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

Abstract

Provision of a polycarbonate polyol composition, etc., which can provide a polyurethane film with a long pot life, excellent handling properties, good appearance, and excellent weather resistance. Polycarbonate polyol composition comprising: polycarbonate polyol with terminal hydroxyl groups, an (A) component: a compound represented by the following formula (A), and a (B) component: a compound represented by the following formula (B), characterized in that the mass ratio ((A) / (B)) of the (A) component to the (B) component is 0.0001 to 0.1000, wherein R1 is hydrogen or an alkyl group with 1 to 12 carbon atoms, and R2 is an alkylene group with 1 to 12 carbon atoms, and wherein R3 is an alkylene group with 2 to 12 carbon atoms, which may have a straight-chain alkylene group, a divalent alicyclic hydrocarbon group, or a branched alkylene group.Selected drawing.

Description

TECHNICAL AREA

[0001] The present invention relates to a polycarbonate polyol composition, an adhesive composition, water-based polyurethane, a water dispersion composition, polyurethane for artificial leather and an artificial leather, etc. STATE OF THE ART

[0002] Polycarbonate polyols are known as raw materials for urethane, exhibiting both flexibility and toughness, and are used, for example, as soft segments in polyurethanes and thermoplastic elastomers. Among these, polycarbonate polyols are known for their hydrolysis resistance, acid resistance, and similar properties. Various polycarbonate polyols have been tested and are known.

[0003] For example, JP 3874664 B discloses polycarbonate diol, in which the ratio of primary terminal OH groups to total terminal groups is within a certain range, as a polycarbonate polyol exhibiting high polymerization reactivity and high polymerization rate in polyurethaneization reactions and reactions for the production of polyester elastomers.

[0004] Furthermore, JP 2013-064140 A discloses polycarbonate diol with the ratio of primary terminal OH groups in a certain range as polycarbonate diol which stabilizes the reaction and, when used as a component of a paint, gives a coating which has neither the roughness caused by fine gel-like substances nor the stickiness caused by low molecular weight substances, and achieves a good balance of properties such as hydrolysis resistance and heat resistance. OVERVIEW OF THE INVENTION TASK TO BE SOLVED BY THE INVENTION

[0005] However, when using polycarbonate diols disclosed in JP 3874664 B or JP 2013-064140 A, although excellent reaction rates and coating properties can be easily achieved, new problems have been found that, unexpectedly, the pot life is shortened when mixed with isocyanate, gelation occurs, it becomes difficult to obtain polyurethane with a good appearance, and the weather resistance of the polyurethane obtained is reduced.

[0006] The present invention was developed in light of the aforementioned problems. That is to say, the present invention aims to provide a polycarbonate polyol composition, etc., that can form a polyurethane film which, when used as a polyurethane component, for example in paints, adhesives, and artificial leathers, exhibits a long pot life, excellent handling properties, a pleasing appearance, and weather resistance. Furthermore, the present invention aims to provide a polycarbonate polyol composition, an adhesive composition, water-based polyurethane, a water dispersion composition, polyurethane for artificial leather, and an artificial leather, etc., that can form a polyurethane which is distinguished by its pleasing handling properties, a pleasing appearance, and weather resistance. MEANS OF SOLVING THE TASK

[0007] The present inventors have undertaken intensive deliberations taking into account the aforementioned problems. As a result, they have developed a new polycarbonate polyol composition comprising polycarbonate polyol with terminal hydroxyl groups, and the following (A) component and the following (B) component, wherein the ratio of the following (A) component and the following (B) component is within a specific range, and they have found that the use of this polycarbonate polyol composition can solve the aforementioned problems, which led to the completion of the present invention.

[0008] That is, the present invention provides various specific aspects, which are shown below: <1> Polycarbonate polyol composition, containing: Polycarbonate polyol with terminal hydroxyl groups, one (A) component: a compound represented by the following formula (A), and a (B)-component: a compound represented by the following formula (B), characterized in that the mass ratio ((A) / (B)) of the (A) component to the (B) component is 0.0001 to 0.1000, wherein R1 is hydrogen or an alkyl group with 1 to 12 carbon atoms and R2 is an alkylene group with 1 to 12 carbon atoms, where R3 is an alkylene group with 2 to 12 carbon atoms, which may be a straight-chain alkylene group, a divalent alicyclic hydrocarbon group, or a branched alkylene group. <2> Polycarbonate polyol composition according to paragraph <1> , wherein, when measured using ICP (ICP-MS: Inductively Coupled Plasma Mass Spectrometry), the content of at least one metal element selected from the group consisting of titanium, ytterbium, tin, zirconium, magnesium, calcium, lithium, sodium and manganese, is 0.0001 to 0.050 mass-%. <3> Polycarbonate polyol composition according to paragraph <1> or <2> , where, when measured using ICP (ICP-MS: Inductively Coupled Plasma Mass Spectrometry), the phosphorus content is 0.0001 to 0.050 mass-%. <4> Polycarbonate polyol composition according to one of the paragraphs <1> until <3> , where, under the compound represented by formula (A) and the compound represented by formula (B), a number obtained by adding two carbon atoms to the sum of the total number of carbon atoms of R1 and R2 corresponds to the number of carbon atoms of R3. <5> Polycarbonate polyol composition according to one of the paragraphs <1> until <4> , wherein the polycarbonate polyol with terminal hydroxyl groups has repeating units derived from 1,5-pentanediol and / or 1,6-hexanediol, wherein the compound represented by formula (A) contains a compound selected from the group consisting of a compound in which R1 in formula (A) is a hydrogen atom and R2 is an alkylene group with 4 or 3 carbon atoms, a compound in which R1 in formula (A) is an alkylene group with 1 carbon atom and R2 is an alkylene group with 3 or 2 carbon atoms, and a compound in which R1 in formula (A) is an alkylene group with 2 carbon atoms and R2 is an alkylene group with 2 or 1 carbon atoms, and wherein a number obtained by adding two carbon atoms to the sum of the total number of carbon atoms of R1 and R2 of the compound represented by formula (A) is 5 or 6, and this corresponds to the number of carbon atoms of R3 of the compound represented by formula (B). <6> Polycarbonate polyol composition according to one of the paragraphs <1> until <5> , which further contains a (B') component, characterized in that the mass ratio ((B') / (B)) of the (B') component to the (B) component is 0.0001 to 1.000, where R4 is an alkylene group with 1 to 4 carbon atoms. <7> Polycarbonate polyol composition according to one of the paragraphs <1> until <6> , which further contains a polyol compound having an ester repeat structure and / or an ether repeat structure. <8> Polycarbonate polyol composition according to paragraph <7> , wherein the total molar ratio of carbonate repeat structure:ester repeat structure and ether repeat structure contained in the polycarbonate polyol and the polyol compound with the ester repeat structure and / or the ether repeat structure is in the range of 20:80 to 80:20. <9> Polycarbonate polyol composition according to one of the paragraphs <1> until <8> , where the mass ratio ((A) / (B)) is 0.0001 to 0.0075. <10> Polycarbonate polyol composition according to one of the paragraphs <1> until <9> , where the mass ratio ((A) / (B)) is 0.0001 to 0.069. <11> Polycarbonate polyol composition according to one of the paragraphs <1> until <10> , where the mass ratio ((A) / (B)) is 0.0001 to 0.010. <12> Polycarbonate polyol composition according to one of the paragraphs <1> until <11> , where the mass ratio ((A) / (B)) is 0.006 to 0.010. <13> Polycarbonate polyol composition according to one of the paragraphs <1> until <12> , wherein the polycarbonate polyol with terminal hydroxyl groups has a constitutional unit which is represented by the following formula (P), where 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> Adhesive composition comprising a polycarbonate polyol composition according to one of the paragraphs <1> until <13> includes. <15> Water-based polyurethane, which uses a polycarbonate polyol composition according to one of the paragraphs <1> until <13> is manufactured. <16> Water dispersion composition prepared using a polycarbonate polyol composition according to one of the paragraphs <1> until <13> is manufactured. <17> Polyurethane for artificial leather, which uses a polycarbonate polyol composition according to one of the paragraphs <1> until <13> is manufactured. <18> Artificial leather made using a polycarbonate polyol composition according to one of the paragraphs <1> until <13> is manufactured. <19> Urethane-cured product made using a polycarbonate polyol composition according to one of the paragraphs <1> until <13> is manufactured. <20> Interior trim material of a vehicle, containing an artificial leather according to paragraph <18> . <21> Method for suppressing the odor of a polycarbonate polyol composition, the polycarbonate polyol composition contains: a polycarbonate polyol with terminal hydroxyl groups, a (A) component: a compound represented by the following formula (A), and a (B)-component: a compound represented by the following formula (B), where the mass ratio ((A) / (B)) of the (A) component to the (B) component is 0.0001 to 0.1000. <22> Method for suppressing the odor of a urethane-cured product, comprising: Selecting a polycarbonate polyol composition that contains: a polycarbonate polyol with terminal hydroxyl groups, a (A) component: a compound represented by the following formula (A), and a (B)-component: a compound represented by the following formula (B), where the mass ratio ((A) / (B)) of the (A) component to the (B) component is 0.0001 to 0.1000, and Curing the polycarbonate polyol composition to produce a urethane-cured product. <23> Method for producing a polycarbonate polyol composition the polycarbonate polyol composition contains: a polycarbonate polyol with terminal hydroxyl groups, a (A) component: a compound represented by the following formula (A), and a (B)-component: a compound represented by the following formula (B), where the mass ratio ((A) / (B)) of the (A) component to the (B) component is set to a range of 0.0001 to 0.1000. <24> Method for producing a urethane-cured product, comprising: Selecting a polycarbonate polyol composition that contains: a polycarbonate polyol with terminal hydroxyl groups, a (A) component: a compound represented by the following formula (A), and a (B)-component: a compound represented by the following formula (B), where the mass ratio ((A) / (B)) of the (A) component to the (B) component is 0.0001 to 0.1000, and Curing of the polycarbonate polyol composition. <25> Methods for the production of artificial leather, comprising: a step to arrange an adhesive layer, an intermediate layer and a surface layer on a base material in the specified order, wherein one of the surface layer, the intermediate layer and the adhesive layer is a urethane-cured product of a polycarbonate polyol composition, and the polycarbonate polyol composition contains: a polycarbonate polyol with terminal hydroxyl groups, a (A) component: a compound represented by the following formula (A), and a (B)-component: a compound represented by the following formula (B), where the mass ratio ((A) / (B)) of the (A) component to the (B) component is 0.0001 to 0.1000. <26> Methods for suppressing the odor of artificial leather, comprising: Selecting a polycarbonate polyol composition that contains: a polycarbonate polyol with terminal hydroxyl groups, a (A) component: a compound represented by the following formula (A), and a (B)-component: a compound represented by the following formula (B), where the mass ratio ((A) / (B)) of the (A) component to the (B) component is 0.0001 to 0.1000, and Using a urethane-cured product of the polycarbonate polyol composition in at least one of the adhesive layer, the intermediate layer and the surface layer. EFFECTS OF INVENTION

