Polycarbonate polyol composition, adhesive composition, water-based polyurethane, water dispersion composition, polyurethane for synthetic leather, and synthetic leather

Abstract

Provided are a polycarbonate polyol composition, an adhesive composition, a water-based polyurethane, a water-dispersed composition, a synthetic leather polyurethane, and a synthetic leather, which provide a polyurethane film having a long pot life, excellent handling, a good appearance, and excellent weather resistance. A polycarbonate polyol composition characterized by comprising: a polycarbonate polyol having a terminal hydroxyl group; an (A) component: a compound represented by the following (A) formula; and a (B) component: a compound represented by the following (B) formula, the mass ratio of the aforementioned (A) component to the aforementioned (B) component ((A) / (B)) being 0.0001 to 0.1000. (In the formula (A), R1 is hydrogen or an alkyl group having 1 to 12 carbon atoms, and R2 is an alkylene group having 1 to 12 carbon atoms.) (In the formula (B), R3 is an alkylene group having 2 to 12 carbon atoms, and optionally has a linear alkylene group, a divalent alicyclic hydrocarbon group, or an alkylene group having a branch.)

Description

Technical Field

[0001] This invention relates to polycarbonate polyol compositions, adhesive compositions, aqueous polyurethanes, water-dispersible compositions, polyurethanes for synthetic leather, and synthetic leather. Background Technology

[0002] Polycarbonate polyols are known to be useful raw materials for urethanes, possessing both flexibility and strength, and can be used as soft segments in products such as polyurethanes and thermoplastic elastomers. Polycarbonate polyols are particularly well-known for their excellent hydrolysis resistance and acid resistance. Various polycarbonate polyols have been previously studied and are widely recognized.

[0003] For example, as a polycarbonate polyol that exhibits high polymerization reactivity and high polymerization rate in polyurethane reaction and reaction used to manufacture polyester elastomers, Patent Document 1 discloses a polycarbonate diol in which the ratio of terminal primary hydroxyl groups to all terminal groups is within a specific range.

[0004] In addition, as a polycarbonate diol that stabilizes the reaction and is used as a component of coatings, it does not have the roughness from fine gel-like substances or the stickiness from low molecular weight substances, and thus can obtain a coating film with a good balance of properties such as hydrolysis resistance and heat resistance. Patent Document 2 discloses a polycarbonate diol with a terminal primary hydroxyl ratio within a specific range.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent No. 3874664

[0008] Patent Document 2: Japanese Patent Application Publication No. 2013-064140 Summary of the Invention

[0009] The problem the invention aims to solve

[0010] However, the following issues have been discovered: If the polycarbonate diol disclosed in Patent Document 1 and Patent Document 2 is used, although there is a tendency to easily obtain excellent reaction rate and coating performance, unexpectedly, the usable time (applicable period) becomes shorter when mixed with isocyanate, and gelation occurs, making it difficult to obtain polyurethane with a good appearance, and the weather resistance of the obtained polyurethane is reduced.

[0011] The present invention was made in view of the aforementioned problems. Specifically, an object of the present invention is to provide polycarbonate polyol compositions, etc., that can provide polyurethane films with long service life, excellent workability, good appearance, and excellent weather resistance when used as, for example, as polyurethane constituent materials in coatings, adhesives, synthetic leather, etc. Another object of the present invention is to provide polycarbonate polyol compositions, adhesive compositions, aqueous polyurethanes, water-dispersible compositions, polyurethanes for synthetic leather, and synthetic leather, etc., that can provide polyurethanes with excellent workability, good appearance, and excellent weather resistance.

[0012] Solution for solving the problem

[0013] The inventors conducted in-depth research on the aforementioned issues. As a result, a new polycarbonate polyol composition comprising a polycarbonate polyol having terminal hydroxyl groups, and components (A) and (B) described below, wherein the proportions of components (A) and (B) are within a specific range, was developed. Furthermore, it was discovered that the aforementioned issues could be resolved by using this polycarbonate polyol composition, thus completing the present invention.

[0014] That is, the present invention provides various specific methods as shown below.

[0015] <1>

[0016] A polycarbonate polyol composition, characterized in that it comprises:

[0017] Polycarbonate polyols with terminal hydroxyl groups;

[0018] (A) Components: The compound represented by formula (A) below; and,

[0019] (B) Component: The compound represented by formula (B) below,

[0020] The mass ratio of the aforementioned component (A) to the aforementioned component (B) ((A) / (B)) is 0.0001 to 0.1000.

[0021]

[0022] (In formula (A), R1 is hydrogen or an alkyl group having 1 to 12 carbon atoms, and R2 is an alkylene group having 1 to 12 carbon atoms.)

[0023]

[0024] (In formula (B), R3 is an alkylene group with 2 to 12 carbon atoms, and may optionally have a straight-chain alkylene group, a divalent alicyclic hydrocarbon group, or a branched alkylene group.)

[0025] <2>

[0026] according to <1> The polycarbonate polyol composition wherein the content of at least one metal element selected from the group consisting of titanium, ytterbium, tin, zirconium, magnesium, calcium, lithium, sodium and manganese, as determined by ICP (ICP-MS: Inductively Coupled Plasma Mass Spectrometry), is 0.0001 to 0.050 by mass.

[0027] <3>

[0028] according to <1> or <2> The polycarbonate polyol composition wherein the phosphorus content, as determined by ICP (ICP-MS: Inductively Coupled Plasma Mass Spectrometry), is 0.0001~0.050 by mass.

[0029] <4>

[0030] according to <1> ~ <3> The polycarbonate polyol composition according to any one of the above formulas (A) and (B) is wherein the sum of the total number of carbon atoms of R1 and R2 plus the number of two carbon atoms is equal to the number of carbon atoms of R3.

[0031] <5>

[0032] according to <1> ~ <4> The polycarbonate polyol composition described in any one of the above statements, wherein the aforementioned polycarbonate polyol having terminal hydroxyl groups has repeating units derived from 1,5-pentanediol and / or 1,6-hexanediol,

[0033] The compound shown in formula (A) above comprises one of the following groups: a compound in formula (A) where R1 is a hydrogen atom and R2 is an alkylene group having 4 or 3 carbon atoms; a compound in formula (A) where R1 is an alkylene group having 1 carbon atom and R2 is an alkylene group having 3 or 2 carbon atoms; and a compound in formula (A) where R1 is an alkylene group having 2 carbon atoms and R2 is an alkylene group having 2 or 1 carbon atoms.

[0034] The sum of the total number of carbon atoms in R1 and R2 of the compound shown in formula (A) plus the number of two carbon atoms results in a number of 5 or 6, which is equal to the number of carbon atoms in R3 of the compound shown in formula (B).

[0035] <6>

[0036] according to <1> ~ <5> The polycarbonate polyol composition described in any one of the following examples is characterized by further comprising component (B').

[0037] The mass ratio of the aforementioned component (B') to the aforementioned component (B) ((B') / (B)) is 0.0001 to 1.000.

[0038]

[0039] (In formula (B'), R4 is an alkylene group having 1 to 4 carbon atoms.)

[0040] <7>

[0041] according to <1> ~ <6> The polycarbonate polyol composition described in any one of the above statements further comprises a polyol compound having an ester repeating structure and / or an ether repeating structure.

[0042] <8>

[0043] according to <7> The polycarbonate polyol composition wherein the molar ratio of the polycarbonate polyol to the polyol compound having an ester repeating structure and / or an ether repeating structure, the sum of the carbonate repeating structure and the ester repeating structure and the ether repeating structure, is in the range of 20:80 to 80:20.

[0044] <9>

[0045] according to <1> ~ <8> The polycarbonate polyol composition according to any one of the following methods, wherein the aforementioned mass ratio ((A) / (B)) is 0.0001 to 0.075.

[0046] <10>

[0047] according to <1> ~ <9> The polycarbonate polyol composition according to any one of the following methods, wherein the aforementioned mass ratio ((A) / (B)) is 0.0001 to 0.069.

[0048] <11>

[0049] according to <1> ~ <10> The polycarbonate polyol composition according to any one of the following methods, wherein the aforementioned mass ratio ((A) / (B)) is 0.0001 to 0.010.

[0050] <12>

[0051] according to <1> ~ <11> The polycarbonate polyol composition according to any one of the following methods, wherein the aforementioned mass ratio ((A) / (B)) is 0.006 to 0.010.

[0052] <13>

[0053] according to <1> ~ <12> The polycarbonate polyol composition according to any one of the following methods, wherein the aforementioned polycarbonate polyol having terminal hydroxyl groups has a structural unit represented by the following formula (P).

[0054] (P)

[0055] (In formula (P), R1 is any divalent aliphatic hydrocarbon group, R2 is hydrogen or any monovalent aliphatic hydrocarbon group, and R3 is any divalent aliphatic hydrocarbon group.)

[0056] <14>

[0057] An adhesive composition comprising <1> ~ <13> The polycarbonate polyol composition described in any one of the following statements.

[0058] <15>

[0059] A water-based polyurethane, which uses <1> ~ <13> It is made from any one of the polycarbonate polyol compositions.

[0060] <16>

[0061] An aqueous dispersion composition, which is used <1> ~ <13> It is made from any one of the polycarbonate polyol compositions.

[0062] <17>

[0063] A polyurethane for synthetic leather, which uses <1> ~ <13> It is made from any one of the polycarbonate polyol compositions.

[0064] <18>

[0065] A type of synthetic leather, which is made using <1> ~ <13> It is made from any one of the polycarbonate polyol compositions.

[0066] <19>

[0067] A urethane cured product, which is used <1> ~ <13> It is made from any one of the polycarbonate polyol compositions.

[0068] <20>

[0069] An automotive interior material comprising <18> The aforementioned synthetic leather.

[0070] <21>

[0071] A method for suppressing odor from a polycarbonate polyol composition, wherein,

[0072] The polycarbonate polyol composition comprises:

[0073] Polycarbonate polyols with terminal hydroxyl groups;

[0074] (A) Components: The compound represented by formula (A) below; and,

[0075] (B) Component: The compound represented by formula (B) below,

[0076] The mass ratio of the aforementioned component (A) to the aforementioned component (B) ((A) / (B)) is 0.0001 to 0.1000.

[0077] <22>

[0078] A method for suppressing the odor of urethane cured products, comprising the following steps:

[0079] A polycarbonate polyol composition is selected, and the aforementioned polycarbonate polyol composition is cured to produce a urethane cured product.

[0080] The polycarbonate polyol composition comprises:

[0081] Polycarbonate polyols with terminal hydroxyl groups;

[0082] (A) Components: The compound represented by formula (A) below; and,

[0083] (B) Component: The compound represented by formula (B) below,

[0084] The mass ratio of the aforementioned component (A) to the aforementioned component (B) ((A) / (B)) is 0.0001 to 0.1000.

[0085] <23>

[0086] A method for manufacturing a polycarbonate polyol composition, wherein,

[0087] The polycarbonate polyol composition comprises:

[0088] Polycarbonate polyols with terminal hydroxyl groups;

[0089] (A) Components: The compound represented by formula (A) below; and,

[0090] (B) Component: The compound represented by formula (B) below,

[0091] The mass ratio of the aforementioned component (A) to the aforementioned component (B) ((A) / (B)) is adjusted to a range of 0.0001 to 0.1000.

[0092] <24>

[0093] A method for manufacturing a urethane cured product, comprising the following steps:

[0094] Select a polycarbonate polyol composition, and cure the aforementioned polycarbonate polyol composition.

[0095] The polycarbonate polyol composition comprises:

[0096] Polycarbonate polyols with terminal hydroxyl groups;

[0097] (A) Components: The compound represented by formula (A) below; and

[0098] (B) Component: The compound represented by formula (B) below,

[0099] The mass ratio of the aforementioned component (A) to the aforementioned component (B) ((A) / (B)) is 0.0001 to 0.1000.

[0100] <25>

[0101] A method for manufacturing synthetic leather, comprising the following steps:

[0102] An adhesive layer, an intermediate layer, and a skin layer are sequentially disposed on the substrate.

[0103] Any one of the aforementioned skin layer, the aforementioned intermediate layer, and the aforementioned adhesive layer is a urethane cured product of the polycarbonate polyol composition.

[0104] The aforementioned polycarbonate polyol composition comprises:

[0105] Polycarbonate polyols with terminal hydroxyl groups;

[0106] (A) Components: The compound represented by formula (A) below; and,

[0107] (B) Component: The compound represented by formula (B) below,

[0108] The mass ratio of the aforementioned component (A) to the aforementioned component (B) ((A) / (B)) is 0.0001 to 0.1000.

[0109] <26>

[0110] A method for suppressing the odor of synthetic leather, comprising the following steps:

[0111] A polycarbonate polyol composition is selected, and a urethane cured product of the aforementioned polycarbonate polyol composition is used in at least one of the adhesive layer, intermediate layer, and skin layer.

[0112] The polycarbonate polyol composition comprises:

[0113] Polycarbonate polyols with terminal hydroxyl groups;

[0114] (A) Components: The compound represented by formula (A) below; and,

[0115] (B) Component: The compound represented by formula (B) below,

[0116] The mass ratio of the aforementioned component (A) to the aforementioned component (B) ((A) / (B)) is 0.0001 to 0.1000.

[0117] The effects of the invention

[0118] According to the present invention, polycarbonate polyol compositions that can achieve a long service life, excellent workability, good appearance, and excellent weather resistance when provided as polyurethane constituent materials for coatings, adhesives, synthetic leather, etc., can also be provided. Furthermore, by using the polycarbonate polyol compositions of the present invention, polycarbonate polyol compositions that can achieve a polyurethane with excellent workability, good appearance, and excellent weather resistance, adhesive compositions, aqueous polyurethanes, water-dispersible compositions, polyurethanes for synthetic leather, and synthetic leather can also be provided. Attached Figure Description

[0119] Figure 1 This is a schematic cross-sectional view showing an example of a synthetic leather laminate using the polycarbonate polyol composition of this embodiment.

[0120] Figure 2 This is a schematic diagram illustrating an example of a method for manufacturing a synthetic leather laminate using the polycarbonate polyol composition of this embodiment.

[0121] Explanation of reference numerals in the attached figures

[0122] 1… Release paper

[0123] 2…epidermis

[0124] 3… Adhesive layer

[0125] 4…Substrate (Polyester Fabric)

[0126] 5… Mixed head (epidermis)

[0127] 6… Mixing head (adhesive layer)

[0128] 7…piece structure (dry synthetic leather products)

[0129] 8… Coating roller

[0130] 9…Crimping roller

[0131] 10… Take-up roller

[0132] 11…dryer Detailed Implementation

[0133] The following describes in detail the method for implementing the present invention (hereinafter referred to as "this embodiment"). It should be noted that the present invention is not limited to the following embodiment, and can be implemented in various modifications within its scope.

