products of ethylene oxide and long-chain fatty alcohols or phenols.

[0131] Furthermore, when preparing an aqueous polyurethane dispersion, it is also possible to mechanically mix water with an emulsifier under high shear force in the presence of an emulsifier, without the need for a neutralization and chlorination step if necessary, to an organic solvent solution of the prepolymer, in order to produce an aqueous polyurethane dispersion.

[0132] The aqueous polyurethane dispersion produced in this manner can be used in a variety of applications. In particular, there is a growing demand for chemical raw materials with a low environmental impact, and this method can replace conventional products that do not use organic solvents.

[0133] Specific applications of the aqueous polyurethane dispersion include, for example, coating agents, water-based paints, adhesives, synthetic leather, and artificial leather. In particular, the aqueous polyurethane dispersion produced using the polycarbonate diol of the present invention has excellent flexibility and heat and humidity resistance, making it more effective as a coating agent and the like compared to conventional aqueous polyurethane dispersions using polycarbonate diol.

[0134] <Storage stability of polyurethane solutions and aqueous polyurethane dispersions> The storage stability of polyurethane solutions and aqueous polyurethane dispersions produced using the polycarbonate diol of the present invention with an organic solvent and / or water can be measured by visually inspecting the solution or dispersion after adjusting the concentration of polyurethane in the solution or dispersion (hereinafter sometimes referred to as "solid content concentration") to 1 to 80% by weight and storing it under specific temperature conditions.

[0135] For example, in the case of a polyurethane solution (N,N-dimethylformamide / toluene mixture, solid content concentration 30% by weight) produced using the polycarbonate diol, 4,4'-dicyclohexylmethane diisocyanate, and isophorone diamine of the present invention by the aforementioned two-step method, the period during which no visible change is observed 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 visible change is observed in the polyurethane solution and 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 the aqueous polyurethane dispersion (dispersed in an N-methyl-2-pyrrolidone / water mixture, solid content concentration: 30% by weight) produced using the polycarbonate diol, 4,4'-dicyclohexylmethane diisocyanate, and ethylenediamine of the present invention, the period during which no visible change is observed in the polyurethane aqueous dispersion when stored at 20°C is preferably 1 day, more preferably 3 days, more preferably 7 days or more, even more preferably 14 days, and particularly preferably 1 month or more.

[0137] <Additives> The polyurethane produced using the polycarbonate diol of the present invention can be mixed with various additives such as heat stabilizers, light stabilizers, colorants, fillers, stabilizers, ultraviolet absorbers, antioxidants, anti-tacks, flame retardants, anti-aging agents, and inorganic fillers, to the extent that they do not impair the properties of the polyurethane.

[0138] Compounds that can be used as heat stabilizers include aliphatic, aromatic, or alkyl-substituted aromatic esters of phosphoric acid and phosphorous acid, hypophosphite derivatives, phosphorus compounds such as phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonates, dialkylpentaerythritol diphosphite, and dialkylbisphenol A diphosphite; phenol derivatives, especially hindered phenol compounds; sulfur-containing compounds such as thioethers, dithioates, mercaptobenzimidazoles, thiocarbanilides, and thiodipropionates; and tin compounds such as sutmarate and dibutyltin monoxide.

[0139] Specific examples of hindered phenol compounds include "Irganox 1010" (product name: manufactured by BASF Japan Ltd.), "Irganox 1520" (product name: manufactured by BASF Japan Ltd.), and "Irganox 245" (product name: manufactured by BASF Japan Ltd.).

[0140] Examples of phosphorus compounds include "PEP-36," "PEP-24G," and "HP-10" (all brand names: manufactured by ADEKA Corporation), and "Irgafos 168" (brand 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 and benzophenone compounds. Specifically, "TINUVIN622LD" and "TINUVIN765" (both manufactured by Ciba Specialty Chemicals Co., Ltd.), and "SANOL LS-2626" and "SANOL LS-765" (both manufactured by Sankyo Co., Ltd.) can be used.

[0143] Examples of UV absorbers include "TINUVIN328" and "TINUVIN234" (both manufactured by Ciba 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 dioxide, zinc oxide, iron oxide, and mica; and organic pigments such as coupling azos, condensation azos, anthraquinones, thioindigos, dioxazones, and phthalocyanines.

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

[0146] Examples of flame retardants include additives 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 individually, or two or more may be used in any combination and ratio. The amount of these additives added, as a weight ratio to the polyurethane, has a lower limit of preferably 0.01% by weight, more preferably 0.05% by weight, even more preferably 0.1% by weight, and an upper limit of preferably 10% by weight, more preferably 5% by weight, and even more preferably 1% by weight. If the amount of additive is too small, its effect cannot be fully obtained, and if it is too large, it may precipitate in the polyurethane or cause turbidity.

[0148] <Polyurethane film / Polyurethane board> When a film is manufactured using the polyurethane of the present invention, the thickness of the film is preferably 10 μm at the lower limit, more preferably 20 μm, even more preferably 30 μm, and preferably 1000 μm at the upper limit, more preferably 500 μm, and even more preferably 100 μm. If the film is too thick, it tends not to provide sufficient moisture permeability, and if it is too thin, it tends to produce pinholes or become prone to blocking, making it difficult to handle.