[0009] According to the present invention, it is possible to provide a polycarbonate polyol composition, etc., that can produce a polyurethane film which, when used as a polyurethane component, for example in paints, adhesives, and artificial leathers, exhibits a long pot life, excellent handling properties, a pleasing appearance, and weather resistance. Furthermore, by using the polycarbonate polyol composition according to the invention, it is possible to provide a polycarbonate polyol composition, an adhesive composition, water-based polyurethane, a water dispersion composition, polyurethane for artificial leather, and an artificial leather, etc., which can provide polyurethane that is distinguished by its pleasing handling properties, a pleasing appearance, and weather resistance. EXPLANATION OF THE DRAWINGS Fig.Figure 1 shows a schematic sectional view illustrating an example of an artificial leather laminate using the polycarbonate polyol composition of the present embodiment; and Fig. Figure 2 shows a schematic view illustrating an example of a manufacturing process for the artificial leather laminate using the polycarbonate polyol composition of the present embodiment. FORMS OF EXECUTION OF THE INVENTION

[0010] The following section describes in detail embodiments of the present invention (hereinafter referred to as "present embodiments"). The present invention is not limited to the following embodiments and can be implemented with various modifications within the scope of its essence. <polycarbonatpolyolzusammensetzung>

[0011] The polycarbonate polyol composition of the present embodiment comprises polycarbonate polyol with terminal hydroxyl groups, an (A) component: a compound represented by the following formula (A), and a (B) component: a compound represented by the following formula (B), characterized in that the mass ratio ((A) / (B)) of the (A) component to the (B) component is 0.0001 to 0.1000: wherein R1 is hydrogen or an alkyl group with 1 to 12 carbon atoms and R2 is an alkylene group with 1 to 12 carbon atoms, wherein R3 is an alkylene group with 2 to 12 carbon atoms, which may have a straight-chain alkylene group, a divalent alicyclic hydrocarbon group, or a branched alkylene group. <polycarbonatpolyol>

[0012] The polycarbonate polyol composition of the present embodiment contains a polycarbonate polyol with terminal hydroxyl groups. The polycarbonate polyol with terminal hydroxyl groups is not specifically restricted insofar as it has a carbonate repeat structure and two or more hydroxyl groups. In addition to the carbonate repeat structure, the polycarbonate polyol with terminal hydroxyl groups may also contain, for example, an ester repeat structure or an ether repeat structure. Specific aspects of the polycarbonate polyol with terminal hydroxyl groups are described below.

[0013] In the present embodiment, the number-average molecular weight (Mn) of the polycarbonate polyol with terminal hydroxyl groups is not particularly limited, but is preferably between 300 and 5000. Because the number-average molecular weight of the polycarbonate polyol with terminal hydroxyl groups is 300 or more, the low-temperature properties of the polyurethane obtained tend to be favorable. Because the number-average molecular weight of the polycarbonate polyol with terminal hydroxyl groups is 5000 or less, the reduction in the formability of the polyurethane obtained tends to be slightly suppressed. Based on the appearance of the coating of the polyurethane obtained, the number-average molecular weight of the polycarbonate polyol is preferably between 300 and 3000, more preferably between 350 and 2000, and even more preferably between 500 and 2000.

[0014] In the present embodiment, the number mean value of the molecular weight (Mn) of the polycarbonate polyol with terminal hydroxyl groups can be measured using the method specified in the following exemplary embodiments.

[0015] In the present embodiment, the hydroxyl number (OH number) of the polycarbonate polyol with terminal hydroxyl groups is not particularly limited; however, the lower limit is preferably 20 mg KOH / g or more, more preferably 30 mg KOH / g or more, more preferably 50 mg KOH / g or more, further 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 number (OH number) of the polycarbonate polyol with terminal hydroxyl groups is not particularly limited; however, it is preferably 700 mg KOH / g or less, more preferably 500 mg KOH / g or less, more preferably 400 mg KOH / g or less, further preferably 350 mg KOH / g or less, particularly preferably 300 mg KOH / g or less, and most preferably 230 mg KOH / g or less.Because the hydroxyl number (OH number) of the polycarbonate polyol with terminal hydroxyl groups falls within the aforementioned preferred numerical range, a polycarbonate polyol with terminal hydroxyl groups that exhibits low viscosity, is distinguished in handling properties and compatibility with inert organic solvents, tends to be easily obtained, and furthermore, the stress, tensile strength and chemical resistance of the polyurethane obtained tend to be higher by using such a polycarbonate polyol with terminal hydroxyl groups.

[0016] In the present embodiment, the method for controlling the hydroxyl number of the polycarbonate polyol with terminal hydroxyl groups within the above-mentioned range is not particularly limited; however, for example, a method for control by adding and / or removing alcohol compounds during the production of the polycarbonate polyol is mentioned.