[0134] <Polycarbonate polyol composition>

[0135] The polycarbonate polyol composition of this embodiment is characterized in that it comprises: a polycarbonate polyol having terminal hydroxyl groups; (A) component: the compound shown in formula (A) below; and (B) component: the compound shown in formula (B) below, wherein the mass ratio of component (A) to component (B) is 0.0001 to 0.1000.

[0136]

[0137] (In formula (A), R1 is hydrogen or an alkyl group having 1 to 12 carbon atoms, and R2 is an alkylene group having 1 to 12 carbon atoms.)

[0138]

[0139] (In formula (B), R3 is an alkylene group with 2 to 12 carbon atoms, and may optionally have a straight-chain alkylene group, a divalent alicyclic hydrocarbon group, or a branched alkylene group.)

[0140] <Polycarbonate polyols>

[0141] The polycarbonate polyol composition of this embodiment comprises a polycarbonate polyol having terminal hydroxyl groups. There are no particular limitations on the polycarbonate polyol having terminal hydroxyl groups, as long as it has a carbonate repeating structure and has two or more hydroxyl groups. In addition to carbonate repeating structures, the polycarbonate polyol having terminal hydroxyl groups may also contain, for example, ester repeating structures, ether repeating structures, etc. Specific configurations of the polycarbonate polyol having terminal hydroxyl groups are shown below.

[0142] In this embodiment, the number average molecular weight (Mn) of the polycarbonate polyol having terminal hydroxyl groups is not particularly limited, but is preferably 300 to 5000. By making the number average molecular weight of the polycarbonate polyol having terminal hydroxyl groups 300 or more, the low-temperature properties of the obtained polyurethane tend to be better. By making the number average molecular weight of the polycarbonate polyol having terminal hydroxyl groups 5000 or less, the reduction in the molding processability of the obtained polyurethane tends to be more easily suppressed. From the perspective of the coating appearance of the obtained polyurethane, the number average molecular weight of the polycarbonate polyol is preferably 300 or more and 3000 or less, more preferably 350 or more and 2000 or less, and even more preferably 500 or more and 2000 or less.

[0143] It should be noted that, in this embodiment, the number-average molecular weight (Mn) of the polycarbonate polyol having terminal hydroxyl groups can be determined by the method described in the examples below.

[0144] In this embodiment, the hydroxyl value (OH value) of the polycarbonate polyol with terminal hydroxyl groups is not particularly limited, but the lower limit is preferably 20 mg KOH / g or more, more preferably 30 mg KOH / g or more, further preferably 50 mg KOH / g or more, even more preferably 60 mg KOH / g or more, particularly preferably 70 mg KOH / g or more, and most preferably 74 mg KOH / g or more. Furthermore, the upper limit of the hydroxyl value (OH value) of the polycarbonate polyol with terminal hydroxyl groups is not particularly limited, but it is preferably 700 mg KOH / g or less, more preferably 500 mg KOH / g or less, further preferably 400 mg KOH / g or less, even more preferably 350 mg KOH / g or less, particularly preferably 300 mg KOH / g or less, and most preferably 230 mg KOH / g or less. By setting the hydroxyl value (OH value) of the polycarbonate polyol with terminal hydroxyl groups within the aforementioned preferred range, it is easy to obtain a polycarbonate polyol with terminal hydroxyl groups that has low viscosity, excellent processability, and excellent compatibility with inactive organic solvents. Furthermore, by using such a polycarbonate polyol with terminal hydroxyl groups, the stress, elongation at break, and chemical resistance of the obtained polyurethane tend to be improved.

[0145] In this embodiment, the method for controlling the hydroxyl value of the polycarbonate polyol having terminal hydroxyl groups within the aforementioned range is not particularly limited. For example, a method that controls the hydroxyl value by adding and / or removing alcohol compounds during the manufacture of the polycarbonate polyol can be cited.

[0146] When polycarbonate polyols with terminal hydroxyl groups are manufactured using hydroxyl compounds and carbonate compounds as raw materials, for example, hydroxyl compounds (e.g., polyfunctional diols) and carbonate compounds (e.g., carbonates) can be used as raw materials and synthesized by transesterification reactions as described, for example, in "Polymer Reviews Vol. 9, pp. 9-20".

[0147] In this embodiment, hydroxyl compounds that can be used as raw materials for polycarbonate polyols with terminal hydroxyl groups can be, for example, diols. Specific examples of diols are not particularly limited; for example, diols having a divalent aliphatic or alicyclic hydrocarbon skeleton having 3 to 15 carbon atoms can be included. By making the diol have 3 or more carbon atoms, in addition to lowering the viscosity of the polycarbonate polyol composition and reducing the amount of inactive organic solvent used, the resulting synthetic leather tends to have improved softness and low-temperature properties. By making the diol compound have 15 or fewer carbon atoms, the resulting synthetic leather tends to have excellent chemical resistance. Specific examples include: 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, and other diols without side chains; 2-methyl-1,8-octanediol, 2-ethyl... Diols with side chains, such as 1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, and 2,2-dimethyl-1,3-propanediol; and cyclic diols, such as 1,4-cyclohexanediol, 2-bis(4-hydroxycyclohexyl)-propane, and 1,4-cyclohexanediol, but not particularly limited to these. One or more of these can be used as raw materials for polycarbonate polyols with terminal hydroxyl groups. By using two or more diols in combination, the regularity of the structural units of the resulting polycarbonate diol decreases, and its crystallinity decreases, thus tending to readily obtain polycarbonate diols that are liquid at room temperature (25°C). Therefore, there is a tendency to suppress the amount of inactive organic solvent used.

[0148] From the viewpoint of improving the chemical resistance and mechanical strength of the coating film, it is more preferable to use one or more diols without side chains as raw materials for polycarbonate polyols with terminal hydroxyl groups. Specifically, as linear diols, one or more are preferably selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and 1,9-nonanediol. Among these, as raw material diols, two diols selected from the group consisting of 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are more preferable, and 1,5-pentanediol and 1,6-hexanediol are even more preferable.

[0149] In the manufacture of polycarbonate polyols with terminal hydroxyl groups, when using two or more diols as raw materials, the proportion of these raw material diols used is not particularly limited. It is preferable to appropriately set the proportion of the raw material diols used so that the resulting polycarbonate polyol with terminal hydroxyl groups is liquid at room temperature. For example, when using two diols as raw materials, it is preferable to set the input amount in a molar ratio between 20:80 and 80:20. If within this range, the crystallinity of the polycarbonate diol decreases, tending to result in synthetic leather with high softness, good low-temperature properties, and a pleasant feel. Furthermore, the resulting polycarbonate polyol with terminal hydroxyl groups tends to be liquid, and the amount of inactive organic solvent used is easily reduced. When using two diols as raw materials, in a preferred embodiment, the molar ratio can be 30:70 or higher, 40:60 or higher, or 70:30 or lower, tending to be liquid even below 0°C; therefore, the molar ratio can be 60:40 or lower.

[0150] Furthermore, without excessively impairing the performance of the polycarbonate polyol composition of this embodiment, compounds having three or more hydroxyl groups per molecule, such as trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, etc., can also be used as raw materials for polycarbonate polyols with terminal hydroxyl groups. However, if too many compounds having three or more hydroxyl groups per molecule are used as raw materials for polycarbonate polyols with terminal hydroxyl groups, crosslinking may sometimes occur during the polymerization reaction of the polycarbonate polyol, leading to gelation. Therefore, when using compounds having three or more hydroxyl groups per molecule as raw materials, the proportion of this compound used is preferably 0.1 to 5 mol%, more preferably 0.1 to 1 mol%, relative to the total molar number of the raw material diols used as raw materials for polycarbonate polyols with terminal hydroxyl groups.

[0151] In this embodiment, specific examples of carbonates that can be used as raw materials for polycarbonate polyols with terminal hydroxyl groups are not particularly limited. Examples include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate; diaryl carbonates such as diphenyl carbonate; and alkyl carbonates such as ethylene carbonate, trimethylol carbonate, 1,2-propyl carbonate, 1,2-butyl carbonate, 1,3-butyl carbonate, and 1,2-pentyl carbonate. One or more of these can be used as raw materials for polycarbonate polyols with terminal hydroxyl groups. From the viewpoint of ease of acquisition and ease of setting polymerization reaction conditions, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, dibutyl carbonate, and / or ethylene carbonate are preferred as raw material carbonates.

[0152] In this embodiment, the synthesis of polycarbonate polyols with terminal hydroxyl groups can be carried out by methods known in the art, without particular limitation. For example, it can be carried out in the presence or absence of a catalyst. From the viewpoint of reaction efficiency, synthesis in the presence of a catalyst is preferred. As such a catalyst, catalysts known in the art can be appropriately used, without particular limitation, for example, alkali metals such as lithium, sodium, and potassium, alkaline earth metals such as magnesium, calcium, strontium, and barium, alkali metals, hydrides, oxides, amides, carbonates, hydroxides, nitrogen-containing borates, and further basic alkali metal salts and alkaline earth metal salts of organic acids can be mentioned. In addition, as such a catalyst, there is no particular limitation, for example, metals such as aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, indium, tin, antimony, tungsten, rhenium, osmium, iridium, platinum, gold, thallium, lead, bismuth, and ytterbium, their metal salts, their metal alkoxides, and organic compounds containing such metals can be mentioned. They can be used individually or, appropriately, two or more can be selected for use.

[0153] Among these, the polymerization of polycarbonate polyols proceeds well when one or more catalysts are used from metals such as lithium, sodium, potassium, magnesium, calcium, titanium, zirconium, tin, lead, manganese, ytterbium, their metal salts, their metal alkoxides, or organic compounds containing the metal, and the effect on the urethane reaction using the obtained polycarbonate polyol is also minimal, therefore it is preferred.

[0154] As the aforementioned catalyst, it is more preferable to use one or more catalysts containing one or more metal elements selected from the group consisting of titanium, ytterbium, tin, zirconium, magnesium, calcium, lithium, sodium and manganese. It is even more preferable to use one or more catalysts containing one or more metal elements selected from the group consisting of titanium, ytterbium, tin, magnesium, calcium, lithium and manganese. Particularly preferred are organic compounds containing titanium, tin, magnesium, calcium, lithium and / or manganese.

[0155] The polycarbonate polyol composition of this embodiment may contain a catalyst comprising the aforementioned metal element. In the polycarbonate polyol composition of this embodiment, the content of the catalyst, based on the metal element content determined using ICP (ICP-MS: Inductively Coupled Plasma Mass Spectrometry), preferably comprises 0.0001 to 0.050% by mass. If the catalyst content is within the aforementioned range, the polymerization of the polycarbonate polyol proceeds well, and the effect on the urethane reaction using the polycarbonate polyol composition is minimal. In a preferred embodiment, the catalyst content, based on the metal element content determined using ICP, may be 0.0005% by mass or more, or 0.020% by mass or less.

[0156] The following illustrates one method for manufacturing polycarbonate polyols with terminal hydroxyl groups according to this embodiment. The manufacturing of polycarbonate polyols with terminal hydroxyl groups is not particularly limited; for example, the transesterification reaction can be carried out in two stages according to the following steps.

[0157] Specifically, a glycol and carbonate are mixed in a molar ratio (glycol:carbonate) of, for example, 20:1 to 1:10, and the first stage reaction is carried out at 100 to 300°C under normal or reduced pressure, in the absence or presence of a transesterification catalyst. For example, when dimethyl carbonate is used as the carbonate, the generated methanol can be removed as a mixture with dimethyl carbonate to obtain a low molecular weight polycarbonate polyol. Distillation removes the alcohol derived from the carbonate generated in the reaction. For example, when diethyl carbonate is used as the carbonate, the generated ethanol can be removed as a mixture with diethyl carbonate to obtain a low molecular weight polycarbonate polyol. Alternatively, for example, when ethylene carbonate is used as the carbonate, the generated ethylene glycol can be removed as a mixture with ethylene carbonate to obtain a low molecular weight polycarbonate polyol. Next, as the second stage of the reaction, the reaction product of the first stage is heated under reduced pressure at 160~300°C to remove unreacted diols and carbonates, and the low molecular weight polycarbonate polyol is condensed to obtain a polycarbonate polyol with a specified molecular weight.

[0158] Furthermore, by adding hydroxyl compounds with different skeletons to the obtained polycarbonate polyols with terminal hydroxyl groups, and adding an ester exchange catalyst as needed, the reaction can be carried out under normal or reduced pressure at 100–300 °C, thereby further introducing different structures. If necessary, the low-boiling-point hydroxyl compounds can be removed by heating under reduced pressure at 120–300 °C, while simultaneously condensing the low molecular weight polycarbonate polyol, to obtain a polycarbonate polyol with terminal hydroxyl groups of a specified molecular weight.

[0159] In this embodiment, the melt viscosity of the polycarbonate polyol with terminal hydroxyl groups at 50°C is not particularly limited, but is preferably 500 to 200,000 mPa·s, more preferably 1,000 to 180,000 mPa·s, and even more preferably 1,500 to 165,000 mPa·s. By setting the melt viscosity at 50°C to 500 mPa·s or higher, the stress, elongation at break, and chemical resistance of the obtained polyurethane tend to be improved. By setting the melt viscosity at 50°C to 180,000 mPa·s or lower, the wettability (contact efficiency) of the resulting composition with the substrate is improved, thus tending to exhibit high adhesive strength. In addition, when used as a sealant raw material, the composition is also filled into fine parts, which can exhibit high insulation reliability.

[0160] In this embodiment, the method for controlling the melt viscosity of the polycarbonate polyol with terminal hydroxyl groups at 50°C within the aforementioned range is not particularly limited; for example, adjusting the number of carbon atoms in the glycol and the number-average molecular weight can be used. For instance, if the type of raw material is adjusted to decrease the number of carbon atoms in the glycol, the melt viscosity of the polycarbonate polyol with terminal hydroxyl groups tends to increase. Similarly, if the manufacturing conditions are adjusted to increase the number-average molecular weight, the melt viscosity of the polycarbonate polyol with terminal hydroxyl groups tends to increase.

[0161] The method for measuring melt viscosity in this embodiment is not particularly limited; for example, the following apparatus can be used to measure viscosity.

[0162] Rotational viscometer: Type E viscometer (manufactured by Toki Sangyo Co., Ltd., TVE-22HT, cone plate: No. 6)

[0163] The polycarbonate polyol composition of this embodiment may comprise a polycarbonate polyol and a polyol compound having an ester repeating structure and / or an ether repeating structure.