[0149] <Molecular weight> The molecular weight of the polyurethane of the present invention is adjusted as appropriate depending on its application and is not particularly limited, but it is preferably 50,000 to 500,000 as a weight-average molecular weight (Mw) in polystyrene equivalent as measured by GPC, and more preferably 100,000 to 300,000. If Mw is smaller than the lower limit, sufficient strength and hardness may not be obtained, and if it is larger than the upper limit, it tends to impair handling properties such as processability.

[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. The upper limit is usually 3.5, and preferably 3.0. When the molecular weight distribution exceeds the above upper limit, moldability and handling properties tend to decrease, and when attempting to produce polyurethane with a molecular weight distribution below the above lower limit, advanced purification operations may be required. Furthermore, by using the polycarbonate diol of the present invention produced using dihydroxy compound (1), it is possible to produce polyurethane with a small molecular weight distribution.

[0151] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of polyurethane are usually determined from gel permeation chromatography (GPC) measurements and converted to standard polystyrene equivalents.

[0152] <Tensile elongation and strength at break in room temperature tensile tests> The polyurethane of the present invention preferably exhibits the following tensile elongation at break and breaking strength when measured on a strip-shaped sample with 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 tensile speed of 500 mm / min, a temperature of 23°C, and a relative humidity of 55%. The lower limit of the elongation at break is preferably 200%, more preferably 300%, and even more preferably 350%, while the upper limit is preferably 1000%, more preferably 800%, and even more preferably 600%. If the elongation at break is below the lower limit, it tends to impair handling properties such as processability, and if it exceeds the upper limit, sufficient solvent resistance may not be obtained. Furthermore, the lower limit of the breaking strength is preferably 30 MPa, more preferably 40 MPa, and even more preferably 50 MPa, while 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, it tends to impair workability and other handling properties, and if it exceeds the upper limit, flexibility may be impaired.

[0153] <Heat and moisture resistance> The polyurethane obtained using the polycarbonate diol of the present invention exhibits excellent resistance to moisture and heat. For example, in the moisture and heat resistance tests shown in the Examples section below, it typically exhibits excellent moisture and 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, good flexibility, and mechanical strength, and can therefore be widely used in foams, elastomers, elastic fibers, paints, fibers, adhesives, flooring materials, sealants, medical materials, artificial leather, synthetic leather, coatings, water-based polyurethane paints, active energy ray curable polymer compositions, and the like. In particular, when polyurethane, as 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, and coatings, it provides a good balance of solvent resistance, flexibility, and mechanical strength. This results in high durability in areas that come into contact with human skin or are exposed to cosmetic agents or disinfectant alcohols, while also offering sufficient flexibility and resistance to physical impacts. Furthermore, it is suitable for automotive applications such as automotive components where heat resistance is required, and for outdoor applications where weather resistance is necessary.

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

[0156] The polyurethane of the present invention is also applicable as a thermoplastic elastomer. For example, it can be used in tubes and hoses, spiral tubes, fire hoses, etc., in pneumatic equipment, painting equipment, analytical instruments, scientific and chemical instruments, metering pumps, water treatment equipment, industrial robots, etc., used in the food and medical fields. It can also be used as belts such as round belts, V-belts, and flat belts in various power transmission mechanisms, spinning machines, packaging machines, printing machines, etc. It can also be used in footwear heel tops and soles, couplings, packing, ball joints, bushings, gears, rolls and other equipment parts, sporting goods, leisure goods, watch straps, etc. Furthermore, examples of automotive parts include oil stoppers, gearboxes, spacers, chassis parts, interior parts, and tire chain substitutes. It can also be used in films such as keyboard films and automotive films, coiled 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, and sporting goods. It can also be used as a tar epoxy urethane for automotive repair. The polyurethane of the present invention can be used as a component of moisture-curing one-component paints, blocked isocyanate solvent paints, alkyd resin paints, urethane-modified synthetic resin paints, UV-curing paints, water-based urethane paints, etc. For example, it can be applied to paints for plastic bumpers, strippable paints, coatings for magnetic tapes, overprint varnishes for floor tiles, flooring materials, paper, wood grain printed films, etc., wood varnishes, high-processing coil coatings, optical fiber protective coatings, solder resists, topcoats for metal printing, basecoats for vapor deposition, white coats for food cans, etc.

[0158] The polyurethane of the present invention can also be applied as an adhesive or bonding agent to 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, grafting materials, microcapsules, granular fertilizers, granular pesticides, polymer cement mortar, resin mortar, rubber chip binders, recycled foams, 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 shrinkage prevention, wrinkle prevention, water repellency, and the like. When the polyurethane of the present invention is used as an elastic fiber, the method of fiber formation is not particularly limited as long as it is a method that allows for spinning. For example, a melt spinning method can be employed in which the material is first pelletized, then melted, and directly spun through a spinneret. When obtaining elastic fibers from the polyurethane of the present invention by melt spinning, the spinning temperature is preferably 250°C or lower, more preferably 200°C to 235°C.

