Polycarbonate diol and its manufacturing method

Abstract

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

Description

Technical Field

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

Background Art

[0002] Polycarbonate diol is used as a raw material for the soft segment part of polyurethanes and thermoplastic elastomers, paints, adhesives, etc., and is widely used as a raw material that imparts high durability excellent in weather resistance, heat resistance, hydrolysis resistance, and moist heat resistance, which are regarded as the drawbacks of polyether polyol and polyester polyol.

[0003] Conventionally, polyurethanes using polycarbonate diol obtained using lower alkyldiols such as 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol as raw materials are generally known, but these do not sufficiently satisfy the required performance in terms of moist heat resistance and elongation. For this reason, in order to solve this problem, polycarbonate diols with various structures have been proposed.

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

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Non-Patent Documents

[0006]

Non-Patent Document 1

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0007] Patent Documents 1 and 2 and Non-Patent Document 1 describe polycarbonate diols using long-chain dihydroxy compounds. However, there has been no examination of the influence of the impurity content in the dihydroxy compound on the resulting polycarbonate diol and the physical properties of the polyurethane when the polycarbonate diol is used to form a polyurethane. There are still problems with the color tone of the resulting polycarbonate diol and the physical properties of the polyurethane obtained using the polycarbonate diol, particularly flexibility (elongation) and resistance to wet heat.

[0008] The present invention provides a polycarbonate diol using a long-chain dihydroxy compound, which is a polycarbonate diol that could not be achieved by the prior art, that is, has a good color tone and can impart excellent flexibility (elongation) and resistance to wet heat to the resulting polyurethane when used as a raw material compound (raw material monomer) of the polyurethane.

MEANS FOR SOLVING THE PROBLEMS

[0009] As a result of intensive studies to solve the above problems, the present inventors have found that when producing a polycarbonate diol using a specific long-chain dihydroxy compound as the dihydroxy compound, by using a long-chain dihydroxy compound having an acid value within a specific range, a polycarbonate diol having a good color tone and capable of imparting excellent flexibility (elongation) and resistance to wet heat to the resulting polyurethane when used as a raw material compound (raw material monomer) of the polyurethane can be provided, leading to the present invention. That is, the gist of the present 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 this. 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 this. 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] Elastic fiber using the polyurethane described in

[11] .

[0024]

[15] Aqueous polyurethane paint using the polyurethane described in

[11] .

[0025]

[16] An adhesive or bonding agent using the polyurethane described in

[11] .

[0026]

[17] An aqueous polyurethane dispersion using the polycarbonate diol described in any one of [6] to

[10] .

[0027]

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

[10] . [Advantages of the Invention]

[0028] The polycarbonate diol provided by the present invention has a good color tone, and when used as a raw material compound (raw material monomer) of polyurethane, it can impart excellent flexibility (elongation) and wet heat resistance to the obtained polyurethane. Therefore, the polycarbonate diol of the present invention and the polyurethane obtained by using the polycarbonate diol of the present invention are suitable for elastic fibers, synthetic or artificial leather, paints, and high-functional elastomer applications, and are extremely useful industrially. [Modes for Carrying Out the Invention]

[0029] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made and implemented within the scope of the gist thereof.

[0030] [Polycarbonate Diol] The polycarbonate diol of the present invention is a polycarbonate diol obtained by subjecting a dihydroxy compound and a carbonate compound to a transesterification reaction in the presence of a transesterification catalyst, wherein the dihydroxy compound 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. This polycarbonate diol is produced by subjecting a dihydroxy compound (1) having an acid value of 0.04 mgKOH / g or more and 15.00 mgKOH / g or less and a carbonate compound to a transesterification reaction in the presence of a transesterification catalyst according to the method for producing the polycarbonate diol of the present invention. HO-R 1 -OH …(1) (In the above formula (1), R 1 represents a divalent hydrocarbon group having 10 to 12 carbon atoms.)

[0031] Note that the polycarbonate diol of the present invention may contain, as impurities, those that are not hydroxy-terminated, raw material compounds (dihydroxy compound (1) and carbonate compound) remaining after the transesterification reaction, the transesterification catalyst, and by-products such as phenols by-produced during the reaction, in the production process of the polycarbonate diol. From this viewpoint, it can also be referred to as a "polycarbonate diol composition" rather than a "polycarbonate diol". However, usually, it is difficult to obtain a compound consisting of 100% of the target product by a chemical reaction, and it is common general knowledge in the art that the product is in a state containing a small amount of impurities. Therefore, in the present invention, the polycarbonate diol containing impurities such as residues after the reaction is referred to as a "polycarbonate diol" rather than a "polycarbonate diol composition". The amount of impurities such as residual raw material compounds in the polycarbonate diol of the present invention is determined as the value measured when the polycarbonate diol is subjected to the measurement method for each impurity content.

[0032] <Dihydroxy compound> The dihydroxy compound that serves 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 compounds (1) include the following. Terminal dihydroxy compounds of linear hydrocarbons such as 1,10-decanediol, 1,11-undecanediol, and 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, and 1,10-dodecanediol;

[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, and 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 through one or more reactions including the reduction of carbonyl compounds such as aldehydes, ketones, carboxylic acids, carboxylic acid derivatives, etc., and the hydration reaction of alkenyl compounds. Among them, dihydroxy compounds produced through one or more reactions including the reduction reaction of carboxylic acids or carboxylic acid derivatives are preferred in that it is easy to control the acid value within the range defined in the present invention, and the effect of the present invention of controlling the acid value can be effectively exerted. Examples of the above carboxylic acid derivatives include ester compounds, amide compounds, acid anhydrides, acid halides, nitrile compounds, etc.

[0036] Also, it is preferable that the dihydroxy compound (1) is derived from plants from the viewpoint of reducing environmental load. Examples of the dihydroxy compound (1) applicable as being derived from plants include 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, etc.

[0037] The acid value of the dihydroxy compound (1) serving as 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] When the acid value of the dihydroxy compound (1) exceeds the above upper limit, the chemical resistance and heat and humidity resistance of the urethane using the obtained polycarbonate diol decrease. On the other hand, when it is less than the above lower limit, the color tone and thermal stability of the obtained polycarbonate diol deteriorate. Also, when the acid value of the dihydroxy compound (1) is less than the above lower limit, the cost of the purification process of the dihydroxy compound (1) increases, which is also disadvantageous economically.

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

[0040] In order to make the acid value of the dihydroxy compound (1) fall within the above range, the conversion rate of the raw material for obtaining the dihydroxy compound (1), for example, a carboxylic acid or a carboxylic acid derivative, to the dihydroxy compound (1) in the reduction reaction may be lowered, or the degree of purification of the dihydroxy compound (1) obtained by the above reaction may be reduced. Further, before using the dihydroxy compound (1) as a raw material for the method for producing a 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 the acid value to the above range.

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

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

[0043] Specific examples of the dialkyl carbonate, diaryl carbonate, and alkylene carbonate of the carbonic acid diester 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, ethyl isobutyl carbonate, etc., and preferably dimethyl carbonate and diethyl carbonate.

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

[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., and preferably ethylene carbonate.

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

[0048] Among these, diaryl carbonate is preferable because it is rich in reactivity and efficient in industrial production. Among them, diphenyl carbonate, which can be easily and inexpensively obtained as an industrial raw material, is more preferable.

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

[0050] <Transesterification catalyst> As the transesterification catalyst (hereinafter sometimes simply referred to as "catalyst"), any metal generally having transesterification ability can be used without limitation.

[0051] Examples of the catalyst metal 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; lanthanoid metals such as lanthanum, cerium, europium, and ytterbium. Among these, from the viewpoint of increasing the transesterification reaction rate, Group 1 metals of the periodic table, Group 2 metals of the periodic table, Group 4 metals of the periodic table, Group 5 metals of the periodic table, Group 9 metals of the periodic table, Group 12 metals of the periodic table, Group 13 metals of the periodic table, and Group 14 metals of the periodic table are preferred, Group 1 metals of the periodic table and Group 2 metals of the periodic table are more preferred, and Group 2 metals of the periodic table are still 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 still 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 still more preferred.