[0164] Examples of polyol compounds with repeating ester structures include polyester polyols. There are no particular limitations on the diols used as raw materials for polyester polyols; examples include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, and 1,15-pentadecanediol, which are diols without side chains; 2-methyl-1,8-octanediol, 2-ethyl-1,6-hexanediol, and 2-methyl-1... Diols with side chains, such as 3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, and 2,2-dimethyl-1,3-propanediol; cyclic diols, such as 1,4-cyclohexanediol, 2-bis(4-hydroxycyclohexyl)propane, and 1,4-cyclohexanediol, are preferred examples. Examples of preferred diols include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, and 3-methyl-1,5-pentanediol. One or more of these diols can be used as raw materials for polyester polyols.

[0165] There are no particular limitations on the dicarboxylic acids used as raw materials for polyester polyols. Examples include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, and sebacic acid; and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. More preferably, examples include succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid. One or more of these dicarboxylic acids may be used as raw materials for polyester polyols.

[0166] Cyclic ester compounds can be used as raw materials for polyester polyols through ring-opening polymerization. There are no particular limitations on the cyclic ester compounds; examples include cyclic ester compounds with 3 to 12 carbon atoms such as β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, β-butyrolactone, 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, and heptanolactone (7-heptanolactone). ε-caprolactone is preferred. One or more cyclic ester compounds can be used as raw materials for polyester polyols.

[0167] Examples of polyol compounds having repeating ether structures include polyether polyols. There are no particular limitations on polyether polyols; examples include polypropylene glycol, polyethylene glycol, polytetramethylene glycol, and propylene oxide-ethylene oxide copolymers.

[0168] In the polyol composition, the molar ratio of carbonate repeating structures to ester repeating structures and / or ether repeating structures 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, more preferably in the range of 40:60 to 75:35, and even more preferably in the range of 45:55 to 70:30. By making the molar ratio of carbonate repeating structures to ester repeating structures and / or ether repeating structures 20:80 or higher, the polyol composition tends to have low melt viscosity and excellent workability. By making the molar ratio of carbonate repeating structures to ester repeating structures and / or ether repeating structures 80:20 or lower, the polyurethane obtained from this polyol composition exhibits improved resin properties such as chemical resistance, which is therefore ideal.

[0169] Carbonate repeating structures: The molar ratios of the components in ester and ether repeating structures can be based on [the following description]. 13 The integral ratio calculated by C-NMR determination is derived from the carbon molar ratio of each structure. Furthermore, polycarbonate polyol compositions can be separated into individual components using methods such as liquid chromatography, taking advantage of differences in molecular weight and polarity. In addition to the analytical methods mentioned above, identification can also be performed using NMR, IR, TOF-SIMS, etc., as needed.

[0170] <(A) ingredient>

[0171] The polycarbonate polyol composition of this embodiment contains the compound shown in formula (A) below (component (A)).

[0172]

[0173] (In formula (A), R1 is hydrogen or an alkyl group having 1 to 12 carbon atoms, and R2 is an alkylene group having 1 to 12 carbon atoms.)

[0174] Specific examples of component (A) include 2-buten-1-ol, 3-buten-1-ol, 2-penten-1-ol, 3-penten-1-ol, 4-penten-1-ol, 3-methyl-2-penten-1-ol, 3-methyl-3-penten-1-ol, 3-methyl-5-penten-1-ol, 3-methyl-4-penten-1-ol, 2-hexen-1-ol, 3-hexen-1-ol, 4-hexen-1-ol, 5-hexen-1-ol, etc. Alcohols, 2-hepten-1-ol, 3-hepten-1-ol, 4-hepten-1-ol, 5-hepten-1-ol, 6-hepten-1-ol, 2-octen-1-ol, 3-octen-1-ol, 4-octen-1-ol, 5-octen-1-ol, 6-octen-1-ol, 7-octen-1-ol, 2-nonen-1-ol, 3-nonen-1-ol, 4-nonen-1-ol, 5-nonen-1-ol, 6-nonen-1-ol, 7-nonen-1-ol Alcohols, 8-nonen-1-ol, 2-decen-1-ol, 3-decen-1-ol, 4-decen-1-ol, 5-decen-1-ol, 6-decen-1-ol, 7-decen-1-ol, 8-decen-1-ol, 9-decen-1-ol, 2-undecen-1-ol, 3-undecen-1-ol, 4-undecen-1-ol, 5-undecen-1-ol, 6-undecen-1-ol, 7-undecen-1-ol, 8-undecen-1-ol Carben-1-ol, 9-undecen-1-ol, 10-undecen-1-ol, 2-dodecen-1-ol, 3-dodecen-1-ol, 4-dodecen-1-ol, 5-dodecen-1-ol, 6-dodecen-1-ol, 7-dodecen-1-ol, 8-dodecen-1-ol, 9-dodecen-1-ol, 10-dodecen-1-ol, 11-dodecen-1-ol, etc., but not specifically limited to these. They can be used alone or in combination. Stereoisomers can be either cis or trans. Of these, from the viewpoint of their impact on service life and weather resistance, component (A) is preferably 2-buten-1-ol, 3-buten-1-ol, 3-penten-1-ol, 4-penten-1-ol, 5-hexen-1-ol and / or 4-hexen-1-ol, more preferably 4-hexen-1-ol and / or 5-hexen-1-ol. These can be a source of odor, therefore, from the viewpoint of suppressing the generation of odor in the obtained polyurethane and synthetic leather, a low content is preferred.

[0175] The content of component (A) in the polycarbonate polyol composition is not particularly limited, but is preferably 0.01 ppm (0.000001 wt%) or more and 20 wt% or less relative to the total mass of the polycarbonate polyol composition. More preferably, the lower limit can be 0.1 ppm (0.00001 wt%) or more, 0.5 ppm (0.00005 wt%) or more, or 1 ppm (0.0001 wt%) or more. In a preferred embodiment, the upper limit can be 10 wt% or less, 5 wt% or less, 1 wt% or less, or 0.5 wt% or less. By being within this preferred numerical range, there is a tendency for the polycarbonate polyol to be less prone to coloring during production, and coloring at heating above 150°C is also tended to be suppressed. Furthermore, the coloring of the resulting polyurethane is also suppressed, and the light stability is improved. It should be noted that component (A) can be a byproduct of the synthesis of polycarbonate polyols or an externally added component.

[0176] <(B) Component>

[0177] The polycarbonate polyol composition of this embodiment contains the compound shown in formula (B) below (component (B)).

[0178]

[0179] (In formula (B), R3 is an alkylene group with 2 to 12 carbon atoms, and may optionally have a straight-chain alkylene group, a divalent alicyclic hydrocarbon group, or a branched alkylene group.)

[0180] Specific examples of component (B) include, but are not particularly limited to, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol. One or more of these components may be used. From the viewpoint of its impact on pot life and weather resistance, component (B) is preferably 1,5-pentanediol and / or 1,6-hexanediol, more preferably 1,5-pentanediol and 1,6-hexanediol.

[0181] The proportion of component (B) in the polycarbonate polyol composition is not particularly limited, but it is preferably 1 ppm (0.0001% by mass) or more and 40% by mass or less relative to the total mass of the polycarbonate polyol composition. In a preferred embodiment, the lower limit can be 10 ppm (0.001% by mass) or more, or 100 ppm (0.01% by mass) or more. In a preferred embodiment, the upper limit can be 30% by mass or less, 20% by mass or less, or 10% by mass or less. By being within this preferred numerical range, in addition to keeping the viscosity of the obtained polycarbonate polyol within a good range, component (B) functions as a chain extender and acts as a hard segment site when reacting with isocyanate to prepare urethane, thereby improving resin properties such as chemical resistance, which is therefore preferred. It should be noted that component (B) can be a by-product of the synthesis of polycarbonate polyol or a separately added component.

[0182] <(B') component>

[0183] The polycarbonate polyol composition of this embodiment may further include the compound ((B') component) shown in the following formula (B').

[0184]

[0185] (In formula (B'), R4 is an alkylene group having 1 to 4 carbon atoms.)

[0186] Specific examples of component (B') include methanol, ethanol, propanol, and butanol. They can be used alone or in combination. From the viewpoint of their impact on service life and weather resistance, component (B') is preferably methanol and / or ethanol.

[0187] The content of component (B') in the polycarbonate polyol composition is not particularly limited, but is preferably 0.1 ppm (0.00001 wt%) or more and 10 wt% or less relative to the total mass of the polycarbonate polyol composition. In a preferred embodiment, the lower limit can be 1 ppm (0.0001 wt%) or more, or 10 ppm (0.001 wt%) or more. In a preferred embodiment, the upper limit can be 5 wt% or less, 3 wt% or less, or 1 wt% or less. By being within this preferred numerical range, in addition to keeping the viscosity of the obtained polycarbonate polyol within a good range, component (B') functions as a capping agent when reacting with isocyanate to prepare urethane, inhibiting gelation during urethane synthesis. It should be noted that component (B') can be a by-product of polycarbonate polyol synthesis or a separately added component.

[0188] Furthermore, the mass ratio of the aforementioned component (B') to the aforementioned component (B) ((B') / (B)) is not particularly limited, but is preferably 0.0001 to 1.000. By being within this preferred numerical range, in addition to keeping the viscosity of the obtained polycarbonate polyol within a good range, component (B') functions as a capping agent when reacting with isocyanate to prepare urethane, suppressing gelation during urethane synthesis.

[0189] <(A) mass ratio relative to (B) component>

[0190] As for the content ratio of the aforementioned component (B) to component (A), the mass ratio of the total amount of component (A) to the total amount of component (B) ((A) / (B)) is preferably 0.0001 to 0.1000, more preferably 0.0005 to 0.0800, and even more preferably 0.0010 to 0.0700. By keeping the mass ratio ((A) / (B)) within this preferred range, there is a tendency to control the pot life of the urethane esterification reaction within an appropriate range, suppress the coloring of the obtained polyurethane, and improve its light stability.

[0191] <Preferred method>

[0192] In one embodiment, the aforementioned polycarbonate polyol having terminal hydroxyl groups preferably has repeating units derived from 1,5-pentanediol and / or 1,6-hexanediol. Additionally, the compound shown in formula (A) preferably comprises one of the following groups: a compound in formula (A) where R1 is a hydrogen atom and R2 is an alkylene group having 4 or 3 carbon atoms; a compound in formula (A) where R1 is an alkylene group having 1 carbon atom and R2 is an alkylene group having 3 or 2 carbon atoms; and a compound in formula (A) where R1 is an alkylene group having 2 carbon atoms and R2 is an alkylene group having 2 or 1 carbon atoms.

[0193] Furthermore, in the compounds represented by formula (A) and (B), it is preferable that the sum of the total number of carbon atoms of R1 and R2 is equal to the number of carbon atoms of R3. More specifically, it is preferable that the sum of the total number of carbon atoms of R1 and R2 in the compound represented by formula (A), plus the number of two carbon atoms, results in a number of 5 or 6, which is equal to the number of carbon atoms of R3 in the compound represented by formula (B).

[0194] <Best approach>

[0195] For the preferred embodiment described above, as a specific example of component (A), 4-penten-1-ol, 3-penten-1-ol, 4-hexen-1-ol, and / or 5-hexen-1-ol are preferred. As raw materials constituting the repeating unit of the polycarbonate polyol, 1,5-pentanediol and 1,6-hexanediol are preferred. As a specific example of component (B), 1,5-pentanediol and 1,6-hexanediol are preferred. In this case, the mass ratio of component (A) to component (B) is preferably 0.0001 to 0.1000, more preferably 0.0001 to 0.075, further preferably 0.0001 to 0.069, even more preferably 0.0001 to 0.010, and particularly preferably 0.006 to 0.010.

[0196] The analytical methods for components (A) and (B) mentioned above are not particularly limited. From the viewpoint of analyzing trace components, gas chromatography (GC) and gas chromatography-mass spectrometry (GC / MS) are preferred. The dissolution of the sample in the above analysis can be performed using methods commonly employed by those skilled in the art. For example, the sample can be analyzed by dissolving 1 μl of 2.0 g of the polycarbonate composition in a 20 ml volumetric flask, adding chloroform to the mark, and allowing it to dissolve.

[0197] <Metal element content>

[0198] In one embodiment, for the polycarbonate polyol composition, the content of at least one metal element selected from the group consisting of titanium, ytterbium, tin, zirconium, magnesium, calcium, lithium, sodium, and manganese, as determined by ICP, is not particularly limited, but is preferably 0.0001 to 0.050% by mass, more preferably 0.0005 to 0.020% by mass, relative to the total amount of the polycarbonate polyol composition. In this polycarbonate polyol composition, the content of titanium, ytterbium, tin, magnesium, calcium, lithium, and manganese, as determined by ICP, is preferably 0.0001 to 0.050% by mass, more preferably 0.0005 to 0.020% by mass, relative to the total amount of the polycarbonate polyol composition.

[0199] In another embodiment, for the polycarbonate polyol composition, the content of at least one metal element selected from the group consisting of titanium, tin, magnesium, calcium, lithium and / or manganese as determined by ICP is not particularly limited, and is preferably 0.0001 to 0.050% by mass relative to the total amount of the polycarbonate polyol composition, more preferably 0.0005 to 0.020% by mass.

[0200] It should be noted that, in this embodiment, the content of metal elements in the polycarbonate polyol composition can be determined by the method described in the examples below.

[0201] <Phosphorus compounds>

[0202] In this embodiment, when the polycarbonate polyol composition is used as a raw material for polyurethane, it is preferable to treat the catalyst used in the manufacture of the polycarbonate polyol with a phosphorus compound. The phosphorus compound is not particularly limited, and examples include trimethyl phosphate, triethyl phosphate, tributyl phosphate, di-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, toluene / diphenyl phosphate, and other triphosphates; methyl phosphate, ethyl phosphate, propyl phosphate, isopropyl phosphate, butyl phosphate, lauryl phosphate, stearyl phosphate, 2-ethylhexyl phosphate, isodecanyl phosphate, butoxyethyl phosphate, oleyl phosphate, tetradecyl phosphate, ethynyl glycol phosphate, 2-hydroxyethyl methacrylate phosphate, dibutyl phosphate, monobutyl phosphate, monoisodecyl phosphate, bis(2-ethylhexyl) phosphate, and other acidic phosphates; triphenyl phosphite, trinonylphenyl phosphite, and other acidic phosphates. Phosphite esters include tricresyl ester, triethyl phosphite, tri(2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tri(tetrazyl) phosphite, trioleinyl phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl(monodel) phosphite, trilauryl phosphite, diethylhydrophosphite, bis(2-ethylhexyl)hydrophosphite, dilauryl hydrogen phosphite, dioleinyl hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyldipropylene glycol diphosphite, bis(decyl)pentaerythritol diphosphite, tristearyl phosphite, distearate pentaerythritol diphosphite, tri(2,4-di-tert-butylphenyl) phosphite, etc.; and further, phosphoric acid, phosphorous acid, hypophosphite, etc., but are not particularly limited to these. They can be used alone or in combination.