[0160] Polyurethane elastic fibers can be used as bare yarns or coated with other fibers to be used as coated yarns. Examples of other fibers include conventionally known fibers such as polyamide fibers, wool, cotton, and polyester fibers, but polyester fibers are particularly preferred in this invention. Furthermore, the polyurethane elastic fibers of this invention may contain a dye-type disperse dye.

[0161] The polyurethane of the present invention can be used as a sealant / caulking agent in concrete walls, induced joints, around window frames, wall-type PC (Precast Concrete) joints, ALC (Autoclaved Lightweight Concrete) joints, board joints, sealants for composite glass, heat-insulating window frame sealants, automotive sealants, and the like.

[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. The polyurethane of the present invention can be used as a raw material for UV-curable paints, electron beam-curable paints, photosensitive resin compositions for flexographic printing plates, and photocurable optical fiber coating compositions by modifying the ends of the polyurethane.

[0163] <Urethane (meth)acrylate oligomers> Using the polycarbonate diol of the present invention, a urethane (meth)acrylate oligomer can be produced by an addition reaction between polyisocyanate and hydroxyalkyl (meth)acrylate. When other raw material compounds such as polyols and chain extenders are used in combination, the urethane (meth)acrylate oligomer can be produced by further adding these other raw material compounds to the polyisocyanate.

[0164] In this invention, when "(meth)acrylic" is used, as in (meth)acrylate or (meth)acrylic acid, it means acrylic and / or methacrylic. Furthermore, the mixing ratio of each raw material compound in this process shall be substantially equivalent to, or identical to, the composition of the target urethane (meth)acrylate oligomer. In urethane (meth)acrylate oligomers, the total amount of isocyanate groups and the total amount of functional groups that react with isocyanate groups, such as hydroxyl groups and amino groups, are usually theoretically equivalent in moles.

[0165] When producing urethane (meth)acrylate oligomers, the amount of hydroxyalkyl (meth)acrylate used is usually 10 mol% or more, preferably 15 mol% or more, more preferably 25 mol% or more, and usually 70 mol% or less, preferably 50 mol% or less, relative to the total amount of hydroxyalkyl (meth)acrylate, the polycarbonate diol of the present invention, and other raw material compounds such as polyols used as needed, and compounds containing functional groups that react with isocyanates such as chain extenders. The molecular weight of the resulting urethane (meth)acrylate oligomer can be controlled according to this ratio. A higher proportion of hydroxyalkyl (meth)acrylate tends to result in a lower molecular weight of the urethane (meth)acrylate oligomer, while a lower proportion tends to result in a higher molecular weight.

[0166] It is preferable that the amount of polycarbonate diol of the present invention used is 25 mol% or more, more preferably 50 mol% or more, and even more preferably 70 mol% or more, relative to the total amount of polycarbonate diol of the present invention and other polyols used. When the amount of polycarbonate diol of the present invention used is above the lower limit mentioned above, the resulting cured product tends to have good elongation, hardness, weather resistance, and stain resistance, which is preferable.

[0167] Furthermore, the amount of polycarbonate diol of the present invention 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, relative to the total amount of polycarbonate diol of the present invention and other polyols used. When the amount of polycarbonate diol of the present invention used is above the lower limit mentioned above, the viscosity of the resulting composition decreases, improving workability, and the mechanical strength, hardness, and wear resistance of the resulting cured product tend to improve, which is preferable.

[0168] Furthermore, when using a chain extender, it is preferable that the amount of the polycarbonate diol and other polyols of the present invention used be 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more, relative to the total amount of the compound combining the polycarbonate diol of the present invention, other polyols, and the chain extender. Exceeding the aforementioned lower limit tends to improve liquid stability, which is preferable.

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

[0170] In the production of urethane (meth)acrylate oligomers, the total content of the generated urethane (meth)acrylate oligomers and their raw material compounds is preferably 20% by weight or more, and 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. A total content of 20% by weight or more of urethane (meth)acrylate oligomers and their raw material compounds is preferable because it tends to increase the reaction rate and improve production efficiency.

[0171] Addition catalysts can be used in the production of urethane (meth)acrylate oligomers. Examples of such addition catalysts include dibutyltin laurate, dibutyltin dioctoate, dioctyltin dilaurate, and dioctyltin dioctoate. One type of addition catalyst may be used alone, or two or more types may be used in mixture. Of these, dioctyltin dilaurate is preferred as the addition catalyst from the viewpoint of environmental adaptability, catalytic activity, and storage stability.

[0172] The addition reaction catalyst is used at an upper limit of typically 1000 ppm by weight, preferably 500 ppm by weight, and a lower limit of typically 10 ppm by weight, preferably 30 ppm by weight, relative to the total content of the resulting urethane (meth)acrylate oligomer and its raw material compound.

