Polycarbonate polyols, polyurethanes, adhesives, paints, sealants, water-based polyurethanes, water-dispersible compositions, and synthetic leathers

Abstract

For example, we provide polycarbonate polyols and the like that can provide polyurethanes with excellent heat resistance and weather resistance, in which discoloration due to heat during polyurethane manufacturing and discoloration over time are suppressed. [Solution] A polycarbonate polyol characterized by having repeating structural units represented by the following formula (1) and structural units represented by the following formula (2). JPEG2026091285000021.jpg22170 (In formula (1), R1 is any divalent aliphatic hydrocarbon group.) JPEG2026091285000022.jpg12170 (In formula (2), R2 is any monovalent aliphatic hydrocarbon group, and R3 is any divalent aliphatic hydrocarbon group.)

Description

[Technical Field]

[0001] This invention relates to polycarbonate polyols, polyurethanes, adhesives, paints, sealants, and water-based materials. This invention relates to polyurethane, aqueous dispersion compositions, and synthetic leather, etc. [Background technology]

[0002] Polycarbonate polyols are similar to polyester polyols and polyether polyols. Similarly, by reacting with isocyanate compounds, polyurethane resins and urethane acrylates can be produced. It is useful as a raw material for manufacturing, as well as for engineering plastics, adhesives, paints, etc. It is also used as a modifier for polyester and other materials. -[ORO(CO)]-( Polycarbonate having repeating units represented by the formula (wherein R represents a divalent hydrocarbon group) Polyurethanes and engineering plastics manufactured using polyols have hydrolysis resistance. It has advantages such as excellent weather resistance and heat resistance, and is easy to manufacture industrially.

[0003] For example, Patent Document 1 describes dioxane produced as a by-product during the manufacture of polycarbonate polyols. To reduce the occurrence of defects and to manufacture polyurethane with excellent flexibility, mechanical strength, solvent resistance, etc. A method for producing polycarbonate polyols is described. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2024-003246 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, even in the polycarbonate polyol disclosed in Patent Document 1, when heated during use in polyurethane production, it may be colored, and there were further problems regarding the coloring after the weather resistance test of the obtained polyurethane.

[0006] The present invention has been made in view of the above problems. That is, the present invention aims to provide, for example, a polycarbonate polyol capable of providing a polyurethane with excellent heat resistance and weather resistance, in which coloring due to heat or the like during polyurethane production and coloring over time are suppressed. Another object of the present invention is to provide a polyurethane, an adhesive, a paint, a sealing material, an aqueous polyurethane, a water-dispersion composition, and synthetic leather, etc., which are excellent in weather resistance (heat resistance) and have suppressed coloring. [[ID=2O]]

Means for Solving the Problems

[0007] The present inventors intensively studied in view of the above problems. As a result, they newly developed a polycarbonate polyol having a specific structure with an ethylenically unsaturated bond, and found that the above problems can be solved by using the polycarbonate polyol, thus completing the present invention.

[0008] That is, the present invention provides the following various specific embodiments. <1> A polycarbonate polyol, characterized by having a repeating structural unit represented by the following formula (1) and a structural unit represented by the following formula (2).

Chemical Formula

Chemical Formula

[0009] <2> The content of the constituent unit represented by formula (2) above is between 0.001 ppm and 30,000 ppm. be, <1> Polycarbonate polyol as described above.

[0010] <3> The content of the constituent unit represented by formula (2) above is 5 ppm to 170 ppm. <1> Polycarbonate polyol as described above.

[0011] <4> The repeating structural unit represented by formula (1) and the structural unit represented by formula (2) are combined. The constituent unit is represented by the following formula (11): <1> ~ <3> A polycarbonate polyol as described in any one of the items. [ka] (In formula (11), R1 is any divalent aliphatic hydrocarbon group, and R2 is any monovalent aliphatic hydrocarbon group) It is an aliphatic hydrocarbon group, and R3 is any divalent aliphatic hydrocarbon group.

[0012] <5> It further comprises a constituent unit represented by the following formula (3): <1> ~ <4> A polycarbonate polyol as described in any one of the items. [ka] (In formula (3), R5 is any divalent aliphatic hydrocarbon group, and R4 is a group having 1 to 12 carbon atoms) (It is an aliphatic hydrocarbon group.)

[0013] <6> The sum of the constituent units represented by formula (2) and R4 in formula (3) is given by the formula ( 2) The mass ratio of the constituent units is 0.000001 to 0.20. <5> Polycarbonate polyol as described above.

[0014] <7> The hydroxyl group end purity is 90 mol% to 98 mol%. <1> ~ <6> A polycarbonate polyol as described in any one of the items.

[0015] <8> The repeating structural unit represented by formula (1) is one of two or more types of formula (1) in which R1 is different. Includes repeating structural units represented by ), <1> ~ <7> A polycarbonate polyol as described in any one of the items.

[0016] <9> The repeating structural unit represented by formula (1) above is composed of two or more different carbon number units where R1 is different. Contains 20 aliphatic structures, <1> ~ <7> A polycarbonate polyol as described in any one of the items.

[0017] <10> In formula (1) above, the ratio of the two aliphatic hydrocarbon groups of R1 is 0.1 to 0.9. <9> Polycarbonate polyol as described above.

[0018] <11> The repeating structural unit represented by formula (1) is an aliphatic structure in which the number of carbon atoms in R1 is 5. and includes an aliphatic structure in which R1 has 6 carbon atoms. The content of the constituent unit represented by formula (2) above is 5 ppm to 170 ppm. <1> ~ <7> A polycarbonate polyol as described in any one of the items.

[0019] <12> The number-average molecular weight is between 300 and 5000. <1> ~ <11> A polycarbonate polyol as described in any one of the items.

[0020] <13> The hydroxyl value is between 20 mg KOH / g and 700 mg KOH / g. <1> ~ <12> A polycarbonate polyol as described in any one of the items.

[0021] <14> The constituent unit represented by formula (2) above is an unsaturated monohydroxy alcohol having 4 to 9 carbon atoms. It is the structure from which it originates. <1> ~ <13> A polycarbonate polyol as described in any one of the items.

[0022] <15> <1> ~ <14> A polycarbonate polyol as described in any one of the items, and an ester structure Includes polyol compounds having a crystalline and / or ether structure, Polyol composition.

[0023] <16> The polycarbonate polyol and the ester structure and / or ether structure Polyol compounds containing polycarbonate structure: ester structure and ether The total molar ratio of the structure is in the range of 20:80 to 80:20. <15> The polyol composition described above.

[0024] <17> The polycarbonate polyol and the ester structure and / or ether structure Polyol compounds containing polycarbonate structure: ester structure and ether The total molar ratio of the structure is in the range of 30:70 to 75:25. <15> The polyol composition described above.

[0025] <18> <1> ~ <14> Polycarbonate polyol or as described in any one of the items <15> ~ <17> A polyol composition described in any one of the items, and an isocyanate compound It is a polymer of Polyurethane.

[0026] <19> <18> Including the polyurethane described above, glue.

[0027] <20> <18> Including the polyurethane described above, paint.

[0028] <21> <18> Including the polyurethane described above, Sealing material.

[0029] <22> <1> ~ <14> Polycarbonate polyol or as described in any one of the items <15> ~ <17> Obtained using the polyol composition described in any one of the following items: Water-based polyurethane.

[0030] <23> <1> ~ <14> Polycarbonate polyol or as described in any one of the items <15> ~ <17> Obtained using the polyol composition described in any one of the following items: Water dispersion composition.

[0031] <24> <1> ~ <14> Polycarbonate polyol or as described in any one of the items <15> ~ <17> Obtained using the polyol composition described in any one of the following items: Synthetic leather.

[0032] <25> <24> Automotive interior materials, including synthetic leather as described above.

[0033] <26> <1> A method for producing polycarbonate polyols as described above, A polyol having repeating structural units represented by formula (1) above, An unsaturated bond-containing hydroxy compound having a structural unit represented by formula (2) is added. The manufacturing process involves reacting the product by heating and stirring at 120°C to 180°C under normal or reduced pressure. Construction method. [Effects of the Invention]

[0034] According to the present invention, discoloration caused by heat during polyurethane manufacturing, for example, and discoloration over time are suppressed. Polycarbonate polio It is possible to provide materials such as polyols. Furthermore, by using the polycarbonate polyol of the present invention... Therefore, polyurethane, adhesives, paints, and sealants with excellent heat resistance and weather resistance, and suppressed discoloration. We can also provide materials, water-based polyurethanes, water-dispersible compositions, and synthetic leather, etc. [Modes for carrying out the invention]

[0035] The following describes embodiments for carrying out the present invention (hereinafter abbreviated as "this embodiment") in detail. I will explain in detail. It should be noted that the present invention is not limited to the following embodiments, but rather its gist is... It can be implemented with various modifications within the given range.

[0036] When describing the general formulas of compounds used in this specification, individual descriptions are provided in the specification. Unless otherwise specified, use definitions that conform to the Nomenclature rules established by IUPAC. However, common names may be used for the specific group names and the names of the example compounds. Furthermore, when the number of atoms, substituents, or quantities are described in this specification, all of them shall be integers. It represents

[0037] [Polycarbonate polyol] The polycarbonate polyol of this embodiment has a repeating structure represented by the following formula (1). It is characterized by having a position and a constituent unit represented by the following formula (2). [ka] (In formula (1), R1 is any divalent aliphatic hydrocarbon group.) [ka] (In formula (2), R2 is any monovalent aliphatic hydrocarbon group, and R3 is any divalent aliphatic hydrocarbon group) It is a hydrocarbon group.

[0038] The polycarbonate polyol of this embodiment has ethylenically unsaturated bonds as described above. By having a specific structure, it is possible to color polycarbonate polyols and polyurethanes. The rapid increase in viscosity during manufacturing is suppressed. Furthermore, the polycarbonate polyo of this embodiment By using this material, mechanical properties such as breaking strength, elongation at break, abrasion resistance, adhesion, and heat resistance can be improved. Furthermore, polyurethane with excellent weather resistance can also be obtained.

[0039] <Repeating structural unit represented by formula (1)> The polycarbonate polyol of this embodiment has a repeating structure represented by the above formula (1). It has a position. In the above formula (1), R1 is not particularly limited as long as it is any divalent aliphatic hydrocarbon group. However, for example, a linear molecule with 2 to 20 carbon atoms that may contain heteroatoms and is divalent. It is a linear, branched, or cyclic aliphatic hydrocarbon group. R1 is linear, branched, or R may be alicyclic, but is preferably linear or branched. The number of carbon atoms in the aliphatic hydrocarbon group 1 is more preferably 2 to 12, and more preferably 2 to 10. It is even more preferable that it be 2 to 6. When prime numbers are within a desirable range, the resulting polyurethane exhibits desirable properties such as chemical resistance and tensile strength. The intensity tends to increase.

[0040] Furthermore, the polycarbonate polyol of this embodiment is one of two or more types of the above formula (1 If the repeating structural unit is represented by ), then R1 is two or more aliphatic atoms with 2 to 20 carbon atoms. It is preferable that it has a structure. If R1 is of two or more types, the resulting polycarbonate poly The viscosity of the solvent becomes lower, improving the productivity of polyurethane, and the resulting polyurethane This is preferable because it tends to improve the elongation, flexibility, and scratch resistance of the tongue. Furthermore, for example, When used as an adhesive composition, after conducting a humidity and heat resistance test (the conditions for the humidity and heat resistance test are not limited) However, it tends to have superior adhesive strength and retention rate under conditions such as a temperature of 85°C and humidity of 85%. It is preferable. For the second type R1, an aliphatic hydrocarbon group with 2 to 10 carbon atoms is more preferable. More preferably, an aliphatic hydrocarbon group having 2 to 6 carbon atoms is preferred. Polyurethane strength Since both carbon and elongation tend to be excellent, the aliphatic hydrocarbon group of R1 has a carbon number Preferably, two or more aliphatic hydrocarbon groups are selected from 3 to 7 aliphatic hydrocarbon groups, and the number of carbon atoms is 3 or more. It is even more preferable that two or more aliphatic hydrocarbon groups are selected from 6 or fewer aliphatic hydrocarbon groups. Here, specifically The combination of carbon atoms in the aliphatic hydrocarbon group that is selected is the combination of 3 and 4. A combination of 3 and 5, a combination of 3 and 6, a combination of 4 and 5, a combination of 4 and 6 In addition, the combination of 5 and 6 is particularly preferable. Due to its excellent flexibility, the aliphatic of R1 is preferred. Two or more aliphatic hydrocarbon groups with 6 to 10 carbon atoms are selected as hydrocarbon groups. Preferably, two or more aliphatic hydrocarbon groups having 8 to 10 carbon atoms are selected. That is even more preferable.