[0203] The polycarbonate polyol composition of this embodiment may contain phosphorus compounds. In the polycarbonate polyol composition of this embodiment, the content of phosphorus compounds is not particularly limited, but the content of phosphorus (P) as determined by ICP, relative to the total amount of the polycarbonate polyol composition, is preferably 0.0001 to 0.050% by mass. As long as the content of phosphorus compounds in the polycarbonate polyol composition of this embodiment is within the aforementioned preferred range, for example, when used as a raw material for polyurethane, the influence of the catalyst used in the manufacture of the polyurethane is almost negligible in the polyurethane manufacturing reaction, and further, the influence of phosphorus compounds on the polyurethane manufacturing reaction and the physical properties of the reaction products tends to be reduced. In this polycarbonate polyol composition, the content of phosphorus (P) as determined by ICP, relative to the total amount of the polycarbonate polyol composition, is more preferably 0.0005 to 0.020% by mass.

[0204] The polycarbonate polyol of this embodiment may have a structural unit shown in the following formula (P) with the structural unit shown in formula (A) above bonded to its end.

[0205] (P)

[0206] (In formula (P), R1 is any divalent aliphatic hydrocarbon group, R2 is hydrogen or any monovalent aliphatic hydrocarbon group, and R3 is any divalent aliphatic hydrocarbon group, which has the same meaning as R1~R3 ​​in formula (A) above.)

[0207] In the polycarbonate polyol of this embodiment, terminal groups other than hydroxyl groups may be present. There are no particular limitations on the terminal groups other than hydroxyl groups, and examples include alkyl, vinyl, and aryl groups.

[0208] It should be noted that, in this embodiment, the amount of hydroxyl groups in the terminal groups can be determined using the method described later.

[0209] terminal hydroxyl purity

[0210] The purity of the terminal hydroxyl groups can be calculated using the following formula.

[0211] [1] Purity of terminal hydroxyl groups = [[2] Amount of terminal hydroxyl groups in polycarbonate polyol] / [[3] Amount of terminal groups in polycarbonate polyol]

[0212] [2] The amount of terminal hydroxyl groups in polycarbonate polyols = [[4] Total hydroxyl group amount] - [[5] The amount of hydroxyl groups in residual hydroxyl compounds]

[0213] [4] Total hydroxyl content: The amount of hydroxyl content calculated from the hydroxyl value (the total amount of terminal hydroxyl groups in polycarbonate polyols and the amount of hydroxyl groups in residual hydroxyl compounds).

[0214] [5] Residual hydroxyl content: The total hydroxyl content of each free hydroxyl compound determined in b below.

[0215] [3] The amount of terminal groups in polycarbonate polyols = [[2] The amount of terminal hydroxyl groups in polycarbonate polyols] + [[6] The amount of monohydroxyl groups in the backbone of polycarbonate polyols]

[0216] [6] The amount of monohydroxyl groups in the backbone of polycarbonate polyols = [[7] Total amount of monohydroxyl groups] - [[8] Free amount of monohydroxyl groups]

[0217] [7] Total amount of monohydroxyl groups: The total amount of hydroxyl groups of all monohydroxyl compounds measured in a below.

[0218] [8] Amount of free monohydroxyl groups: The amount of hydroxyl groups of all free monohydroxyl compounds measured in b below.

[0219] <Analysis of all hydroxy compounds constituting the polycarbonate polyol>

[0220] The ratio of the structural units of the polycarbonate polyol can be determined by the following method.

[0221] Add 1 g of polycarbonate polyol to a 100 mL eggplant-shaped flask, add 0.1 g of diethylene glycol diethyl ether as an internal standard, further add 30 g of ethanol and 4 g of potassium hydroxide, and carry out a hydrolysis reaction at 100 °C for 1 hour. After cooling to room temperature, add 2 - 3 drops of phenolphthalein as an indicator to the aforementioned eggplant-shaped flask and neutralize with hydrochloric acid. After cooling the aforementioned eggplant-shaped flask in a refrigerator for 1 hour, filter off the precipitated salt to obtain a composition analysis solution. Analyze the components of the hydroxy compounds contained in the polycarbonate polyol in the obtained composition analysis solution by gas chromatography (GC). Regarding the concentration of each hydroxy compound, a standard curve can be prepared in advance from each hydroxy compound known as a reference substance, and the mass% can be calculated from the area ratio obtained by gas chromatography (GC).

[0222] <b. Analysis of residual hydroxy compounds in polycarbonate polyol>

[0223] Dissolve 1 g of polycarbonate polyol and 0.1 g of diethylene glycol diethyl ether as an internal standard in 10 g of acetone, and determine the content of residual hydroxy compounds by GC analysis.

[0224] <Water content>

[0225] In the polycarbonate polyol composition of the present embodiment, the water content is not particularly limited, and is preferably 10 - 500 ppm relative to the total amount of the polycarbonate polyol composition. If the water content of the polycarbonate polyol composition of the present embodiment is 500 ppm or less, there is a tendency that cloudiness caused by the reaction of water and isocyanate is not easily generated, and thus it is preferred. In addition, if the water content of the polycarbonate polyol composition of the present embodiment is 10 ppm or more, there is a tendency to suppress side reactions during urethanization and easily obtain a urethane coating film with excellent yellowing resistance, and thus it is preferred. In this polycarbonate polyol composition, the water content is more preferably 15 - 200 ppm relative to the total amount of the polycarbonate polyol composition.

[0226] <Other additives>

[0227] When using the polycarbonate polyol composition of the present embodiment to manufacture polyurethane, a curing accelerator (catalyst), filler, flame retardant, dye, organic or inorganic pigment, mold release agent, fluidity regulator, plasticizer, antioxidant, ultraviolet absorber, light stabilizer, defoaming agent, leveling agent, colorant, foaming agent, etc. can be added according to various uses.

[0228] There are no particular limitations on what can be used as a curing accelerator; examples include amines and metal catalysts.

[0229] As an amine effect enhancer, there are no particular limitations; examples include monoamines such as triethylamine and N,N-dimethylcyclohexylamine, diamines such as tetramethylethylenediamine, as well as triamines, cyclic amines, dimethylethanolamine, and other alkanolamines and ether amines. As a metal catalyst, there are no particular limitations; examples include potassium acetate, potassium 2-ethylhexanoate, calcium acetate, lead octanoate, dibutyltin dilaurate, tin octanoate, bismuth neodecanoate, bismuth oxycarbonate, bismuth 2-ethylhexanoate, zinc octanoate, zinc neodecanoate, phosphine, and phosphazene.

[0230] As fillers and pigments, there are no particular limitations. Examples include woven fabrics, glass fibers, carbon fibers, polyamide fibers, mica, kaolin, bentonite, metal powders, azo pigments, carbon black, clay, silica, talc, gypsum, alumina white, barium carbonate, and calcium carbonate.

[0231] As a release agent, flow regulator, or leveling agent, there are no particular limitations. Examples include silicone, Aerosil, wax, stearates, and polysiloxanes such as BYK-331 (manufactured by BYK-Chemie GmbH).

[0232] As additives used in the manufacture of polyurethane using the polycarbonate polyol composition of this embodiment, antioxidants, light stabilizers, heat stabilizers, and flame retardants are preferably used.

[0233] As antioxidants, there are no particular limitations. For example, phosphoric acid, aliphatic, aromatic or alkyl-substituted aromatic esters of phosphorous acid, hypophosphite derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonates, dialkyl pentaerythritol diphosphite, dialkyl bisphenol A diphosphite, and other phosphorus compounds can be used; phenolic derivatives, especially hindered phenolic compounds, thioether compounds, dithioester compounds, mercaptobenzimidazole compounds, mesolepisine thiourea compounds, thiodipropionate, and other sulfur-containing compounds can be used; tin compounds such as tin maleate and dibutyltin monoxide can also be used. They can be used alone or in combination of two or more.

[0234] <Non-reactive organic solvents>

[0235] To improve workability during urethane manufacturing, the polycarbonate polyol composition of this embodiment may include a non-reactive organic solvent as needed. The content of the non-reactive organic solvent relative to the total amount of the polycarbonate polyol composition is preferably 40% by mass or less, more preferably 3% by mass or more and 30% by mass or less, and even more preferably 5% by mass or more and 20% by mass or less. Adding a non-reactive organic solvent is effective in reducing the viscosity of the polycarbonate polyol composition, improving workability during synthetic leather manufacturing, and further improving the appearance of the resulting synthetic leather. However, solvents used in the process are released into the atmosphere during the drying process unless introduced into an expensive solvent recovery device, thus raising concerns about an increase in VOCs (Volatile Organic Compounds). From the viewpoint of reducing environmental impact, the content of the non-reactive organic solvent is preferably kept to a small amount, or ideally, no solvent is used at all.

[0236] There are no particular limitations on inactive organic solvents as long as they are substantially inactive for polyisocyanates; those without active hydrogen are preferred. As inactive organic solvents, there are no particular limitations; examples include hydrocarbons such as pentane, hexane, heptane, octane, decane, petroleum ether, petroleum benzine, ligroin, petroleum spirit, cyclohexane, and methylcyclohexane; fluorinated inactive liquids such as trichlorofluoroethane, tetrachlorodifluoroethane, and perfluoroether; and perfluorocyclohexane, perfluorobutyltetrahydrofuran, perfluoronaphthalene, perfluoron-butylamine, perfluoropolyether, and dimethylpolysiloxane. They can be used alone or in mixtures. Other examples of non-reactive organic solvents include methyl ethyl ketone (also referred to as MEK), acetone, ethyl acetate, butyl acetate, toluene, xylene, dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide, diethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, tetrahydrofuran (THF), and dioxane, either alone or in mixtures.

[0237] It should be noted that, in this specification, "active hydrogen" refers to hydrogen atoms bonded to oxygen, sulfur, nitrogen, silicon, etc., as well as hydrogen atoms in terminal methylene groups. Additionally, "active hydrogen" refers to hydrogen contained in groups such as -OH, -C(=O)OH, -C(=O)H, -SH, -SO3H, -SO2H, -SOH, -NH2, -NH-, -SiH, and -C≡CH.

[0238] The polycarbonate polyol composition of this embodiment can be a curable composition, which can form polyurethane through curing. Furthermore, the polyurethane obtained through this reaction can be used as synthetic leather. Here, "synthetic leather" in this specification includes not only synthetic leather using knitted or woven fabrics as the base fabric, but also artificial leather using nonwoven fabrics as the base fabric. During curing, isocyanates can be used as curing agents as needed. There are no particular limitations on such isocyanates. Examples include aromatic diisocyanates such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and mixtures thereof, diphenylmethane-4,4'-diisocyanate (MDI), naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-biphenyl diisocyanate (TODI), and polymethylene polyphenylene polyisocyanate (PMDI); aromatic aliphatic diisocyanates such as phenyl dimethylene diisocyanate (XDI) and phenyl diisocyanate; and 4,4'-methylene dicyclohexyl diisocyanate (hydrogenated, also known as hydrogenated diisocyanate (MD)). I) Aliphatic diisocyanates such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and cyclohexane diisocyanate (hydrogenated XDI); etc. Polyisocyanates with an average of 2.1 or more isocyanate groups per molecule can also be used. As polyisocyanates with an average of 2.1 or more isocyanate groups per molecule, aromatic polyisocyanates such as crude MDI and crude TDI can be used; derivatives of aliphatic isocyanates such as HDI and IPDI, specifically diisocyanate derivatives such as biuret, urethane, urea diketone, and isocyanurate; and polyol adduct types.In addition, commercially available isocyanates include, for example, Sumidur 44S and 44V70 (both manufactured by Sumika Bayer Urethane), Desmodur HL (manufactured by Sumika Bayer Urethane), a copolymer of TDI and HDI, and various Durnate products manufactured by Asahi Kasei Corporation, namely Durnate 24A-100, Durnate 22A-75PX, Durnate 18H-70B, Durnate 21S-75E, Durnate THA-100, Durnate TPA-100, Durnate TKA-100, Durnate TLA-100, Durnate TUL-100, Durnate MFA-75X, Durnate TSA-100, Durnate TSS-100, Durnate TSE-100, Durnate D-101, Durnate D-201, and Durnate... Duranate ME20-B80S, Duranate WB40-100, Duranate WB40-80D, Duranate WT20-100, Duranate WT30-100, etc.

[0239] <Method for manufacturing polycarbonate polyol compositions>

[0240] The polycarbonate polyol composition of this embodiment can be manufactured using conventional industrial manufacturing methods.

[0241] The polycarbonate polyol composition of this embodiment can be manufactured, for example, by a method (hereinafter referred to as the "one-step method") of mixing a polycarbonate polyol having terminal hydroxyl groups, and an inactive organic solvent and additives as needed, and then reacting them. Alternatively, the polycarbonate polyol composition of this embodiment can be manufactured, for example, by a method (hereinafter referred to as the "prepolymer method") of pre-preparing an isocyanate-terminated prepolymer derived from a polycarbonate polyol having terminal hydroxyl groups, or a hydroxyl-terminated prepolymer derived from a polycarbonate polyol having terminal hydroxyl groups, and mixing these prepolymers with isocyanates and / or polyols, and an inactive organic solvent and additives as needed, and then reacting them. Here, one or more prepolymers may be used.

[0242] <Manufacturing Methods of Synthetic Leather>

[0243] Synthetic leather can be manufactured using the method of manufacturing polyurethane using the polycarbonate polyol composition of this embodiment. There are no particular limitations on the method for manufacturing synthetic leather using the polycarbonate polyol composition of this embodiment; for example, the following methods can be used: a wet method in which the polyurethane manufactured using the polycarbonate polyol composition of this embodiment is coated or impregnated onto a substrate (base fabric) and then wet-cured; a dry method in which the polyurethane manufactured using the polycarbonate polyol composition of this embodiment is coated onto release paper or a substrate (base fabric) and then dried; etc. Furthermore, as a method for manufacturing synthetic leather, a transfer coating method (a type of dry method) can also be used: after coating the polyurethane manufactured using the polycarbonate polyol composition of this embodiment onto release paper to form a skin material, the polyurethane manufactured using the polycarbonate polyol composition of this embodiment is used as an adhesive layer on it, and then it is bonded to the substrate (base fabric) and the release paper is removed. That is, the composition of this embodiment can be used as an adhesive layer for synthetic leather. For the polycarbonate polyol composition of this embodiment, a dry method (transfer coating method) is suitable in order to suppress the amount of inactive organic solvent used.