[0052] These metals may be used as simple substances of the metal or as metal compounds such as hydroxides and salts. Examples of salts when used as salts include halide salts such as chlorides, bromides, and iodides; carbonates; carboxylates such as acetates, formates, and benzoates; sulfonates such as methanesulfonate, toluenesulfonate, and trifluoromethanesulfonate; phosphorus-containing salts such as phosphates, hydrogen phosphates, and dihydrogen phosphates; acetylacetonate salts; and the like. The catalyst metal can also be used as an alkoxide such as methoxide or ethoxide.

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

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

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

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

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

[0058] The amount of the transesterification catalyst used is preferably an amount that does not affect the performance even if it remains in the resulting polycarbonate diol. As the weight ratio of the metal to the weight of the dihydroxy compound used as a raw material, the upper limit 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 an amount that can obtain sufficient polymerization activity.

[0059] <Reaction conditions> The reaction temperature during the transesterification reaction can be arbitrarily adopted as long as a practical reaction rate can be obtained. The temperature is not particularly limited, but the lower limit is usually 70°C, preferably 100°C, more preferably 130°C. The upper limit of the reaction temperature is usually 250°C, preferably 200°C, more preferably 190°C, even more preferably 180°C, and particularly preferably 170°C. If the reaction temperature is lower than the above lower limit, the transesterification reaction may not proceed at a practical rate. Also, if it exceeds the above upper limit, quality problems such as the resulting polycarbonate diol being colored or the formation of an ether structure may occur.

[0060] The reaction can be carried out at normal pressure, but the transesterification reaction is an equilibrium reaction, and the reaction can be biased towards the production system by distilling off the monohydroxy compound produced out of the system. Therefore, usually, it is preferable to adopt reduced pressure conditions in the latter half of the reaction to distill off the monohydroxy compound while reacting. Alternatively, it is also possible to gradually lower the pressure from the middle of the reaction and react while distilling off the monohydroxy compound produced.

[0061] Particularly, when the reaction is carried out at a higher degree of reduced pressure at the end of the reaction, it is preferable because by-products such as monohydroxy compounds such as phenols, dihydroxy compounds, and residual monomers such as carbonic acid diesters can be distilled off. The reaction pressure at the end of the reaction at this time is not particularly limited, but usually the upper limit is 10 kPa, preferably 5 kPa, 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 an inert gas such as nitrogen, argon, or helium into the reaction system.

[0062] When using a diester carbonate or dihydroxy compound with a low boiling point during the transesterification reaction, in the initial stage of the reaction, the reaction can be carried out near the boiling point of the diester carbonate or dihydroxy compound, and as the reaction progresses, the temperature can be gradually increased to further promote the reaction. This method can also be adopted. In this case, it is preferable because unreacted diester carbonate or dihydroxy compound can be prevented from distilling off in the initial stage of the reaction. Furthermore, in order to prevent the distillation of the raw materials in the initial stage of these reactions, a reflux pipe can be attached to the reactor, and the transesterification reaction can be carried out while refluxing the diester carbonate and dihydroxy compound and distilling off the monohydroxy compound. In this case, it is preferable because the charged raw material monomers are not lost and the molar ratio of the reagents can be accurately adjusted.

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

[0064] <Deactivation of the catalyst> When a catalyst is used during the transesterification reaction, usually the catalyst remains in the obtained polycarbonate diol, and the remaining metal catalyst may cause the reaction to be uncontrollable when performing the polyurethane-forming reaction. In order to suppress the influence of this remaining catalyst, a catalyst deactivator approximately equimolar to the used catalyst, for example, a phosphorus-based or sulfur-based compound that is acidic or decomposes into an acidic compound, may be added. Furthermore, after the addition, heat treatment as described below can efficiently deactivate the transesterification catalyst.

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

[0066] The amount of the phosphorus compound or the like used for deactivating the catalyst is not particularly limited. However, as described above, it may be approximately equimolar to the transesterification catalyst used. Specifically, the upper limit is preferably 5 mol, more preferably 2 mol, and the lower limit is preferably 0.8 mol, more preferably 1.0 mol, per 1 mol of the transesterification catalyst used. When an amount of the phosphorus compound or the like less than this is used, deactivation of the transesterification catalyst is insufficient, and when the obtained polycarbonate diol is used as a raw material for polyurethane production, for example, the reactivity of the polycarbonate diol with respect to the isocyanate group may not be sufficiently reduced. Further, when a phosphorus compound or the like exceeding this range is used, the obtained polycarbonate diol may be colored.

[0067] Deactivation of the transesterification catalyst by adding a phosphorus compound or the like can be carried out even at room temperature, but heat treatment is more efficient. The temperature of this heat treatment is not particularly limited, but the upper limit is preferably 150 °C, more preferably 120 °C, still more preferably 100 °C, and the lower limit is preferably 50 °C, more preferably 60 °C, still more preferably 70 °C. When the temperature is lower than this, it takes time to deactivate the transesterification catalyst and is not efficient, and deactivation may be insufficient. On the other hand, when the temperature exceeds 150 °C, the obtained polycarbonate diol may be colored.

[0068] The time for reacting with the phosphorus compound or the like is not particularly limited, but is usually 1 to 5 hours.

[0069] <Purification> The reaction product obtained by the transesterification reaction contains impurities having no hydroxyl group at the polymer terminal, phenol, raw material dihydroxy compound, raw material carbonate compound, by-produced low-boiling cyclic carbonate, added catalyst, etc., and thus can be purified for the purpose of removing these. For the purification at that time, for the low-boiling compound, a method of distilling off by distillation can be adopted. As a specific method of distillation, there is no particular limitation on its form such as vacuum distillation, steam distillation, thin-film distillation, etc., and any method can be adopted, but among them, thin-film distillation is effective.

[0070] There is no particular limitation on the thin-film distillation conditions, but the temperature during thin-film distillation preferably has an upper limit of 250 °C, more preferably 200 °C. Also, the lower limit is preferably 120 °C, more preferably 150 °C. By setting the lower limit of the temperature during thin-film distillation to the above value, the removal effect of the low-boiling components becomes sufficient. Also, by setting the upper limit to 250 °C, it is possible to prevent the polycarbonate diol obtained after thin-film distillation from coloring.

[0071] The pressure during thin-film distillation preferably has an upper limit of 500 Pa, more preferably 150 Pa, and even more preferably 50 Pa. By setting the pressure during thin-film distillation to be equal to or lower than the above upper limit value, a sufficient removal effect of the low-boiling components can be obtained. Also, the temperature for keeping the polycarbonate diol warm immediately before thin-film distillation preferably has an upper limit of 250 °C, more preferably 150 °C. Also, the lower limit is preferably 80 °C, more preferably 120 °C.

[0072] By setting the temperature for keeping the polycarbonate diol warm immediately before thin-film distillation to be equal to or higher than the above lower limit, it is possible to prevent the fluidity of the polycarbonate diol immediately before thin-film distillation from decreasing. On the other hand, by setting it to be equal to or lower than the above upper limit, it is possible to prevent the polycarbonate diol obtained after thin-film distillation from coloring.

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

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

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

[0076] Here, Mw is the weight average molecular weight and Mn is the number average molecular weight, and it can usually be determined by measurement 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] <Ratio of terminal alkyloxy group or aryloxy group · Hydroxyl value> The polycarbonate diol of the present invention basically has a hydroxyl group at the terminal structure of the polymer, that is, a hydroxy terminal. However, in the reaction product obtained by the reaction of a dihydroxy compound and a diester carbonate, there may be a case where some of the polymer terminals have a structure other than a hydroxyl group as impurities. Specific examples of the structure include those having an alkyloxy group or an aryloxy group at the molecular chain terminal, and many are structures derived from a diester carbonate. The ratio of the hydroxyl group (hydroxy terminal), alkyloxy group, and aryloxy group is usually 1 Calculated by H-NMR.