[0041] When using two types of aliphatic hydrocarbon groups as R1, their ratio can be adjusted according to the desired performance. It can be set as desired, and is not particularly limited, by the molar ratio of R1 of type 1 to R2 of type 2. Setting the preparation amount within the range of 0.01 to 0.99 will result in the obtained polycarbonate top layer This is preferable from the viewpoint of making the riol low viscosity. More preferably 0.05 to 0.95. More preferably 0.1 to 0.9, particularly preferably 0.2 to 0.8, and most preferably The range is 0.3 to 0.7. Being within the above preferred range, the resulting polycarbonate The nate diol has lower viscosity and is easier to handle, and the resulting polycarbonate diol is The flexibility and mechanical strength, such as tensile strength, of the polyurethane used tend to be higher, and the obtained The adhesive strength of the adhesive composition tends to increase.

[0042] In one embodiment, the overall structure of the repeating structural unit represented by formula (1) above is a carbon It can be formed by the transesterification reaction of a nate and a hydroxy compound. Specific examples of exchange reactions and carbonates used as raw materials for the carbonate skeleton will be discussed later.

[0043] In one embodiment, R1 of the polycarbonate polyol of this embodiment is an aliphatic diol It can be formed from. In this case, the aliphatic diol raw material is, for example, ethylene Recall, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol 1,6-Hexanediol, 1,7-Heptanediol, 1,8-Octanediol L, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol It does not have side chains such as 1,12-dodecanediol and 1,14-tetradecanediol. i diol; 2-methyl-1,8-octanediol, 2-ethyl-1,6-hexanediol ol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol L, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol 2-butyl-2-ethyl-1,3-propanediol, 2,2-dimethyl Diols with side chains such as 1,3-propanediol; 1,4-cyclohexanedimeth cyclic diols such as 2-bis(4-hydroxycyclohexyl)-propane are These include, but are not limited to, one type alone or two or more types. These can be used in combination. Productivity, the elongation and flexibility of the polyurethane obtained, From the viewpoint of scratch resistance, chemical resistance, mechanical strength, etc., two or more types of aliphatic diol raw materials are used. It is preferable to do so. Preferably, the aliphatic diol raw material used is 1,3-propane Diol (PnDO), 1,4-butanediol (BDO), 1,5-pentanediol (PDO), 1,6-Hexanediol (HDO), 1,7-Heptanediol (HeD O), 1,8-octanediol (ODO), 1,9-nonanediol (NDO), 1, 10-decanediol (DDO), 2-methyl-1,3-propanediol, 3-methyl Examples include -1,5-pentanediol. Among these, 1,3-propanediol Lu, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 2-methyl-1,3-propanediol 3-methyl-1,5-pentanediol is more preferred.

[0044] Furthermore, the polycarbonate polyol of this embodiment is the polycarbonate polyol of this embodiment. Within the limits that do not excessively impair the performance of Riol, the alcohol-derived structures other than R1 mentioned above and For example, a polyfunctional compound having three or more hydroxyl groups in one molecule, such as trimethylol. Tan, trimethylolpropane, hexanetriol, pentaerythritol, ditrimethylol It may have a structure derived from tyrolpropane, dipentaerythritol, etc. The crosslinking density of polyurethane obtained by having a structure derived from functional compounds is improved, and resistance Mechanical properties such as chemical resistance, coating hardness, scratch resistance, and stress resistance are improved. The valency of the polyfunctional compound Preferably, 3-valent to 8-valent, more preferably 3-valent to 6-valent, and even more preferably 3 The valency is between 0 and 4. Here, it is a polyfunctional compound having 3 or more hydroxyl groups in one molecule. If too much is used, crosslinking and gelation will occur during the polymerization reaction of polycarbonate polyols. This can happen. Therefore, polyfunctionalization with three or more hydroxyl groups in one molecule is necessary. When using a compound as a raw material, a polyfunctional compound having 3 or more hydroxyl groups in one molecule. The usage ratio is 0.01% to 20% by mass relative to the total amount of the raw material diols that form R1. Preferably, it is 0.01% by mass or more and 10% by mass or less, More preferably, the amount is 0.1% by mass or more and 5% by mass or less.

[0045] <Constituent units represented by equation (2)> The polycarbonate polyol of this embodiment has a constituent unit represented by the above formula (2). In the above formula (2), R2 is not particularly limited as long as it is any monovalent aliphatic hydrocarbon group. However, for example, a heteroatom may be present, with 1 to 10 carbon atoms, in a linear, branched, or It is a cyclic monovalent aliphatic hydrocarbon group. R2 is linear, branched, or alicyclic. Any of these is acceptable, but linear or branched chains are preferred. Also, the aliphatic carbon of R2 is preferred. The number of carbon atoms in the hydrogen group is more preferably 1 to 6, and more preferably 1 to 3. More preferably, it is particularly preferable that it is 1 or more and 2 or less, and most preferably that it is 1. In the above formula (2), R3 is not particularly limited as long as it is any divalent aliphatic hydrocarbon group. For example, a molecule having 1 to 10 carbon atoms, which may contain heteroatoms, in a linear, branched, or ring configuration. It is a divalent aliphatic hydrocarbon group. R3 can be linear, branched, or alicyclic. However, it is preferable that it be linear or branched. Also, the number of carbon atoms in R3 is 1 It is more preferable that the number is 6 or less, and even more preferable that it is 1 or more and 4 or less, and 1 or more It is particularly preferable that the value is 3 or less above. Being within the above preferred range, the resulting polycarbonate Polycarbonate diols have superior heat resistance, and the resulting polycarbonate diols are used in Polyurethane is showing a tendency towards improved heat resistance and weather resistance.

[0046] Furthermore, the overall structure of formula (2) above is characterized by having 4 to 12 carbon atoms and internal ethylenicity. It is preferable that it consists of the portion of a monohydroxy compound having an unsaturated bond from which the hydroxyl group has been removed. Furthermore, it is preferable that the hydroxyl group and the unsaturated bond are not directly bonded. The hydroxyl group is preferably a primary or secondary hydroxyl group, and is preferably a primary hydroxyl group. More preferable. The constituent unit represented by the above formula (2) has 4 to 12 carbon atoms, preferably a carbon number It is preferable that the structure is derived from an unsaturated monohydroxy alcohol, as in 4-9.

[0047] In one embodiment, the polycarbonate polyol of this embodiment is represented by the above formula (2) The constituent units can be formed from unsaturated aliphatic monoalcohols. Examples of Japanese aliphatic monoalcohol raw materials include 2-buten-1-ol and 2-penten- 1-ol, 3-penten-1-ol, 3-methyl-2-penten-1-ol, 3- Methyl-3-penten-1-ol, 2-hexen-1-ol, 3-hexen-1-ol 4-Hexen-1-ol, 2-Hepten-1-ol, 3-Hepten-1-ol Lu, 4-heptene-1-ol, 5-heptene-1-ol, 2-octen-1-ol , 3-octane-1-all, 4-octane-1-all, 5-octane-1-all, 6-Octene-1-All, 2-Nonen-1-All, 3-Nonen-1-All, 4-No Nen-1-ol, 5-nonen-1-ol, 6-nonen-1-ol, 7-nonen-1 -All, 2-Decen-1-All, 3-Decen-1-All, 4-Decen-1-All , 5-decen-1-all, 6-decen-1-all, 7-decen-1-all, 8-decen Sen-1-All, 2-Undesen-1-All, 3-Undesen-1-All, 4-U Ndesen-1-all, 5-Undesen-1-all, 6-Undesen-1-all, 7 -Undescen-1-all, 8-Undescen-1-all, 9-Undescen-1-all , 2-dodecene-1-ol, 3-dodecene-1-ol, 4-dodecene-1-ol, 5-dodecene-1-ol, 6-dodecene-1-ol, 7-dodecene-1-ol, 8 -dodecene-1-ol, 9-dodecene-1-ol, 10-dodecene-1-ol, etc. These include, but are not limited to, one type alone or two or more types. They can be used in combination.

[0048] (Content of the constituent units represented by formula (2)) The polycarbonate polyol of this embodiment contains the constituent unit represented by the above formula (2). The amount can be set appropriately according to the desired performance and is not particularly limited, but polycarbonate A polyol that forms the constituent unit represented by the above formula (2) in a total amount of 100% by mass The amount of ethanol is preferably 0.001 ppm or more and 30,000 ppm or less. It is more preferably 1 ppm to 30,000 ppm, and more preferably 10 ppm to 20 It is even more preferable that the concentration be 100 ppm or less, and 10,000 ppm or more. It is particularly preferable that the concentration be between 200 ppm and 5,000 ppm. More preferably, the concentration is 500 ppm or more and 3,000 ppm or less, and more preferably 5 ppm It is particularly preferable that the concentration be between 170 ppm and 100 ppm, and between 40 ppm and 100 ppm. It is most preferable that it is within this preferred numerical range. Polyols tend to become less colorable during manufacturing, and also when heated above 150°C. The coloration of the resulting polyurethane also tends to be suppressed. There is a tendency for stability against light to improve.

[0049] (Hydroxygen group end purity) In the polycarbonate polyol of this embodiment, the amount of hydroxyl groups at the end of all end groups ( The hydroxyl group end purity can be set appropriately according to the desired performance and is not particularly limited, Preferably 90 mol% or more, more preferably 92 mol% or more, and 94 It is even more preferable that the purity is 100 mol% or more. The purity of the hydroxyl group terminus is 100 mol% or less. It is possible to do so, and it is preferable that the amount is 99 mol% or less, and more preferably 98 mol% or less. It is desirable. Being within this preferred numerical range results in a paint composition with superior drying properties, and It tends to become easier to form coatings and / or polyurethanes that are more durable. . Furthermore, the total amount of terminal groups in polycarbonate polyols is W(g) of polycarbonate poly It is calculated using the following formula, with the average number of functional groups (F) and number-average molecular weight (Mn) of OLL. It is a value. Total terminal group amount=W / Mn*F

[0050] The amount of hydroxyl groups in all terminal groups of the polycarbonate polyol of this embodiment is within the above range. One method of control is, for example, the addition of a monoalcohol and subsequent heat treatment, as described later. Yes. The amount of this monoalcohol added is in the polycarbonate diol before heat treatment. Terminal hydroxyl group purity, hydroxyl value, amount of polycarbonate diol processed, substances added during heat treatment. You can calculate it based on the molecular weight of the alcohol, etc.

[0051] The polycarbonate polyol of this embodiment has a repeating structure represented by the above formula (1). A component unit represented by the following formula (11) is formed by combining a position with a component unit represented by the above formula (2). It is preferable to have it. [ka] (In formula (11), R1 is any divalent aliphatic hydrocarbon group, and R2 is any monovalent aliphatic hydrocarbon group) It is an aliphatic hydrocarbon group, and R3 is any divalent aliphatic hydrocarbon group, and the above formula (1) and This is equivalent to R1 to R3 in equation (2) above.

[0052] In the polycarbonate polyol of this embodiment, the terminal groups other than hydroxyl groups are Other terminal groups besides the hydroxyl group are not particularly limited, but for example, alkyl groups, vinyl Examples include aryl groups and other similar groups.

[0053] In this embodiment, the amount of hydroxyl groups in the terminal groups is as described in the examples below. It can be measured using the method.

[0054] <Constituent units represented by formula (3)> The polycarbonate polyol of this embodiment further comprises the constituent units represented by the following formula (3). They may have it. [ka] (In formula (3), R5 is any divalent aliphatic hydrocarbon group, and R4 is a group having 1 to 12 carbon atoms) (It is an aliphatic hydrocarbon group.)

[0055] In this embodiment, the polycarbonate polyol has a hydroxyl group end amount (hydroxyl group end purity) as described above. To adjust within the range, it is preferable to have further constituent units represented by the above formula (3). The constituent units represented by this equation (3) are not particularly limited, but for example, the unsaturated bonds described later Formed by transesterification reaction between a monohydroxy compound that does not contain a carbonate. This can be achieved. The constituent unit represented by this formula (3) allows for the aforementioned amount of hydroxyl group at the end (hydroxyl group purity). By adjusting the ratio to ), the isocyanate reacts without excessively impairing the effects of this embodiment. This process suppresses the rapid increase in viscosity of the resulting polyurethane, resulting in a highly durable polyurethane. It tends to be possible to obtain this. In the above formula (3), R4 is a fat with any number of carbon atoms from 1 to 12. It is a group hydrocarbon group, and the number of carbon atoms in R4 is more preferably 1 or more than 6. It is more preferably 3 or less, particularly preferably 1 or more and 2 or less, and 1. This is the most preferable outcome.

[0056] The hydroxy compound without an unsaturated bond used herein is not particularly limited. However, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-pig Isoamyl alcohol, isodecyl alcohol, 2-ethyl-1-hexanol saturated primary alcohols such as 1-nonyl alcohol, 1-octanol, and 1-decanol. Saturated secondary alcohols such as isopropyl alcohol, cyclohexanol, and cyclopentanol Examples include ethanol; saturated tertiary alcohols such as t-butyl alcohol; etc. It is not particularly limited to these. Among these, saturated primary monoalcohols are compared to other alcohols. Because it is more reactive, it is preferred as the monoalcohol used here.