[0017] The polycarbonate polyol with terminal hydroxyl groups can be used, for example, with a hydroxyl compound (e.g., a polyfunctional diol) and a carbonate compound (e.g., a carbonate ester) as raw materials, and can be synthesized, for example, by an ester exchange reaction, as described in "Polymer Reviews, Volume 9, pp. 9-20".

[0018] In the present embodiment, diols are cited as examples of hydroxyl compounds that can be used as raw materials for polycarbonate polyol with terminal hydroxyl groups. Specific examples of diols are not particularly limited; however, diols with a divalent aliphatic or alicyclic hydrocarbon skeleton with 3 to 15 carbon atoms are mentioned. A diol with 3 or more carbon atoms can tend to suppress the viscosity of the polycarbonate polyol composition, reduce the amount of inert organic solvent used, and improve the flexibility and low-temperature properties of the resulting artificial leather. A diol compound with 15 or fewer carbon atoms tends to result in excellent chemical resistance of the resulting artificial leather. Specific examples include, for example...Diols without side chains such as 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; Diols with side chains such as 2-methyl-1,8-octanediol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-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-cyclohexanedimethanol, 2-bis(4-hydroxycyclohexyl)propane, and 1,4-cyclohexanediol are listed, but are not specifically limited to these. One or more than two of these types can be used as raw materials for polycarbonate polyols with terminal hydroxyl groups.The combined use of one or more than two types of diols tends to reduce the regularity of the structural units in the resulting polycarbonate diol and decrease its crystallinity, thus making it easier to obtain a polycarbonate diol that is liquid at room temperature (25°C). This, in turn, tends to reduce the amount of inert organic solvent required.

[0019] From the perspective of increasing the chemical resistance and mechanical strength of the coating, it is more preferred to use one or more than two types of side-chain-free diols as raw materials for polycarbonate polyols with terminal hydroxyl groups. Specifically, one or more than two types of straight-chain diols 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 are preferred. Among these, two types of diols selected from the group consisting of 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are more preferred, and 1,5-pentanediol and 1,6-hexanediol are further preferred.

[0020] When two or more types of diols are used as raw materials in the production of terminal hydroxyl polycarbonate polyol, the ratio of these raw material diols is not particularly restricted. It is preferred to determine the ratio of the raw material diols used according to the circumstances, such that the resulting terminal hydroxyl polycarbonate polyol is liquid at room temperature. For example, when two types of diols are used as raw materials, it is preferred to determine the preparation quantity within the molar ratio of 20:80 to 80:20.Within this range, the crystallinity of the polycarbonate diol tends to decrease, resulting in a synthetic leather with high flexibility, good low-temperature properties, and a pleasant feel. Furthermore, the resulting polycarbonate polyol with terminal hydroxyl groups tends to have a liquid consistency, making it easier to reduce the amount of inert organic solvent used. When using two types of diols as raw materials, the molar ratio can be 30:70 or greater, 40:60 or greater, and 70:30 or less in preferred applications. The molar ratio can also be 60:40 or less, as it tends to be liquid even at 0°C or below.

[0021] Furthermore, within a range that does not unduly impair the performance of the polycarbonate polyol composition of the present embodiment, compounds with three or more hydroxyl groups per molecule, such as trimethyl olethane, trimethylolpropane, hexanetriol, and pentaerythritol, can also be used as raw materials for polycarbonate polyol with terminal hydroxyl groups. However, using too high a proportion of compounds with three or more hydroxyl groups per molecule as raw materials for the polycarbonate polyol can lead to crosslinking and gelation during the polymerization reaction of the polycarbonate polyol. Therefore, when using these compounds as raw materials, the proportion of the compound is preferably 0.1 to 5 mol%, and more preferably 0.1 to 1 mol%, based on the total number of moles of the raw material diol used as raw material for the polycarbonate polyol with terminal hydroxyl groups.

[0022] In the present embodiment, specific examples of carbonates that can be used as raw materials for polycarbonate polyols with terminal hydroxyl groups are not particularly limited; however, examples include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate; diaryl carbonates such as diphenyl carbonate; and alkylene carbonates such as ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 1,2-pentylene carbonate, etc. One or more than two of these can be used as raw materials for polycarbonate polyols with terminal hydroxyl groups. From the perspective of ease of procurement and the simplicity of defining the polymerization reaction conditions, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, dibutyl carbonate, and / or ethylene carbonate are preferred as raw material carbonates.

[0023] In the present embodiment, the synthesis of the polycarbonate polyol with terminal hydroxyl groups can be carried out using industrially known processes and is not particularly limited. It can, for example, be performed in the presence or absence of a catalyst. From the perspective of reaction efficiency, the synthesis is preferably carried out in the presence of a catalyst. Catalysts generally known in industry can be selected and are not particularly limited; for example, alkali metals such as lithium, sodium, and potassium; alcoholates of alkaline earth metals such as magnesium, calcium, strontium, and barium; hydrides, oxides, amides, carbonates, hydroxides, nitrogenous borates, as well as basic alkali metal salts of organic acids and alkaline earth metal salts are mentioned. Furthermore, the aforementioned catalyst is not particularly limited; 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 these metals are listed. These can be used individually or by appropriately selecting two or more types.

[0024] If one or more catalysts made of metals such as lithium, sodium, potassium, magnesium, calcium, titanium, zirconium, tin, lead, manganese and ytterbium, their metal salts, their metal alkoxides and the organic compounds with the metals are used, the polymerization of polycarbonate polyols proceeds favorably, and the influence on urethane reactions using the obtained polycarbonate polyols is also minimal, which is preferred.

[0025] It is more preferred 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; further preferred 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; and organic compounds containing titanium, tin, magnesium, calcium, lithium and / or manganese are particularly preferred.

[0026] The polycarbonate polyol composition of the present embodiment can contain a catalyst with the aforementioned metal elements. In the polycarbonate polyol composition of the present embodiment, the catalyst content, as measured by ICP (ICP-MS: Inductively Coupled Plasma Mass Spectrometry), is preferably 0.0001 to 0.050 wt%. When the catalyst content is within the aforementioned range, the polymerization of the polycarbonate polyol proceeds favorably, and the influence on urethane reactions using the polycarbonate polyol composition is also minimal. In a preferred aspect, the catalyst content, as measured by ICP, can be 0.0005 wt% or more and 0.020 wt% or less.

[0027] One aspect of the process for producing a polycarbonate polyol with terminal hydroxyl groups in the present embodiment is shown below. The production of the polycarbonate polyol with terminal hydroxyl groups is not particularly limited; however, for example, an ester exchange reaction can be carried out in two steps according to the following steps.

[0028] Specifically, a diol and a carbonate are mixed in a molar ratio (diol:carbonate) of, for example, 20:1 to 1:10, and the first-stage reaction is then carried out at 100 to 300°C under atmospheric pressure or reduced pressure, with or without an ester exchange catalyst. If, for example, dimethyl carbonate is used as the carbonate, the resulting methanol can be removed as a mixture with dimethyl carbonate to obtain a low molecular weight polycarbonate polyol. The alcohol obtained from the carbonate (carbonic acid ester) formed during the reaction is distilled off. If, for example, diethyl carbonate is used as the carbonate, the resulting ethanol can be removed as a mixture with diethyl carbonate to obtain a low molecular weight polycarbonate polyol. Furthermore, if, for example,Using ethylene carbonate as the carbonate, the resulting ethylene glycol, as a mixture with ethylene carbonate, can be removed to obtain a low molecular weight polycarbonate polyol. In the second stage, the reaction product from the first stage is then heated under reduced pressure at 160 to 300°C to remove unreacted diol and carbonate and to condense a low molecular weight polycarbonate polyol, thereby yielding a polycarbonate polyol with a predetermined molecular weight.

[0029] Furthermore, by adding a hydroxyl compound with a different framework to the resulting polycarbonate polyol with terminal hydroxyl groups, optionally with the addition of an ester exchange catalyst, and by reacting at 100 to 300°C under atmospheric pressure or reduced pressure, another different structure can be introduced. If required, low-boiling hydroxyl compounds are removed by heating under reduced pressure at 120 to 300°C, while simultaneously condensing low molecular weight polycarbonate polyols to obtain polycarbonate polyols with terminal hydroxyl groups exhibiting a predetermined molecular weight.