[0173] Furthermore, when the reaction system contains a (meth)acryloyl group during the production of urethane (meth)acrylate oligomers, 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. A single polymerization inhibitor may be used, or two or more may be used in combination. Among these, phenols are preferred as polymerization inhibitors.

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

[0175] In the production of urethane (meth)acrylate oligomers, the reaction temperature is usually 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 preferable because it tends to increase the reaction rate and improve production efficiency. The reaction temperature is usually 120°C or lower, preferably 100°C or lower. A reaction temperature of 120°C or lower is preferable because it makes side reactions such as alohanate formation less likely to occur. Furthermore, if the reaction system contains a solvent, the reaction temperature is preferably below the boiling point of the solvent, and if (meth)acrylate is present, it is preferably 70°C or lower from the viewpoint of preventing the reaction of (meth)acryloyl groups. The reaction time is usually about 5 to 20 hours.

[0176] The number-average molecular weight of the urethane (meth)acrylate oligomer obtained in this way is preferably 500 or more, particularly preferably 1,000 or more, preferably 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 lower limit, the resulting cured film exhibits good three-dimensional processing suitability and tends to have an excellent balance between three-dimensional processing suitability and stain resistance, which is preferable. When the number-average molecular weight of the urethane (meth)acrylate oligomer is below the upper limit, the cured film obtained from the composition exhibits good stain resistance and tends to have an excellent balance between three-dimensional processing suitability and stain resistance, which is also preferable. This is presumed to be because three-dimensional processing suitability and stain resistance depend on the distance between crosslinking points in the network structure; a longer distance results in a flexible and easily stretchable structure with excellent three-dimensional processing suitability, while a shorter distance results in a rigid network structure with excellent stain resistance.

[0177] <Polyester-based 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 mainly made of aromatic polyester and a soft segment mainly made of aliphatic polyether, aliphatic polyester, or aliphatic polycarbonate. When the polycarbonate diol of the present invention is used as a component of the soft segment, it exhibits superior physical properties such as heat resistance and water resistance compared to cases where aliphatic polyether or aliphatic polyester is used. Furthermore, compared to known polycarbonate diols, it has fluidity during melting, i.e., a melt flow rate suitable for blow molding and extrusion molding, and is a polycarbonate polyester elastomer with an excellent balance of mechanical strength and other physical properties, making it suitable for use in various molding materials including fibers, films, and sheets, such as elastic yarns and molding materials for boots, gears, tubes, and gaskets. Specifically, it can be effectively applied to joint boots for automobile and home appliance parts, etc., and to wire coating materials, where heat resistance and durability are required.

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

[0179] In this specification, the calculated inter-crosslinking molecular weight of a composition represents the average 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 inter-crosslinking molecular weight correlates with the network area when the network structure is formed, and the larger the calculated inter-crosslinking molecular weight, the smaller the crosslinking density. In reactions by active energy ray curing, when a compound having only one active energy ray reactive group (hereinafter sometimes referred to as a "monofunctional compound") reacts, it becomes a linear polymer, while when a compound having two or more active energy ray reactive groups (hereinafter sometimes referred to as a "polyfunctional compound") reacts, it forms a network structure.

[0180] Therefore, the active energy ray reactive groups in the polyfunctional compound are considered to be the crosslinking sites, and the calculation of the molecular weight between crosslinking sites in the calculated network is centered on the polyfunctional compound having crosslinking sites. Monofunctional compounds are treated as having the effect of extending the molecular weight between crosslinking sites of the polyfunctional compound, and the molecular weight between crosslinking sites in the calculated network is calculated accordingly. Furthermore, the calculation of the molecular weight between crosslinking sites in the calculated network is performed under the assumption that all active energy ray reactive groups have the same reactivity and that all active energy ray reactive groups react upon irradiation with active energy rays.

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

[0182] If a composition contains monofunctional compounds, assuming that each monofunctional compound reacts with an equivalent mole at each active energy ray reactant (i.e., a crosslinking site) of the polyfunctional compound, and that the monofunctional compound is positioned at the center of the molecular chain formed by the linkage at the crosslinking sites, the extension of the molecular chain by the monofunctional compound at one crosslinking site is half the value obtained by dividing the total molecular weight of the monofunctional compound by the total number of active energy ray reactants of the polyfunctional compound in the composition. Here, since the calculated molecular weight between crosslinking sites is considered to be twice the average molecular weight per crosslinking site, the extension by the monofunctional compound relative to the calculated molecular weight between crosslinking sites of 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 reactants of the polyfunctional compound 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 reaction groups of the polyfunctional compound is 2 × 4 = 8. Therefore, the extension due to the monofunctional compound in the calculated molecular weight between crosslinking points of the network is 100 × 40 / 8 = 500. In other words, the calculated molecular weight between crosslinking points of the network of the composition is 1000 + 500 = 1500.

[0184] From the above, 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 a mixture with moles, the molecular weight between crosslinking points of the composition can be expressed by the following formula.