[0057] In the above formula (3), R5 is not particularly limited as long as it is any divalent aliphatic hydrocarbon group. For example, a divalent, linear, branched chain having 2 to 20 carbon atoms, which may contain heteroatoms. It is a linear or cyclic aliphatic hydrocarbon group. R5 is linear, branched, or alicyclic. Either is acceptable, but linear or branched chains are preferred. Also, the aliphatic R5 is preferred. The number of carbon atoms in the hydrocarbon group is more preferably 2 to 12, and more preferably 2 to 10. Preferably, it is 2 to 6.

[0058] (For the sum of the constituent units represented by equation (2) and R4 in equation (3), the expression in equation (2) (The mass ratio of the constituent units) In one aspect, the sum of the constituent units represented by equation (2) and R4 in equation (3) The mass ratio of the constituent units represented by formula (2) is the shape of the constituent units represented by formula (2). The ratio of the amount of alcohol that makes up the product to the amount of alcohol that forms the structure of R4 in formula (3) above. A value of 0.000001 or higher is preferable, and a value of 0.000001 or higher and 0.20 or lower is more preferable. Furthermore, a value of 0.00001 or more and 0.10 or less is more preferable, and 0.00003 or more and 0.05 or less is preferable. The lower range is particularly preferred, and 0.00005 to 0.01 is most preferred. Being enclosed in a structure, the resulting polycarbonate diol has superior heat resistance, and isocyanate The rapid increase in viscosity of the polyurethane obtained by reacting with the t can be further suppressed, and the resulting polyurethane Urethane is showing a tendency towards increased heat resistance, weather resistance, and durability.

[0059] The polycarbonate polyol of this embodiment is a repeating polyol represented by the above formula (1). The constituent units, the constituent units represented by the above formula (2), and the components which may be included as needed. In addition to the constituent units represented by formula (3), other structures may also be included. For example, this implementation The polycarbonate polyol in its form further includes ester structures, ether structures, etc. It's okay to be there.

[0060] [Method for producing polycarbonate polyols] The method for producing polycarbonate polyols according to this embodiment has the above-described configuration. This can be done using methods known in the industry, to the extent possible, and is not limited to such methods, for example. , hydroxy compounds (e.g., polyfunctional diols) and carbonate compounds (e.g., carbonated esters) It can be produced by polymerizing (Lu) and by transesterification. For example, "Po Transesterification reactions described in "Lymer Reviews, Vol. 9, pp. 9-20," etc. It can be synthesized by the above formula (2). Furthermore, a method for introducing the structure of formula (2) is as follows: As long as the configuration described can be obtained, it is not particularly limited, but for example, polycarbonate Todiol is prepared by transesterification by adding an unsaturated bond-containing hydroxy compound and heating. It can be made.

[0061] The transesterification reaction in the method for producing polycarbonate polyols according to this embodiment is For example, this can be carried out in or without the presence of a catalyst. From the viewpoint of reaction efficiency, the catalyst It is preferable to synthesize in the presence of [unspecified substance]. Method for producing polycarbonate polyol according to this embodiment Specific examples are shown below.

[0062] One embodiment of the method for producing the polycarbonate polyol of this embodiment is shown below. The production of polycarbonate polyols is not particularly limited, but for example, by following the procedure below. The transesterification reaction can be carried out in two stages.

[0063] Specifically, the molar ratio of the hydroxy compound to the carbonate compound (hydroxy compound: (Carbonate compounds) are mixed in a ratio of, for example, 20:1 to 1:10, and if necessary, Add a sterl exchange catalyst and carry out the first reaction at atmospheric pressure or reduced pressure at 100-250°C. Example For example, when dimethyl carbonate is used as the carbonate compound, the methanol produced Remove the mixture with dimethyl carbonate to obtain a low molecular weight polycarbonate diol. It can be obtained. At this time, the carbonate (carbonate ester) produced during the reaction is derived from Remove the ethanol by distillation. For example, when diethyl carbonate is used as the carbonate compound. Then, the resulting ethanol is removed as a mixture with diethyl carbonate to produce a low molecular weight polymer. Carbonate diols can be obtained. Also, for example, ethinopropyl alcohol can be obtained as a carbonate compound. When using ethylene carbonate, the resulting ethylene glyco is combined with ethylene carbonate. The mixture can be removed to obtain a low molecular weight polycarbonate diol. Then, As the second step of the reaction, the reaction product from the first step is heated under reduced pressure at 120-250°C. In addition to removing unreacted diols and carbonates, low molecular weight polycarbonate diols are also removed. By condensing the ols, a polycarbonate diol with a predetermined molecular weight can be obtained.

[0064] Furthermore, a hydroxy compound with a different skeleton than the above was added to the obtained polycarbonate diol. In addition, a transesterification catalyst is added as needed, and the mixture is heated at atmospheric pressure or reduced pressure at 100-250°C. Further different structures can be introduced by carrying out the reaction. Low boiling point hydros can be added as needed. The roxy compound is removed by heating under reduced pressure at 120-250°C, and low molecular weight polycarbonate is also removed. Condensing polycarbonate diols yields a polycarbonate diol with a predetermined molecular weight. It is possible.

[0065] (Example of a method for introducing the constituent units represented by equation (2)) The terminal hydroxyl group purity and hydroxyl value of the obtained polycarbonate polyol were determined, and the formula ( Add an unsaturated bond-containing hydroxy compound having the skeleton of 2), and perform transesterification as necessary. The catalyst is added and the reaction is carried out by heating and stirring at 120°C to 180°C under atmospheric pressure or reduced pressure. This can be done. The reaction temperature is preferably 130°C to 160°C. If the heating temperature is 120°C or higher Being superior tends to lead to faster reactions, shorter processing times, and economic advantages. By keeping the temperature below 80°C, the reflux rate of low-boiling-point monoalcohols can be appropriately controlled, and the concentration in the reaction solution can be reduced. Because the temperature can be maintained, the reaction tends to proceed quickly. The heat treatment time is the reaction temperature. It varies depending on the temperature and processing method, but it is usually 15 minutes to 10 hours. Furthermore, if necessary, After adding the activator, the low-boiling point hydroxyl compounds are removed by heating under reduced pressure at 120-180°C. It is possible.

[0066] (Removal of residual hydroxyl compounds) Furthermore, the monoalcohol remaining after the reaction of polycarbonate polyol with monoalcohol... Hydroxyl, a raw material for polycarbonate polyols produced as a by-product of kohl and transesterification reactions. The compound is then subjected to a deactivator as needed, followed by the low-boiling point hydroxy compound being subjected to a reduced pressure of 12 It is preferable to remove them by heating at 0-180°C. The amount of these remaining hydroxy compounds is Preferably, the amount relative to the recarbonate polyol is 15% by mass or less, and 10% by mass or less. It is more preferably less than 6% by mass. Because the compound is within this range, the polycarbonate polyol obtained using that compound is Polyurethane tends to have superior tensile strength, flexibility, chemical resistance, and heat resistance.

[0067] (Carbonate compounds) The carbonate compound of the raw materials used in the method for producing polycarbonate polyols of this embodiment The material is not particularly limited, but for example, dimethyl carbonate, diethyl carbonate Dialkyl carbonates such as dipropyl carbonate and dibutyl carbonate; Diaryl carbonates such as phenyl carbonate; ethylene carbonate, trimethyl carbonate 1,2-propylene carbonate, 1,2-butylene carbonate, Alkylene carbonates such as 1,3-butylene carbonate and 1,2-pentylene carbonate Examples include ions. These can be used individually or in combination of two or more. This is possible. From the standpoint of ease of obtaining and ease of setting polymerization reaction conditions, raw material carbohydrates Examples of nates include dimethyl carbonate, diethyl carbonate, and diphenyl carbonate. It is preferable to use dibutyl carbonate or ethylene carbonate.

[0068] (Transesterification catalyst) The transesterification catalyst in the method for producing polycarbonate polyols of this embodiment and For example, alkalis such as lithium, sodium, and potassium are also used. Metals, magnesium, calcium, strontium, barium and other alkaline earth metals Alcoates, hydrides, oxides, amides, carbonates, hydroxides, nitrogen-containing borates, Other examples include basic alkali metal salts and alkaline earth metal salts of organic acids. The catalyst can be, but is not limited to, aluminum, titanium, vanadium, or chromium. Manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, zirconium Molybdenum, niobium, molybdenum, ruthenium, rhodium, palladium, silver, indium, tin, Antimony, tungsten, rhenium, osmium, iridium, platinum, gold, thallium metals such as lead, bismuth, and ytterbium, their metal salts, their metal alkoxides, and Examples include organic compounds containing metals. These can be used individually or in pairs. The above can be selected and used as appropriate. Among these, sodium, potassium, and Metals such as magnesium, potassium, titanium, zirconium, tin, lead, and ytterbium. One or more catalysts from the metal salt, the metal alkoxide, or the organic compound containing the metal. When used, polymerization of polycarbonate polyol proceeds well, and the resulting polycarbonate It is preferable because it has little effect on the urethane reaction using the nate polyol. And metals such as titanium, ytrivium, tin, zirconium, magnesium, and gold A more preferable use is when a group salt, its metal alkoxide, or an organic compound containing that metal is used. .

[0069] Here, even if the polycarbonate polyol contains a catalyst containing the above metal element, Good. The amount of catalyst remaining in the polycarbonate polyol is not particularly limited, but ICP (Emission spectroscopy, Inductively Coupled Plasma) The lower limit of the measured metallic element content (concentration in terms of catalyst metal) is 0.00001%. Preferably % by amount or more, more preferably 0.00005% by mass or more, and 0.0001% by mass or less. The upper limit is even more preferable, and 0.0005% by mass or more is particularly preferable. Also, the upper limit is 0.1% by mass. Preferably less than % by amount, more preferably 0.05% by mass or less, and even more preferably 0.03% by mass or less. It is more preferably 0.02% by mass or less, and even more preferably 0.015% by mass or less. Furthermore, a concentration of 0.01% by mass or less is particularly preferred, and 0.005% by mass or less is most preferred.

[0070] The transesterification catalyst used in the transesterification reaction was a polycarbonate polyol. If heat treatment is performed immediately after manufacturing, since it is not consumed in the transesterification reaction, It can be calculated based on the amount of tel exchange reaction catalyst used. Commercially available polycarbonate diol is used. In some cases, the amount of metal in the transesterification catalyst contained in the polycarbonate diol. ICP (Inductively Coupled Plasma Spectroscopy) It is determined by measuring using the following method: Recarbonate diols deactivate the transesterification catalyst used in their production. Alternatively, a catalyst poison such as an organic acid neutralizing agent may be added.

[0071] (Neutralizing agent) Examples of the neutralizing agents mentioned above include phosphoric acid, inorganic acids such as hydrochloric acid, sulfonic acid groups, and sulfamines. Examples include organic acids having acidic groups, and their esters, acyl halides, etc. These are not limited to these. They may be used individually or in combination of two or more as appropriate. It is possible to do so. Among these, from the standpoint of ease of handling, phosphoric acid and phosphoric acid Phosphorus compounds such as sterol, phosphite, and phosphite esters are preferred.

[0072] The ratio of neutralizing agent used for polycarbonate polyols can be set as appropriate. While not limited to this, 0.0001 to 1% by mass is preferred, and more preferably 0.001 to 0 It is 0.1% by mass. When the amount of neutralizing agent added is less than the lower limit of the preferred numerical range above, it is obtained. The turbidity and number of colors of polycarbonate polyols tend to increase, and if the upper limit is exceeded, the polycarbonate The reactivity of polyols tends to be slower. Also, in relation to transesterification catalysts... The equivalent amount of the compound can be set as appropriate and is not particularly limited, but it is preferably between 0.1 and 50. More preferably 0.3 to 25, even more preferably 0.5 to 10, and 0. A ratio of 8 to 5 is particularly preferred. If the amount of neutralizing agent is too little relative to the transesterification catalyst, gelation will occur. These side reactions cannot be sufficiently suppressed, and if the amount of the transesterification catalyst is too much, turbidity And the number of colors tends to be high.

[0073] (number average molecular weight) The number-average molecular weight (Mn) of the polycarbonate polyol in this embodiment is not particularly limited. However, it is preferable that it be between 300 and 5,000. Having a number-average molecular weight of 300 or more results in good low-temperature properties for the resulting polyurethane. This tends to be the case. The number-average molecular weight of polycarbonate polyols is 5,000 or less. Therefore, when used as a component material in paints, the paint solids content concentration and other factors are not restricted. Furthermore, the decrease in the moldability of the resulting polyurethane tends to be easily suppressed. In one embodiment, the number-average molecular weight of the polycarbonate polyol is 450 or more. It may be 500 or more, 3,000 or less, and 2,500 or less. It may be 2,000 or less. Also, if it is 1,500 or less, the resulting polycarbonate It is extremely preferable from the viewpoint of viscosity and solvent solubility of the polyol. On the other hand, the obtained poly From the perspective of uretan's elongation and flexibility, the number-average molecular weight of polycarbonate polyols is 1 Preferably, it is between 1,000 and 5,000, and more preferably between 2,000 and 4,500. Preferred. In this embodiment, the number-average molecular weight (Mn) is as described in the examples below. It can be measured by the method.