[0078] For example, when diphenyl carbonate is used as the diester carbonate, a phenoxy group (PhO-) is used as the aryloxy group, when dimethyl carbonate is used, a methoxy group (MeO-) is used as the alkyloxy group, when diethyl carbonate is used, an ethoxy group (EtO-) is used as the alkyloxy group, and when ethylene carbonate is used, a hydroxyethoxy group (HOCH2CH2O-) may remain as the terminal group (here, Ph represents a phenyl group, Me represents a methyl group, and Et represents an ethyl group).

[0079] In the present invention, the ratio of the structure having a hydroxy terminal rather than an alkyloxy group or an aryloxy group among the molecular chain terminals contained in the polycarbonate diol is usually 95 mol% or more, preferably 98.5 mol% or more, more preferably 99 mol% or more, based on the total number of terminal groups. The upper limit of the ratio of the number of hydroxy terminals in this molecular chain is not particularly limited, usually 99.9 mol%, preferably 99.999 mol%, and most preferably 100 mol%. When the ratio of the hydroxy terminal is large, the degree of polymerization can be sufficiently increased during the polyurethane-forming reaction, and the reaction can proceed smoothly.

[0080] The polycarbonate diol of the present invention has a ratio of the number of terminal groups of the molecular chain being an alkyloxy group or an aryloxy group of usually 5 mol% or less as described above, and both terminal groups of the molecular chain are basically hydroxyl groups (hydroxy terminals). During the polyurethane-forming reaction, these hydroxyl groups can react with isocyanates.

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

[0082] The hydroxyl value can be measured by a generally known method. 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 usually exhibits a waxy solid state near room temperature, but its viscosity can be reduced by heating, making it easier to handle. It can also be dissolved in amide solvents such as dimethylformamide and dimethylacetamide, ester solvents such as γ-butyrolactone, and sulfoxide solvents such as dimethyl sulfoxide, which may make transfer and reaction easier.

[0084] <Hazen color number> The color of the polycarbonate diol of the present invention preferably has a range that does not affect the color of the resulting polyurethane. The value when the degree of coloring is represented by the Hazen color number (conforming to JIS K0071-1 (1998)) (hereinafter referred to as the "Hazen color number value") is not particularly limited, but 50 or less is preferred, more preferably 40 or less, still more preferably 30 or less, and particularly preferably 20 or less.

[0085] <Residual catalyst amount> In the polycarbonate diol of the present invention, a transesterification catalyst used in the production of the polycarbonate diol of the present invention may remain. However, if an excessive amount of catalyst remains, it becomes difficult to control the reaction during the polyurethane formation reaction, and the polyurethane formation reaction may be promoted more than expected and gelation may occur, resulting in a situation where a uniform polyurethane cannot be obtained. 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. However, from the viewpoint of obtaining a homogeneous polyurethane from this polycarbonate diol, the content in terms of catalyst metal is usually 100 ppm by weight, preferably 50 ppm by weight, more preferably 30 ppm by weight, and particularly preferably 10 ppm by weight. Examples of the type of metal remaining include the metals of the catalyst active components having the aforementioned transesterification ability.

[0087] Also, the lower limit of the amount of catalyst remaining in the polycarbonate diol of the present invention is not particularly limited. However, the content in terms of catalyst metal 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. Usually, it is difficult to remove the catalyst used in the production of polycarbonate diol after production, and in many cases, it is difficult to make the remaining amount of catalyst less than the lower limit value of the usage amount described later.

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

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

[0090] (Carbonic acid diester) In the polycarbonate diol of the present invention, the carbonic acid diester used as a raw material during production may remain. The residual amount of the carbonic acid diester in the polycarbonate diol of the present invention is not limited, but less is preferred. Usually, the upper limit is 5% by weight, preferably 3% by weight, more preferably 1% by weight. If the carbonic acid diester content of the polycarbonate diol is too high, the reaction during polyurethane formation may be inhibited. On the other hand, the lower limit is not particularly limited and is 0.1% by weight, preferably 0.01% by weight, more preferably 0% by weight.

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

[0092] [Polyurethane] Using the polycarbonate diol of the present invention, polyurethanes and polyurethane aqueous dispersions can be produced. The produced polyurethane is another form of the present invention.

[0093] The method for producing polyurethane using the polycarbonate diol of the present invention usually employs known polyurethane-forming reaction conditions for producing polyurethane. For example, polyurethane can be produced by reacting a polycarbonate diol, a polyisocyanate, and a chain extender in the range from room temperature to 200°C. Alternatively, a polycarbonate diol and an excess of polyisocyanate are first reacted to produce a prepolymer having isocyanate groups at the terminals, and then the degree of polymerization is increased using a chain extender to produce a polyurethane.

[0094] [Polyisocyanate] Examples of the polyisocyanate used in producing polyurethane using the polycarbonate diol 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 dimer acid into 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, 1,3-bis(isocyanatomethyl)cyclohexane, and 1,4-bis(isocyanatomethyl)cyclohexane; aromatic diisocyanates such as xylylene diisocyanate, 4,4'-diphenyl diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate, and m-tetramethylxylylene diisocyanate. These may be used alone or in combination of two or more.

[0095] Among these, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and isophorone diisocyanate are preferred in terms of the favorable balance of the physical properties of the resulting polyurethane and the availability in large quantities at low cost industrially.

[0096] <Chain extender> The chain extender used in the production of polyurethane is a low-molecular-weight compound having at least two active hydrogens that react with isocyanate groups in the case of producing a prepolymer having an isocyanate group described later, and usually, polyols, polyamines, etc. can be mentioned.

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

[0098] Among these, in terms of the favorable balance of the physical properties of the resulting polyurethane and the availability of large quantities at low industrial cost, 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, 4,4'-diaminodicyclohexylmethane are preferred.

[0099] In addition, the chain extender in the production of the prepolymer having a hydroxyl group described later is a low-molecular-weight compound having at least two isocyanate groups, and specifically, compounds as described in <Polyisocyanate> can be mentioned.

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

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

[0102] <Polyol other than the polycarbonate diol of the present invention> In the polyurethane-forming reaction for producing polyurethane, the polycarbonate diol of the present invention and, if necessary, a polyol other than the polycarbonate diol of the present invention (hereinafter also referred to as "other polyol") may be used in combination. Here, the other polyol is not particularly limited as long as it is used in the production of ordinary polyurethane. Examples include polyether polyol, polycarbonate polyol, polyester polyol, polycaprolactone polyol, and polycarbonate diol other than the polycarbonate diol of the present invention. For example, when used in combination with a polyether polyol, a polyurethane with further improved flexibility, which is a characteristic of the polycarbonate diol of the present invention, can be obtained.

[0103] When using the other polyol 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 polyol is preferably 70% or more, more preferably 90% or more. If the weight ratio of the polycarbonate diol of the present invention is small, 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, other polyols, and other raw materials need to be sufficiently compatible. If the compatibility is not sufficient, the urethanization reaction proceeds unevenly, the molecular weight distribution of the resulting polyurethane broadens, or the molecular weight decreases, which may cause the polyurethane solution to gel, the storage stability to deteriorate, or the strength, solvent resistance, weather resistance, and heat resistance of the polyurethane to decrease.

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

[0106] <Polyurethane production method> As a method for producing polyurethane using the above reaction reagents, generally, production methods used experimentally or industrially can be used. Examples thereof include a method of mixing and reacting the polycarbonate diol of the present invention, other polyols used as necessary, polyisocyanates, and chain extenders all at once (hereinafter sometimes referred to as the "one-step method"), and a method in which first the polycarbonate diol of the present invention, other polyols, and polyisocyanates are reacted to prepare a prepolymer having 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] In the two-step method, the polycarbonate diol of the present invention and other polyols used as necessary are reacted in advance with 1 equivalent or more of polyisocyanate to prepare an isocyanate intermediate having both ends corresponding to the soft segment of polyurethane. In this way, when the prepolymer is once prepared and then reacted with a chain extender, it may be easy to adjust the molecular weight of the soft segment portion, and it is useful when it is necessary to surely perform phase separation between the soft segment and the hard segment.