[0185]

number

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

[0187] When the calculated molecular weight between crosslinking points of the network is 10,000 or less, the cured film obtained from the composition tends to have good stain resistance and exhibits an excellent balance between three-dimensional workability and stain resistance, which is preferable. Furthermore, when the calculated molecular weight between crosslinking points of the network is 500 or more, the resulting cured film tends to have good three-dimensional workability and exhibits an excellent balance between three-dimensional workability and stain resistance, which is also preferable. This is presumed to be because three-dimensional workability and stain resistance depend on the distance between crosslinking points in the network structure; a longer distance results in a flexible and easily stretchable structure with excellent three-dimensional workability, while a shorter distance results in a rigid network structure with excellent stain resistance.

[0188] The active energy ray-curable polymer composition may further contain other components besides the urethane (meth)acrylate oligomer. Examples of such other components include active energy ray-reactive monomers, active energy ray-curable oligomers, polymerization initiators, photosensitizers, additives, and solvents.

[0189] In an active energy ray-curable polymer composition, the content of urethane (meth)acrylate oligomers is preferably 40% by weight or more, and more preferably 60% by weight or more, relative to the total amount of active energy ray-reactive components including urethane (meth)acrylate oligomers. The upper limit of this content is 100% by weight. A urethane (meth)acrylate oligomer content of 40% by weight or more is preferable because it results in good curability, and the mechanical strength of the cured product does not become excessively high, while tending to improve suitability for three-dimensional processing.

[0190] Furthermore, in an active energy ray-curable polymer composition, a higher content of urethane (meth)acrylate oligomers is preferable in terms of elongation and film-forming properties, while a lower content is preferable in terms of viscosity reduction. From this viewpoint, the content of urethane (meth)acrylate oligomers is preferably 50% by weight or more, and more preferably 70% by weight or more, based on the total amount of all components, including the active energy ray-reactive component and other components. The upper limit for the content of urethane (meth)acrylate oligomers is 100% by weight, and it is preferable that the content is less than or equal to this.

[0191] Furthermore, in the active energy ray curable polymer composition, the total amount of the active energy ray reactive component, 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 hardening properties, and the absence of tack residue. The upper limit of this content is 100% by weight.

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

[0193] Examples of such active energy ray-reactive monomers include vinyl ethers, (meth)acrylamides, and (meth)acrylates. Specifically, for example, 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, trimethylolpropanediallyl ether, and allyl glycidyl ether; (meth)acrylamide, N,N-dimethylacrylamide, N,(Meth)acrylamides such as N-dimethylmethacrylamide, N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, Nt-butyl(meth)acrylamide, (meth)acryloylmorpholine, methylenebis(meth)acrylamide; (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, 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 glycoside di(meth)acrylate. Glycol, 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 di(meth)acrylate ester hydroxypivalate, 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, Trimethylolprop Examples of polyfunctional (meth)acrylates include pantrioxyethyl (meth)acrylate, trimethylolpropanetrioxypropyl (meth)acrylate, trimethylolpropanepolyoxyethyl (meth)acrylate, trimethylolpropanepolyoxypropyl (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, tricyclodecanedimethanol di(meth)acrylate, bisphenol A epoxy di(meth)acrylate, and bisphenol F epoxy di(meth)acrylate.

[0194] Among these, monofunctional (meth)acrylates having a ring structure within the molecule, such as (meth)acryloylmorpholine, (meth)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 particularly preferred for applications requiring good applicability. On the other hand, for applications where the mechanical strength of the resulting cured product is required, polyfunctional (meth)acrylates such as 1,4-butanediol di(meth)acrylic acid, 1,6-hexanediol di(meth)acrylic acid, 1,9-nonanediol di(meth)acrylic acid, neopentyl glycol di(meth)acrylic acid, tricyclodecane di(meth)acrylic acid, 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 an active energy ray curable polymer composition, the content of the active energy ray 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 as a mixture of two or more types. Examples of the active energy ray-curable oligomer include epoxy (meth)acrylate oligomers and acrylic (meth)acrylate oligomers. In an active energy ray curable polymer composition, the content of the active energy ray 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 resulting cured product.

[0197] The polymerization initiator is mainly used to improve the initiation efficiency of polymerization reactions that proceed by irradiation with active energy rays such as ultraviolet rays and electron beams. Generally, photoradical polymerization initiators, which are compounds that generate radicals upon exposure to light, are used as polymerization initiators, and any known photoradical polymerization initiator can be used. A single polymerization initiator may be used alone, or two or more may be used in combination. Furthermore, a photoradical polymerization initiator and a photosensitizer may be used in combination.

[0198] Examples of photoradical polymerization initiators 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, benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl Examples include ethers, benzoin isobutyl ether, methylbenzoyl formate, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,6-dimethylbenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoyl diphenylphosphine 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-methylpropionyl)-benzyl]-phenyl]-2-methyl-propan-1-one.

[0199] Among these, benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl 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 because they have a fast curing rate and can sufficiently increase the crosslinking density, and 1-hydroxycyclohexylphenyl 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 because they have a fast curing rate and can sufficiently increase the crosslinking density.