[0074] (Melting viscosity at 50°C) The melt viscosity of the polycarbonate polyol in this embodiment at 50°C is not particularly limited. However, it is preferably 500 to 200,000 mPa·s, more preferably 1.0 0 to 180,000 mPa·s, more preferably 1,500 to 165,000 mPa·s It is s. The obtained P is obtained when the melt viscosity at 50℃ is 500 mPa·s or more. Polyurethane tends to have higher stress, tensile elongation, and chemical resistance. The melt viscosity at 50°C is By being 180,000 mPa·s or less, the wettability (contact) of the resulting composition with the substrate is improved. Because the tactile efficiency is improved, high adhesive strength tends to be more easily achieved. Also, the sealant raw material Even when used as a material, the composition fills even the smallest details, resulting in high insulation reliability. ru.

[0075] In this embodiment, the melt viscosity of the polycarbonate polyol at 50°C is set to the above range. The method of control is not particularly limited, but for example, adjusting the aromatic concentration or number-average molecular weight. One example is adjusting the raw material ratio so that the aromatic concentration is high. The melt viscosity of recarbonate polyols tends to be high. Similarly, the number-average molecular weight is high. When manufacturing conditions are adjusted to reduce the viscosity, the melt viscosity tends to increase. In this case, the melt viscosity can be measured by the method described in the examples below.

[0076] (Hydroxyl value) The hydroxyl value (OH value) of the polycarbonate polyol in this embodiment is not particularly limited. However, it is preferable that the lower limit be 20 mg KOH / g or higher, and 30 mg KOH / g or higher. It is more preferable that the concentration be 50 mg KOH / g or higher, and even more preferably 60 mg It is even more preferable that the KOH / g is 70 mg KOH / g or more. Particularly preferred, and most preferably 74 mg KOH / g or more. The upper limit of the hydroxyl value (OH value) of polycarbonate polyols is not particularly limited, but is 70. Preferably, the concentration is 0 mg KOH / g or less, and preferably 500 mg KOH / g or less. Preferably, it is 400 mg KOH / g or less, and even more preferably 350 mg KOH It is even more preferable that the amount be less than or equal to / g, and particularly preferable that it be less than or equal to 300 mg KOH / g. Preferably, the KOH content is 230 mg / g or less. When the hydroxyl value (OH value) of OH is within the aforementioned preferred range, the viscosity becomes low and easy to remove. A polycarbonate polyol with excellent handling properties and compatibility with inert organic solvents can be obtained. It tends to be easily damaged, and by using such polycarbonate polyols, Polyurethane tends to exhibit increased stress, tensile elongation, and chemical resistance.

[0077] In this embodiment, the hydroxyl value of the polycarbonate polyol is controlled to be within the above range. The law is not particularly limited, but for example, when manufacturing the polycarbonate polyol... Methods include controlling the reaction by adding and / or removing alcohol compounds. In this embodiment, the hydroxyl value is calculated using the method described in the examples below. It is possible.

[0078] (Composition analysis method) In this embodiment, the content of each structure of the polycarbonate polyol is polycarbonate The polyol is analyzed by hydrolyzing it and quantifying it using gas chromatography. This can be done. More specifically, it can be analyzed using the method described in the examples.

[0079] [Polyurethane] The polyurethane in this embodiment is isocyanated with the above-mentioned polycarbonate polyol. It is a polymer of a compound. Using the polycarbonate polyol of this embodiment, In the method for producing the compound, there are no particular limitations, but usually an isocyanate compound (for example) A curing agent such as polyisocyanate, and a chain extender as needed, are used. In a method for producing polyurethane using polycarbonate polyol in an applied form, A mixture of each constituent component may also be used as a curable composition (hereinafter referred to as "one-shot"). (referred to as the "Isocyanate method"), and the polycarbonate polyol of this embodiment is prepared in advance by isocyanine Prepare an isocyanate-terminated prepolymer composition obtained by reacting it with an isocyanate compound, and A mixture comprising an isocyanate-terminated prepolymer composition and a chain extender is used as a curable composition. This method may be used (hereinafter referred to as the "prepolymer method"). Here, one type of prepolymer is used. Even if only two types are used, more than two types may be used. Also, the polycarbonate polyol of this embodiment, It is obtained by mixing a socianate compound and, if necessary, other polyols or organic solvents. A polyurethane coating can also be manufactured using this coating composition.

[0080] (Isocyanate compounds) The isocyanate compound is not particularly limited, but it must be a polyisocyanate. Preferred. Typically, polyisocyanates with an average of 2 to 6 functional groups per molecule are used. This can be done. Examples of polyisocyanates include 2,4-tolylene diisocyanate. , 2,6-tolylene diisocyanate and mixtures thereof, diphenylmethane-4,4'-di Isocyanate (MDI), naphthalene-1,5-diisocyanate (NDI), 3,3 '-dimethyl-4,4' biphenylenediisocyanate (TODI), polymethylene poly Aromatic diisocyanates such as phenylene polyisocyanate (PMDI); xylylene Aromatic aliphatic diisocyanates such as isocyanates (XDI) and phenylenediisocyanate 4,4'-Methylenebiscyclohexyl diisocyanate (hydrogenated) )MDI), Hexamethylene diisocyanate (HDI), Isophorone diisocyanate Aliphatic diisocyanates such as (IPDI), cyclohexane diisocyanate (hydrogenated XDI), etc. Examples include, but are not limited to, polyisocyanates. For example, lower alcohols such as butanol and 2-ethylhexanol, and methyl ethyl ketone oxide. Known bromides such as cymides, lactams, phenols, imidazoles, and active methylene compounds. This product uses so-called blocked isocyanates, in which the isocyanate group is blocked with a blocking agent. It is also possible.

[0081] As a polyisocyanate, it has an average of 2.1 or more isocyanate groups in one molecule. Polyisocyanates can also be used. Each molecule contains an average of 2.1 or more isocyanates. Examples of polyisocyanates having a t-group include aromatic polyisocyanates such as crude MDI and crude TDI. Isocyanates; derivatives of aliphatic isocyanates such as HDI and IPDI, specifically biuretic isocyanates. Diisocyanate derivatives such as lett, allophanate, uretdione, and isocyanurate ; and polyhydric alcohol adduct type can be used. Also, isocyanates Examples of products sold include Sumijool 44S and 44V70 (both from Sumika Bayer Urethane). Dismodule HL (Sumika Bayer Urethane), a copolymer of TDI and HDI. Various duranates manufactured by Asahi Kasei Corporation, namely duranate 24A-100, Duranate 22A-75PX, Duranate 18H-70B, Duranate 21S-7 5E, Duranate THA-100, Duranate TPA-100, Duranate TKA -100, Duranate TLA-100, Duranate TUL-100, Duranate M FA-75X, Duranate TSA-100, Duranate TSS-100, Duranate TSE-100, Duranate D-101, Duranate D-201, Duranate P -301-75E, Duranate E-402-90T, Duranate E-402-90T Duranate E-405-80T, Duranate ME20-100, Duranate 17 B-60PX, Duranate TPA-B80X, Duranate MF-B60X, Duranate E-402-B80T, Duranate ME20-B80S, Duranate WB40- 100, Duranate WB40-80D, Duranate WT20-100, Duranate WT30-100 and similar models are available.

[0082] Among these, aromatic polyisocyanates such as MDI are used as polyisocyanates. It is preferable to use it. By using aromatic polyisocyanates, excellent mechanical properties are obtained. Polyurethanes are more easily obtained. Also, aliphatic polyisocyanates such as hydrogenated MDI When this is used in a curable composition, a synthetic leather with excellent weather resistance can be obtained from the curable composition. Because it is easily damaged, aliphatic polyisocyanates are used in hardening compositions for synthetic leather for the epidermal layer. This is preferably used.

[0083] (Chain extender) When producing polyurethane using the polycarbonate polyol of this embodiment, Depending on the circumstances, a chain extender may be used. The chain extender reduces the wear of the resulting polyurethane. It can be used to increase the properties and strength of the polyurethane, but on the other hand, it reduces the flexibility of the resulting polyurethane. It may also cause this, so it is used as appropriate and as needed. As a chain extender, it is not particularly limited. However, for example, short-chain diols such as ethylene glycol and 1,4-butanediol; Trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol Examples include polyhydric alcohols such as tol and glycerin; and others. In addition, as chain extenders, particularly Examples include, but are not limited to, ethylenediamine, propylenediamine, and hexamethylenediamine. Amine, tolylenediamine, xylylenediamine, diphenyldiamine, diaminodiamine Nylmethane, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, iso Holone diamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA Examples include diamines such as ) and water.

[0084] The amount of chain extender added can be set appropriately according to the desired performance, and is not particularly limited. In this embodiment, the total of the polycarbonate polyol and isocyanate compound is favorable. More preferably 30% by mass or less, more preferably 3% by mass or more and 20% by mass or less, even more preferably The concentration is 5% by mass or more and 15% by mass or less. In addition, polyhydric alcohols are used as chain extenders. This increases the crosslinking density of the resulting polyurethane, improving its strength, abrasion resistance, and chemical resistance. It tends to enhance sexual performance.

[0085] Use of polycarbonate polyol, isocyanate compound and chain extender in this embodiment The quantity can be set appropriately according to the desired performance and is not particularly limited, but [isocyanate [Isocyanate equivalent of compound] / [Polycarbonate polyol and chain extension of this embodiment] When expressed as the total hydroxyl group equivalents of the long-acting compound, it is preferably 0.7 to 1.3, more preferably The ratio is 0.8 to 1.2, more preferably 0.9 to 1.1. The ratio is 0.7 to 1.3. As a result of the following, the molecular weight of the resulting polyurethane can be appropriately controlled, and its strength and elongation can be improved. It tends to have excellent mechanical properties such as wear resistance.

[0086] When producing polyurethane using the polycarbonate polyol of this embodiment, To adjust the workability during urethane manufacturing, inert organic solvents may be used as needed. The content of the inert organic solvent is preferably 80% by mass or less relative to the polyurethane. Preferably, the viscosity of the curable composition is 70% by mass or less, and more preferably 60% by mass or less. To lower the degree of curvature, improve workability, and further enhance the appearance of the resulting polyurethane. Adding an inert organic solvent is effective in this case.

[0087] (Inert organic solvent) Inert organic solvents are any organic solvent that is substantially inert to polyisocyanates. It is not limited thereto, and it is preferably one having no active hydrogen. Examples of the inert organic solvent include Although not particularly limited, for example, pentane, hexane, heptane, octane, decane, petroleum ether, petroleum benzine, ligroin, petroleum spirit, cyclohexane, methylcyclo hexane and other hydrocarbons; fluorinated inert liquids such as fluorinated oils such as trichlorofluoroethane, tetrachlorodifluoroethane , perfluoroether, etc.; perfluorocyclohexane , perfluorobutyltetrahydrofuran, perfluorodecalin, perfluoro-n -butylamine, perfluoropolyether, dimethylpolysiloxane and the like. These may be used alone or as a mixture. Examples of the inert organic solvent further include methyl ethyl ketone (also referred to as MEK), acetone, N,N-dimethylform amide (DMF), ethyl acetate, butyl acetate, toluene, xylene and other single or mixed solvents can be mentioned.

[0088] In this specification, "active hydrogen" means a hydrogen atom bonded to an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, etc., and a hydrogen atom of a terminal methine group. Also, " active hydrogen" means, for example, hydrogen contained in atomic groups such as -OH group, -C(=O)OH group, -C(=O)H group, -SH group, -SO3H group, -SO2H group, -SOH group, -NH2 group, -NH- group, -SiH group, -C≡ CH group, etc. When producing polyurethane using the polycarbonate polyol of this embodiment,

[0089] if necessary, a polyol other than the polycarbonate polyol of this embodiment may be used in combination. The polyol other than the polycarbonate polyol of this embodiment is not particularly limited. ​ However, for example, other polycarbonate polyols, polyether-based polyols, Polyester polyols, polycarbonate polyols, polyolefin polyols Examples include polybutadiene-based polyols, polyacrylic-based polyols, and oil-modified polyols. The amount of polyols other than polycarbonate polyol added in this embodiment is particularly The polycarbonate polyol of this embodiment and the polycarbonate of this embodiment Preferably, the amount is 50% by mass or less of the total mass of polyols other than the polyol. 30% by mass or less is more preferable, and 20% by mass or less is even more preferable.