[0244] In summary, a preferred embodiment of the polycarbonate polyol composition of this embodiment is an adhesive composition. Furthermore, a preferred embodiment of the polycarbonate polyol composition of this embodiment is a water-based polyurethane. Moreover, a preferred embodiment of the polycarbonate polyol composition of this embodiment is a water-dispersible composition.

[0245] Taking the dry process as an example, the following describes the manufacturing method of polyurethane for synthetic leather and synthetic leather.

[0246] As a substrate (base fabric), various substrates can be used without particular limitation; for example, fibrous substrates can be used. As a fibrous substrate, there are no particular limitations; for example, a fiber assembly formed by shaping fibers into nonwoven fabric, woven fabric, mesh fabric, or polished napped fabric, or a substrate formed by bonding the fibers of a fiber assembly with an elastic polymer, etc., can be used. As for the fibers used in this fiber assembly, there are no particular limitations; for example, natural fibers such as cotton, hemp, and wool, regenerated or semi-synthetic fibers such as rayon and cellulose acetate, and synthetic fibers such as polyamide, polyester, polyacrylonitrile, polyvinyl alcohol, and polyolefins, etc., can be used. These fibers can be individually spun fibers or blended spun fibers. As for other substrates, there are no particular limitations; for example, paper, release paper, polyester and polyolefin plastic films, metal plates such as aluminum, and glass plates, etc., can be used.

[0247] The polycarbonate polyol composition of this embodiment can be applied as an adhesive composition, a composition for synthetic leather, or even a polyurethane for synthetic leather using conventional methods. The application method is not particularly limited; examples include a floating knife coater, a knife over roll coater, a reverse roll coater, a roll doctor coater, a gravure roll coater, and a licker coater.

[0248] <Synthetic Leather>

[0249] The resulting synthetic leather can be used directly. Alternatively, for the purpose of further imparting various properties, the synthetic leather can also be obtained by coating a polymer solution or emulsion of polyurethane resin, vinyl chloride, cellulose resin, etc., onto the synthetic leather. Furthermore, the synthetic leather can also be obtained by laminating a coating obtained by drying a separately coated release paper with the aforementioned polymer solution or emulsion, and then peeling off the release paper to obtain a laminate. The synthetic leather obtained from the polycarbonate polyol composition of this embodiment exhibits excellent workability, good appearance, and excellent weather resistance. In a more preferred embodiment, a synthetic leather with a good balance of physical properties, including low odor and excellent chemical resistance, can be further achieved.

[0250] Hereinafter, this embodiment will be described with reference to the accompanying drawings. The drawings and manufacturing conditions described below are one embodiment of this embodiment, and this embodiment is not limited thereto.

[0251] Figure 1 Through Figure 2 The diagram shows a schematic cross-sectional view of a synthetic leather laminate manufactured using the dry process. The laminate has a skin layer 2 on a substrate (polyester fabric) 4, separated by an adhesive layer 3. A release paper 1, used during manufacturing, is attached to the outermost layer but is peeled off before use.

[0252] Figure 2 This is a schematic diagram illustrating one of the manufacturing methods for a dry synthetic polyurethane leather laminate sheet manufactured using the polycarbonate polyol composition of this embodiment. In this manufacturing method, firstly, a polycarbonate polyol composition (for the outer layer) is poured onto release paper 1 (typically with a leather-like pattern applied). The polycarbonate polyol composition (for the outer layer) is obtained by mixing the raw materials of the pre-prepared polycarbonate polyol composition of this embodiment in a mixing head 5 at a specified temperature.

[0253] In the one-step method, the polycarbonate polyol composition of this embodiment, along with the required inactive organic solvent and additives, are fed continuously into the mixing head 5, respectively or simultaneously, and mixed, flowing down onto the release paper 1. The polyol component can be one type, or two or more types can be used simultaneously.

[0254] When using the prepolymer method, isocyanate-terminated prepolymers and polyols derived from the polycarbonate polyol composition of this embodiment, or hydroxyl-terminated prepolymers and isocyanates derived from the polycarbonate polyol composition of this embodiment, are continuously fed into the mixing head 5 as needed in the form of a mixture with inactive organic solvents and additives, mixed, and flowed down onto the release paper 1.

[0255] Before mixing, the components are typically adjusted to a temperature of 20-80°C, preferably 30-70°C, and more preferably 40-60°C. Similarly, the temperature of the mixing head 5 is typically adjusted to 20-80°C, preferably 30-70°C, and more preferably 40-60°C. By setting the temperatures of the components before mixing and the mixing head 5 to 20°C or higher, there is a tendency to suppress the viscosity of the raw materials used and stabilize the flow rate. Furthermore, by setting the temperatures of the components before mixing and the mixing head 5 to 80°C or lower, there is a tendency to appropriately control the curing speed of the polycarbonate polyol composition of this embodiment, suppress a sharp increase in the viscosity of the polycarbonate polyol composition, and obtain a uniform thickness of the synthetic leather.

[0256] Afterwards, the material is coated onto a sheet of a certain thickness using a coating roller 8, and then cured and dried using a dryer 11 with a non-reactive organic solvent to form the outer layer 2 of the synthetic leather. The temperature of the dryer is typically set to 60~150℃, preferably 70~130℃, and more preferably 80~110℃. The drying time is typically 2 minutes~15 minutes, preferably 3 minutes~10 minutes, and more preferably 4 minutes~7 minutes.

[0257] Next, the polycarbonate polyol composition of this embodiment is allowed to flow down to form the adhesive layer 3. This polycarbonate polyol composition is obtained by mixing the raw materials of the pre-prepared polycarbonate polyol composition of this embodiment in a mixing head 6 (for the adhesive layer) at a specified temperature. In the case of using a one-step method in the manufacture of the adhesive layer, the polycarbonate polyol composition of this embodiment, along with any desired inactive organic solvent and additives, are fed separately or simultaneously and continuously into the mixing head 6 and mixed, then flow down onto the skin layer. In the case of using a prepolymer method in the manufacture of the adhesive layer, the prepolymer composition, unprepolymerized polyols, any desired inactive organic solvents, and additives are fed separately or simultaneously and continuously into the mixing head 6 and mixed, then flow down onto the skin layer.

[0258] Before mixing, the components are typically adjusted to a temperature of 20-60°C, preferably 30-50°C, and more preferably 35-45°C. Similarly, the temperature of the mixing head 6 is typically adjusted to 20-60°C, preferably 30-50°C, and more preferably 35-45°C. By maintaining the temperatures of the components before mixing and the mixing head 6 at 20°C or higher, there is a tendency to suppress the viscosity of the raw materials used and stabilize the flow rate. Furthermore, by maintaining the temperatures of the components before mixing and the mixing head 6 at 60°C or lower, there is a tendency to appropriately control the curing speed of the polycarbonate polyol composition of this embodiment, suppress a sharp increase in the viscosity of the polycarbonate polyol composition, and obtain a uniform thickness of the synthetic leather.

[0259] Afterwards, the material is coated with a sheet of a certain thickness using a coating roller 8, and then cured and dried with a non-reactive organic solvent using a dryer 11 to form the adhesive layer 3 of the synthetic leather. Next, the substrate 4 is overlapped with the adhesive layer 3 and pressed together using a pressing roller 9 to obtain a sheet structure 7, which is then wound up using a take-up roller 10 to obtain the desired synthetic leather laminate. The temperature of the dryer 11 is typically set to 50~110°C, preferably 60~100°C, and more preferably 70~90°C. The drying time is typically 2 minutes to 15 minutes, preferably 3 minutes to 10 minutes, and more preferably 4 minutes to 7 minutes.

[0260] Figure 2The example shown depicts a synthetic leather manufacturing example comprising three layers: a skin layer, an adhesive layer, and a substrate. However, a synthetic leather laminate comprising only the skin layer and the substrate, omitting the adhesive layer, can also be manufactured using the same equipment. The adhesion between the skin layer and the substrate is controlled by adjusting the curing state of the polycarbonate polyol composition. Specifically, it can be obtained by pressing the polycarbonate polyol composition of this embodiment onto the substrate without completely curing it. Therefore, the curing temperature of the dryer 11 is set to 50~110°C, preferably 60~100°C, and more preferably 70~90°C. The drying time is typically set to 2 minutes~15 minutes, preferably 3 minutes~10 minutes, and more preferably 4 minutes~7 minutes.

[0261] It should be noted that a surface treatment agent can be applied to the surface layer to create a synthetic leather laminate containing four layers: surface treatment agent, surface layer, adhesive layer, and substrate. Alternatively, a synthetic leather laminate containing three layers can be created.

[0262] <Application>

[0263] Synthetic leather obtained from polyurethane / urethane cured products manufactured using the polycarbonate polyol composition of this embodiment can be used for automotive interior materials such as car seats, furniture such as sofas, clothing, shoes, bags, and other miscellaneous products. It is particularly suitable for use as synthetic leather (polyurethane for synthetic leather) as an automotive interior material. Furthermore, the polyurethane manufactured using the polycarbonate polyol composition of this embodiment can also be used in adhesive compositions, laminating agents for various films, surface protectants, etc. Moreover, the aqueous polyurethane / water-dispersible composition made using the polycarbonate polyol composition of this embodiment can be used not only as synthetic leather but also as coatings, coating agents, and various other materials.

[0264] [Manufacturing method of water-based polyurethane]

[0265] The method for manufacturing the aqueous polyurethane in this embodiment is not particularly limited, and known methods can be used. For example, it can be manufactured by the following steps: a step of manufacturing a urethane prepolymer with isocyanate groups at the ends by reacting a polyol, a polyisocyanate, and a compound containing hydrophilic groups (prepolymer step); and a step of reacting the aforementioned urethane prepolymer with a chain extender (chain extension step).

[0266] (Polyols)

[0267] The polycarbonate polyol of this embodiment can be used in the manufacture of aqueous polyurethane. In addition to the polycarbonate polyol of this embodiment, polyester polyol, acrylic polyol, polyether polyol, polyolefin polyol, fluorinated polyol, etc., may be used alone or in combination of two or more, but are not limited thereto.

[0268] From the viewpoint of the softness and durability of the urethane cured product obtained by using an aqueous composition containing an aqueous polyurethane, in addition to the polycarbonate polyol of this embodiment, polyester polyol, polyether polyol, and fluorinated polyether can also be preferred, a combination of polycarbonate polyol, polyester polyol and polyether polyol of this embodiment is more preferred, and a combination of polycarbonate polyol and polyester polyol of this embodiment is even more preferred.

[0269] (Polyisocyanates)

[0270] Examples of polyisocyanates used in the manufacture of waterborne polyurethanes include aromatic polyisocyanates such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimide diphenylmethane polyisocyanate; and polyisocyanates with aliphatic or alicyclic structures such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, phenylene diisocyanate, tetramethylphenylene diisocyanate, dimer acid diisocyanate, and norbornene diisocyanate, but these are not limited to these. They can be used alone or in combination of two or more.

[0271] Among these, from the viewpoint of the durability of urethane cured products obtained by using aqueous compositions containing aqueous polyurethane, polyisocyanates having an alicyclic structure are preferred, and isophorone diisocyanate and dicyclohexylmethane diisocyanate are more preferred.

[0272] (Compounds containing hydrophilic groups)

[0273] Examples of isocyanate compounds used in the manufacture of waterborne polyurethanes include carboxyl polyols such as 2,2'-dimethylolpropionic acid, 2,2'-dimethylolbutyric acid, 2,2'-dimethylolbutyric acid, and 2,2'-dimethylolvalerate, as well as polyols with sulfonic acid groups such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5-[4-sulfophenoxy]isophthalic acid, but these are not limited to these. They can be used alone or in combination of two or more.

[0274] (Chain extender)

[0275] Chain extenders used in the manufacture of waterborne polyurethanes include, for example, diamines such as ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophorone diamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, and 1,4-cyclohexanediamine; and N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, and N-methylaminopropylamine. Diamines with one primary amino group and one secondary amino group; polyamines such as diethylenetriamine, dipropylenetriamine, and triethylenetetramine; hydrazides such as N,N'-dimethylhydrazine and 1,6-hexamethylenedihydrazine; diacylhydrazines such as succinic dihydrazide, adipate dihydrazide, glutarate dihydrazide, sebacylhydrazide, and isophthalic dihydrazide; and aminoureas such as β-aminourea propionic hydrazide, 3-aminourea-propyl-hydrazylcarbamate, and aminourea-3-aminourea-methyl-3,5,5-trimethylcyclohexane, etc., but not limited to these. They can be used alone or in combination of two or more.

[0276] (Organic solvent)

[0277] Organic solvents may be used in the aforementioned prepolymerization process during the manufacture of waterborne polyurethane, as needed. Examples of organic solvents that can be used in the aforementioned prepolymerization process include: ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetates such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; and amides such as dimethylformamide and N-methylpyrrolidone. One or more of these solvents may be used alone or in combination.

[0278] [(C) Component: Curing Agent]

[0279] In addition to the above-mentioned water-dispersible polyol (component A) and water-based polyurethane (component B), the aqueous composition of this embodiment may also contain a curing agent (component C).

[0280] As a curing agent (component C), there are no particular limitations as long as it has reactive groups that can react with the hydroxyl groups of the water-dispersible polyol (component A) and / or the terminal groups and / or hydrophilic groups of the above-mentioned water-based polyurethane (component B). It is preferred to use a curing agent with two or more reactive groups.

[0281] Examples of compounds having such reactive groups include isocyanate compounds, carbodiimide compounds, and aziridine compounds, but these are not particularly limited to. Among these, isocyanate compounds are preferred.

[0282] Isocyanate compounds can be synthesized using commercially available products or well-known methods.

[0283] As commercially available isocyanate compounds, the same substances as described above can be used, and repeated descriptions are omitted here.

[0284] (NCO / OH ratio)

[0285] When isocyanate is used in the curing agent, regarding the content of isocyanate compound in the aqueous composition, from the viewpoint of the durability of the urethane cured product obtained using the aqueous composition, the ratio of the number of moles of isocyanate groups (NCO groups) contained in component (C) to the number of moles of hydroxyl groups (OH groups) contained in component (A) and component (B) (moles of NCO groups / moles of OH groups) is preferably 0.2 to 7.0, more preferably 0.5 to 5.0, further preferably 0.8 to 3.0, particularly preferably 0.8 to 2.5, and most preferably 0.8 to 2.0.