[0200] Furthermore, the active energy ray curable polymer composition contains epoxy groups along with radical polymerizable groups, etc. If a compound having a cationic polymerizable group is included, the above photoradioactive group is used as a polymerization initiator. A photocationic polymerization initiator may be included along with the CAL polymerization initiator. Any known agent can be used.

[0201] The content of these polymerization initiators in the active energy ray curable polymer composition is preferably 10 parts by weight or less, and more preferably 5 parts by weight or less, per 100 parts by weight of the total active energy ray reactive components. A polymerization initiator content of 10 parts by weight or less is preferable because it makes it less likely for the mechanical strength to decrease due to initiator decomposition products.

[0202] The photosensitizer can be used for the same purpose as the polymerization initiator. The photosensitizer may be used alone or in a mixture of two or more types. Any known photosensitizer can be used as the photosensitizer, 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 ray 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, per 100 parts by weight of the total active energy ray reactive components. A photosensitizer content of 10 parts by weight or less is preferable because it is less likely to cause a decrease in mechanical strength due to a decrease in crosslinking density.

[0204] The aforementioned additives are optional, and various materials used in compositions for similar purposes can be used as additives. Additives may be used individually or in mixtures of two or more. Examples of such additives include fillers such as glass fibers, glass beads, silica, alumina, calcium carbonate, mica, zinc oxide, titanium oxide, talc, kaolin, metal oxides, metal fibers, iron, lead, and metal powders; carbon materials such as carbon fibers, 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, etc. Modifiers such as HALS (hindered amine light stabilizers), anti-fingerprint agents, surface hydrophilic agents, antistatic agents, lubrication agents, plasticizers, mold release agents, defoaming agents, leveling agents, anti-settling agents, surfactants, thixotropy agents, lubricants, flame retardants, flame retardant aids, 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 their oligomers or inorganic components; etc.

[0205] In the active energy ray 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, per 100 parts by weight of the total active energy ray reactive components. A content of 10 parts by weight or less of the additive is preferable because it makes it less likely for a decrease in mechanical strength due to a decrease in crosslinking density to occur.

[0206] The solvent can be used, for example, to adjust the viscosity of the active energy ray-curable polymer composition, depending on the coating method for forming the coating film of the active energy ray-curable polymer composition. The solvent may be used alone or in mixture of two or more. Any known solvent can be used as the solvent within the range in which 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 solids of the active energy ray-curable polymer composition.

[0207] There are no particular limitations on the method for incorporating the aforementioned additives or other optional components into the active energy ray curable polymer composition, and conventionally known mixing and dispersion methods can be used. In order to more reliably disperse the optional components, it is preferable to perform the dispersion treatment using a disperser. Specifically, examples of methods include processing with 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 segregator triter, a planetary agitator, a high-speed impeller disperser, a high-speed stone mill, a high-speed impact mill, a kneader, a homogenizer, an ultrasonic disperser, and the like.

[0208] The viscosity of the active energy ray-curable polymer composition can be appropriately adjusted depending on the application and manner of use of the composition. However, from the viewpoint of handling, coating properties, moldability, and three-dimensional molding properties, the viscosity at 25°C measured on an E-type viscometer (rotor 1°34'×R24) is preferably 10 mPa·s or more, more preferably 100 mPa·s or more, while it is preferably 100,000 mPa·s or less, and more preferably 50,000 mPa·s or less. The viscosity of the active energy ray-curable polymer composition can be adjusted, for example, by the content of the aforementioned urethane (meth)acrylate oligomer, the type of the aforementioned optional components, and their blending ratios.

[0209] Known methods such as the bar coater method, applicator method, curtain flow coater method, roll coater method, spray method, gravure coater method, comma coater method, reverse roll coater method, lip coater method, die coater method, slot die coater method, air knife coater method, and dip coater method can be applied as coating methods for active energy ray curable polymer compositions, but among these, the bar coater method and gravure coater method are preferred.

[0210] An active energy ray-curable polymer composition can be cured by irradiating it with active energy rays. Infrared rays, visible light, ultraviolet rays, X-rays, electron beams, alpha rays, beta rays, gamma rays, etc., can be used as active energy rays when curing the above composition. 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 irradiation dose of the active energy ray can be appropriately selected depending on the type of active energy ray. For example, when curing is performed by electron beam irradiation, the irradiation dose is preferably 1 to 10 Mrad. In the case of ultraviolet irradiation, it is 50 to 1,000 mJ / cm². 2 This is preferable. The atmosphere during curing may be air, an inert gas such as nitrogen or argon. Alternatively, irradiation may be performed in a sealed space between the film or glass and the metal mold.

[0212] The thickness of the cured film is determined appropriately according to the intended application, but the lower limit is preferably 1 μm, more preferably 3 μm, and most preferably 5 μm. The upper limit is preferably 200 μm, more preferably 100 μm, and most preferably 50 μm. A film thickness of 1 μm or more is preferable because it results in good design and functionality after 3D processing, while a film thickness of 200 μm or less is preferable because it provides good internal curability and suitability for 3D processing. Furthermore, for industrial use, the lower limit of the cured film thickness is preferably 1 μm, the upper limit is preferably 100 μm, more preferably 50 μm, most preferably 20 μm, and most preferably 10 μm.