[0108] <One-step method> The one-step method, also called the one-shot method, is a method of performing a reaction by charging the polycarbonate diol of the present invention, other polyols, polyisocyanates, and chain extenders all at once. The amount of polyisocyanate used in the one-step method is not particularly limited. However, 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 equivalent, more preferably 0.8 equivalent, still more preferably 0.9 equivalent, and particularly preferably 0.95 equivalent, and the upper limit is preferably 3.0 equivalents, more preferably 2.0 equivalents, still more preferably 1.5 equivalents, and particularly preferably 1.1 equivalents.

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

[0110] <Two-step method> The two-step method is also called the prepolymer method and mainly includes the following methods. (a) A method of reacting the polycarbonate diol and other polyols of the present invention and an excess of polyisocyanate in an amount such that the reaction equivalent ratio of polyisocyanate / (the polycarbonate diol and other polyols of the present invention) exceeds 1 and is 10.0 or less to produce a prepolymer having isocyanate groups at the molecular chain ends, and then adding a chain extender thereto to produce a polyurethane. (b) A method of reacting polyisocyanate and an excess of the polycarbonate diol and other polyols of the present invention in an amount such that the reaction equivalent ratio of polyisocyanate / (the polycarbonate diol and other polyols of the present invention) is 0.1 or more and less than 1.0 to produce a prepolymer having hydroxyl groups at the molecular chain ends, and then reacting a polyisocyanate having isocyanate groups at the ends therewith as a chain extender to produce a polyurethane.

[0111] The two-step method can be carried out either without a solvent or in the presence of a solvent. The production of polyurethane by the two-step method can be carried out by any of the methods (1) to (3) described below. (1) Without using a solvent, first directly react a polyisocyanate with the polycarbonate diol of the present invention and other polyols to synthesize a prepolymer, and use it directly for the chain extension reaction. (2) Synthesize a prepolymer by the method of (1), then dissolve it in a solvent, and use it for the subsequent chain extension reaction. (3) Use a solvent from the beginning, react a polyisocyanate with the polycarbonate diol of the present invention and other polyols, and then carry out a chain extension reaction.

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

[0113] If the amount of isocyanate used is too large, excessive isocyanate groups will cause side reactions and it is difficult to reach the physical properties of the desired polyurethane. For example, the viscosity becomes too high and the flexibility of the obtained polyurethane decreases, or the handling is poor and the productivity is inferior. If it is too small, the molecular weight of the obtained polyurethane may not increase sufficiently and the strength and thermal stability may be low. Although the amount of the chain extender used is not particularly limited, based on 1 equivalent of the number of isocyanate groups contained in the prepolymer, the lower limit is preferably 0.1 equivalent, more preferably 0.5 equivalent, still more preferably 0.8 equivalent, and the upper limit is preferably in the range of 5.0 equivalents, more preferably 3.0 equivalents, still more preferably 2.0 equivalents.

[0114] When carrying out the above chain extension reaction, for the purpose of adjusting the molecular weight, monofunctional organic amines or alcohols may coexist.

[0115] Also, the amount of the polyisocyanate used when preparing the prepolymer having a hydroxyl group at the terminal in the method of the two-step process (b) is not particularly limited, but based on the number of isocyanate groups when the total number of hydroxyl groups of the polycarbonate diol of the present invention and other polyols is 1 equivalent, the lower limit is preferably 0.1 equivalent, more preferably 0.5 equivalent, still more preferably 0.7 equivalent, and the upper limit is preferably 0.99 equivalent, more preferably 0.98 equivalent, still more preferably 0.97 equivalent.

[0116] If the amount of the isocyanate used is too small, the process until the desired molecular weight is obtained in the subsequent chain extension reaction tends to be long and the production efficiency tends to decrease. If it is too large, the viscosity becomes too high, the flexibility of the obtained polyurethane decreases, or the handleability becomes poor and the productivity deteriorates.

[0117] Although the amount of the chain extender used is not particularly limited, when the total number of hydroxyl groups of the polycarbonate diol of the present invention and other polyols used in the prepolymer is 1 equivalent, based on the total equivalent obtained by adding the equivalent of the isocyanate groups used in the prepolymer, the lower limit is preferably 0.7 equivalent, more preferably 0.8 equivalent, still more preferably 0.9 equivalent, and the upper limit is preferably less than 1.0 equivalent, more preferably 0.99 equivalent, still more preferably 0.98 equivalent.

[0118] When carrying out the above chain extension reaction, for the purpose of adjusting the molecular weight, monofunctional organic amines or alcohols may coexist.

[0119] The chain extension reaction is usually carried out at a temperature of 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 is no particular limitation. If the temperature is too low, the progress of the reaction may be slow, or the production time may be prolonged due to low solubility of the raw materials and polymers. If the temperature is too high, side reactions and decomposition of the resulting polyurethane may occur. The chain extension reaction may be carried out while degassing under reduced pressure.

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

[0121] <Aqueous polyurethane dispersion> Using the polycarbonate diol of the present invention, it is also possible to produce an aqueous polyurethane dispersion, and a more highly dispersible aqueous polyurethane dispersion can be produced as compared with conventional polycarbonate diols. In addition, the aqueous polyurethane dispersion has excellent storage stability because it rarely aggregates during storage. In that case, when producing a prepolymer by reacting a polyol containing the polycarbonate diol of the present invention with an excess of polyisocyanate, at least one hydrophilic functional group and a compound having at least two isocyanate-reactive groups are mixed to form a prepolymer, and through a neutralization salification step of the hydrophilic functional group, an emulsification step by adding water, and a chain extension reaction step, an aqueous polyurethane dispersion is obtained. 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 aforementioned polyurethane production.

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

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

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

[0125] When producing an aqueous polyurethane dispersion, in the prepolymer step, the reaction may be carried out in the presence of a solvent such as methyl ethyl ketone, acetone, or N-methyl-2-pyrrolidone, or the reaction may be carried out without a solvent. When using a solvent, it is preferable to distill off 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, still more preferably 3,000, and particularly preferably 2,000. The lower limit of the number average molecular weight is preferably 300, more preferably 500, still more preferably 800. If the number average molecular weight determined from the hydroxyl value exceeds the above upper limit or is less than the above lower limit, it may be difficult to form a dispersion.

[0127] When producing an aqueous polyurethane dispersion, the polycarbonate diol of the present invention may be used in combination with other polyols as necessary. Here, other polyols are not particularly limited as long as they are those used in ordinary polyurethane production. Examples include polyether polyols, polycarbonate polyols, polyester polyols, polycaprolactone polyols, and polycarbonate diols other than the polycarbonate diol of the present invention. For example, when used in combination with a polyether polyol, a polyurethane with further improved flexibility, which is a characteristic of the polycarbonate diol of the present invention, can be obtained.

[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 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 small, the characteristics and handleability of the polyurethane, which are the features of the present invention, may be lost.

[0129] When other polyols are used in combination during the production of an aqueous polyurethane dispersion, the polycarbonate diol of the present invention, other polyols used as necessary, and other raw materials need to be sufficiently dispersed or dissolved in the aqueous solvent. If the dispersibility is not sufficient, the urethanization reaction proceeds unevenly, the molecular weight distribution of the resulting aqueous polyurethane dispersion broadens, or the molecular weight decreases, resulting in aggregation of the aqueous polyurethane dispersion or poor storage stability. In addition, the strength, solvent resistance, weather resistance, heat resistance, etc. of the polyurethane obtained from the aqueous polyurethane dispersion may deteriorate.

[0130] In the synthesis or storage of an aqueous polyurethane dispersion, an anionic surfactant represented by higher fatty acids, resin acids, acidic fatty alcohols, sulfates, higher alkyl sulfonates, alkylaryl sulfonates, sulfonated castor oil, sulfosuccinic esters, etc., a cationic surfactant such as a primary amine salt, secondary amine salt, tertiary amine salt, quaternary amine salt, pyridinium salt, or a nonionic surfactant represented by a known reaction product of ethylene oxide and a long-chain fatty alcohol or phenols may be used in combination to maintain emulsion stability.

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

[0132] The aqueous polyurethane dispersion thus produced can be used for various applications. In particular, recently, chemical raw materials with a small environmental impact have been demanded, and it is possible to replace conventional products for the purpose of not using organic solvents.