[0030] In the present embodiment, the melt viscosity at 50°C of the polycarbonate polyol with terminal hydroxyl groups is not particularly limited, but is preferably 500 to 200,000 mPa·s, more preferably 1,000 to 180,000 mPa·s, and further preferably 1,500 to 165,000 mPa·s. A melt viscosity at 50°C of 500 mPa·s or higher tends to increase the stress, tensile strength, and chemical resistance of the polyurethane obtained. A melt viscosity at 50°C of 180,000 mPa·s or less tends to improve the wettability (contact efficiency) of the resulting composition with the base material, thus facilitating the achievement of high adhesion strength. Furthermore, when used as a sealant raw material, the composition fills even fine details, thereby achieving high insulation reliability.

[0031] In the present embodiment, the method for controlling the melt viscosity at 50°C of the polycarbonate polyol with terminal hydroxyl groups within the aforementioned range is not particularly limited, but it does, for example, involve adjusting the number of carbon atoms in the diol or the number-average molecular weight. For example, adjusting the raw material type to reduce the number of carbon atoms in the diol tends to increase the melt viscosity of the polycarbonate polyol with terminal hydroxyl groups. Similarly, adjusting the manufacturing conditions to increase the number-average molecular weight tends to increase the melt viscosity of the polycarbonate polyol with terminal hydroxyl groups.

[0032] The method for measuring the melt viscosity in the present embodiment is not particularly limited; however, the viscosity can be measured, for example, using the following device: Rotational viscometer: Type E viscometer (manufactured by Toki Sangyo Co., Ltd, TVE-22HT, cone: No. 6)

[0033] The polycarbonate polyol of the present embodiment can contain a polycarbonate polyol composition and a polyol compound having an ester repeat structure and / or an ether repeat structure.

[0034] Polyester polyol, etc., is listed as a polyol compound with an ester repeat structure. The diols used as raw materials for polyester polyol are not particularly limited; however, for example,Diols without a side chain such as 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-dodecanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, and 1,15-pentadecanediol; Side chain diols such as 2-methyl-1,8-octanediol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-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-cyclohexanedimethanol, 2-bis(4-hydroxycyclohexyl)propane, and 1,4-cyclohexanediols are listed, but ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, and 3-methyl-1,5-pentanediol are preferred. One or more than two of these diols can be used as raw materials for polyester polyol.

[0035] The dicarboxylic acids used as raw materials for polyester polyol are not particularly limited; however, aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, cortic acid, azelaic acid, and sebacic acid are mentioned, as well as aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, and the like. Succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid are mentioned as particularly preferred. One or more than two of these dicarboxylic acids can be used as raw materials for polyester polyol.

[0036] Cyclic ester compounds can be used as raw materials for polyester polyol and subjected to ring-opening polymerization. The cyclic ester compounds are not particularly limited; however, certain types are used. Examples include 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, enantolactone (7-heptalidone), and other cyclic ester compounds with 3 to 12 carbon atoms, with ε-caprolactone being preferred. One or more than two types of cyclic ester compounds can be used as raw materials for polyester polyol.

[0037] Polyol compounds exhibiting ether repeat structures include polyether polyols, etc. While the list of polyether polyols is not particularly limited, examples include polypropylene glycol, polyethylene glycol, polytetramethylene glycol, and propylene oxide-ethylene oxide copolymers, etc.

[0038] In the polyol composition, the molar ratio of the carbonate repeat structure to the ester repeat structure and / or ether repeat structure is not particularly restricted, 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 further preferably in the range of 45:55 to 70:30. A molar ratio of 20:80 or higher tends to result in a polyol composition with a low melt viscosity and excellent handling properties. A molar ratio of 80:20 or less is desirable because it improves the resin properties, such as the chemical resistance of the polyurethane obtained from the polyol composition.

[0039] The molar ratio of each component of the carbonate repeat structure, ester repeat structure, and ether repeat structure can be determined based on the formula described later. 13 The integral ratio can be calculated from 13C NMR measurements and from the carbon-to-mole ratio of each structure. Furthermore, the polycarbonate polyol composition can be separated into each component as needed by liquid chromatography, etc., exploiting differences in molecular weight and polarity. In addition to the analytical methods described above, identification can be performed using NMR, IR, TOF-SIMS, etc., if required. <(A)-Component>

[0040] The polycarbonate polyol composition of the present embodiment contains a compound ((A) component) which is represented by the following formula (A): where R1 is hydrogen or an alkyl group with 1 to 12 carbon atoms and R2 is an alkynyl group with 1 to 12 carbon atoms.

[0041] Als konkrete Beispiele für (A)-Komponente werden z. B. 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, 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, 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, 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-Dodecan-1-ol, 7-Dodecan-1-ol, 8-Dodecan-1-ol, 9-Dodecan-1-ol, 10-Dodecan-1-ol, 11-Dodecan-1-ol usw.The following are listed, however, they are not particularly limited. These can be used individually or in combination with two or more types. If stereoisomers are present, either the cis or the trans form can be used. Among these, the (A) component, with regard to its effects on pot life and weather resistance, 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, and more preferably 4-hexen-1-ol and / or 5-hexen-1-ol. Since these can cause odors, it is preferred that they are present in low concentrations to suppress odor formation in the resulting polyurethane or synthetic leather.

[0042] The proportion of component (A) in the polycarbonate polyol composition is not particularly restricted; however, the total mass of component (A) relative to the total mass of the polycarbonate polyol composition is 0.01 ppm (0.000001 wt%) or more and 20 wt% or less. More preferably, the lower limit may 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 aspect, the upper limit may be 10 wt% or less, 5 wt% or less, 1 wt% or less, or 0.5 wt% or less. By having the values ​​within this preferred numerical range, the polycarbonate polyol tends to be less prone to discoloration during its manufacture, and discoloration upon heating to 150°C or more tends to be suppressed.Furthermore, the discoloration of the resulting polyurethane is suppressed, and its light stability is generally improved. The (A) component can be a byproduct formed during the synthesis of the polycarbonate polyol or a separately added component. <(B)-Component>

[0043] The polycarbonate polyol composition of the present embodiment includes a compound ((B)-component) which is represented by the following formula (B): where R3 is an alkylene group having 2 to 12 carbon atoms, which may have a straight-chain alkylene group, a divalent alicyclic hydrocarbon group or a branched alkylene group.

[0044] Specific examples of (B)-component include 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, 1,12-dodecanediol, etc., but these are not particularly limited. These can be used individually or in combination with other types. Among these, with regard to their effects on pot life and weather resistance, 1,5-pentanediol and / or 1,6-hexanediol are preferred, and 1,5-pentanediol and 1,6-hexanediol are more preferred.

[0045] The proportion of component (B) in the polycarbonate polyol composition is not particularly restricted; however, the total mass of component (B) relative to the total mass of the polycarbonate polyol composition is preferably 1 ppm (0.0001 wt%) or more and 40 wt% or less. In a preferred aspect, the lower limit may be 10 ppm (0.001 wt%) or more and 100 ppm (0.01 wt%) or more. In a preferred aspect, the upper limit may be 30 wt% or less, 20 wt% or less, or 10 wt% or less.Because the values ​​lie within this preferred numerical range, not only can the viscosity of the resulting polycarbonate polyol be kept within a favorable range, but the (B) component of the formula also acts as a chain extender and as a hard segment part in the reaction with isocyanate to form urethane, thereby improving the resin properties such as chemical resistance, which is preferred. The (B) component can be a byproduct formed in the synthesis of the polycarbonate polyol or a separately added component. <(B')-component>

[0046] The polycarbonate polyol composition of the present embodiment may further include a compound ((B')-component) which is represented by the following formula (B'): where R4 is an alkylene group with 1 to 4 carbon atoms.