[0090] Examples of polyol compounds having an ester structure include polyester polyols. The diol used as a raw material for polyester polyols is not particularly limited, but for example... For example, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4 -Butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7- Butanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-deca Undecanediol, 1,11-Undecanediol, 1,12-Dodecanediol, 1,13- Tridecanediol, 1,14-Tetradecanediol, 1,15-Pentadecanediol Diols without side chains such as 2-methyl-1,8-octanediol, 2-ethyl -1,6-Hexanediol, 2-Methyl-1,3-Propanediol, 3-Methyl-1 ,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-die Thiru-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol , diols with side chains such as 2,2-dimethyl-1,3-propanediol; 1,4- Cyclohexanedimethanol, 2-bis(4-hydroxycyclohexyl)-propane, Examples of cyclic diols include 1,4-cyclohexanediol, but preferably ethyl acetate. Ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol ol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl Examples include ru-1,5-pentanediol, etc. These can be used individually or in combination of two or more types. The above can also be used as a raw material for polyester polyol.

[0091] The dicarboxylic acid used as a raw material for polyester polyols is not particularly limited, but for example... For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberin. Acids, azelaic acid, sebaic acid and other aliphatic dicarboxylic acids; phthalic acid, isophthalic acid, tetraphosphate Examples include aromatic dicarboxylic acids such as lephthalic acid and naphthalenedicarboxylic acid, but Preferably succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid Examples include polyacids, etc. These are used individually or in combination of two or more polyester polyacids. It may be used as a raw material for ru.

[0092] A cyclic ester compound is used as a raw material for polyester polyols, and this is subjected to ring-opening polymerization. This may be done. The cyclic ester compound is not particularly limited, but for example, β-propyl Olactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, β-butyrolactone loractone, γ-valerolactone, α-methyl-ε-caprolactone, β-methyl-ε- Caprolactone, γ-methyl-ε-caprolactone, β,δ-dimethyl-ε-caprolactone, 3,3,5-trimethyl ε-caprolactone, enanthlactone (7-heptanolide), and other cyclic ester compounds having 3 to 12 carbon atoms can be mentioned. Among these, preferably ε-caprolactone and the like can be mentioned. The cyclic ester compound may be used alone or in combination of two or more as a raw material for the polyester polyol. Examples of the polyol compound having an ether structure include polyether polyol and the like. The polyether polyol is not particularly limited, and examples thereof include polypropylene glycol, polyethylene glycol, polytetramethylene glycol, propylene oxide-ethylene oxide copolymer, and the like. In the polyol composition, the molar ratio of the polycarbonate structure: ester structure and / or ether structure contained in the polycarbonate polyol and the polyol compound having an ester structure and an ether structure is not particularly limited, but is preferably in the range of 20:80 to 80:20, more preferably in the range of 30:70 to 75:35, still more preferably in the range of 40:60 to 75:35, and even more preferably in the range of 45:55 to 70:30. When the molar ratio of the polycarbonate structure: ester structure and / or ether structure is 20:80 or more, the melt viscosity of the polyol composition tends to be low and the handleability is excellent. When the molar ratio of the polycarbonate structure: ester structure and / or ether structure is 80:20 or less, the polyol composition has excellent hydrolysis resistance. Preferably, ε-caprolactone and the like can be mentioned. The cyclic ester compound may be used alone or in combination of two or more as a raw material for the polyester polyol. Examples of the polyol compound having an ether structure include polyether polyol and the like. The polyether polyol is not particularly limited, and examples thereof include polypropylene glycol, polyethylene glycol, polytetramethylene glycol, propylene oxide-ethylene oxide copolymer, and the like.

[0093] Examples of the polyol compound having an ether structure include polyether polyol and the like. The polyether polyol is not particularly limited, and examples thereof include polypropylene glycol, polyethylene glycol, polytetramethylene glycol, propylene oxide-ethylene oxide copolymer, and the like. Examples thereof include polypropylene glycol, polyethylene glycol, polytetramethylene glycol, propylene oxide-ethylene oxide copolymer, and the like. In the polyol composition, the molar ratio of the polycarbonate structure: ester structure and / or ether structure contained in the polycarbonate polyol and the polyol compound having an ester structure and an ether structure is not particularly limited, but is preferably in the range of 20:80 to 80:20, more preferably in the range of 30:70 to 75:35, still more preferably in the range of 40:60 to 75:35, and even more preferably in the range of 45:55 to 70:30.

[0094] When the molar ratio of the polycarbonate structure: ester structure and / or ether structure is 20:80 or more, the melt viscosity of the polyol composition tends to be low and the handleability is excellent. When the molar ratio of the polycarbonate structure: ester structure and / or ether structure is 80:20 or less, the polyol composition has excellent hydrolysis resistance. In the polyol composition, the molar ratio of the polycarbonate structure: ester structure and / or ether structure contained in the polycarbonate polyol and the polyol compound having an ester structure and an ether structure is not particularly limited, but is preferably in the range of 20:80 to 80:20, more preferably in the range of 30:70 to 75:35, still more preferably in the range of 40:60 to 75:35, and even more preferably in the range of 45:55 to 70:30. When the molar ratio of the polycarbonate structure: ester structure and / or ether structure is 20:80 or more, the melt viscosity of the polyol composition tends to be low and the handleability is excellent. When the molar ratio of the polycarbonate structure: ester structure and / or ether structure is 80:20 or less, the polyol composition has excellent hydrolysis resistance. In the polyol composition, the molar ratio of the polycarbonate structure: ester structure and / or ether structure contained in the polycarbonate polyol and the polyol compound having an ester structure and an ether structure is not particularly limited, but is preferably in the range of 20:80 to 80:20, more preferably in the range of 30:70 to 75:35, still more preferably in the range of 40:60 to 75:35, and even more preferably in the range of 45:55 to 70:30. When the molar ratio of the polycarbonate structure: ester structure and / or ether structure is 20:80 or more, the melt viscosity of the polyol composition tends to be low and the handleability is excellent. When the molar ratio of the polycarbonate structure: ester structure and / or ether structure is 80:20 or less, the polyol composition has excellent hydrolysis resistance. When the molar ratio of the polycarbonate structure: ester structure and / or ether structure is 80:20 or less, the polyol composition has excellent hydrolysis resistance. This is desirable because it improves the resin properties of polyurethane obtained from the riol composition, such as chemical resistance. In particular, having an ether structure in the aforementioned ratio results in a low melt viscosity of the polyol composition. It offers excellent handling properties, and the resulting polyurethane has superior flexibility (high elongation, low stress) and moisture and heat resistance. This is particularly preferable. Furthermore, having the ester structure in the above ratio allows the melt viscosity of the polyol composition to be Because it has a low degree of hardness and is easy to handle, and the resulting polyurethane has excellent heat resistance and chemical resistance, Particularly preferred. In one embodiment, the polycarbonate polyol and the ester structure Polycarbonate structure contained in the polyol compound having the ether structure: The molar ratio of the ester structure and / or ether structure is preferably 30:70 to 75 The range is 25.

[0095] Carbonate repeating structure: Each component of ester repeating structure and ether repeating structure The molar ratio will be discussed later. 13 Based on the integral ratio calculated by 13C-NMR measurement, each structure It can be calculated by the carbon molar ratio. Also, polycarbonate polyol composition If necessary, liquid-phase chromatography or other methods are used to utilize the differences in molecular weight and polarity of each component. It can be separated into these components, and in addition to the analytical methods described above, NMR, IR, and TOF can be used as needed. -It can be identified using SIMS, etc.

[0096] <Other additives> In the process of producing polyurethane using the polycarbonate polyol composition of this embodiment Depending on the application, curing accelerators (catalysts), fillers, flame retardants, dyes, and organic or inorganic materials may be used. Pigments, mold release agents, flow modifiers, plasticizers, antioxidants, UV absorbers, light stabilizers Heat stabilizers, defoamers, leveling agents, thixotropes, colorants, foaming agents, etc. can be added. ru.

[0097] Examples of curing accelerators include, but are not limited to, amines and metal catalysts. The effect enhancers for amines are not particularly limited, but for example, monoamines are used. Triethylamine, N,N-dimethylcyclohexylamine, and diamine tetramethyl Ethylenediamine, other triamines, cyclic amines, dimethylethanolamine, etc. Examples include alcoholamines and etheramines. The metal catalyst is not particularly limited. However, for example, potassium acetate, potassium 2-ethylhexanoate, calcium acetate, oc Lead cylate, dibutyltin dilaurate, tin octoate, bismuth neodecanoate, bismuth Sodium oxycarbonate, bismuth 2-ethylhexanoate, zinc octoate, zinc tetraphosphate Examples include decanoates, phosphines, and phospholines. These can be used individually or Often, two or more types can be used in combination.

[0098] The fillers and pigments are not particularly limited, but examples include woven fabrics, glass fibers, carbon fibers, Polyamide fibers, mica, kaolin, bentonite, metal powders, azo pigments, carbon black Examples include clay, silica, talc, gypsum, alumina white, barium carbonate, and calcium carbonate. These can be used individually or in combination of two or more.

[0099] The matting agent is not particularly limited, but examples include organic fine powders, inorganic fine powders, etc. These can be used individually or in combination of two or more types.

[0100] Leveling agents are not particularly limited, but examples include silicone, aerosil, and wax. Polysiloxanes such as stearate, BYK-331 (manufactured by BYK Chemicals) These are used. They can be used individually or in combination of two or more. can.

[0101] As a thixotropic agent, the thixotropic agent has been conventionally used in the thermosetting resin composition of solder paste. A scat agent can be used. Specifically, a scat agent is not limited to, but for example... Examples include castor oil, hydrogenated castor oil, and sorbitol-based thixotropic agents. These are 1 It can be used individually, or two or more species can be used in combination.

[0102] The fillers and pigments are not particularly limited, but examples include woven fabrics, glass fibers, carbon fibers, Polyamide fibers, mica, kaolin, bentonite, metal powders, azo pigments, carbon black Examples include clay, silica, talc, gypsum, alumina white, and barium carbonate. It may be used alone, or two or more types may be used in combination.

[0103] The release agent, flow modifier, and leveling agent are not particularly limited, but for example, silico Aerosil, wax, stearate, BYK-331 (manufactured by BYK Chemicals) Examples include polysiloxanes.

[0104] When producing polyurethane using the polycarbonate polyol or the like of this embodiment, It is preferable to use antioxidants, light stabilizers, heat stabilizers, and flame retardants as additives. The inhibitor is not particularly limited, but for example, phosphoric acid or phosphite, aliphatic, aromatic or aluminum Kill group-substituted aromatic esters, hypophosphite derivatives, phenylphosphonic acid, phenylphosphine Acids, diphenylphosphonic acid, polyphosphonates, dialkylpentaerythritol diphos Phosphorus compounds such as phytes and dialkylbisphenol A diphosphite; phenolic inducers Conductors, especially hindered phenol compounds, thioethers, dithioates, and mercaptobenes. Sulfur-containing compounds such as zuimidazole, thiocarbanilide, and thiodipropionate esters. Compounds; tin-based compounds such as stin maleate and dibutyltin monooxide can be used. These can be used individually or in combination of two or more types.

[0105] [Curable composition (polycarbonate polyol composition)] The polycarbonate polyol composition of this embodiment may be a curable composition, and curing This makes it possible to form polyurethane.

[0106] The polycarbonate polyol composition of this embodiment is manufactured in a manner commonly used in industry. It can be manufactured by a certain method.

[0107] The polycarbonate polyol composition of this embodiment is, for example, polycarbonate polyol A method of reacting by mixing a solvent, and if necessary, an inert organic solvent and additives, all at once ( It can be manufactured by the method described below, which is referred to as the "one-shot method." Polycarbonate polyol compositions are, for example, derived from polycarbonate polyols. Derived from isocyanate-terminated prepolymers or polycarbonate polyols Prepare hydroxyl-terminated prepolymers in advance, and combine these prepolymers with iso Cyanates and / or polyols, and optionally inert organic solvents and additives. It can be manufactured by a method of mixing and reacting (hereinafter referred to as the "prepolymer method"). Yes, it is possible. Here, one type of prepolymer or two or more types may be used.

[0108] [Uses of polyurethane] Polyurethane produced by the above method is suitable for the following applications.

[0109] [glue] The adhesive of this embodiment contains the polyurethane described above. The inclusion of polyurethane tends to result in superior dimensional stability, adhesion, and durability.

[0110] [paint] The paint of this embodiment contains the polyurethane described above. The inclusion of urethane tends to result in superior adhesion and scratch resistance.

[0111] [Sealing material] The sealing material of this embodiment includes the polyurethane described above. The inclusion of polyurethane tends to result in superior dimensional stability and durability.

[0112] [Manufacturing of polyurethane coatings] The polycarbonate polyol of this embodiment and a curing agent such as the aforementioned isocyanate compound. The mixture is mixed to create a paint composition (curable composition) (mixing step), and the obtained paint composition ( A curable composition is applied (coating step), and the applied coating composition is then dried ( (Drying process) A polyurethane coating can be obtained. The polycarbonate poly of this embodiment By using oars, a polyurethane coating with excellent chemical resistance, scratch resistance, and mechanical strength can be obtained. It can be obtained.

[0113] (Mixing process) The mixing process involves mixing polycarbonate polyol, a curing agent, and, if necessary, an untreated compound. Mix an active organic solvent, a curing accelerator, other polyols, and / or other additives and apply. This is the process of obtaining the material composition.