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

[0134] <Storage Stability of Polyurethane Solution and Aqueous Polyurethane Dispersion> Using an organic solvent and / or water, the storage stability of the polyurethane solution and aqueous polyurethane dispersion produced using the polycarbonate diol of the present invention can be measured visually or the like by 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, and then checking for any changes in the solution or dispersion.

[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 isophoronediamine of the present invention by the aforementioned two-step method, the period during which no visual change is observed in the polyurethane solution when stored at -10°C is preferably 8 hours, more preferably 1 day or more, still more preferably 3 days or more, and even more preferably 7 days or more. Also, when stored at 0°C, the period during which no visual change is observed in the polyurethane solution and the polyurethane dispersion is preferably 1 month, more preferably 3 months or more, still more preferably 6 months or more.

[0136] Also, for example, regarding an 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 visual change is observed in the polyurethane aqueous dispersion when stored at 20°C is preferably 1 day, more preferably 3 days, still more preferably 7 days or more, even more preferably 14 days, and particularly preferably 1 month or more.

[0137] <Additive> Various additives such as heat stabilizers, light stabilizers, colorants, fillers, stabilizers, ultraviolet absorbers, antioxidants, anti-adhesion agents, flame retardants, anti-aging agents, and inorganic fillers can be added and mixed into the polyurethane of the present invention produced using the polycarbonate diol of the present invention, as long as the properties of the polyurethane are not impaired.

[0138] Examples of compounds that can be used as heat stabilizers include phosphoric acid, aliphatic, aromatic or alkyl-substituted aromatic esters of phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonates, dialkyl pentaerythritol diphosphite, dialkyl bisphenol A diphosphite and other phosphorus compounds; phenolic derivatives, especially hindered phenol compounds; sulfur-containing compounds such as thioether-based, dithiocarboxylate-based, mercaptobenzimidazole-based, thiocarbanyl-based, thiodipropionate-based compounds; tin-based compounds such as tin maleate, dibutyltin monoxide, etc. can be used.

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

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

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

[0142] Examples of light stabilizers include benzotriazole-based, benzophenone-based compounds, etc. Specifically, "TINUVIN622LD", "TINUVIN765" (both manufactured by Ciba Specialty Chemicals Inc.), "SANOL LS-2626", "SANOL LS-765" (both manufactured by Sankyo Co., Ltd.), etc. can be used.

[0143] Examples of the ultraviolet absorber include "TINUVIN 328", "TINUVIN 234" (both manufactured by Ciba Specialty Chemicals Inc.), and the like.

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

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

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

[0147] These additives may be used alone, or two or more of them may be combined in any combination and ratio. The addition amount of these additives, as a weight ratio to the polyurethane, preferably has a lower limit of 0.01% by weight, more preferably 0.05% by weight, still more preferably 0.1% by weight, and an upper limit of preferably 10% by weight, more preferably 5% by weight, still more preferably 1% by weight. If the addition amount of the additive is too small, the addition effect cannot be sufficiently obtained, and if it is too large, precipitation or turbidity may occur in the polyurethane.

[0148] <Polyurethane film - Polyurethane plate> When producing a film using the polyurethane of the present invention, the thickness of the film preferably has a lower limit of 10 μm, more preferably 20 μm, still more preferably 30 μm, and an upper limit of preferably 1000 μm, more preferably 500 μm, still more preferably 100 μm. If the film thickness is too thick, sufficient moisture permeability tends not to be obtained. On the other hand, if it is too thin, pinholes tend to occur, and the film tends to be blocked and difficult to handle.

[0149] <Molecular weight> The molecular weight of the polyurethane of the present invention is appropriately adjusted according to its use and is not particularly limited. However, the weight average molecular weight (Mw) in terms of polystyrene measured by GPC is preferably 50,000 to 500,000, and more preferably 100,000 to 300,000. If Mw is smaller than the above lower limit, sufficient strength and hardness may not be obtained. If it is larger than the above upper limit, handling properties such as processability tend to be impaired.

[0150] The molecular weight distribution (Mw / Mn) of the polyurethane of the present invention is not particularly limited. However, the lower limit is usually 1.5, preferably 1.7, and more preferably 1.8. The upper limit is usually 3.5, preferably 3.0. When the molecular weight distribution exceeds the above upper limit, the moldability and handling properties tend to decrease. When attempting to produce a polyurethane with a molecular weight distribution less than the above lower limit, an advanced purification operation may be required. In addition, by using the polycarbonate diol of the present invention produced using the dihydroxy compound (1), an effect of being able to produce a polyurethane with a small molecular weight distribution is also achieved.

[0151] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polyurethane are usually determined by standard polystyrene conversion from the measured values of gel permeation chromatography (GPC).

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

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

[0154] <Applications> The polyurethane of the present invention is excellent in solvent resistance and has good flexibility and mechanical strength. Therefore, it can be widely used in foams, elastomers, elastic fibers, paints, fibers, adhesives, binders, floor materials, sealants, medical materials, artificial leather, synthetic leather, coating agents, water-based polyurethane paints, active energy ray curable polymer compositions, etc. In particular, when using the polyurethane which is one form of the present invention for applications such as artificial leather, synthetic leather, water-based polyurethane, adhesives, elastic fibers, medical materials, floor materials, paints, coating agents, etc., it has a good balance of solvent resistance, flexibility, and mechanical strength. Therefore, it has high durability in parts where it touches human skin or where cosmetic drugs or disinfecting alcohol are used, sufficient flexibility, and can impart good characteristics of being strong against physical impacts, etc. Also, it can be suitably used for automotive applications such as automotive parts that require heat resistance and outdoor applications that require weather resistance.

[0155] The polyurethane of the present invention can be used in thermosetting elastomers and cast polyurethane elastomers. As its specific applications, there are rolls such as rolling rolls, paper-making rolls, office equipment, and pretension rolls, solid tires such as forklifts, automotive vehicle neutrams, carts, and transport vehicles, casters, etc. As industrial products, there are conveyor belt idlers, guide rolls, pulleys, steel pipe linings, rubber screens for ore, gears, connection rings, liners, impellers of pumps, cyclone cones, cyclone liners, etc. In addition, it can also be used in belts of OA equipment, paper feed rolls, cleaning blades for copying, snow plows, toothed belts, surf rollers, etc.

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

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

[0158] The polyurethane of the present invention can also be 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 adhesives for low temperatures and hot melts. The polyurethane of the present invention can be used as a binder for magnetic recording media, inks, castings, fired bricks, graft materials, microcapsules, granular fertilizers, granular pesticides, polymer cement mortars, resin mortars, rubber chip binders, recycled foams, glass fiber sizings, etc.

[0159] The polyurethane of the present invention can be used as a component of fiber processing agents for shrink-proofing, wrinkle-proofing, water-repellent processing, etc. When the polyurethane of the present invention is used as an elastic fiber, the method of fiberizing it can be carried out without particular limitation as long as it can be spun. For example, after once pelletizing, a melt spinning method of melting and directly spinning through a spinneret can be adopted. When elastic fibers are obtained from the polyurethane of the present invention by melt spinning, the spinning temperature is preferably 250°C or lower, more preferably 200°C or higher and 235°C or lower.

[0160] The polyurethane elastic fiber can be used as a bare yarn as it is, or can be coated with other fibers and used as a coated yarn. Examples of other fibers include conventionally known fibers such as polyamide fibers, wool, cotton, and polyester fibers. Among them, polyester fibers are preferably used in the present invention. Further, the elastic fiber using the polyurethane of the present invention may contain a disperse dye of the dyeing type.

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

[0162] The polyurethane of the present invention can be used as a medical material. As a blood-compatible material, it can be used for tubes, catheters, artificial hearts, artificial blood vessels, artificial valves, etc. Also, as a disposable material, it can be used 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, photocurable optical fiber coating compositions, etc. by modifying the terminals.

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

[0164] In the present invention, when expressed as "(meth)acryl" such as (meth)acrylate or (meth)acrylic acid, it means acrylic and / or methacrylic. Also, the charging ratio of each raw material compound at that time is made substantially equivalent to or the same as the composition of the target urethane (meth)acrylate-based oligomer. In the urethane (meth)acrylate-based oligomer, the amount of all isocyanate groups and the amount of all functional groups that react with isocyanate groups such as hydroxyl groups and amino groups are usually stoichiometrically equivalent.