[0286] From the viewpoint of the durability of urethane cured products, the curing agent preferably has a cyclic structure, and more preferably has an isocyanurate ring.

[0287] [Curing composition]

[0288] The curable composition of this embodiment includes the above-described aqueous composition. The curable composition of this embodiment can be made from the polycarbonate polyol of this embodiment. Examples of curable compositions that include coatings, polyurethanes, and coating agents containing the above-described aqueous composition are also possible. By including the above-described aqueous composition, the curable composition of this embodiment tends to have advantages such as shortened drying time, thin film formation of the cured product, and excellent flexibility and high durability.

[0289] The curable composition of this embodiment may contain other components besides the aqueous composition described above. These other components are not particularly limited, and examples include polyol compounds, water-dispersible polyester polyols, acrylic polyol emulsions, water-dispersible polyether polyols, water-dispersible polyolefin polyols, water-dispersible fluorinated polyols, and other water-dispersible polyols.

[0290] In addition to the above, the curable composition of this embodiment may contain other additives such as curing accelerators (catalysts), matting agents, anti-settling agents, leveling agents, fillers, dispersants, flame retardants, dyes, organic or inorganic pigments, release agents, flow modifiers, plasticizers, antioxidants, UV absorbers, light stabilizers, defoamers, colorants, and solvents, depending on the application. By appropriately including these other additives, curable compositions with different properties, such as soft-feel coatings and transparent coatings, can be obtained.

[0291] [Carbamate Cured Products]

[0292] The urethane cured product of this embodiment is obtained by curing the polycarbonate polyol of this embodiment and / or the curable composition of this embodiment. Examples of urethane cured products include urethane coatings, urethane films, and urethane resins. The urethane cured product of this embodiment, obtained from the polycarbonate polyol of this embodiment and / or the curable composition of this embodiment, tends to have excellent flexibility and high durability.

[0293] It should be noted that this disclosure also provides a method for suppressing the odor of a polycarbonate polyol composition. Specifically, a method for suppressing the odor of a polycarbonate polyol composition, wherein the aforementioned polycarbonate polyol composition comprises: a polycarbonate polyol having terminal hydroxyl groups; (A) component: a compound represented by formula (A) below; and (B) component: a compound represented by formula (B) below, such that the mass ratio of the aforementioned (A) component to the aforementioned (B) component ((A) / (B)) is 0.0001 to 0.1000.

[0294] In addition, this disclosure also provides a method for suppressing the odor of urethane cured products. Specifically, a method for suppressing the odor of urethane cured products includes the following steps: selecting a polycarbonate polyol composition, and curing the aforementioned polycarbonate polyol composition to produce a urethane cured product, wherein the polycarbonate polyol composition comprises: a polycarbonate polyol having terminal hydroxyl groups; (A) component: a compound represented by formula (A) below; and (B) component: a compound represented by formula (B) below, wherein the mass ratio of the aforementioned (A) component to the aforementioned (B) component ((A) / (B)) is 0.0001 to 0.1000.

[0295] Furthermore, this disclosure also provides a method for manufacturing a polycarbonate polyol composition. Specifically, a method for manufacturing a polycarbonate polyol composition, wherein the aforementioned polycarbonate polyol composition comprises: a polycarbonate polyol having terminal hydroxyl groups; (A) component: a compound represented by formula (A) below; and (B) component: a compound represented by formula (B) below, wherein the mass ratio ((A) / (B)) of the aforementioned (A) component relative to the aforementioned (B) component is adjusted to a range of 0.0001 to 0.1000.

[0296] In addition, this disclosure also provides a method for manufacturing a urethane cured product. That is, a method for manufacturing a urethane cured product includes the following steps: selecting a polycarbonate polyol composition, and curing the aforementioned polycarbonate polyol composition, wherein the polycarbonate polyol composition comprises: a polycarbonate polyol having terminal hydroxyl groups; (A) component: a compound represented by formula (A) below; and (B) component: a compound represented by formula (B) below, wherein the mass ratio of the aforementioned (A) component to the aforementioned (B) component ((A) / (B)) is 0.0001 to 0.1000.

[0297] Furthermore, this disclosure also provides a method for manufacturing synthetic leather. Specifically, a method for manufacturing synthetic leather includes the following steps: sequentially disposing an adhesive layer, an intermediate layer, and an epidermis layer on a substrate, wherein any one of the aforementioned epidermis layer, the aforementioned intermediate layer, and the aforementioned adhesive layer is a urethane cured product of a polycarbonate polyol composition, the aforementioned polycarbonate polyol composition comprising: a polycarbonate polyol having terminal hydroxyl groups; (A) component: a compound represented by formula (A) below; and (B) component: a compound represented by formula (B) below, wherein the mass ratio of the aforementioned (A) component to the aforementioned (B) component ((A) / (B)) is 0.0001 to 0.1000.

[0298] In addition, this disclosure also provides a method for suppressing the odor of synthetic leather. That is, a method for suppressing the odor of synthetic leather includes the following steps: selecting a polycarbonate polyol composition, using a urethane cured product of the aforementioned polycarbonate polyol composition in at least one of an adhesive layer, an intermediate layer, and an epidermis layer, said polycarbonate polyol composition comprising: a polycarbonate polyol having terminal hydroxyl groups; (A) component: a compound represented by formula (A) below; and (B) component: a compound represented by formula (B) below, wherein the mass ratio of the aforementioned (A) component to the aforementioned (B) component ((A) / (B)) is 0.0001 to 0.1000.

[0299] Example

[0300] The present invention will be further described in detail below with examples and comparative examples, but the present invention is not limited to these examples as long as it does not depart from its spirit. In the following examples and comparative examples, the methods for analyzing and evaluating the physical properties of each component are described below. Regarding the analytical peripheral equipment, equipment with equivalent performance can be used to carry out the analysis.

[0301] [Analysis and Evaluation of Polycarbonate Polyol Compositions]

[0302] The formulations of the polycarbonate polyol compositions are shown in Tables 1 and 2.

[0303] <Hydroxy value of polycarbonate polyol composition>

[0304] The determination was performed according to JIS K1557-1. It should be noted that the number-average molecular weight of the polycarbonate polyol composition was also calculated based on the hydroxyl value of the obtained composition.

[0305] <Integral Component Analysis (ICP) of Polycarbonate Polyol Compositions>

[0306] The following analysis was performed on the components of the polycarbonate polyol composition. First, the sample was weighed into a Teflon (registered trademark) decomposition container, and high-purity nitric acid (manufactured by Kanto Chemical) was added. Decomposition was then performed using a microwave decomposition apparatus (manufactured by Milestone General Co., Ltd., ETHOS TC). The sample was completely decomposed, and the resulting decomposition solution became colorless and transparent. Pure water was added to the decomposition solution to prepare a detection solution. The resulting detection solution was then quantified using a dielectric-coupled plasma analyzer (manufactured by Thermo Fisher Scientific, iCAP6300 Duo) based on standard solutions of each element.

[0307] Analysis of components (A) and (B) in the polycarbonate polyol composition

[0308] Analysis was performed using gas chromatography (GC). For GC analysis, a GC-2014 gas chromatograph (manufactured by Shimadzu Corporation, Japan) equipped with a DB-HeavyWAX (manufactured by J&W, USA) column was used. A standard curve was prepared using the absolute standard curve method with standards, and a flame ionization detector (FID) was used as the detector for quantitative analysis of each component. It should be noted that the column temperature profile was as follows: after holding at 40°C for 1 minute, the temperature was increased to 280°C at a rate of 10°C / min and held for 10 minutes.

[0309] It should be noted that the following reagents are used as standards in the preparation of the standard curve.

[0310] 5-Hexen-1-ol: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0311] 4-Hexen-1-ol (cis-form): Manufactured by Tokyo Chemical Industry Co., Ltd.

[0312] 4-Penten-1-ol: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0313] Ethylene glycol: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0314] 1,4-Butanediol: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0315] 1,5-Pentanediol: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0316] 1,6-Hexanediol: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0317] 2-Methyl-1,3-propanediol: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0318] 3-Methyl-1,5-pentanediol: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0319] <Confirmation of the properties of the polycarbonate polyol composition>

[0320] The polycarbonate polyol composition heated to 60°C was placed into transparent sample vials, and its state after cooling to room temperature (23°C) was observed visually. The state of the transparent vial with slight fluidity when tilted was described as "liquid", and the state of the vial that was opaque or did not change even when tilted, as well as both, was described as "solid".

[0321] Composition of the polycarbonate polyol composition (copolymer ratio)

[0322] Measure 1 g of the polycarbonate polyol composition sample into a 100 mL round-bottom flask, add 30 g of ethanol and 4 g of potassium hydroxide, and react at 100 °C for 1 hour. After cooling the reaction solution to room temperature, add 2-3 drops of phenolphthalein as an indicator and neutralize with hydrochloric acid. After cooling in a refrigerator for 1 hour, remove the precipitated salt by filtration, and analyze separately using gas chromatography (GC). For GC analysis, a GC-2014 gas chromatograph (manufactured by Shimadzu Corporation, Japan) equipped with a DB-WAX (manufactured by J&W, USA) column was used, with diethylene glycol diethyl ether as an internal standard and a flame ionization detector (FID) as the detector for quantitative analysis of each component. It should be noted that the column temperature profile was set at 60 °C for 5 minutes, then increased to 250 °C at a rate of 10 °C / min.

[0323] Based on the molar ratios of each alcohol component detected by the above analysis results, the composition (copolymerization ratio) of polycarbonate polyols is determined.

[0324] <Molar ratio of the sum of repeating carbonate structures: ester repeating structures and ether repeating structures>

[0325] Carbonate repeating structures, ester repeating structures, and ether repeating structures are based on 1 H-NMR and 13 Identification was performed using C-NMR. The following apparatus was used for NMR-based measurements. 13 In C-NMR, the repeating structure of carbonates is represented by the peak around 150–155 ppm (-O-). C=OO-, a specific peak originating from the 1 C element of the carbonate group in the repeating structural unit), the ester repeating structure uses a peak around 170~175ppm (- C =OO-, a specific peak originating from the two C elements of the ester group in the repeating structural unit), the ether repeating structure uses a peak around 70 ppm in the case of polytetramethylene glycol, and a peak around 77~70 ppm in the case of polypropylene glycol (- C -O- C - A specific peak originating from the ether group in the repeating structural unit (two C elements) is used to calculate the molar ratio of the repeating structural unit by the ratio of their signal intensities. It should be noted that if there are two or more C elements corresponding to the specific peak, the molar ratio of the repeating structural unit is calculated by dividing the signal intensity by the number of C elements. The apparatus and measurement conditions are set as follows.

[0326] 1 H-NMR

[0327] Device: JEOL-ECZ500 (SC) (product name)

[0328] Solvent: Deuterated chloroform (containing 1 vol% tetramethylsilane)

[0329] Total number of times: 120

[0330] Sample concentration: 10 wt / vol%

[0331] Chemical shift reference: Tetramethylsilane is set to 0.0 ppm.

[0332] 13 C-NMR

[0333] Device: JEOL-ECZ500 (SC) (product name)

[0334] Solvent: Deuterated chloroform (containing 1 vol% tetramethylsilane)

[0335] Total number of times: 5120

[0336] Sample concentration: 30 wt / vol%

[0337] Chemical shift standard: Deuterated chloroform is set at 77.0 ppm.

[0338] <Average number of functional groups in the polycarbonate polyol composition>

[0339] The average number of functional groups in a polycarbonate polyol composition synthesized using only diol monomers as raw materials is denoted as 2. In the case of polyfunctional monomers as raw materials, the average number of functional groups is determined as follows. The number-average molecular weight (Mn) of the polycarbonate polyol composition is determined by gel permeation chromatography (GPC) analysis using a standard curve prepared with standard polystyrene of known molecular weight (GPC apparatus and analytical conditions are described below). Based on the hydroxyl value obtained from separate analysis and the number-average molecular weight (Mn) determined by GPC, the average number of functional groups (n) per molecule is determined by equation (5).

[0340] Average number of functional groups (n) = [Mn] × ([OH value] × 10) -3 / 56.1)(5)

[0341] (GPC apparatus and analytical conditions)

[0342] GPC device: HLC-8320 manufactured by Tosoh Corporation

[0343] Column: TSKgel G4000H 1 column

[0344] G3000H 1 piece

[0345] G2000H 2 sticks

[0346] Eluent: Tetrahydrofuran (THF)

[0347] Flow rate: 1.0 mL / min

[0348] Column temperature: 40℃

[0349] RI detector: RI (built into device HLC-8320)

[0350] <Determination of the pot life of carbamate reaction>

[0351] 60 g of the polycarbonate polyol compositions synthesized in the Examples and Comparative Examples were added to 200 mL wide-mouth glass bottles, respectively. After thorough nitrogen purging, the mixtures were heated in an oil bath set to 60 °C. Subsequently, MDI was added at an NCO / OH ratio of 1.1, and the viscosity increase behavior was confirmed using a torque stirrer, determined according to the following evaluation criteria.

[0352] <Evaluation Criteria>

[0353] 〇 (Very good): Able to mix for 8 minutes

[0354] △ (Good): Do not stir during 5-8 minutes.

[0355] × (Bad): Cannot be stirred within ~5 minutes after addition.

[0356] <Odor Confirmation of Polycarbonate Polyol Compositions>

[0357] The odor assessment of the polycarbonate polyol composition was conducted by eight inspectors. 40 g of the polycarbonate polyol composition was measured into a 50 mL capped glass bottle, left to stand at 23°C for one day, then the cap was opened, and the odor was assessed by smell. The evaluation results of the eight inspectors were categorized according to the following scoring criteria, and the average value was taken. Subsequently, the final assessment was determined according to the following evaluation criteria.

[0358] <Score Benchmark>

[0359] 0: No odor or no noticeable odor

[0360] 1: I smelled a faint odor.

[0361] 2: The stench is clearly noticeable.

[0362] 3: I smell a strong stench

[0363] <Evaluation Criteria>

[0364] 〇 (Very good): The average score of the 8 inspectors was below 1.

[0365] △ (Good): The average score of the 8 inspectors is greater than 1 and less than 2.

[0366] × (Bad): The average score of the 8 inspectors is greater than 2 and less than 3.