[0114] The solvent content in the paint composition can be set appropriately according to the desired performance, and is not particularly limited. However, it is not done, but the amount is, for example, 10% by mass or more and 90% by mass or less of the total mass of the paint composition. It can be, for example, 15% by mass or more and 70% by mass or less, for example 20% by mass It can be 50% by mass or less.

[0115] The mixing method is not particularly limited, but for example, it may involve using a stirrer or the like. After stirring at a rotation speed of 50 rpm to 1000 rpm for 5 minutes to 60 minutes, use a vacuum degasser. One method involves performing a degassing operation using [a specific method].

[0116] (Coating process) In the method for manufacturing a polyurethane coating film of this embodiment, the coating step is to coat the coating composition This is the process of weaving.

[0117] The method of applying the paint composition is not particularly limited, but for example, each component is applied immediately before application. After mixing, the mixture is applied to the substrate using a spray, roller, brush, etc. Another method involves mixing all ingredients except the curing agent, adding the hardening agent just before application, mixing thoroughly, and then applying the mixture. It is possible.

[0118] (drying process) In the method for manufacturing a polyurethane coating film of this embodiment, the drying step is performed on the coated coating composition This is the process of drying a material to obtain a coating.

[0119] The drying time in the drying process can be set appropriately according to the desired performance, and is not particularly limited. It is not possible, but it is preferable that it be 5 to 55 minutes after application, and preferably 10 to 50 minutes after application. More preferably, 15 to 45 minutes after application, and even more preferably 20 to 3 minutes after application. It is particularly preferable that the drying time is 0 minutes. If the drying time is within the aforementioned preferred numerical range, the physical properties will be It tends to be easier to obtain a coating film with superior layer quality.

[0120] The drying temperature in the drying process can be set appropriately according to the desired performance, and is not particularly limited. It is not possible, but it is preferable that it be between 40°C and 200°C, and more preferably between 50°C and 175°C. Preferably, the temperature is 60°C to 150°C, and more preferably, 60°C to 120°C. This is particularly preferable, and a temperature of 60°C to 100°C is most preferable.

[0121] The drying method in the drying process is not particularly limited, but examples include natural drying and forced drying. Drying and heat drying are examples of methods used.

[0122] The thickness of the polyurethane coating in this embodiment can be set appropriately according to the desired performance. While not particularly limited, the particle size is preferably 1 μm to 100 μm, and preferably 2 μm to 90 μm. It is more preferable that the particle size be 3 μm to 80 μm, and even more preferably 5 μm to 50 μm. It is particularly preferable that the value be m, and most preferably 10 μm to 50 μm.

[0123] [Other uses] The polycarbonate polyol of this embodiment can be suitably used for the following applications.

[0124] [Water dispersion composition] A water-dispersible composition can be obtained using the polycarbonate polyol of this embodiment. .

[0125] [Water-based polyurethane] Using the polycarbonate polyol of this embodiment, a water-based polyurethane can be obtained. Cut.

[0126] [film] The film obtained using the polycarbonate polyol of this embodiment has excellent durability. It can be done.

[0127] [Artificial leather, synthetic leather] The artificial leather and synthetic leather obtained using the polycarbonate polyol, etc. of this embodiment are It has excellent durability. Hereinafter, in this specification, "artificial leather" refers to a material using nonwoven fabric as the base fabric. "Leather" refers to genuine leather, while "synthetic leather" refers to leather that uses knitted or woven fabric as the base material.

[0128] (Manufacturing methods for artificial leather and synthetic leather) A method for producing polyurethane using the polycarbonate polyol of this embodiment. This can be applied to manufacture artificial leather or synthetic leather. The polycarbonate of this embodiment Methods for manufacturing artificial leather or synthetic leather using nate polyols are not limited to the following: Although not specified, for example, it can be manufactured using the polycarbonate polyol composition of this embodiment. A wet method in which polyurethane is applied to or impregnated into a substrate (base fabric) and wet-coagulated; this implementation Polyurethane manufactured using polycarbonate polyols of a specific form is attached to a release paper or base Examples include dry methods in which the material (base fabric) is applied and dried. Furthermore, artificial leather or synthetic leather As a method for manufacturing leather, the polycarbonate polyol composition of this embodiment is applied to the release paper. After applying polyurethane manufactured using the present invention to form a surface material, the present invention Polyurethane manufactured using polycarbonate polyol is used as the adhesive layer. , a transfer coating method in which the release paper is removed after bonding the substrate (base fabric) ( A type of dry process can also be used. That is, the polycarbonate polio of this embodiment The solvent and curing composition can be used as adhesive layers for artificial leather or synthetic leather. The polycarbonate polyols of this embodiment allow for a reduction in the amount of inert organic solvents used. Therefore, a dry method (transfer coating method) is preferably used.

[0129] From the above, a preferred embodiment of the polycarbonate polyol of this embodiment is a contact It may be an adhesive composition. In addition, a preferred one of the polycarbonate polyols in this embodiment The embodiment may be a water-based polyurethane. Furthermore, the polycarbonate polyurethane of this embodiment A preferred embodiment of the composition may be an aqueous dispersion composition.

[0130] The polyurethane produced using the polycarbonate polyol, etc. of this embodiment is It can be used as a laminating adhesive for seed films, a surface protective agent, etc. Water-based polyurethanes made using polycarbonate polyols, etc., are the same as described above. It can be used as a variety of materials, including artificial leather, synthetic leather, paints, and coatings. Furthermore, artificial leather obtained using the polycarbonate polyol of this embodiment or Synthetic leather is used for automotive interior materials such as car seats, furniture such as sofas, clothing, and shoes. It can be used for bags, other miscellaneous goods, etc.

[0131] This disclosure provides a method for producing polycarbonate polyol according to this embodiment. It is also the case that the method for producing polycarbonate polyol in this embodiment is the formula ( A polyol having repeating structural units represented by 1) is given the structural units represented by formula (2) Add an unsaturated bond-containing hydroxy compound having a position, and infuse under normal or reduced pressure at 120°C to 18°C. This is a manufacturing method that includes reacting the product by heating and stirring at 0°C. [Examples]

[0132] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is These examples are not limited to those described above, unless they exceed the gist of the above. Unless otherwise specified, "%" means "mass %" and "ppb" means "mass ppb". In addition, "ppm" means "mass ppm". Furthermore, in the following examples and comparative examples... The methods for analyzing and evaluating the physical properties of each component are as follows. Regarding the analytical peripheral equipment, This can be carried out using equipment with the following capabilities.

[0133] <Number-average molecular weight of polycarbonate polyols> Gel permeation chromatography with calibration curves prepared using standard polystyrene of known molecular weight. —(GPC) analysis (see below for GPC instrument and analysis conditions) revealed that polycarbonate The number-average molecular weight (Mn) of the polyol was measured by the following method. The polycarbonate polyols obtained in the examples and comparative examples described below were used as samples. The concentration of the agent is 0.5% by mass. Prepared using the following GPC apparatus, the polycarbonate poly-poly The number-average molecular weight (Mn) of the ruth was measured. (GPC instrument and analysis conditions) GPC device: Tosoh Corporation HLC-8320 Column: TSKgel G4000H (1 piece) G3000H (1 unit) G2000H (2 bottles) Eluent: Tetrahydrofuran (THF) Flow rate: 1.0mL / min Column temperature: 40℃ RI detector: RI (built into the HLC-8320 device) Calibration curve: Standard polystyrene (manufactured by Tosoh Corporation) ·F-20 (molecular weight: 1.90×10 5 ) ·F-10 (molecular weight: 9.64×10 4 ) ·F-4 (molecular weight: 3.79×10 4 ) ·F-2 (molecular weight: 1.81×10 4 ) ·F-1 (molecular weight: 1.02×10 4 ) ·A-5000 (molecular weight: 5.97×10 3 ) ·A-2500 (molecular weight: 2.63×10 3 ) · A-500 · A-1000

[0134] <Carbonate repeating structure: sum of ester repeating structure and ether repeating structure> Mole ratio > The carbonate repeating structure, ester repeating structure, and ether repeating structure are, 1 H-NMR and 13 Identification was made based on 1C-NMR. The following instruments were used for the NMR measurement. They used it. 13 In C-NMR, the repeating structure of the carbonate group is 150-1 Peak around 55 ppm (-O-) C =OO- (derived from carbonate group), esterification The return structure shows a peak around 165-180 ppm (- C =OO-, derived from the ester group) The ether repeating structure shows a peak around 50-90 ppm (- C -O- C -,ether Using the source, the molar ratio of repeating structural units was calculated from the ratio of their signal intensities. Furthermore, if there are two or more C elements corresponding to a particular peak, the signal intensity will be determined by the number of C elements. The molar ratio of the repeating structural units was calculated by dividing by the given value. The apparatus and measurement conditions were set as follows: provided. 1 H-NMR Device: JEOL “JEOL-ECZ500(SC)” (product name) Solvent: Deuterated chloroform (containing 1 vol% tetramethylsilane) Total number of times: 120 Sample concentration: 10 wt / vol% Chemical shift standard: Tetramethylsilane was set to 0.0 ppm. 13 C-NMR Device: JEOL “JEOL-ECZ500(SC)” (product name) Solvent: Deuterated chloroform (containing 1 vol% tetramethylsilane) Total number of times: 5120 Sample concentration: 30 wt / vol% Chemical shift standard: Deuterated chloroform was set at 77.0 ppm.

[0135] <Hydroxyl value of polycarbonate polyols> The hydroxyl values ​​of the polycarbonate polyols obtained in the examples and comparative examples described below are as follows: It was measured using the method described. First, using a volumetric flask, add pyridine to 12.5 g of acetic anhydride to make 50 mL, and A cetylation reagent was prepared. Then, 2.5 g of the sample was added to a 100 mL round-bottom flask. Weighed it. Then, put 5 mL of acetylation reagent and 10 mL of toluene into the round-bottom flask. After adding with a pipette, attach a cooling tube and heat the solution in the eggplant flask at 100 °C for 1 hour. Next, add 2.5 mL of distilled water to the eggplant flask with a pipette, and then heat and stir the solution in the eggplant flask for another 10 minutes. After cooling the solution in the eggplant flask for 2 - 3 minutes, add 12.5 mL of ethanol to the eggplant flask. Next, add 2 - 3 drops of phenolphthalein as an indicator to the eggplant flask and titrate with 0.5 mol / L ethanolic potassium hydroxide. Then, put 5 mL of acetylating reagent, 10 mL of toluene, and 2.5 mL of distilled water into a 100 mL eggplant flask, heat and stir the solution in the eggplant flask for 10 minutes, and then perform titration in the same manner (blank test). Based on this result, calculate the hydroxyl value of the polycarbonate polyol using the following formula (i). In formula (i), E represents the titration volume (mL) of the sample, F represents the titration volume (mL) of the blank test, G represents the sample mass (g), and f represents the factor of the titrant. Hydroxyl value (mgKOH / g) = {(F - E) × 28.05 × f} / G ··· (i)

[0136] <Viscosity> Measure the melt viscosity of the carbonate group - containing polyol at 23 °C using an E - type viscometer (manufactured by Toki Sangyo Co., Ltd., TVE - 22HT, cone: No. 6) for the carbonate group - containing polyols obtained in the following Examples and Comparative Examples.

[0137] <a. Analysis of all hydroxy compounds constituting the polycarbonate polyol ) Measure the ratio of the constituent units of the polycarbonate polyols obtained in the following Examples and Comparative Examples as follows. Take 1 g of polycarbonate polyol into a 100 mL eggplant flask and use an internal standard substance As a quality, 0.1 g of diethylene glycol diethyl ether, further 30 g of ethanol and 4 g of potassium hydroxide were added, and a hydrolysis reaction was carried out at 100 °C for 1 hour. After cooling to room temperature , 2 to 3 drops of phenolphthalein were added to the eggplant flask as an indicator, and neutralized with hydrochloric acid . After cooling the eggplant flask in the refrigerator for 1 hour, the precipitated salt was removed by filtration to obtain a composition analysis solution. The obtained composition analysis solution was analyzed for the hydroxy compound components contained in the polycarbonate polyol by gas chromatography (GC) . The concentration of each hydroxy compound was prepared from each hydroxy compound known as a standard substance in advance to create a calibration curve , and the mass% was calculated from the area ratio obtained by gas chromatography (GC). The analysis was performed using a gas chromatograph GC-14B equipped with DB-WAX (manufactured by J&W) as a column manufactured by Shimadzu Corporation), and using a flame ionization detector (FID) as a detector . The temperature rising profile of the column was a profile in which it was held at 60 °C for 5 minutes and then heated to 250 °C at 10 °C / min .

[0138] <b. Analysis of residual hydroxy compounds in polycarbonate polyol> 1 g of polycarbonate polyol and 0.1 g of diethylene glycol diethyl ether as an internal standard substance were dissolved in 10 g of acetone, and the content of residual hydroxy compounds was measured under the same conditions as the above GC analysis .

[0139] <Calculation of the ratio of each structural unit> From the results of the above hydroxyl value, the analysis of a above, and the analysis of b above, the terminal hydroxyl purity was calculated as follows .