[0047] Specific examples of the (B') component include methanol, ethanol, propanol, butanol, etc. These can be used individually or in combination with two or more types. Among these, methanol and / or ethanol are preferred as the (B') component with regard to their effects on pot life and weather resistance.

[0048] The proportion of the (B') component in the polycarbonate polyol composition is not particularly restricted; however, the total mass of the (B') component relative to the total mass of the polycarbonate polyol composition is preferably 0.1 ppm (0.00001 wt%) or more and 10 wt% or less. In a preferred aspect, the lower limit may be 1 ppm (0.0001 wt%) or more and 10 ppm (0.001 wt%) or more. In a preferred aspect, the upper limit may be 5 wt% or less, 3 wt% or less, and 1 wt% or less. By keeping the values ​​within this preferred numerical range, not only can the viscosity of the resulting polycarbonate polyol be maintained within a favorable range, but the (B') component also acts as a terminal inhibitor in the reaction with isocyanate to form urethane, suppressing gelation during urethane synthesis.The (B') component can be a by-product formed during the synthesis of the polycarbonate polyol, or a separately added component.

[0049] Furthermore, the mass ratio ((B') / (B)) of the (B') component to the (B) component is not particularly restricted, but preferably lies between 0.0001 and 1.000. Because the value lies within this preferred numerical range, not only can the viscosity of the resulting polycarbonate polyol be kept within a favorable range, but the (B') component also acts as a terminal inhibitor in the reaction with isocyanate to form urethane, suppressing gelation during urethane synthesis. <Massenverhältnis der (A)-Komponente zu (B)-Komponente>

[0050] The mass ratio ((A) / (B)) of the total amount of component (A) to the total amount of component (B) described above is preferably 0.0001 to 0.1000, more preferably 0.0005 to 0.0800, and more preferably 0.0010 to 0.0700. By keeping the mass ratio ((A) / (B)) within this preferred numerical range, the pot life of the urethane reaction is maintained within a suitable range, discoloration of the resulting polyurethane is suppressed, and its light stability is tended to be improved. <Angemessener Aspekt>

[0051] In one aspect, the polycarbonate polyol described above has terminal hydroxyl groups, preferably repeating units derived from 1,5-pentanediol and / or 1,6-hexanediol, and furthermore, the compound represented by formula (A) preferably contains one from the group consisting of a compound in which R1 in formula (A) is a hydrogen atom and R2 is an alkylene group with 4 or 3 carbon atoms, a compound in which R1 in formula (A) is a hydrogen atom and R2 is an alkylene group with 3 or 2 carbon atoms, and a compound in which R1 in formula (A) is an alkylene group with 2 carbon atoms and R2 is an alkylene group with 2 or 1 carbon atoms.

[0052] Furthermore, it is preferred that, in the compound represented by formula (A) and the compound represented by formula (B), the sum of the total number of carbon atoms of R1 and R2 is equal to the number of carbon atoms of R3. Specifically, it is preferred that the number obtained by adding two carbon atoms to the sum of the total number of carbon atoms of R1 and R2 in the compound represented by formula (A) is 5 or 6, and that this corresponds to the number of carbon atoms of R3 in the compound represented by formula (B). <Optimaler Aspekt>

[0053] Specific examples of the (A) component in the preferred aspect described above are preferred 4-penten-1-ol, 3-penten-1-ol, 4-hexen-1-ol, and / or 5-hexen-1-ol, and the raw materials forming the repeating units of the polycarbonate polyol preferably include 1,5-pentanediol and 1,6-hexanediol. Specific examples of the (B) component are preferably 1,5-pentanediol and 1,6-hexanediol. In this case, the mass ratio of the (A) component to the (B) component is preferably 0.0001 to 0.1000, more preferably 0.0001 to 0.0075, further preferably 0.0001 to 0.069, more preferably 0.0001 to 0.010, and particularly preferably 0.006 to 0.010.

[0054] The analytical methods for the above-described (A) and (B) components are not particularly restricted; however, from the perspective of analyzing trace components, gas chromatography (GC) or gas chromatography-mass spectrometry (GC / MS) are preferred. Sample dissolution for the above-mentioned analyses can be carried out by methods commonly used by those skilled in the art. For example, an injection sample can be analyzed by placing 2.0 g of the polycarbonate composition into a 20 mL volumetric flask, dissolving it by adding chloroform to the label, and then extracting 1 mL of this sample. <metallelementgehalt>

[0055] In one aspect, the content of at least one metal element in the polycarbonate polyol composition, selected from the group consisting of titanium, ytterbium, tin, zirconium, magnesium, calcium, lithium, sodium, and manganese, as measured by ICP, is preferably 0.0001 to 0.050 wt% and more preferably 0.0005 to 0.020 wt%, based on the total amount of the polycarbonate polyol composition, although this is not particularly limited. The content of titanium, ytterbium, tin, magnesium, calcium, lithium, and manganese in the polycarbonate polyol composition, as measured by ICP, is preferably 0.0001 to 0.050 wt% and more preferably 0.0005 to 0.020 wt%, based on the total amount of the polycarbonate polyol composition.

[0056] In a further embodiment, the polycarbonate polyol composition contains titanium, tin, magnesium, calcium, lithium and / or manganese, as measured by ICP, not particularly limited, but preferably amounts to 0.0001 to 0.050 wt%, based on the total amount of the polycarbonate polyol composition, and more preferably 0.0005 to 0.020 wt%.

[0057] In the present embodiment, the content of the metal element in the polycarbonate polyol composition can be measured by the method described in the following exemplary embodiments. <phosphorverbindung>

[0058] In the polycarbonate polyol composition of the present embodiment, it is preferred to treat the catalyst used in the production of the polycarbonate polyol with a phosphorus compound, for example, when it is used as a raw material for polyurethane. The phosphorus compound is not particularly limited; however, examples include: phosphorus triesters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, di-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, and cresyldiphenyl phosphate; acid phosphate esters such as methyl phosphate, ethyl phosphate, propyl phosphate, isopropyl phosphate, butyl phosphate, lauric phosphate, stearyl phosphate, 2-ethylhexyl phosphate, isodecyl phosphate, butoxyethyl phosphate, oleyl phosphate, tetracosyl phosphate, acylene glycol phosphate, 2-hydroxyethyl methacrylate phosphate, dibutyl phosphate, monobutyl phosphate, monoisodecyl phosphate, and bis(2-ethylhexyl) phosphate;Phosphite esters such as triphenyl phosphite, trisnonylphenyl phosphite, tricresyl phosphite, triethyl phosphite, tris(2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tris(tridecyl) phosphite, trioleyl phosphite, diphenyl mono(2-ethylhexyl) phosphite, Diphenyl monodecyl phosphite, diphenyl (monodecyl) phosphite, trilauryl phosphite, diethyl hydrogen phosphite, bis (2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyl dipropylene glycol diphosphite, Bis(decyl)pentaerythritol diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, and tris(2,4-di-tert-butylphenyl)phosphite; furthermore, phosphoric acid, hypophosphoric acid, hypophosphoric acid, etc., which are not particularly limited. These can be used individually or in combination with two or more types.

[0059] The polycarbonate polyol composition of the present embodiment may contain phosphorus compounds. The phosphorus compound content in the polycarbonate polyol composition of the present embodiment is not particularly limited; however, the phosphorus content (P), measured by ICP, is preferably 0.0001 to 0.050 wt%, based on the total amount of the polycarbonate polyol composition. Provided that the phosphorus compound content is within the aforementioned preferred numerical range, it is possible, for example, with the polycarbonate polyol composition of the present embodiment, which is used as a raw material for polyurethane, to minimize the influence of the catalyst used in the production of the polycarbonate polyol composition on the polyurethane production reaction, and furthermore to reduce the influence of the phosphorus compound on the polyurethane production reaction or the physical properties of the reaction product.In the aforementioned polycarbonate polyol composition, the phosphorus content (P), measured by ICP, is preferably 0.0005 to 0.020 wt%, based on the total amount of the polycarbonate polyol composition.