[0165] When producing a urethane (meth)acrylate-based oligomer, the usage amount of hydroxyalkyl (meth)acrylate 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, based on the total usage amount of hydroxyalkyl (meth)acrylate, the polycarbonate diol of the present invention, and other raw material compounds such as polyols and compounds containing functional groups that react with isocyanates such as chain extenders used as needed. According to this ratio, the molecular weight of the obtained urethane (meth)acrylate-based oligomer can be controlled. When the ratio of hydroxyalkyl (meth)acrylate is large, the molecular weight of the urethane (meth)acrylate-based oligomer tends to be small, and when the ratio is small, the molecular weight tends to be large.

[0166] It is preferable that the usage amount of the polycarbonate diol of the present invention is 25 mol% or more, more preferably 50 mol% or more, and still more preferably 70 mol% or more, based on the total usage amount of the polycarbonate diol of the present invention and other polyols. When the usage amount of the polycarbonate diol of the present invention is at or above the above lower limit value, the elongation, hardness, weather resistance, and stain resistance of the obtained cured product tend to be good, which is preferable.

[0167] In addition, with respect to the total usage amount of the polycarbonate diol of the present invention and other polyols, the usage amount of the polycarbonate diol of the present invention is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, and particularly preferably 70% by weight or more. When the usage amount of the polycarbonate diol of the present invention is at least the above lower limit value, the viscosity of the resulting composition decreases and the workability improves, and the mechanical strength, hardness, and abrasion resistance of the resulting cured product tend to improve, which is preferable.

[0168] Furthermore, when using a chain extender, with respect to the total usage amount of the polycarbonate diol of the present invention, other polyols, and the compound combined with the chain extender, the usage amount of the polycarbonate diol of the present invention and other polyols is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and particularly preferably 95 mol% or more. When exceeding the above lower limit value, the liquid stability tends to improve, which is preferable.

[0169] When producing a urethane (meth) acrylate - based oligomer, a solvent can be used for the purpose of adjusting the viscosity. The solvent may be used alone or in combination of two or more. Any known solvent can be used as the solvent. Preferred solvents include toluene, xylene, ethyl acetate, butyl acetate, cyclohexanone, methyl ethyl ketone, and methyl isobutyl ketone. The solvent can usually be used in an amount of less than 300 parts by weight with respect to 100 parts by weight of the solid content in the reaction system.

[0170] When producing a urethane (meth) acrylate - based oligomer, the total content of the resulting urethane (meth) acrylate - based oligomer and its raw material compounds is preferably 20% by weight or more, more preferably 40% by weight or more, with respect to the total amount of the reaction system. Note that the upper limit of this total content is 100% by weight. When the total content of the urethane (meth) acrylate - based oligomer and its raw material compounds is 20% by weight or more, the reaction rate increases and the production efficiency tends to improve, which is preferable.

[0171] When producing urethane (meth)acrylate oligomers, an addition reaction catalyst can be used. Examples of such addition reaction catalysts include dibutyltin laurate, dibutyltin dioctoate, dioctyltin dilaurate, and dioctyltin dioctoate. The addition reaction catalyst may be used alone or in combination of two or more. Among these, dioctyltin dilaurate is preferable from the viewpoints of environmental adaptability, catalytic activity, and storage stability.

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

[0173] Also, when producing urethane (meth)acrylate oligomers, if the reaction system contains a (meth)acryloyl group, 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. The polymerization inhibitor may be used alone or in combination of two or more. Among these, phenols are preferable.

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

[0175] When producing a urethane (meth)acrylate-based oligomer, the reaction temperature is usually 20°C or higher, preferably 40°C or higher, and more preferably 60°C or higher. When the reaction temperature is 20°C or higher, the reaction rate increases, and the production efficiency tends to improve, which is preferable. Also, the reaction temperature is usually 120°C or lower, preferably 100°C or lower. When the reaction temperature is 120°C or lower, side reactions such as allophanatization reactions are less likely to occur, which is preferable. Further, when the reaction system contains a solvent, the reaction temperature is preferably below the boiling point of the solvent, and when (meth)acrylate is present, it is preferably 70°C or lower from the viewpoint of preventing the reaction of the (meth)acryloyl group. The reaction time is usually about 5 to 20 hours.

[0176] The number average molecular weight of the urethane (meth)acrylate-based oligomer thus obtained 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-based oligomer is at least the above lower limit, the three-dimensional processing suitability of the resulting cured film becomes good, and the balance between three-dimensional processing suitability and stain resistance tends to be excellent, which is preferable. When the number average molecular weight of the urethane (meth)acrylate-based oligomer is at most the above upper limit, the stain resistance of the cured film obtained from the composition becomes good, and the balance between three-dimensional processing suitability and stain resistance tends to be excellent, which is preferable. This is presumably because the three-dimensional processing suitability and stain resistance depend on the distance between crosslinking points in the network structure. When this distance becomes long, the structure becomes flexible and easy to stretch, with excellent three-dimensional processing suitability, and when this distance becomes short, the network structure becomes a strong structure with excellent stain resistance.

[0177] <Polyester-based elastomer> The polycarbonate diol of the present invention can be used as a polyester-based elastomer. A polyester-based elastomer is a copolymer composed mainly of a hard segment made of an aromatic polyester and a soft segment made mainly of an aliphatic polyether, an aliphatic polyester, or an aliphatic polycarbonate. When the polycarbonate diol of the present invention is used as a constituent component of the soft segment, physical properties such as heat resistance and water resistance are superior compared to the case where an aliphatic polyether or an aliphatic polyester is used. Further, compared with known polycarbonate diols, it has a melt viscosity at the time of melting, that is, a melt flow rate suitable for blow molding and extrusion molding, and becomes a polycarbonate polyester elastomer excellent in balance with mechanical strength and other physical properties, and can be suitably used for various molding materials such as fibers, films, and sheets, for example, molding materials such as elastic yarns and boots, gears, tubes, and packings. Specifically, it can be effectively applied to uses such as joint boots for automobiles and home appliance parts that require heat resistance and durability, and wire coating materials.

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

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

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

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

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

[0183] For example, in a composition composed of a mixture of 40 moles of a monofunctional compound having a molecular weight of 100 and 4 moles of a bifunctional compound having a molecular weight of 1,000, the number of active energy ray reactive groups of the polyfunctional compound is 2×4 = 8, so the elongation due to the monofunctional compound in the molecular weight between the calculated network crosslinking points is 100×40 / 8 = 500. That is, the molecular weight between the calculated network crosslinking points of the composition is 1000 + 500 = 1500.

[0184] From the above, a monofunctional compound M A with a molecular weight of W A moles, a polyfunctional compound M B with a functionality of f B and a molecular weight of W B moles, a polyfunctional compound M C with a functionality of f C and a molecular weight of W CIn a mixture with moles, the molecular weight between the calculated network crosslinking points of the composition can be expressed by the following formula.

[0185] [Number]

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

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

[0188] The active energy ray curable polymer composition may further contain other components other than the urethane (meth) acrylate-based 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 the active energy ray-curable polymer composition, the content of the urethane (meth) acrylate oligomer is preferably 40% by weight or more, more preferably 60% by weight or more, based on the total amount of the active energy ray-reactive components including the urethane (meth) acrylate oligomer. The upper limit of this content is 100% by weight. When the content of the urethane (meth) acrylate oligomer is 40% by weight or more, the curability is good, the mechanical strength of the cured product does not become too high, and the three-dimensional processability tends to improve, which is preferable.

[0190] Also, in the active energy ray-curable polymer composition, the content of the urethane (meth) acrylate oligomer is preferably larger in terms of elongation and film-forming property, while it is preferably smaller in terms of viscosity reduction. From such a viewpoint, the content of the urethane (meth) acrylate oligomer is preferably 50% by weight or more, more preferably 70% by weight or more, based on the total amount of all components including other components in addition to the active energy ray-reactive components. The upper limit value of the content of the urethane (meth) acrylate oligomer is 100% by weight, and this content is preferably 100% by weight or less.