[0140] 1. Content of structural units represented by formula (2) The mass of the hydroxy compound having the structure of formula (2) measured in a above is used for polycarbonate Divided by the mass of the polyol (excluding the residual hydroxyl compound measured in b above) The content of the structural unit represented by formula (2) was defined as the content of the structural unit.

[0141] 2. Structure represented by equation (2) and R 4 The sum of the structures is given by the structure represented by formula (2) above. Mass ratio of the structure The mass of the hydroxy compound having the structure of formula (2) measured in a above is measured in a above. The mass of the hydroxy compound having the structure of formula (2) and the structure of R4 measured in b above The result obtained by dividing the total mass of the hydroxy compound having the structure represented by formula (2) by R This was the mass ratio of the structure represented by formula (2) to the total mass of the structures in 4.

[0142] 3. Hydroxyl group end purity The hydroxyl group end purity was calculated using the following formula. [1] Hydroxyl group terminal purity = [[2] Amount of terminal hydroxyl groups in polycarbonate polyol] / [[3 [End group content of polycarbonate polyols] [2] Amount of terminal hydroxyl groups in polycarbonate polyol = [[4] Total amount of hydroxyl groups] - [[5] Remainder [Hydroxy compound hydroxyl group] [4] Total amount of hydroxyl groups: Amount of hydroxyl groups calculated from the hydroxyl value (of polycarbonate polyols) (Total of terminal hydroxyl groups and residual hydroxyl compound hydroxyl groups) [5] Amount of hydroxyl groups in the remaining hydroxyl compounds: The sum of the free hydroxyl compounds measured in b above Total amount of hydroxyl groups [3] End group weight of polycarbonate polyol = [2] Polycarbonate polyol [Terminal hydroxyl group amount] + [[6] Monohydroxyl group amount in the backbone of polycarbonate polyols] [6] Amount of monohydroxy groups in the backbone of polycarbonate polyols = [7] Total monohydroxy [Amount of roxy groups]-[[8] Amount of free monohydroxy groups] [7] Total amount of monohydroxy groups: The total amount of hydroxyl groups in the monohydroxy compound measured in a above. [8] Amount of free monohydroxy groups: The total amount of free monohydroxy compounds measured in b above. Hydroxyl group

[0143] <Confirmation of the properties of polycarbonate diol> The polycarbonate diol heated to 60°C was placed in separate transparent sample bottles, and then at room temperature. Each sample was visually observed after it had cooled to (23°C). The sample bottle was transparent and If there is even a slight fluidity when tilted, it is called "liquid," while if it is opaque or if the sample bottle is tilted... In either case where the state does not change, or both cases, it is represented as a "solid."

[0144] <Thermal stability> The coloration of the polycarbonate polyols obtained in the examples and comparative examples described below upon heating is as follows: It was evaluated using the following method. Place 50g of carbonate-containing polyol into a 100cc eggplant-shaped flask and stir with a stirring bar. The sample was placed in an oil bath at 150°C under a nitrogen atmosphere and heated for one week. Based on the change in APHA before and after, the coloring properties were evaluated according to the following criteria. (Evaluation Criteria) ◎(Excellent): APHA increase after heating is less than 5. ○ (Good): APHA level increases by 5 or more but less than 10 after heating. △(Poor): APHA increase after heating is between 10 and 20. × (Bad): APHA level increases by 20 or more after heating. (APHA value) Measurement was performed by comparing the standard solution in a colorimetric tube, in accordance with JIS K0071-1 (1998). It was determined. The reagent used was a chromaticity standard solution of 1000 degrees (1 mg Pt / mL) (Kishida Chemical). Also, up to APHA 50, the solution was prepared and judged in 5 - step increments.

[0145] <Reactivity Evaluation> 60 g of polycarbonate polyol was charged into a 200 - mL wide - mouth glass bottle, and after sufficient nitrogen substitution, it was heated in an oil bath set at 80 °C. Then, MDI heated at 80 °C was added so that the NCO / OH ratio became 1. 2, and the increase in viscosity was confirmed using a stirrer equipped with a torque monitor. The viscosity increase rate (= torque value after 30 minutes / initial torque value) was calculated and determined according to the evaluation criteria described below. (Evaluation Criteria) ◎(Excellent): The viscosity increase rate is less than 2. 〇(Good): The viscosity increase rate is 2 or more and less than 3. △(Poor): The viscosity increase rate is 3 or more and less than 5. ×(Bad): The viscosity increase rate is 5 or more, or the evaluation is not possible.

[0146] [Example 1] Synthesis of Polycarbonate Polyol P - 1 A 3 - L glass flask equipped with a rectification column filled with regular packing and a stirring device (hereinafter also referred to as the "reactor") was charged with 731 g (7.03 mol) of 1,5 - pentanediol, 830 g (7.03 mol) of 1,6 - hexanediol, and 12 39 g (12.8 mol) of ethylene carbonate (EC). Then, 0.1393 g of titanium tetra - n - butoxide was further added into the reactor as a catalyst. While distilling off the low - boiling components under normal pressure, the reaction was carried out for 25 hours while raising the temperature from 9 0 °C to 185 °C. Next, the reactor was directly connected to a condenser, the pressure was gradually lowered, and the reaction was carried out for another 5 hours. Then, the pressure was returned to normal pressure with nitrogen and 1 ​​​​After cooling to 50°C, add 1.73g (0.0376mol) of ethanol and 4-hexene-1 -Add 0.00377g (0.0376 mmol) of ALL and stir for 3 hours. Then Cool to 100°C and add 0.103 g (0.891 mmol) of 85% phosphoric acid aqueous solution. After stirring for 5 hours, the temperature is raised to 170°C and the pressure is gradually reduced to remove low-boiling components. Next, 1820g of polycarbonate polyol P-1, which is liquid at 23°C, was obtained. Various physical properties of the polycarbonate polyol P-1 were measured by the above method. The hydroxyl value of recarbonate polyol P-1 was 56.2 mgKOH / g. The number-average molecular weight of the obtained polycarbonate polyol P-1 was 1996. The terminal hydroxyl group purity of the polycarbonate polyol P-1 is 96%, and the terminal intermediate hydroxyl group purity is 96%. The ratio of 2-hexen-1-ol in the alcohol skeleton (=M2 / (M1+M2)) is 0.001 The results are shown in Tables 2 and 3.

[0147] [Examples 2-9, Comparative Examples 1-5] The raw material polyol used in Example 1 was changed to the raw material polyol type and amount listed in Table 2. Except for the changes made, the polycarbonate polyols P-2 to P-9 were produced in the same manner as in Example 1. B-1 to B-5 were obtained. The obtained polycarbonate polyols P-2 to P-9 The various physical properties of B-1 to B-5 were measured using the method described above. The results are shown in Tables 2 and 3. The abbreviations used in Tables 2 and 3 are as follows:

[0148] (A): Aliphatic hydroxy compound (aliphatic diol) of formula (1) HDO: 1,6-Hexanediol PDO: 1,5-pentanediol BDO: 1,4-butanediol PnDO: 1,3-propanediol (B):Catalyst Ti: Titanium tetra-n-butoxide (C): Neutralizing agent phosphoric acid TEP: Triethyl phosphate

[0149] (M1): Monoalcohol MeOH: methanol IPA: Isopropyl alcohol 2EHOH:2-ethylhexanol (M2): Unsaturated bond-containing compound [Table 1]

[0150] [Table 2]

[0151] [Table 3]

[0152] [Application Examples 1-9 and Comparative Application Examples 1-5] Urethane Evaluation [Polyurethane manufacturing] Polycarbonate polyols P-1 to P-9 and B-1 to B obtained in the examples and comparative examples. Using -5, polyurethane films were manufactured as follows: thermocouple and cooling tube. In a 500 mL separable flask equipped with [a component], add 38 g of polycarbonate polyol. Dimethylformamide (hereinafter sometimes abbreviated as DMF) 224g, 1% dibutyl 0.26 g of tin dilaurate toluene solution (total of MDI and polycarbonate polyol) (50 ppm relative to mass) was added and heated in an oil bath at 40°C. Nitrogen atmosphere inside the flask. While stirring the solution in the flask at 100 rpm below the air pressure, add 14.8 g of MDI (polycarbonate Add 3.09 times the amount of OH [mol] of the phosphate polyol dropwise, and then... The solution in the lasco was stirred for about 1.5 hours. The isocyanate group concentration was analyzed, and the theoretical amount consumed was determined. After confirming that this had been done, the prepolymer was obtained. Next, the essential isocyanate was calculated from the remaining isocyanate. The required amount of 1,4-butanediol (1,4-BD), 3.2 g, was divided and added to the flask. After stirring the solution in the flask for about 1 hour, add about 1 g of ethanol, and then stir the solution in the flask further. The liquid was stirred for 30 minutes to obtain a polyurethane solution. Next, using a 0.8mm thick applicator, a glass plate (JIS R3202, 2mm) was used. The obtained polyurethane solution was dropped onto a 100mm x 150mm sheet, and the dry film thickness was 50mm. The coating was applied to a thickness of ~150 μm, and then placed on a hot plate at a surface temperature of 60°C for 2 hours, followed by 8 It was dried in an oven at 0°C for 12 hours. Then, it was dried again at a constant temperature and humidity of 23°C and 55% RH for 12 hours. After standing for more than an hour, the polyurethane films of Application Examples 1-9 and Application Comparative Examples 1-5 are each The obtained polyurethane films were evaluated for various physical properties using the following method. The samples were provided. The evaluation results are shown in Table 4.

[0153] <Tensile Test> In accordance with JIS K6301 (2010), width 10 mm, length 100 mm, thickness approximately 0.5 mm Test specimens of polyurethane coating, cut into strips of mm in length, were subjected to a tensile testing machine (Orientec Co., Ltd.). Using a product manufactured by the company, product name "Tensilon, model RTE-1210"), the distance between chucks is 20 A tensile test was conducted at a tensile speed of 100 mm / min at a temperature of 23°C (relative humidity 55%). The fracture strength and fracture elongation were measured. (Evaluation Criteria) • Breaking strength ◎(Excellent): Breaking strength of 50 MPa or higher. ○(Good): Breaking strength is 30 MPa or more and less than 50 MPa. △ (Poor): Breaking strength is between 20 MPa and less than 30 MPa. × (Bad): Items with a fracture strength of less than 20 MPa, or items that cannot be evaluated. • Breaking elongation ◎(Excellent): Elongation at fracture is 700% or more. ○ (Good): Elongation at the breaking point is 400% or more but less than 700%. △ (Poor): Breaking elongation is 200% or more but less than 400%. × (Bad): Items with a fracture elongation of less than 200%, or items that cannot be evaluated.

[0154] <Evaluation of chemical resistance> 3cm x 3cm test pieces were cut from the polyurethane coating. Testing was performed using a precision balance. After measuring the mass of the piece, a 250 mL volume gas containing 50 mL of oleic acid was used as the test solvent. The samples were placed in glass bottles and left to stand for 16 hours in a constant temperature bath under a nitrogen atmosphere at 80°C. Next, the test specimen was removed, lightly wiped on both sides with a paper wiper, and then its mass was measured using a precision balance. Next, calculate the mass change rate (increase rate: oleic acid swelling resistance rate) from before the test, and then... It was evaluated according to the following criteria. (Evaluation Criteria) ◎ (Excellent): Products with a mass increase rate of less than 4% ○ (Good): Products with a mass increase rate of 4% or more but less than 6%. △ (Poor): Mass increase rate is 6% or more but less than 20%. × (Bad): Items with a mass increase rate of 20% or more, or items that cannot be evaluated.

[0155] <Number average molecular weight of polyurethane> A portion of the above polyurethane film is cut, and the polyurethane concentration is 0.1% by mass. Prepare an N,N-dimethylacetamide solution and use a GPC apparatus [manufactured by Tosoh Corporation, product Name: "HLC-8320" (Column: Tskgel SuperHM-H, 4 tubes), Eluent [For this, use a solution of 2.6g of lithium bromide dissolved in 1L of dimethylacetamide.] The number-average molecular weight (Mn) was measured using a standard polystyrene equivalent.

[0156] [Table 4]

[0157] [Application Examples 10-18, Comparative Application Examples 6-10] Coating Film Evaluation The main components are polycarbonate polyols P-1 to P-9 obtained in the examples and comparative examples. B-1 to B-5, and Duranate TPA-100 (manufactured by Asahi Kasei Corporation, NC) as a hardening agent. Using 0%=23.1), the hydroxyl groups contained in the polycarbonate polyol used ( The ratio of the number of moles of OH groups to the number of moles of isocyanate groups (NCO groups) contained in the curing agent. Hereinafter also referred to as "NCO / OH ratio," the main component and hardener are mixed in a poly container so that the ratio is 1.1. Weigh it out, and add dibutyltin dilaurate as the catalyst relative to the total mass of the main component and the hardener. 100 ppm was added. The final paint composition was prepared so that the solid content was 42% by mass. Butyl acetate is added as a solvent, and the mixture is stirred using a stirrer until uniform, and the paint composition 1 is then... Each of the obtained paint compositions 1 was used to paint a polycarbonate sheet ("Takiron PC- "1600" (product name), 2mm x 70mm x 150mm) with a dry film thickness of 40μm Each was applied in such a manner. The paint composition 1 applied to the polycarbonate sheet was then applied to the 6 It was dried by baking at 0 °C for 30 minutes and cured at room temperature for 24 hours to obtain polyurethane films, respectively. For each of the obtained polyurethane films, various properties were evaluated by the method described below. The evaluation results are shown in Table 5.