[0060] The polycarbonate polyol of the present embodiment can have a structural unit represented by the following formula (P), to the end of which is bonded a structural unit represented by the above formula (A), wherein R1 is any divalent aliphatic hydrocarbon group, R2 is hydrogen or any monovalent aliphatic hydrocarbon group and R3 is any divalent aliphatic hydrocarbon group, and these are synonymous with R1 to R3 in formula (A).

[0061] The polycarbonate polyol of the present embodiment can also have end groups other than a hydroxyl group. Such end groups other than a hydroxyl group are not particularly limited; however, examples include alkyl groups, vinyl groups, aryl groups, etc.

[0062] In the present embodiment, the amount of hydroxyl group in the end group can be measured using the method described below. Purity of the hydroxyl end group

[0063] The purity of the hydroxyl end group can be calculated using the following formula: [1] Purity of the hydroxyl end group = [[2]Amount of the terminal hydroxyl group of the polycarbonate polyol / [[3]Amount of the end group of the polycarbonate polyol] [2] Amount of terminal hydroxyl group of polycarbonate polyol = [[4]Total amount of hydroxyl group] − [[5]Amount of hydroxyl group in the remaining hydroxyl compounds] [4] Total amount of hydroxyl group: Amount of hydroxyl group calculated from the hydroxyl number (sum of the amount of terminal hydroxyl group of the polycarbonate polyol and the amount of hydroxyl group of the remaining hydroxyl compounds). [5] Amount of hydroxyl group of the remaining hydroxyl compounds: Total amount of hydroxyl group in each free hydroxyl compound, measured by b below. [3] Amount of the end group of the polycarbonate polyol = [[2]Amount of the terminal hydroxyl group of the polycarbonate polyol] + [[6]Amount of the monohydroxyl group in the framework of the polycarbonate polyol] [6] Amount of monohydroxyl group in the polycarbonate polyol framework = [[7]Total amount of monohydroxyl groups] − [[8]Amount of free monohydroxyl groups] [7]Total amount of monohydroxyl groups: Amount of hydroxyl groups of the total monohydroxyl compounds, measured by a below. [8]Amount of free monohydroxyl group: Amount of the hydroxyl group of the total free monohydroxyl compounds, measured by b below. <a. Analyse der gesamten Hydroxylverbindungen, die das Polycarbonatpolyol ausbilden >

[0064] The proportion of the structural unit in the polycarbonate polyol can be measured using the following method.

[0065] One gram of polycarbonate polyol is placed in a 100-mL round-bottom flask, 0.1 g of diethylene glycol diethyl ether is added as an internal standard, followed by 30 g of ethanol and 4 g of potassium hydroxide. Hydrolysis is carried out at 100°C for one hour. After cooling to room temperature, two to three drops of phenolphthalein are added to the round-bottom flask as an indicator and neutralized with hydrochloric acid. After cooling the round-bottom flask in a refrigerator for one hour, the precipitated salt is removed by filtration to obtain the composition analysis solution. The resulting composition analysis solution is analyzed by gas chromatography (GC) to determine the hydroxyl compound components present in the polycarbonate polyol.Regarding the concentration of each hydroxyl compound, a calibration curve can be created from each hydroxyl compound known as a standard substance, and the mass percentage can be calculated from the area ratio obtained by gas chromatography (GC). <b. Analyse der restlichen Hydroxylverbindungen im Polycarbonatpolyol>

[0066] 1 g of polycarbonate polyol and 0.1 g of diethylene glycol diethyl ether as an internal standard substance are dissolved in 10 g of acetone, and the content of remaining hydroxyl compounds is measured by GC analysis. <wassermenge>

[0067] In the polycarbonate polyol composition of the present embodiment, the amount of water is not particularly limited, but is preferably 10 to 500 ppm, based on the total amount of the polycarbonate polyol composition. The polycarbonate polyol composition of the present embodiment is preferred if the amount of water is 500 ppm or less, as this tends to reduce turbidity due to the reaction between water and isocyanate. Furthermore, the polycarbonate polyol composition of the present embodiment is preferred if the amount of water is 10 ppm or more, as this tends to suppress side reactions during urethanization and facilitates the production of urethane coatings with excellent resistance to yellowing. In the aforementioned polycarbonate polyol composition, it is more preferred if the amount of water is 15 to 200 ppm, based on the total amount of the polycarbonate polyol composition. <Sonstige Additive>

[0068] In the production of polyurethane using the polycarbonate polyol composition of the present embodiment, depending on the intended use, curing accelerators (catalysts), fillers, flame retardants, dyes, organic or inorganic pigments, mold release agents, flow modifiers, plasticizers, antioxidants, UV absorbers, light stabilizers, defoamers, leveling agents, dyes, blowing agents, etc., may be added.

[0069] Hardening accelerators are not particularly limited, however, amines and metal catalysts are mentioned, for example.

[0070] The types of catalysts that can accelerate the reaction of amines are not particularly limited; however, examples include triethylamine (a monoamine), N,N-dimethylcyclohexylamine and tetramethylethylenediamine (diamines), other triamines, cyclic amines, alcoholamines such as dimethylethanolamine, etheramines, etc. Similarly, the types of metal catalysts that can accelerate the reaction are not particularly limited; however, examples include potassium acetate, potassium 2-ethylhexanoate, calcium acetate, lead octanoate, dibutyltin dilaurate, tin octoate, bismuth neodecanoate, bismuth oxocarbonate, bismuth 2-ethylhexanoate, zinc octanoate, zinc neodecanoate, phosphine, phosphorine, etc.

[0071] The fillers and pigments are not particularly limited, but examples include fabrics, glass fibers, carbon fibers, polyamide fibers, mica, kaolin, bentonite, metal powders, azo pigments, soot, clay, silicon dioxide, talc, gypsum, aluminum oxide white, barium carbonate, calcium carbonate, etc.

[0072] The types of release agents, flow modifiers and leveling agents that can be used are not particularly limited, however, silicones, aerogels, waxes, stearates and polysiloxanes such as BYK-331 (manufactured by BYK Chemical KK) etc. are listed.

[0073] In the production of polyurethane using the polycarbonate polyol composition of the present embodiment, it is preferred to use antioxidants, light stabilizers, heat stabilizers and flame retardants as additives.

[0074] Antioxidants are not particularly restricted; however, for example, aliphatic, aromatic, or alkyl-substituted aromatic esters of phosphoric acid, phosphorous acid, and hypophosphoric acid derivatives; phosphorus compounds such as phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonates, dialkylpentaerythritol diphosphite, and dialkylbisphenol A diphosphite; phenol derivatives, especially hindered phenolic compounds; sulfur-containing compounds such as thioethers, dithioic acid salts, mercaptobenzimidazoles, thiocarbanilides, and thiodipropionic acid esters; and tin compounds such as tin marate and dibutyltin oxide can be used. These can be used individually or in combination with two or more types. <Inertes organisches Lösungsmittel>

[0075] The polycarbonate polyol composition of the present embodiment can optionally contain an inert organic solvent, which serves to adjust the handling properties during urethane production. The content of inert organic solvent is preferably 40% by weight or less, more preferably 3% by weight or more and 30% by weight or less, and further preferably 5% by weight or more and 20% by weight or less, based on the total amount of the polycarbonate polyol composition. The addition of an inert organic solvent is effective in reducing the viscosity of the polycarbonate polyol composition, improving the handling properties during the production of artificial leather, and also further improving the appearance of the resulting artificial leather.However, unless expensive solvent recovery systems are used, the solvents used in the process steps are released into the atmosphere after drying, which can lead to increased VOCs (volatile organic compounds). From the perspective of reducing environmental impact, it is preferable to minimize the content of inert organic solvents or, ideally, to use no solvents at all.