[0191] Also, in the active energy ray-curable polymer composition, the content of the total amount of the active energy ray-reactive components including the urethane (meth) acrylate oligomer is preferably 60% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, particularly preferably 95% by weight or more, based on the total amount of the composition, from the aspects of excellent curing rate and surface curability of the composition and no remaining tack. The upper limit of this content is 100% by weight.

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

[0193] Examples of such active energy ray-reactive monomers include vinyl ethers, (meth)acrylamides, and (meth)acrylates. Specifically, for example, aromatic vinyl monomers such as styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, divinylbenzene; vinyl ester monomers such as vinyl acetate, vinyl butyrate, N-vinylformamide, N-vinylacetamide, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, divinyl adipate; vinyl ethers such as ethyl vinyl ether, phenyl vinyl ether; allyl compounds such as diallyl phthalate, trimethylolpropane diallyl ether, 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, N-t-butyl(meth)acrylamide, (meth)acryloylmorpholine, methylenebis(meth)acrylamide; monofunctional (meth)acrylates such as (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 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, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, tricyclodecane (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, allyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate; and di(meth)acrylates such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate (n = 5 - 14), propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate (n = 5 - 14), 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol, polybutylene glycol di(meth)acrylate (n = 3 - 16), poly(1-methylbutylene glycol) di(meth)acrylate (n = 5 - 20), 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, dicyclopentane diol di(meth)acrylate, tricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane trioxyethyl (meth)acrylate, trimethylolpropane trioxypropyl (meth)acrylate, trimethylolpropane polyoxyethyl (meth)acrylate, trimethylolpropane polyoxypropyl (meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, ethylene oxide adduct bisphenol A di(meth)acrylate, ethylene oxide adduct bisphenol F di(meth)acrylate, propylene oxide adduct bisphenol A di(meth)acrylate, propylene oxide adduct bisphenol F di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, bisphenol A epoxy di(meth)acrylate, bisphenol F epoxy di(meth)acrylate and other polyfunctional (meth)acrylates; are mentioned.,

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

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

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

[0197] The polymerization initiator is mainly used for the purpose of improving the initiation efficiency of the polymerization reaction that proceeds by irradiation with active energy rays such as ultraviolet rays and electron beams. As the polymerization initiator, a photo radical polymerization initiator, which is a compound having the property of generating radicals by light, is generally used, and any known photo radical polymerization initiator can be used. The polymerization initiator may be used alone or in combination of two or more. Further, a photo radical polymerization initiator and a photosensitizer may be used in combination.

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

[0199] Among these, from the viewpoint of fast curing rate and sufficient increase in crosslink density, benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl]-2-methyl-propan-1-one are preferable, and 1-hydroxycyclohexylphenylketone, 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 preferable.

[0200] In addition, when the active energy ray-curable polymer composition contains a compound having a cationic polymerizable group such as an epoxy group together with a radically polymerizable group, a photo cationic polymerization initiator may be included together with the above-mentioned photo radical polymerization initiator as a polymerization initiator. Any known photo cationic polymerization initiator can also be used. When the active energy ray-curable polymer composition contains a compound having a cationic polymerizable group such as an epoxy group together with a radically polymerizable group, a photo cationic polymerization initiator may be included together with the above-mentioned photo radical polymerization initiator as a polymerization initiator. Any known photo cationic polymerization initiator can also be used. When the active energy ray-curable polymer composition contains a compound having a cationic polymerizable group such as an epoxy group together with a radically polymerizable group, a photo cationic polymerization initiator may be included together with the above-mentioned photo radical polymerization initiator as a polymerization initiator. Any known photo cationic polymerization initiator can also be used. When the active energy ray-curable polymer composition contains a compound having a cationic polymerizable group such as an epoxy group together with a radically polymerizable group, a photo cationic polymerization initiator may be included together with the above-mentioned photo radical polymerization initiator as a polymerization initiator. Any known photo cationic polymerization initiator can also 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, more preferably 5 parts by weight or less, based on 100 parts by weight in total of the above-mentioned active energy ray-reactive components. When the content of the polymerization initiator is 10 parts by weight or less, it is preferable because a decrease in mechanical strength due to initiator decomposition products is less likely to occur.

[0202] The photo sensitizer can be used for the same purpose as the polymerization initiator. The photo sensitizer may be used alone or in combination of two or more. As the photo sensitizer, any known photo sensitizer can be used as long as the effects of the present invention can be obtained. Examples of such photo sensitizers 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 photo sensitizer is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, based on 100 parts by weight in total of the above-mentioned active energy ray-reactive components. When the content of the photo sensitizer is 10 parts by weight or less, it is preferable because a decrease in mechanical strength due to a decrease in crosslinking density is less likely to occur.

[0204] The additive is optional, and various materials added to compositions used for the same purpose can be used as the additive. The additive may be used alone or in combination of two or more. Such additives include, for example, fillers such as glass fiber, glass beads, silica, alumina, calcium carbonate, mica, zinc oxide, titanium oxide, talc, kaolin, metal oxides, metal fibers, iron, lead, and metal 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, HALS (hindered amine light stabilizers), fingerprint-resistant agents, surface hydrophilizing agents, antistatic agents, slip agents, plasticizers, mold release agents, defoaming agents, leveling agents, anti-settling agents, surfactants, thixotropy-imparting agents, lubricants, flame retardants, flame retardant aids, polymerization inhibitors, fillers, silane coupling agents, and other modifiers; colorants such as pigments, dyes, and hue adjusters; and monomers or / and their oligomers, or curing agents, catalysts, and curing accelerators required for the synthesis of 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, more preferably 5 parts by weight or less, based on 100 parts by weight in total of the active energy ray reactive components. When the content of the additive is 10 parts by weight or less, it is preferable because a decrease in mechanical strength due to a decrease in crosslink density is less likely to occur.

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

[0207] There is no particular limitation on the method of incorporating optional components such as the aforementioned additives into the active energy ray curable polymer composition, and examples include conventionally known mixing and dispersion methods. In order to more reliably disperse the optional components, it is preferable to perform a dispersion treatment using a disperser. Specifically, for example, methods of treatment using a two-roll mill, a three-roll mill, a bead mill, a ball mill, a sand mill, a pebble mill, a trommel mill, a sand grinder, a segva riator, a planetary stirrer, a high-speed impeller disperser, a high-speed stone mill, a high-speed impact mill, a kneader, a homogenizer, an ultrasonic disperser, etc. can be mentioned.

[0208] The viscosity of the active energy ray curable polymer composition can be appropriately adjusted according to the use and mode of use of the composition, etc. From the viewpoints of handleability, coatability, moldability, three-dimensional modeling property, etc., the viscosity at 25°C measured with an E-type viscometer (rotor 1°34’×R24) is preferably 10 mPa·s or more, more preferably 100 mPa·s or more. On the other hand, it is preferably 100,000 mPa·s or less, 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 and blending ratio of the aforementioned optional components, etc.

[0209] As a coating method for the active energy ray-curable polymer composition, 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, dip coater method, etc. can be applied. Among them, the bar coater method and the gravure coater method are preferred.

[0210] The active energy ray-curable polymer composition can be made into a cured film by irradiating it with active energy rays. As the active energy rays used when curing the above composition, infrared rays, visible light rays, ultraviolet rays, X-rays, electron beams, α-rays, β-rays, γ-rays, etc. can be used. From the viewpoints of equipment cost and productivity, it is preferable to use electron beams or ultraviolet rays. As the light source, an electron beam irradiation device, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an Ar laser, a He-Cd laser, a solid laser, a xenon lamp, a high frequency induction mercury lamp, sunlight, etc. are suitable.

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

[0212] The film thickness of the cured film is appropriately determined according to the intended use. The lower limit is preferably 1 μm, more preferably 3 μm, and particularly preferably 5 μm. The upper limit is preferably 200 μm, more preferably 100 μm, and particularly preferably 50 μm. When the film thickness is 1 μm or more, the design and functionality after three-dimensional processing are favorably exhibited. When it is 200 μm or less, the internal curability and three-dimensional processability are good, which is preferable. In addition, for industrial use, the lower limit of the film thickness of the cured film is preferably 1 μm, the upper limit is preferably 100 μm, more preferably 50 μm, particularly preferably 20 μm, and most preferably 10 μm.