[0367] <Peroxide Value (POV)>

[0368] The samples of the polycarbonate polyol compositions obtained in the examples and comparative examples described later were immersed in the test section of POV test paper (Shibata Scientific Co., Ltd.), left for 3 minutes, and then rinsed with pure water. The POV test paper of the sample was compared with a standard color sample, and the peroxide value (POV) of the sample was determined as follows.

[0369] [Judgment Criteria]

[0370] ○ (Excellent): Detected as 0 meq / kg or higher and 3 meq / kg or lower in standard color samples.

[0371] △ (Good): Exceeding 3 meq / kg but below 10 meq / kg, equivalent to 10 in the standard color sample.

[0372] × (Bad): Exceeding 10 meq / kg but below 40 meq / kg, equivalent to 30 in the standard color sample.

[0373] [Production of polyurethane]

[0374] (Raw materials used)

[0375] • Main component: Polycarbonate polyol compositions (PC-1~26) obtained in the examples and comparative examples.

[0376] • Curing agent: Diphenylmethane-4,4'-diisocyanate (MDI, NCO%=33.5%)

[0377] • Catalyst: 1% by mass dibutyltin dilaurate toluene solution (prepared by FUJIFILM Wako Pure Chemical Corporation, dissolved in toluene to prepare a 1% by mass solution)

[0378] • Solvent: Methyl ethyl ketone (MEK, manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0379] (Preparation method)

[0380] In a nitrogen-sealed 200mL detachable flask with a stirring blade, 30g of a polycarbonate polyol composition (PC-1~26) preheated to 60°C, 0.3g of a 1% (w / w) solution of dibutyltin dilaurate as a catalyst, and MDI pre-dissolved at 80°C were added to achieve an NCO / OH ratio of 1.1. Methyl ethyl ketone (MEK) was then added to achieve a solids concentration of 30% (w / w). The mixture was stirred at 60°C for 3 minutes to obtain polyurethane solutions. These solutions were then coated onto polypropylene resin sheets (100mm wide, 1200mm long, 1mm thick) with a width of 80mm, a length of 100mm, and a thickness of 0.6mm. The coating was dried on a hot plate at 60°C for 2 hours, followed by drying in an oven at 100°C for 12 hours. After standing at a constant temperature and humidity of 23°C and 55%RH for at least 12 hours, polyurethane films were obtained.

[0381] <Operability in Polyurethane Fabrication>

[0382] The operability of polyurethane production shall be determined according to the following evaluation criteria.

[0383] 〇 (Very good): A polyurethane solution can be obtained.

[0384] The number-average molecular weight measured by GPC is over 50,000.

[0385] △ (Good): A polyurethane solution can be obtained.

[0386] However, the number-average molecular weight measured by GPC is below 30,000.

[0387] × (Bad): Polyurethane solution cannot be obtained.

[0388] <Determination of molecular weight>

[0389] A portion of the polyurethane film was cut off and an N,N-dimethylacetamide solution was prepared with a polyurethane concentration of 0.1% by mass. The number-average molecular weight (Mn) and weight-average molecular weight (Mw) converted to standard polystyrene were determined using a GPC apparatus [manufactured by Tosoh Corporation, product name "HLC-8320" (column: TskgelSuper HM-H•4 columns), and the eluent was a solution of 2.6 g of lithium bromide dissolved in 1 L of dimethylacetamide].

[0390] [Analysis and Evaluation of Polyurethane Coatings]

[0391] <Preparation of Polyurethane Coating>

[0392] (Raw materials used)

[0393] • Main component: Polycarbonate polyol compositions (PC-1~26) obtained in the examples and comparative examples.

[0394] •Curing agent: Duranate TPA-100 (manufactured by Asahi Kasei Co., Ltd., NCO%=23.1)

[0395] • Catalyst: 1 wt% dibutyltin dilaurate toluene solution (prepared by FUJIFILM Wako Pure Chemical Corporation, dissolved in toluene to make a 1 wt% solution)

[0396] • Solvent: Butyl acetate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0397] (Coating composition)

[0398] According to the following coating mixing conditions, measure the raw materials (main agent, curing agent, catalyst, solvent) in a plastic container, and stir them with a mixer to obtain coating compositions.

[0399] (mixing conditions)

[0400] • NCO / OH: 1.2

[0401] • Coating solids content: 40% by weight

[0402] • Catalyst: 1% by mass relative to the total amount of main agent and curing agent.

[0403] (Preparation method)

[0404] The main agent and catalyst were measured in a plastic container under the aforementioned mixing conditions. Solvent was added so that the solid content of the coating composition was 20 wt%, and the mixture was stirred until uniformly dispersed. Then, the curing agent was measured in the aforementioned plastic container with an NCO / OH ratio of 1.25, and stirred until uniformly dispersed, thus obtaining the coating compositions.

[0405] (Coating process)

[0406] The obtained coating compositions were applied to polycarbonate sheets ("TAKIRON PC-1600" (trade name), 2mm×70mm×150mm) with a dry film thickness of 40μm.

[0407] (Drying process)

[0408] The coating composition applied to the polycarbonate board was baked at 60°C to obtain a polyurethane coating film.

[0409] The physical properties of each polyurethane coating were evaluated. The evaluation results are shown in Table 3.

[0410] <Appearance Evaluation of Polyurethane Coatings>

[0411] The surface appearance of the polyurethane films prepared above shall be visually assessed according to the following criteria.

[0412] ○ (Very good): Smooth surface

[0413] △ (Good): A small number of streaks are observed on the surface along the direction of the applicator's movement.

[0414] × (Bad): Numerous streaks were observed on the surface along the direction of the applicator's movement.

[0415] Chemical resistance

[0416] Cut 3cm × 3cm test pieces from the polyurethane coating. After determining the mass of the test pieces using a precision balance, place them into 250mL glass bottles containing 50mL of oleic acid as the test solvent, and let them stand for 16 hours in a constant temperature bath at 80℃ under a nitrogen atmosphere. After the test, remove the test pieces, gently wipe the surface and back with a paper wiper, and then determine the mass using a precision balance. Calculate the rate of change in mass from before the test (increase rate: oleic acid resistance swelling rate), and evaluate according to the following criteria.

[0417] (Evaluation Criteria)

[0418] ○ (Excellent): Quality increase rate less than 6%

[0419] △ (Good): Quality increase rate is 6% or more but less than 20%

[0420] × (Bad): Quality increase rate is 20% or higher or cannot be evaluated.

[0421] <Weather resistance>

[0422] Using the same method as described above, an applicator was used to coat the panel to a thickness of 200 μm after drying. The coating was then cured at 23°C and 50% humidity for 168 hours to obtain urethane films (polyisocyanate cured products). The resulting polyisocyanate cured products were then subjected to a super xenon lamp weathering tester (irradiance: 60 W / m²). 2 In the weathering test, the temperature of the black panel under light exposure was set to 65°C and the humidity to 50%. After 102 minutes, water was sprayed while maintaining a humidity of 95% for 18 minutes, and this cycle was repeated. The L*a*b* (CIE 1976) of the polyisocyanate cured product was measured using a colorimeter before and 2000 hours after the start of the weathering test. Based on the color difference (ΔE) calculated using the following color difference formula, the weathering resistance was evaluated according to the following evaluation criteria.

[0423] ΔE={(ΔL*) 2 +(Δa*) 2 +(Δb*) 2} 1 / 2

[0424] (ΔL*, Δa*, and Δb* are the differences between the measured values ​​of L*, a*, and b* before the start of the weather resistance test and 2000 hours later.)

[0425] (Evaluation Criteria)

[0426] ○ (Very good): ΔE is less than 5

[0427] △ (Good): ΔE is 5 or more and less than 10

[0428] × (Bad): ΔE is 10 or higher

[0429] (Manufacturing Examples 1-3)

[0430] Hexen-1-ol solutions were prepared as described below (1) to (3).

[0431] H1: 4-Hexen-1-ol (trans form): manufactured by Aldrich.

[0432] H2: 4-Hexen-1-ol (cis-form): Manufactured by Tokyo Chemical Industry Co., Ltd.

[0433] H3: 5-Hexen-1-ol: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0434] The above H1, H2 and H3 were mixed in a mass ratio of 1:1:2 to obtain a hexen-1-ol solution (1).

[0435] The above H2 and H3 were mixed at a mass ratio of 1:4 to obtain a hexen-1-ol solution (2).

[0436] The above H2 and H3 were mixed at a mass ratio of 1:20 to obtain a hexen-1-ol solution (3).

[0437] (Example 1)

[0438] In a 2L glass flask equipped with a distillation column filled with a regular packing material and a stirring device, 766g (8.7mol) of ethylene carbonate, 450g (4.3mol) of 1,5-pentanediol, and 520g (4.4mol) of 1,6-hexanediol were added. 0.33g of tetrabutoxytitanium as a catalyst was added to the flask, and the reaction was carried out for 12 hours while the reaction temperature was set at 140-160°C, the pressure was reduced from 10kPa to 2kPa, and the resulting mixture of ethylene glycol and ethylene carbonate was distilled off. Then, simple distillation was used, and the reaction was carried out at 180°C for 4 hours while the pressure was slowly reduced to 0.5kPa, distilling off the monomer. Next, 0.37g of 2-ethylhexyl phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 120°C for 5 hours. Then, 0.09g of a hexen-1-ol solution (1) was added to obtain a polycarbonate polyol composition. The analytical results of the obtained polycarbonate polyol composition are shown in Table 1. This polycarbonate polyol composition is abbreviated as PC-1. The (A) and (B) components of the obtained polycarbonate polyol composition were quantified using the above method, and their ratios are recorded in Table 1. Additionally, the amounts of titanium and phosphorus measured by the above method are recorded in Table 1.

[0439] (Example 2)

[0440] Using the same apparatus as in Example 1 above, 0.07 g of hexen-1-ol solution (2) was added, and the operation was otherwise performed in the same manner as in Example 1 to obtain a polycarbonate polyol composition. This polycarbonate polyol composition is referred to simply as PC-2. The results of the analysis of PC-2 are recorded in Table 1.

[0441] (Example 3)

[0442] Using the same apparatus as in Example 1 above, 0.18 g of tetrabutoxytitanium, 0.20 g of 2-ethylhexyl phosphate, and 0.01 g of hexen-1-ol solution (3) were added. The procedure was otherwise performed in the same manner as in Example 1 to obtain a polycarbonate polyol composition. This polycarbonate polyol composition is referred to simply as PC-3. The results of the analysis of PC-3 are recorded in Table 1.

[0443] (Example 4)

[0444] Using the same apparatus as in Example 1 above, 0.18 g of tetrabutoxytitanium, 0.20 g of 2-ethylhexyl phosphate, and 0.003 g of hexen-1-ol solution (2) were added. Simple distillation was then performed, and the reaction was carried out at 180°C for 7 hours while the pressure was slowly reduced to 0.5 kPa to allow the monomer to distill off. Otherwise, the operation was the same as in Example 1 to obtain a polycarbonate polyol composition. This polycarbonate polyol composition is referred to as PC-4. The results of the analysis of PC-4 are recorded in Table 1.

[0445] (Example 5)

[0446] Using the same apparatus as in Example 1 above, 0.01 g of hexen-1-ol solution (3) was added, and simple distillation was switched to the method described above. The reaction was carried out at 180°C for 3 hours while the pressure was slowly reduced to 0.5 kPa to allow the monomer to distill off. Otherwise, the operation was carried out in the same manner as in Example 1 to obtain a polycarbonate polyol composition. This polycarbonate polyol composition is referred to as PC-5. The results of the analysis of PC-5 are recorded in Table 1.

[0447] (Example 6)

[0448] Using the same apparatus as in Example 1 above, 0.06 g of hexen-1-ol solution (3) was added, and simple distillation was switched to the method described above. The reaction was carried out at 180°C for 1.5 hours while the pressure was slowly reduced to 0.5 kPa to allow the monomer to distill off. Otherwise, the operation was carried out in the same manner as in Example 1 to obtain a polycarbonate polyol composition. This polycarbonate polyol composition is referred to as PC-6. The results of the analysis of PC-6 are recorded in Table 1.

[0449] (Example 7)

[0450] Using the same apparatus as in Example 1 above, 0.01 g of 4-penten-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the procedure was otherwise performed in the same manner as in Example 1 to obtain a polycarbonate polyol composition. This polycarbonate polyol composition is referred to simply as PC-7. The results of the analysis of PC-7 are recorded in Table 1.

[0451] (Example 8)

[0452] Using the same apparatus as in Example 1 above, 766 g (8.7 mol) of ethylene carbonate, 390 g (4.3 mol) of 1,4-butanediol, and 520 g (4.4 mol) of 1,6-hexanediol were added, along with 0.01 g of hexen-1-ol solution (3). The procedure was otherwise performed in the same manner as in Example 1 to obtain a polycarbonate polyol composition. This polycarbonate polyol composition is abbreviated as PC-8. The results of the analysis of PC-8 are recorded in Table 1.

[0453] (Example 9)

[0454] Using the same apparatus as in Example 1 above, 766 g (8.7 mol) of ethylene carbonate, 355 g (3.4 mol) of 1,5-pentanediol, 366 g (3.1 mol) of 1,6-hexanediol, and 378 g (2.2 mol) of 1,10-decanediol were added, along with 0.01 g of hexen-1-ol solution (3). The procedure was otherwise performed in the same manner as in Example 1 to obtain a polycarbonate polyol composition. This polycarbonate polyol composition is abbreviated as PC-9. The results of the analysis of PC-9 are recorded in Table 1.

[0455] (Example 10)

[0456] Using the same apparatus as in Example 1 above, 766 g (8.7 mol) of ethylene carbonate, 450 g (4.3 mol) of 1,5-pentanediol, and 520 g (4.4 mol) of 1,6-hexanediol were added, along with 0.003 g of hexen-1-ol solution (2). The reaction was carried out for 24 hours while distilling off the resulting mixture of ethylene glycol and ethylene carbonate. The reaction was then carried out at 180°C for 5 hours to allow the monomer to distill off. Otherwise, the operation was carried out in the same manner as in Example 1 to obtain a polycarbonate polyol composition. This polycarbonate polyol composition is referred to as PC-10. The results of the analysis of PC-10 are recorded in Table 1.

[0457] (Example 11)

[0458] Using the same apparatus as in Example 1 above, 766 g (8.7 mol) of ethylene carbonate and 1038 g (8.8 mol) of 1,6-hexanediol were added, along with 0.13 g of hexen-1-ol solution (3). The procedure was otherwise performed in the same manner as in Example 1 to obtain a polycarbonate polyol composition. This polycarbonate polyol composition is referred to simply as PC-11. The results of the analysis of PC-11 are recorded in Table 1.