[0076] Inert organic solvents are not particularly restricted, provided they are organic solvents that are essentially inert towards polyisocyanates and preferably do not contain active hydrogen. Inert organic solvents are not particularly restricted; however, examples include hydrocarbons such as pentane, hexane, heptane, octane, decane, petroleum ether, petroleum gasoline, ligroin, petroleum spirit, cyclohexane, and methylcyclohexane; fluorine-based inert liquids such as trichlorofluoroethane, tetrachlorodifluoroethane, perfluoroethers, and other fluorinated oils; perfluorocyclohexane, perfluorobutyltetrahydrofuran, perfluorodecalin, perfluorobutylamine, perfluoropolyether, dimethylpolysiloxane, etc. These can be used individually or in mixtures.Other inert organic solvents include single or mixed solvents such as methyl ethyl ketone (also known as MEK), acetone, ethyl acetate, butyl acetate, toluene, xylene, dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide, diethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, tetrahydrofuran (THF), dioxane, etc.

[0077] In this description, "active hydrogen" refers to hydrogen atoms bonded to oxygen, sulfur, nitrogen, silicon atoms, etc., as well as hydrogen atoms in terminal methine groups. Furthermore, "active hydrogen" refers, for example, to hydrogen contained in atomic groups such as -OH group, -C(=O)OH group, -C(=O)H group, -SH group, -SO3H group, -SO2H group, -SOH group, -NH2 group, -NH group, -SiH group, and -C≡CH group.

[0078] The polycarbonate polyol composition of the present embodiment can be a curable composition, whereby a polyurethane can be formed by curing. The polyurethane obtained by this reaction can be used as artificial leather. The term "artificial leather" in this description includes both artificial leather that uses knitted or woven fabrics as the base fabric and artificial leather that uses nonwoven fabrics as the base fabric. Isocyanates can be used as curing agents during the curing process, as required. Such isocyanates are not particularly limited; however, for example,Aromatic diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and mixtures thereof, diphenylmethane 4,4'-diisocyanate (MDI), naphthalene 1,5-diisocyanate (NDI), 3,3'-dimethyl 4,4'-biphenylene diisocyanate (TODI), and polymethylene polyphenylene polyisocyanate (PMDI); aromatic aliphatic diisocyanates such as xylylene diisocyanate (XDI) and phenylene diisocyanate; and aliphatic diisocyanates such as 4,4'-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and cyclohexanedicarboisocyanate (hydrogenated XDI), etc., can be listed. Furthermore, polyisocyanates having an average of 2,1, or more isocyanate groups per molecule can be used.Polyisocyanates, which have an average of 2, 1, or more isocyanate groups per molecule, can include aromatic polyisocyanates such as crude MDI and crude TDI; derivatives of aliphatic isocyanates such as HDI and IPDI; specifically, diisocyanate derivatives such as biuret, allophanate, uretdione, and isocyanurates; and polyhydric alcohol adducts. Furthermore, commercially available isocyanates include, for example, Sumidur 44S and 44V70 (both manufactured by Sumika Bayer Urethane Co., Ltd.), Desmodur HL (manufactured by Sumika Bayer Urethane Co., Ltd.), which is a copolymer of TDI and HDI, and various Duranate products manufactured by Asahi Kasei Co.Duranate 24A-100, Duranate 22A-75PX, Duranate 18H-70B, Duranate 21S-75E, Duranate THA-100, Duranate TPA-100, Duranate TKA-100 Duranate TLA-100, Duranate TUL-100, Duranate MFA-75X, Duranate TSA-100, Duranate TSS-100, Duranate TSE-100, Duranate D-101, Duranate D-201, Duranate P-301-75E, Duranate E-402-90T, Duranate E-402-90T, Duranate E-405-80T, Duranate ME20-100, Duranate 17B-60PX, Duranate TPA-B80X, Duranate MF-B60X, Duranate E-402-B80T, Duranate ME20-B80S, Duranate WB40-100, Duranate WB40-80D, Duranate WT20-100, Duranate WT30-100 etc. available. <Verfahren zur Herstellung von Polycarbonatpolyolzusammensetzung>

[0079] The polycarbonate polyol composition of the present embodiment can be produced by generally industrially used manufacturing processes.

[0080] The polycarbonate polyol composition of the present embodiment can be produced, for example, by a process (hereinafter referred to as the "one-shot process") in which a polycarbonate polyol with terminal hydroxyl groups and, if required, an inert organic solvent and additives are mixed together and reacted. Furthermore, the polycarbonate polyol composition of the present embodiment can be produced, for example, by...by a process (hereinafter referred to as the "prepolymerization process") in which an isocyanate-terminated prepolymer derived from a polycarbonate polyol with terminal hydroxyl groups, or a hydroxyl-terminated prepolymer derived from a polycarbonate polyol with terminal hydroxyl groups, is prepared in advance, and these prepolymers are then mixed and reacted with isocyanates and / or polyols and, if required, with an inert organic solvent and additives. One or more types of prepolymers may be used. <Verfahren zur Herstellung von Kunstleder>

[0081] Artificial leather can be produced by applying the process for producing polyurethane using the polycarbonate polyol composition of the present embodiment. Processes for producing artificial leather using the polycarbonate polyol composition of the present embodiment are not particularly limited; however, examples include: a wet process in which the polyurethane produced using the polycarbonate polyol composition of the present embodiment is applied to or impregnated onto a base material (base fabric) and wet-cured; or a dry process in which the polyurethane produced using the polycarbonate polyol composition of the present embodiment is applied to release paper or a base material (base fabric) and dried.Furthermore, a transfer coating process (a type of dry process) can be used as a method for producing artificial leather, in which the polyurethane produced using the polycarbonate polyol composition of the present embodiment is applied to form a surface material, and then the polyurethane produced using the polycarbonate polyol composition of the present embodiment is used as an adhesive layer, and after bonding to a base material (base fabric), the release paper is removed. That is, the composition of the present embodiment can be used for the adhesive layer of artificial leather. The dry process (transfer coating process) is appropriately used for the polycarbonate polyol composition of the present embodiment because it allows for a reduced use of inert organic solvents.

[0082] It follows from the above that a preferred aspect of the polycarbonate polyol composition of the present embodiment may be an adhesive composition. Furthermore, a preferred aspect of the polycarbonate polyol composition of the present embodiment may be a water-based polyurethane. In addition, a preferred aspect of the polycarbonate polyol composition of the present embodiment may be a water dispersion composition.

[0083] Using the dry process as an example, the following explains the process for manufacturing polyurethane for artificial leather and synthetic leather. Various base materials (base fabrics) can be used without particular restrictions; however, fibrous base materials are specifically mentioned. Fibrous base materials are not particularly limited; however, examples include fibrous aggregates formed by forming fibers into nonwovens, woven fabrics, mesh fabrics, polished pile fabrics, etc., or fibrous aggregates in which the individual fibers are bonded together by an elastic polymer. The fibers used in this fiber aggregate are not particularly limited; however, examples include natural fibers such as cotton, hemp, and wool; regenerated or semi-synthetic fibers such as rayon and acetate; and synthetic fibers such as polyamide, polyester, polyacrylonitrile, polyvinyl alcohol, and polyolefin.These fibers can be either plain spun or mixed spun fibers. Other base materials are not particularly limited; however, examples include paper, release paper, plastic films such as polyester or polyolefin, metal sheets such as aluminum, glass plates, etc.

[0084] The polycarbonate polyol composition of the present embodiment can be applied as an adhesive composition, artificial leather composition, or polyurethane for artificial leather by commonly used methods. The application methods are not particularly limited; however, examples include flow-knife coating machines, knife-roll coating machines, reverse-roll coating machines, roller doctor coating machines, gravure roller coating machines, and kiss-roll coating machines. <kunstleder>

[0085] The resulting artificial leather can be used as is. Alternatively, this artificial leather can be obtained in a form in which polymer solutions or emulsions, such as polyurethane resin, vinyl chloride, or cellulose-based resins, are applied to the artificial leather to impart various properties. Furthermore, the artificial leather can be obtained as a laminate by peeling off a release liner after bonding it to a coating obtained by drying the polymer solution or emulsion previously applied separately to the release liner. The artificial leather obtained using the polycarbonate polyol composition of the present embodiment exhibits excellent handling properties, a pleasing appearance, and excellent weather resistance.Furthermore, in a more advantageous aspect, it is possible to obtain a material with low odor and an excellent balance of physical properties, including chemical resistance.