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

[0214] As a method for obtaining a laminate having a plurality of layers of cured films, methods such as a method of laminating all layers in an uncured state and then curing with active energy rays, a method of curing or semi-curing the lower layer with active energy rays, then applying the upper layer, and curing again with active energy rays, and a method of applying each layer to a release film or a base film and then laminating the layers together in an uncured or semi-cured state can be applied. From the viewpoint of enhancing the adhesion between layers, a method of laminating in an uncured state and then curing with active energy rays is preferable. As a method of laminating in an uncured state, known methods such as sequential coating in which the upper layer is applied on top of the lower layer after applying the lower layer, and simultaneous multi-layer coating in which two or more layers are simultaneously applied stacked from a multi-slit can be applied, but it is not limited to this.

[0215] Examples of the substrate include various shaped articles such as plates formed of various plastics such as polyester such as polyethylene terephthalate and polybutylene terephthalate, polyolefin such as polypropylene and polyethylene, nylon, polycarbonate, (meth)acrylic resin, glass, or metal.

[0216] The cured film can be a film excellent in stain resistance and hardness against general household contaminants such as ink and ethanol, and a laminate using the cured film as a coating on various substrates can be excellent in design and surface protection properties.

[0217] In addition, 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 has flexibility, elongation at break, mechanical strength, stain resistance, and hardness that can follow deformation during three-dimensional processing. In addition, it is expected that the active energy ray curable polymer composition can easily produce a thin resin sheet by one-layer coating.

[0218] The elongation at break of the cured film is preferably 50% or more, more preferably 75% or more, still more preferably 100% or more, and particularly preferably 120% or more, which is a value measured by cutting the cured film into a width of 10 mm and performing a tensile test using a tensilon tensile tester (manufactured by Orientec, Tensilon UTM-III-100) 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 film for replacing painting, and can be effectively applied to various members such as interior and exterior building materials, automobiles, and home appliances.

Examples

[0220] Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded.

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

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

[0223] [Evaluation method: Polycarbonate diol] <Number average molecular weight, quantification of phenoxy groups and calculation of hydroxy terminal ratio> The polycarbonate diol was dissolved in CDCl3, and 400 MHz 1 1H-NMR (AL-400 manufactured by JEOL Ltd.) was measured. From the signal positions of each component, the phenoxy groups were identified, and the content of phenoxy terminals and the number average molecular weight were calculated from the integral values. The detection limit at that time was 1000 ppm by weight as the content of phenoxy terminals with respect to the total weight of the sample. The hydroxy terminal ratio was calculated as follows. Hydroxy terminal ratio (%) ={(Total number of terminals = 2) - Impurity (phenoxy) terminals} / (Total number of terminals = 2) × 100

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

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

[0226] <Residual amount of dihydroxy compound> A solution prepared by adding 250 mg of monochlorobenzene to 500 mL of N-methylpyrrolidone was used as the internal standard solution. 0.50 g of polycarbonate diol was accurately weighed and dissolved in 5 mL of the above-mentioned internal standard solution weighed with a volumetric pipette. The resulting solution was analyzed by gas chromatography (GC) under the following analysis conditions. The concentration of the dihydroxy compound was determined by preparing a calibration curve from a dihydroxy compound known as a standard substance in advance, and calculating the weight percentage from the area ratio obtained by GC. (Analysis conditions) Apparatus: 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 programming: 150 °C → 190 °C (for 5 minutes), 190 → 245 °C (for 40 minutes)

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

[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 apparatus [manufactured by Tosoh Corporation, product name "HLC-8220" (column: Tskgel GMH-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 onto a fluororesin sheet (Fluorine Tape Nitoflon 900, thickness 0.1 mm, manufactured by Nitto Denko Corporation) using a 9.5 mil applicator, and dried at 60°C for 1 hour, followed by drying at 100°C for 0.5 hour. Further, it was dried at 100°C under vacuum for 0.5 hour and at 80°C for 15 hours, and then left standing for 12 hours or more under constant temperature and humidity of 23°C and 55% RH. A test piece of 10 mm × 70 mm was cut out from the obtained polyurethane film, and for this test piece, in accordance with JIS K6301 (2010), using a tensile testing machine (manufactured by Orientec, product name "Tensilon UTM-III -100"), at a temperature condition of 23°C and a relative humidity of 55%, with a chuck distance of 50 mm and a tensile speed of 500 mm / min, a tensile test was carried out, and the strength and elongation at break were measured. The greater the elongation at which the film breaks, the better the flexibility.

[0230] <Humid Heat Resistance Test> A test piece of 10 mm × 70 mm was cut out from the polyurethane film. This test piece was left standing in a constant temperature and humidity chamber set at a temperature of 70°C and a relative humidity of 95% for 28 days. The weight average molecular weight (Mw) of the test piece after standing was measured by the above method, and the ratio (molecular weight retention rate) to the weight average molecular weight (Mw) before the test was calculated. The higher the molecular weight retention rate, the higher the humid heat resistance.

[0231] [Manufacture and Evaluation of Polycarbonate Diol] [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 to react 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% aqueous phosphoric acid solution was added to deactivate the catalyst and obtain 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 carried out. 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 operation. A separable flask equipped with a thermocouple, a cooling pipe, and a stirring device was placed on an oil bath at 60 °C. 69.78 g of PCD1 preheated to 80 °C, 6.30 g of 1,4-butanediol, and 238.57 g of dehydrated N,N-dimethylformamide (hereinafter sometimes abbreviated as "DMF", manufactured by Wako Pure Chemical Industries, Ltd.) were put in, and then 25.4 g of 4,4'-diphenylmethane diisocyanate (hereinafter sometimes referred to as "MDI") was added. While stirring at 60 rpm under a nitrogen atmosphere in the separable flask, the temperature was raised to 70 °C in about 1 hour. After reaching 70 °C, 0.019 g of Neostan U-830 (hereinafter sometimes referred to as "U-830", manufactured by Nitto Kasei Co., Ltd.) was added as a urethanization reaction catalyst, and stirring was continued at 70 °C for about 2 hours. Then, 1.8 g of MDI was added in portions (the total amount of MDI added was 27.2 g) to adjust the molecular weight, and a polyurethane with a molecular weight of about 156,000 was obtained. The evaluation results 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 amounts described in Table 2 were changed. The evaluation results of the physical properties of the obtained polyurethane are shown in Table 2.

[0240]

Table 2

[0241] It can be seen from Tables 1 and 2 as follows. The polycarbonate diol produced using 1,10-decanediol within the range defined in the present invention has a good color tone, and when used as a raw material for polyurethane, it can provide a polyurethane having 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 a poor color tone. In addition, the polycarbonate diol described in Comparative Example 1, that is, the polycarbonate diol synthesized using 1,10-decanediol whose acid value exceeds the range defined in the present invention, has good color tone. However, in the synthesized polyurethane (Comparative Example 3), compared with Example 4, the result is inferior in hygrothermal resistance. Further, the polyurethane of Comparative Example 3 has a wider molecular weight distribution than the polyurethane of Example 4, and there may be a difficulty in moldability.

Claims

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

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

3. The polycarbonate diol according to claim 1, having a hydroxyl value of 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 residual 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 terminals.

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

7. An artificial leather or synthetic leather using the polyurethane according to claim 6.

8. A paint or coating agent using the polyurethane according to claim 6.

9. An elastic fiber using the polyurethane according to claim 6.

10. A water-based polyurethane paint using the polyurethane according to claim 6.

11. A pressure sensitive adhesive or bonding agent comprising the polyurethane according to claim 6.

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

13. 6. An active energy radiation curable polymer composition comprising a urethane (meth)acrylate oligomer obtained by addition reaction of the polycarbonate diol according to claim 1, a polyisocyanate, and a hydroxyalkyl (meth)acrylate.

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