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

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

[0215] Examples of base materials include various types of plastics such as polyethylene terephthalate and polybutylene terephthalate, polyolefins such as polypropylene and polyethylene, nylon, polycarbonate, (meth)acrylic resin, and plates made of glass or metal, among other shapes.

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

[0217] Furthermore, considering the molecular weight between crosslinking points of the calculated network, the active energy ray curable polymer composition can provide a cured film that simultaneously possesses flexibility to follow deformation during three-dimensional processing, elongation at break, mechanical strength, stain resistance, and hardness. Furthermore, it is expected that the active energy ray curable polymer composition will enable the simple production of thin-film resin sheets by single-layer coating.

[0218] The elongation at break of the cured film is preferably 50% or more, more preferably 75% or more, even more preferably 100% or more, and particularly preferably 120% or more, when measured by tensile testing using a Tensilon tensile testing machine (Tensilon UTM-III-100, manufactured by Orientec Co., Ltd.) under the conditions of a temperature of 23°C, a tensile speed of 50 mm / min, and a chuck distance of 50 mm.

[0219] The above-mentioned cured film and laminate can be used as a paint substitute film and can be effectively applied to various components such as interior and exterior building materials, automobiles, and home appliances. [Examples]

[0220] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples unless it exceeds the essence of the invention.

[0221] The evaluation methods for each physical property are as follows:

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

[0223] [Evaluation method: Polycarbonate diol] <Calculation of number-average molecular weight, quantification of phenoxy groups, and hydroxyl terminology> Dissolve polycarbonate diol in CDCl3 and 400MHz 1 ¹H-NMR (AL-400, JEOL Ltd.) was used to measure the phenoxy group from the signal position of each component. The phenoxy terminus content and number-average molecular weight were calculated from the integrated values. The detection limit was 1000 ppm by weight, representing the phenoxy terminus content relative to the total weight of the sample. The hydroxyl terminology was calculated as follows: Percentage of hydroxyl terminus (%) ={(Total number of terminals = 2) - Impurity (phenoxy) terminals} / (Total number of terminals = 2) × 100

[0224] <Hydroxyl value> The hydroxyl value of polycarbonate diols was measured by automated 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 diols in polystyrene equivalent were determined by GPC measurement under the following conditions. The quantity distribution (Mw / Mn) was calculated. Equipment: Tosoh Corporation HLC-8320 Column: TSKgel superHZM-N (6.0mm I.D. × 15cm L × 4 pieces) Reference column: superHM-H (4.6mm I.D. × 3.5cm L × 1 column) Eluent: THF (tetrahydrofuran) Flow rate: 0.6mL / min Column temperature: 40℃ RI detector: RI (built into the HLC-8320 device)

[0226] <Amount of remaining dihydroxy compounds> A solution prepared by adding 250 mg of monochlorobenzene to 500 mL of N-methylpyrrolidone was used as the internal standard. 0.50 g of polycarbonate diol was accurately weighed and dissolved in 5 mL of the above internal standard solution, weighed using a volumetric pipette. The resulting solution was analyzed by gas chromatography (GC) under the analytical conditions described below. The concentration of the dihydroxy compound was calculated by weight % from the area ratio obtained by GC, using a calibration curve created from previously known dihydroxy compounds as standard substances. (Analysis conditions) Equipment: Agilent 6850 (manufactured by Agilent Technologies) Column: Agilent J&W GC Column DB-WAX Inner diameter 0.25 mm, length 60 m, film thickness 0.25 mm Detector: Flame ionization detector (FID) Temperature increase program: 150℃ → 190℃ (5 minutes) 190℃ → 245℃ (40 minutes)

[0227] <Hazen color values> In accordance with JIS K0071-1 (1998), the Hazen color value was measured by comparing polycarbonate diol with a standard solution 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 prepare a dimethylacetamide solution with a concentration of 0.14% by weight. Using a GPC instrument (Tosoh Corporation, product name "HLC-8220" (columns: TskgelGMH-XL, 2 columns)), the dimethylacetamide solution was injected, and the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polyurethane were measured in terms of standard polystyrene, and the molecular weight distribution (Mw / Mn) was calculated.

[0229] <Tensile Test> A 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 100°C for 0.5 hours. Further drying was performed in a vacuum at 100°C for 0.5 hours and then at 80°C for 15 hours. The film was then left to stand for at least 12 hours under constant temperature and humidity conditions of 23°C and 55% RH. A 10 mm x 70 mm test piece was cut from the resulting polyurethane film. This test piece was subjected to a tensile test in accordance with JIS K6301 (2010) using a tensile testing machine (Orientec Co., Ltd., product name "Tensilon UTM-III -100") with a chuck distance of 50 mm, a tensile speed of 500 mm / min, a temperature of 23°C, and a relative humidity of 55%. The strength and elongation at break were measured. A higher elongation at break indicates greater flexibility.