[0158] <Weather resistance test> Using a super xenon weather meter (irradiance: 60 W / m 2 ), as the conditions for the weather resistance test , the black panel temperature during light irradiation was set to 65 °C and the humidity to 50%, and after 102 minutes, it was repeated in a cycle of 18 minutes at a humidity of 95% while spraying water. Before the start of the weather resistance test and after 2000 hours, gloss (gloss retention rate) and coloring (color resistance) were evaluated.

[0159] <Gloss retention rate> The gloss (45° reflectance of light) before and after the light resistance test was measured using a gloss meter. The gloss retention rate was calculated for each as the percentage obtained by dividing the gloss after 2000 hours by the gloss before the start of the weather resistance test. Based on the calculated gloss retention rate, the weather resistance was evaluated according to the following evaluation criteria. (Evaluation criteria) ○ (Excellent): Gloss retention rate is 9% or more △ (Good): Gloss retention rate is 80% or more and less than 90% ○ (Excellent): Gloss retention rate is 90% or more △ (Good): Gloss retention rate is 80% or more and less than 90%

[0160] <Color resistance> Also, using a color difference meter, L * a * b * (CIE1976) before and after the light resistance test was measured, and based on the color difference (ΔE) calculated by the following color difference formula, the color resistance was evaluated according to the following criteria. From there, based on the color difference (ΔE) calculated by the following color difference formula, the color resistance was evaluated according to the following criteria. The color resistance was evaluated according to the following criteria. ΔE = {(ΔL * ) 2 + (Δa * ) 2 + (Δb* ) 2} 1 / 2 (ΔL * Δa * Δb * L * a * , b * Before the start of each weather resistance test and at 2000 (This is the difference between the measured values ​​at different points in time.) (Evaluation Criteria) ◎(Excellent): ΔE is less than 2 ○ (Good): ΔE is between 2 and 5 (inclusive). △(Poor): ΔE is between 5 and 10 (inclusive). × (Bad): ΔE is 10 or greater

[0161] [Table 5]

[0162] [Application Example 19] Production of Polyol Composition Q-1 50g of the polycarbonate polyol P-3 obtained in Example 3 was weighed and used with Resonaq Poly Ester polyol (Teslac, 2460, molecular weight 2000, liquid polyol) 50g By mixing with the other substances, a polyol composition (Q-1) was obtained. The results of the physical property measurements of Q-1 are shown in Table 6. . 13 Carbonate repeat structure and ester repeat structure calculated by C-NMR measurement Based on the integral ratio of the structures, the calculation showed that the carbonate repeating structure was followed by the ester repeating structure. The molar ratio was 44:56.

[0163] [Application Example 20] Production of Polyol Composition Q-2 The polyester polyol used in Application Example 19 is Kuraray's polyester polyol (K Other than the change to Larele Polyol (P-2010, molecular weight 2000, liquid polyol), A polyol composition (Q-2) was obtained using the same method as in Application Example 1. The results of the physical property measurement of Q-2 are shown below. It is described in section 6. 13 The carbonate repeat structure and escalator were determined by C-NMR measurement. Based on the integral ratio of the ester repeating structure, the carbonate repeating structure: ester was calculated. The repeating structure was 48:52 (molar ratio).

[0164] [Application Example 21] Production of Polyol Composition Q-3 20g of polycarbonate polyol P-3 obtained in Example 3, and the polycarbonate obtained in Example 5 Weigh out 30g of Bonate Polyol P-5 and mix it with Resonax polyester polyol (Tesla Mix with 50g of (2460, molecular weight 2000, liquid polyol) to create a polyol composition. We obtained material (Q-3). The results of the physical property measurements of Q-3 are listed in Table 6. 13 By 1C NMR measurement This was calculated based on the integral ratios of the calculated carbonate repeating structure and ester repeating structure. However, the ratio of carbonate repeating structure to ester repeating structure is 42:58 (molar ratio). .

[0165] [Application Example 22] Production of Polyol Composition Q-4 The polyester polyol used in Application Example 21 is Kuraray's polyester polyol (K Other than the change to Larele Polyol (P-2010, molecular weight 2000, liquid polyol), A polyol composition (Q-4) was obtained using the same method as in Application Example 1. The results of the physical property measurement of Q-4 are shown below. This is described in section 6. The physical property measurement results for Q-3 are listed in Table 6. 13 Calculated by C-NMR measurement This was calculated based on the integral ratio of the carbonate repeating structure and the ester repeating structure. The ratio of carbonate repeating structure to ester repeating structure was 47:53 (molar ratio). .

[0166] [Application Example 23] Production of Polyol Composition Q-5 70g of the polycarbonate polyol P-3 obtained in Example 3 was weighed and used in a Resona poly Ester polyol (Teslac, 2460, molecular weight 2000, liquid polyol) 30g By mixing with the other substances, a polyol composition (Q-5) was obtained. The results of the physical property measurements of Q-5 are shown in Table 6. . 13 Carbonate repeat structure and ester repeat structure calculated by C-NMR measurement Based on the integral ratio of the structures, the calculation showed that the carbonate repeating structure was followed by the ester repeating structure. The molar ratio was 64:36.

[0167] [Application Example 24] Production of Polyol Composition Q-6 The polyester polyol used in Application Example 23 is Kuraray's polyester polyol (K Other than the change to Larele Polyol (P-2010, molecular weight 2000, liquid polyol), A polyol composition (Q-6) was obtained using the same method as in Application Example 1. The results of the physical property measurement of Q-6 are shown below. It is described in section 6. 13 The carbonate repeat structure and escalator were determined by C-NMR measurement. Based on the integral ratio of the ester repeating structure, the carbonate repeating structure: ester was calculated. The repeating structure was 68:32 (molar ratio).

[0168] [Application Example 25] Production of Polyol Composition Q-7 70g of the polycarbonate polyol P-3 obtained in Example 3 was weighed and mixed with a liquid from Mitsubishi Chemical Corporation. Mix with 30g of tetramethylene ether glycol (PTMG2000) and polio A compound (Q-7) was obtained. 13 Carbonate repeats calculated by C-NMR measurement Based on the integral ratio of the structure and the ether repeating structure, the carbonate repeating structure was calculated. Structure: The ether repeating structure was 63:27 (molar ratio).

[0169] [Table 6]

[0170] [Application Examples 26-32] Urethane evaluation of polyol compositions The polycarbonate polyol used in Application Example 1 is used in the polycarbonate polyol obtained in Application Examples 19-25. Except for changing all compositions to Q1~7, the process is the same as in Application Example 1, but each is polymerized. A tan film was obtained. Various materials were obtained from each of the obtained polyurethane films by the method described above. The subjects were subjected to a gender evaluation. The evaluation results are shown in Table 7.

[0171] [Table 7]

[0172] [Application Examples 33-39] Evaluation of Polyol Composition Coatings The polycarbonate polyol used in Application Example 10 was obtained in Application Examples 19-25 Except for the change to Riol compositions Q-1 to Q-7, the same method as in Application Example 10 was used for each poly A polyurethane coating film was obtained. Various physical properties of each obtained polyurethane coating film were determined by the method described above. The samples were subjected to evaluation. The evaluation results are shown in Table 8.

[0173] [Table 8] [Industrial applicability]

[0174] The polycarbonate polyol of the present invention has excellent heat resistance and weather resistance, for example, polyurethane We can provide polyurethane that suppresses discoloration caused by heat during manufacturing and discoloration over time. For example, paints, paint compositions, adhesives, adhesive compositions, sealants, water-based polyurethanes, It is widely used as a constituent material for water-dispersible compositions, polyurethanes for synthetic leather, synthetic leather, etc. It can be used for its intended purpose.

Claims

1. It has a repeating structural unit represented by the following formula (1) and a structural unit represented by the following formula (2). Characterized by, Polycarbonate polyol. 【Chemistry 1】 (In formula (1), R 1 (This is any divalent aliphatic hydrocarbon group.) 【Chemistry 2】 (In formula (2), R 2 is any monovalent aliphatic hydrocarbon group, and R 3 is any bivalent aliphatic It is a hydrocarbon group.

2. The content of the constituent unit represented by formula (2) is between 0.001 ppm and 30,000 ppm. be, The polycarbonate polyol according to claim 1.

3. The content of the constituent unit represented by formula (2) is 5 ppm to 170 ppm. The polycarbonate polyol according to claim 1.

4. The repeating structural unit represented by formula (1) and the structural unit represented by formula (2) are combined. The constituent unit is represented by the following formula (11): The polycarbonate polyol according to claim 1. 【Transformation 3】 (In formula (11), R 1 is any divalent aliphatic hydrocarbon group, and R 2 is any monovalent fat It is a fatty hydrocarbon group, R 3 (This is any divalent aliphatic hydrocarbon group.)

5. It further comprises a constituent unit represented by the following formula (3): The polycarbonate polyol according to claim 1. 【Chemistry 4】 (In formula (3), R 5 is any divalent aliphatic hydrocarbon group, and R 4 This is a carbon-1 to carbon-12 It is an aliphatic hydrocarbon group.

6. The constituent unit represented by the formula (2) and R in the formula (3) 4 With respect to the sum of the above formula ( 2) The mass ratio of the constituent units represented is 0.000001 to 0.

20. The polycarbonate polyol according to claim 5.

7. The hydroxyl group end purity is 90 mol% to 98 mol%. The polycarbonate polyol according to claim 1.

8. The repeating structural unit represented by formula (1) is R 1 Two or more different formulas (1 Includes repeating structural units represented by ), The polycarbonate polyol according to claim 1.

9. The repeating structural unit represented by formula (1) is R １ Two or more different types of carbon-numbered (2 or more) It contains 20 aliphatic structures, The polycarbonate polyol according to claim 1.

10. In the above formula (1), R １ The ratio of the two types of aliphatic hydrocarbon groups is 0.1 to 0.

9. The polycarbonate polyol according to claim 9.

11. The repeating structural unit represented by formula (1) is R １ Aliphatic structure with 5 carbon atoms and R １ It contains an aliphatic structure with 6 carbon atoms, The content of the constituent unit represented by formula (2) is 5 ppm to 170 ppm. The polycarbonate polyol according to claim 1.

12. The number-average molecular weight is between 300 and 5000. The polycarbonate polyol according to claim 1.

13. The hydroxyl value is between 20 mg KOH / g and 700 mg KOH / g. The polycarbonate polyol according to claim 1.

14. The constituent unit represented by formula (2) above is an unsaturated monohydroxy alcohol having 4 to 9 carbon atoms. It is the structure from which it originates. The polycarbonate polyol according to claim 1.

15. The polycarbonate polyol according to claim 1, and an ester structure and / or ether A polyol compound having a poly structure, Polyol composition.

16. The polycarbonate polyol and the ester structure and / or ether structure Polyol compounds containing polycarbonate structure: ester structure and ether The total molar ratio of the structure is in the range of 20:80 to 80:

20. The polyol composition according to claim 15.

17. The polycarbonate polyol and the ester structure and / or ether structure Polyol compounds containing polycarbonate structure: ester structure and ether The total molar ratio of the structure is in the range of 30:70 to 75:

25. The polyol composition according to claim 15.

18. Polycarbonate polyol according to any one of claims 1 to 14 or claim 15 A polymer of a polyol composition described in any one of items ~17 and an isocyanate compound be, Polyurethane.

19. A polyurethane comprising the polyurethane described in claim 18, glue.

20. A polyurethane comprising the polyurethane described in claim 18, paint.

21. A polyurethane comprising the polyurethane described in claim 18, Sealing material.

22. Polycarbonate polyol according to any one of claims 1 to 14 or claim 15 A polyol composition obtained using any one of the items 17 to 17, Water-based polyurethane.

23. Polycarbonate polyol according to any one of claims 1 to 14 or claim 15 A polyol composition obtained using any one of the items 17 to 17, Water dispersion composition.

24. Polycarbonate polyol according to any one of claims 1 to 14 or claim 15 A polyol composition obtained using any one of the items 17 to 17, Synthetic leather.

25. Automotive interior material comprising synthetic leather as described in claim 24.

26. A method for producing a polycarbonate polyol according to claim 1, A polyol having repeating structural units represented by formula (1) above, An unsaturated bond-containing hydroxy compound having a structural unit represented by formula (2) is added. The manufacturing process involves reacting the product by heating and stirring at 120°C to 180°C under normal or reduced pressure. Construction method.

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