[0459] (Example 12)

[0460] Using the same apparatus as in Example 1 above, 0.02 g of hexen-1-ol solution (2) was added, and the procedure was otherwise performed in the same manner as in Example 4 to obtain a polycarbonate polyol composition. This polycarbonate polyol composition is referred to simply as PC-12. The results of the analysis of PC-12 are recorded in Table 1.

[0461] (Example 13)

[0462] Using the same apparatus as in Example 1 above, 0.003 g of hexen-1-ol solution (2) and 0.01 g of methanol were added, and the operation was otherwise performed in the same manner as in Example 4 to obtain a polycarbonate polyol composition. This polycarbonate polyol composition is referred to simply as PC-13. The results of the analysis of PC-13 are recorded in Table 1.

[0463] (Example 14)

[0464] Using the same apparatus as in Example 1 above, 0.26 g of hexen-1-ol solution (3) was added, and the operation was otherwise performed in the same manner as in Example 1 to obtain a polycarbonate polyol composition. This polycarbonate polyol composition is referred to simply as PC-14. The results of the analysis of PC-14 are recorded in Table 2.

[0465] (Example 15)

[0466] Using the same apparatus as in Example 1 above, 0.50 g of hexen-1-ol solution (3) was added, and the operation was otherwise performed in the same manner as in Example 1 to obtain a polycarbonate polyol composition. This polycarbonate polyol composition is referred to simply as PC-15. The results of the analysis of PC-15 are recorded in Table 2.

[0467] (Example 16)

[0468] Using the same apparatus as in Example 1 above, 0.18 g of hexen-1-ol solution (2) was added, and the procedure was otherwise performed in the same manner as in Example 4 to obtain a polycarbonate polyol composition. This polycarbonate polyol composition is referred to simply as PC-16. The results of the analysis of PC-16 are recorded in Table 2.

[0469] (Example 17)

[0470] Weigh 50g of the polycarbonate polyol composition (PC-4) obtained in Example 4 and mix it with 50g of a Resonac-made polyester polyol (Teslac, 2460, molecular weight 2000, liquid polyol) to obtain a polycarbonate polyol composition (PC-17). Based on the... 13The integral ratio of the repeating carbonate structure to the repeating ester structure, calculated by C-NMR, yielded a molar ratio of 41:59. The results of the PC-17 analysis are recorded in Table 2.

[0471] (Example 18)

[0472] Weigh 50g of the polycarbonate polyol composition (PC-4) obtained in Example 4 and mix it with 50g of a Kuraray polyester polyol (Kuraray Polyol, P-2010, molecular weight 2000, liquid polyol) to obtain a polycarbonate polyol composition (PC-18). Based on the... 13 The integral ratio of the repeating carbonate structure to the repeating ester structure, calculated by C-NMR, yielded a molar ratio of 46:54. The results of the PC-18 analysis are recorded in Table 2.

[0473] (Example 19)

[0474] Weigh 50g of the polycarbonate polyol composition (PC-4) obtained in Example 4 and mix it with 50g of polytetramethylene ether glycol (PTMG2000) manufactured by Mitsubishi Chemical to obtain the polycarbonate polyol composition (PC-19). Based on the... 13 The integral ratio of the repeating structures of carbonate and ether was calculated by C-NMR determination, and the result was that the repeating structure of carbonate was 24:76 (molar ratio). The results of the PC-19 analysis are recorded in Table 2.

[0475] (Example 20)

[0476] Weigh 70g of the polycarbonate polyol composition (PC-4) obtained in Example 4 and mix it with 30g of a Resonac-made polyester polyol (Teslac, 2460, molecular weight 2000, liquid polyol) to obtain a polycarbonate polyol composition (PC-20). Based on the... 13 The integral ratio of the repeating structures of carbonate and ester was calculated by C-NMR determination, and the result was that the repeating structure ratio of carbonate to ester was 67:33 (molar ratio). The results of the analysis of PC-20 are recorded in Table 2.

[0477] (Example 21)

[0478] Weigh 70g of the polycarbonate polyol composition (PC-4) obtained in Example 4 and mix it with 30g of Kuraray polyester polyol (Kuraray Polyol, P-2010) to obtain the polycarbonate polyol composition (PC-21). Based on the... 13The integral ratio of the repeating carbonate structure to the repeating ester structure, calculated by C-NMR, yielded a molar ratio of 67:33. The results of the PC-21 analysis are recorded in Table 2.

[0479] (Example 22)

[0480] Weigh 20g of the polycarbonate polyol composition (PC-4) obtained in Example 4, and mix 30g of the polycarbonate polyol composition (PC-6) obtained in Example 6 with 50g of the polyester polyol (Teslac, 2460) manufactured by Resonac to obtain the polycarbonate polyol composition (PC-22). Based on the... 13 The integral ratio of the repeating carbonate structure to the repeating ester structure, calculated by C-NMR, yielded a molar ratio of 44:56. The results of the analysis of PC-22 are recorded in Table 2.

[0481] (Example 23)

[0482] Weigh 20g of the polycarbonate polyol composition (PC-4) obtained in Example 4, and mix 30g of the polycarbonate polyol composition (PC-6) obtained in Example 6 with 50g of Kuraray polyester polyol (Kuraray Polyol, P-2010) to obtain the polycarbonate polyol composition (PC-23). ​​Based on the... 13 The integral ratio of the repeating carbonate structure to the repeating ester structure, calculated by C-NMR, yielded a molar ratio of 44:56. The results of the analysis of PC-23 are recorded in Table 2.

[0483] (Comparative Example 1)

[0484] Using the same apparatus as in Example 1 above, 2.4 g of hexen-1-ol solution (1) was added, and the operation was otherwise performed in the same manner as in Example 1 to obtain a polycarbonate polyol composition. This polycarbonate polyol composition is referred to simply as PC-24. The results of the analysis of PC-24 are recorded in Table 2.

[0485] (Comparative Example 2)

[0486] Using the same apparatus as in Example 1 above, 1.2 g of hexen-1-ol solution (1) was added, and the operation was otherwise performed in the same manner as in Example 1 to obtain a polycarbonate polyol composition. This polycarbonate polyol composition is referred to simply as PC-25. The results of the analysis of PC-25 are recorded in Table 2.

[0487] (Comparative Example 3)

[0488] Using the same apparatus as in Example 1 above, 0.001 g of hexen-1-ol solution (3) was added, and simple distillation was switched to the method described above. The reaction was carried out at 180°C for 7 hours while the pressure was slowly reduced to 0.5 kPa to allow the monomer to distill off. Otherwise, the operation was carried out in the same manner as in Example 1 to obtain a polycarbonate polyol composition. 17 g of 1,5-pentanediol and 18 g of 1,6-hexanediol were added to the obtained polycarbonate polyol composition. This polycarbonate polyol composition is referred to as PC-26. The results of the analysis of PC-26 are recorded in Table 2.

[0489] [Table 1]

[0490]

[0491] [Table 2]

[0492]

[0493] [Table 3]

[0494]

[0495] Industrial availability

[0496] The polycarbonate polyol composition of the present invention can provide a polyurethane film with a long service life, excellent workability, good appearance and excellent weather resistance, and therefore can be widely and effectively used as a constituent material for, for example, coatings, coating compositions, adhesives, adhesive compositions, water-based polyurethanes, water-dispersible compositions, polyurethanes for synthetic leather, synthetic leather and so on.

Claims

1. A polycarbonate polyol composition, characterized in that, Include: Polycarbonate polyols with terminal hydroxyl groups; (A) Components: The compound represented by formula (A) below; and, (B) Component: The compound represented by formula (B) below, The mass ratio of component (A) to component (B), i.e., (A) / (B), is 0.0001 to 0.1000. In formula (A), R1 is hydrogen or an alkyl group having 1 to 12 carbon atoms, and R2 is an alkylene group having 1 to 12 carbon atoms. In formula (B), R3 is an alkylene group with 2 to 12 carbon atoms, and may optionally have a straight-chain alkylene group, a divalent alicyclic hydrocarbon group, or a branched alkylene group.

2. The polycarbonate polyol composition according to claim 1, wherein, The content of at least one metallic element selected from the group consisting of titanium, ytterbium, tin, zirconium, magnesium, calcium, lithium, sodium and manganese, as determined by ICP, is 0.0001 to 0.050% by mass, and the ICP is ICP-MS, i.e., inductively coupled plasma mass spectrometry.

3. The polycarbonate polyol composition according to claim 1, wherein, The phosphorus content determined by ICP is 0.0001~0.050% by mass, and the ICP is ICP-MS, i.e., inductively coupled plasma mass spectrometry.

4. The polycarbonate polyol composition according to claim 1, wherein, In the compounds shown in formula (A) and formula (B), the sum of the total number of carbon atoms of R1 and R2 plus the number of two carbon atoms equals the number of carbon atoms of R3.

5. The polycarbonate polyol composition according to claim 1, wherein, The polycarbonate polyol having terminal hydroxyl groups has repeating units derived from 1,5-pentanediol and / or 1,6-hexanediol. The compound represented by formula (A) comprises one compound selected from the group consisting of a compound in formula (A) where R1 is a hydrogen atom and R2 is an alkylene group having 4 or 3 carbon atoms, a compound in formula (A) where R1 is an alkylene group having 1 carbon atom and R2 is an alkylene group having 3 or 2 carbon atoms, and a compound in formula (A) where R1 is an alkylene group having 2 carbon atoms and R2 is an alkylene group having 2 or 1 carbon atoms. The sum of the total number of carbon atoms in R1 and R2 of the compound shown in formula (A), plus the number of two carbon atoms, results in a number of 5 or 6, which is equal to the number of carbon atoms in R3 of the compound shown in formula (B).

6. The polycarbonate polyol composition according to claim 1, characterized in that, It also contains component (B'). The mass ratio of component (B') to component (B), i.e., (B') / (B), is 0.0001 to 1.

000. In formula (B'), R4 is an alkylene group having 1 to 4 carbon atoms.

7. The polycarbonate polyol composition according to claim 1, further comprising a polyol compound having an ester repeating structure and / or an ether repeating structure.

8. The polycarbonate polyol composition according to claim 7, wherein, The molar ratio of the polycarbonate polyol to the polyol compound having ester repeating structure and / or ether repeating structure, including the sum of carbonate repeating structure, ester repeating structure and ether repeating structure, is in the range of 20:80 to 80:

20.

9. The polycarbonate polyol composition according to claim 1, wherein, The mass ratio, i.e. (A) / (B), is 0.0001 to 0.

075.

10. The polycarbonate polyol composition according to claim 1, wherein, The mass ratio, i.e. (A) / (B), is 0.0001 to 0.

069.

11. The polycarbonate polyol composition according to claim 1, wherein, The mass ratio, i.e. (A) / (B), is 0.0001 to 0.

010.

12. The polycarbonate polyol composition according to claim 1, wherein, The mass ratio, i.e. (A) / (B), is 0.006 to 0.

010.

13. The polycarbonate polyol composition according to claim 1, wherein, The polycarbonate polyol having terminal hydroxyl groups has structural units represented by the following formula (P). （P） In formula (P), R1 is any divalent aliphatic hydrocarbon group, R2 is hydrogen or any monovalent aliphatic hydrocarbon group, and R3 is any divalent aliphatic hydrocarbon group.

14. An adhesive composition comprising the polycarbonate polyol composition according to any one of claims 1 to 13.

15. A water-based polyurethane, which is made using the polycarbonate polyol composition according to any one of claims 1 to 13.

16. An aqueous dispersion composition made using the polycarbonate polyol composition according to any one of claims 1 to 13.

17. A polyurethane for synthetic leather, which is made using the polycarbonate polyol composition according to any one of claims 1 to 13.

18. A synthetic leather made using the polycarbonate polyol composition according to any one of claims 1 to 13.

19. A urethane cured product made using the polycarbonate polyol composition according to any one of claims 1 to 13.

20. An automotive interior material comprising the synthetic leather of claim 18.

21. A method for suppressing odor in a polycarbonate polyol composition, wherein, The polycarbonate polyol composition comprises: Polycarbonate polyols with terminal hydroxyl groups; (A) Components: the compound represented by formula (A); and, (B) Component: The compound represented by formula (B), The mass ratio of component (A) to component (B), i.e., (A) / (B), is 0.0001 to 0.1000.

22. A method for suppressing the odor of urethane cured products, comprising the following steps: A polycarbonate polyol composition is selected, and the polycarbonate polyol composition is cured to produce a urethane cured product. The polycarbonate polyol composition comprises: Polycarbonate polyols with terminal hydroxyl groups; (A) Components: the compound represented by formula (A); and, (B) Component: The compound represented by formula (B), The mass ratio of component (A) to component (B), i.e., (A) / (B), is 0.0001 to 0.1000.

23. A method for manufacturing a polycarbonate polyol composition, wherein, The polycarbonate polyol composition comprises: Polycarbonate polyols with terminal hydroxyl groups; (A) Components: the compound represented by formula (A); and, (B) Component: The compound represented by formula (B), The mass ratio of component (A) to component (B), i.e., (A) / (B), is adjusted to a range of 0.0001 to 0.1000.

24. A method for manufacturing a urethane cured product, comprising the following steps: A polycarbonate polyol composition is selected, and the polycarbonate polyol composition is cured. The polycarbonate polyol composition comprises: Polycarbonate polyols with terminal hydroxyl groups; (A) Components: the compound represented by formula (A); and, (B) Component: The compound represented by formula (B), The mass ratio of component (A) to component (B), i.e., (A) / (B), is 0.0001 to 0.1000.

25. A method for manufacturing synthetic leather, comprising the following steps: An adhesive layer, an intermediate layer, and a skin layer are sequentially disposed on the substrate. Any one of the skin layer, the intermediate layer, and the adhesive layer is a urethane cured product of a polycarbonate polyol composition. The polycarbonate polyol composition comprises: Polycarbonate polyols with terminal hydroxyl groups; (A) Components: the compound represented by formula (A); and, (B) Component: The compound represented by formula (B), The mass ratio of component (A) to component (B), i.e., (A) / (B), is 0.0001 to 0.1000.

26. A method for suppressing the odor of synthetic leather, comprising the following steps: A polycarbonate polyol composition is selected, and a urethane cured product of the polycarbonate polyol composition is used in at least one of the adhesive layer, intermediate layer, and skin layer. The polycarbonate polyol composition comprises: Polycarbonate polyols with terminal hydroxyl groups; (A) Components: the compound represented by formula (A); and, (B) Component: The compound represented by formula (B), The mass ratio of component (A) to component (B), i.e., (A) / (B), is 0.0001 to 0.1000.

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