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

[0231] [Manufacturing and evaluation of polycarbonate diols] [Example 1] A 5L glass separable flask equipped with a stirrer, a distillate trap, and a pressure regulator was charged with 1,10-decanediol (1,10DD) with an acid value of 0.1 mgKOH / g: 1437.8 g, diphenyl carbonate: 1562.2 g, and an aqueous solution of magnesium acetate tetrahydrate: 4.2 mL (concentration: 8.4 g / L, magnesium acetate tetrahydrate: 35 mg), and purged with nitrogen gas. With stirring, the internal temperature was raised to 160 °C to heat and dissolve the contents. Then, after reducing the pressure to 24 kPa over 2 minutes, the reaction was carried out for 90 minutes while removing phenol out of the system. Next, the pressure was reduced to 9.3 kPa over 90 minutes and further to 0.7 kPa over 30 minutes to continue the reaction, and then the temperature was raised to 170 °C and the reaction was carried out for 60 minutes while removing phenol and unreacted diol out of the system to obtain a polycarbonate diol-containing composition. Thereafter, 1.6 mL of a 0.85 wt% phosphoric acid aqueous solution was added to deactivate the catalyst, obtaining a polycarbonate diol-containing composition.

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

[0233] [Example 2] The reaction was carried out in the same manner as in Example 1 except that 1,10-decanediol (1,10DD) with an acid value of 0.4 mgKOH / g was used to obtain a polycarbonate diol. The polycarbonate diol produced in this Example 2 is referred to as "PCD2". The evaluation results of the physical properties of PCD2 are shown in Table 1.

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

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

[0236] [Comparative Example 2] The reaction was carried out 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, and a polycarbonate diol was obtained. The polycarbonate diol produced in this Comparative Example 2 is referred to as "PCD5". The evaluation results of the physical properties of PCD5 are shown in Table 1.

[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. 69.78g of PCD1, preheated to 80°C, 6.30g of 1,4-butanediol, and 238.57g of anhydrous N,N-dimethylformamide (hereinafter sometimes abbreviated as "DMF," manufactured by Wako Pure Chemical Industries, Ltd.) were added. Then, 25.4g of 4,4'-diphenylmethane diisocyanate (hereinafter sometimes referred to as "MDI") was added. The contents of the separable flask were heated to 70°C over approximately 1 hour while stirring at 60 rpm under a nitrogen atmosphere. After reaching 70°C, 0.019g of Neostan U-830 (hereinafter sometimes referred to as "U-830," manufactured by Nitto Chemical Co., Ltd.) was added as a urethane reaction catalyst, and the mixture was stirred at 70°C for a further 2 hours. Subsequently, 1.8g of MDI was added in installments (total MDI added: 27.2g) to adjust the molecular weight, resulting in a polyurethane with a molecular weight of approximately 156,000. The results of the evaluation of the physical properties of this polyurethane are shown in Table 2.

[0239] [Comparative Example 3] 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 quantities were changed as shown in Table 2. The results of the evaluation of the physical properties of the obtained polyurethane are shown in Table 2.

[0240] [Table 2]

[0241] From Tables 1 and 2, the following can be seen. Polycarbonate diols produced using 1,10-decanediol with an acid value within the range defined in this invention have good color tone and, when used as a raw material for polyurethane, can provide polyurethane with excellent elongation and heat and humidity 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 defined in the present invention, has an inferior color tone. Furthermore, the polycarbonate diol synthesized using the polycarbonate diol described in Comparative Example 1, i.e., 1,10-decanediol with an acid value exceeding the range specified in the present invention, had good color tone, but the synthesized polyurethane (Comparative Example 3) showed inferior heat and humidity resistance compared to Example 4. In addition, the polyurethane of Comparative Example 3 had a broader molecular weight distribution compared to the polyurethane of Example 4, which may make it difficult to mold.

Claims

1. In polycarbonate diols, which are transesterification products of dihydroxy compounds and carbonate compounds, The dihydroxy compound consists of a compound represented by the following formula (1) (hereinafter referred to as "dihydroxy compound (1)"), A polycarbonate diol 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 (This represents a divalent linear hydrocarbon group with 10 carbon atoms.)

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

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

4. The polycarbonate diol according to any one of claims 1 to 3, wherein the remaining amount of the dihydroxy compound (1) is less than 0.5% by weight.

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

6. A polyurethane using a polycarbonate diol according to any one of claims 1 to 5.

7. Artificial leather or synthetic leather using polyurethane as described in claim 6.

8. A paint or coating agent using polyurethane as described in claim 6.

9. An elastic fiber using polyurethane as described in claim 6.

10. A water-based polyurethane coating using the polyurethane described in claim 6.

11. Adhesive or bonding agent using polyurethane as described in claim 6.

12. A water-based polyurethane dispersion using a polycarbonate diol according to any one of claims 1 to 5.

13. An active energy ray curable polymer composition containing a urethane (meth)acrylate oligomer obtained by addition reaction of a polycarbonate diol, polyisocyanate, and hydroxyalkyl (meth)acrylate as described in any one of claims 1 to 5.

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