[0086] The present embodiment will now be explained with reference to the drawings. The drawings and manufacturing conditions described below represent one form of the present embodiment and do not limit its scope.

[0087] Fig. Figure 1 is a schematic sectional view of an artificial leather laminate, produced according to the instructions in Fig. The laminate was produced using the dry process shown in section 2. The structure of this laminate comprises a surface layer 2 over an adhesive layer 3 on a base material (polyester fabric) 4. A release paper 1 used in the manufacturing process adheres to the top layer but is peeled off and removed during use.

[0088] Fig. Figure 2 shows a schematic view illustrating an example of a manufacturing process for dry artificial leather laminate film using polyurethane, produced using the polycarbonate polyol composition of the present embodiment. In this manufacturing process, the polycarbonate polyol composition (for the surface layer), obtained by mixing the respective raw materials of the polycarbonate polyol composition of the present embodiment, prepared at a predetermined temperature, using a mixing head 5, is first allowed to flow onto the release paper 1 (usually with a leather-like structure).

[0089] When using the single-shot process, the polycarbonate polyol composition of the present embodiment and, if required, an inert organic solvent and additives are fed either separately or together continuously into the mixing head 5, mixed, and then allowed to flow onto the release paper 1. The polyol component can be of a single type, or two or more types can be used simultaneously.

[0090] In the application of the prepolymerization process, an isocyanate-terminated prepolymer derived from the polycarbonate polyol composition of the present embodiment and polyols, or a hydroxyl group-terminated prepolymer derived from the polycarbonate polyol composition of the present embodiment and isocyanates, is continuously fed into the mixing head 5 as a mixture of an inert organic solvent and additives and mixed as required in order to flow onto the release paper 1.

[0091] The temperature of each component prior to mixing is typically set to 20 to 80°C, preferably 30 to 70°C, and more preferably 40 to 60°C. Furthermore, the temperature of the mixing head 5 is typically set to 20°C to 80°C, preferably 30°C to 70°C, and even more preferably 40°C to 60°C. By maintaining the temperature of each component prior to mixing and the temperature of the mixing head 5 at 20°C or higher, the viscosity of the raw materials used is tended to be suppressed and the flow rate stabilized.Furthermore, by maintaining the temperature of each component before mixing and the temperature of the mixing head 5 at 80°C or lower, the curing rate of the polycarbonate polyol composition of the present embodiment is appropriately controlled; this tends to suppress a sudden increase in the viscosity of the polycarbonate polyol composition and enables a uniform thickness of the artificial leather to be achieved.

[0092] The mixture is then formed into a film of uniform thickness using a coating roller 8 and subsequently passed through a dryer 11 to cure the mixture and dry the inert organic solvent, thereby forming the surface layer 2 of the artificial leather. The drying temperature is typically set to 60 to 150°C, preferably 70 to 130°C, and more preferably 80 to 110°C. The drying time is typically 2 to 15 minutes, preferably 3 to 10 minutes, and more preferably 4 to 7 minutes.

[0093] Next, the polycarbonate polyol composition of the present embodiment, obtained by mixing the respective raw materials of the polycarbonate polyol composition of the present embodiment, which has been pre-heated to a predetermined temperature, is allowed to flow using a mixing head 6 (for the adhesive layer) to form the adhesive layer 3. When applying the single-shot method for producing the adhesive layer, the polycarbonate polyol composition of the present embodiment and, if required, an inert organic solvent and additives are fed separately or simultaneously and continuously into the mixing head 6, mixed, and allowed to flow onto the surface layer.When using the prepolymerization process to produce the adhesive layer, the prepolymer composition and non-prepolymerized polyols, as required together with an inert organic solvent and additives, are fed separately or simultaneously continuously into the mixing head 6, mixed and allowed to flow onto the surface layer.

[0094] Each component is typically pre-mixed to a temperature of 20 to 60°C, preferably 30 to 50°C, and more preferably 35 to 45°C. The temperature of the mixing head 6 is also typically pre-mixed to 20 to 60°C, preferably 30 to 50°C, and more preferably 35 to 45°C. Maintaining the pre-mixing temperature of each component and the temperature of the mixing head 6 at 20°C or higher tends to suppress the viscosity of the raw materials used and stabilize the flow rate.Furthermore, by maintaining the temperature of each component before mixing and the temperature of the mixing head 6 at 60°C or lower, the curing rate of the polycarbonate polyol composition of the present embodiment is appropriately controlled; this tends to suppress a sudden increase in the viscosity of the polycarbonate polyol composition and enables a uniform thickness of the artificial leather to be achieved.

[0095] The mixture is then formed into a film of uniform thickness using the coating roller 8 and subsequently passed through the dryer 11 to cure the mixture and dry the inert organic solvent, thereby forming the adhesive layer 3 of the artificial leather. Next, the base material 4 and the adhesive layer 3 are layered on top of each other and pressed together with a pressure roller 9, resulting in a film structure 7. This film is then wound onto a winding roller 10 to obtain the desired artificial leather laminate. The temperature of the dryer 11 is typically set to 50 to 110°C, preferably 60 to 100°C, and more preferably 70 to 90°C. The drying time is typically 2 to 15 minutes, preferably 3 to 10 minutes, and more preferably 4 to 7 minutes.

[0096] Fig. Figure 2 shows an example of the production of artificial leather consisting of three layers: surface layer, adhesive layer, and base material. However, an artificial leather laminate consisting of two layers—surface layer and base material—where the adhesive layer is omitted, can be produced using the same equipment. The adhesion between the surface layer and the base material is controlled by adjusting the curing state of the polycarbonate polyol composition. Specifically, this can be achieved by pressing the polycarbonate polyol composition and the base material together while the polycarbonate polyol composition of the present embodiment is not yet fully cured. Therefore, the curing temperature of the dryer 11 is set to 50 to 110°C, preferably 60 to 100°C, and more preferably 70 to 90°C.The drying time is usually set at 2 to 15 minutes, preferably 3 to 10 minutes and more preferably 4 to 7 minutes.

[0097] It is also possible to apply a surface treatment agent to the surface layer, to form an artificial leather laminate comprising four layers: surface treatment agent / surface layer / adhesive layer / base material, or an artificial leather laminate comprising three layers: surface treatment agent / surface layer / base material. <anwendungen>

[0098] Artificial leather produced with polyurethane / urethane-cured products manufactured using the polycarbonate polyol composition of the present embodiment can be used for vehicle interior trim such as car seats, furniture like sofas, clothing, shoes, bags, and various other goods, and is particularly suitable for use as artificial leather (polyurethane for artificial leather) for vehicle interior trim. Furthermore, the polyurethane produced using the polycarbonate polyol composition of the present embodiment can also be used in adhesive compositions, laminating adhesives for various films, and surface protectants.Furthermore, the water-based polyurethane / water dispersion composition produced with the polycarbonate polyol composition of the present embodiment can be used not only as the artificial leather described above, but also as various materials, such as paints and coating agents. [Process for the production of water-based polyurethane]

[0099] The process for producing the water-based polyurethane of the present embodiment is not particularly restricted and can use generally known methods. For example, it can be produced by carrying out a step (prepolymer step) to produce a urethane prepolymer having isocyanate groups at its ends by reacting a polyol, a polyisocyanate and a compound containing hydrophilic groups, and a step (chain extension step) to react the urethane prepolymer with a chain extender. (Polyol)

[0100] The polycarbonate polyol of the present embodiment can be used in the production of water-based polyurethanes. In addition to the polycarbonate polyol of the present embodiment, polyester polyol, acrylic polyol, polyether polyol, polyolefin polyol, fluorinated polyol, etc., can be used individually or in combination with two or more types, although this is not limited.

[0101] Among other things, from the point of view of the flexibility and durability of a urethane-cured product obtained using aqueous composition including aqueous polyurethanes, polyester polyols, polyether polyols and fluorinated polyethers can be preferably used in addition to the polycarbonate polyol of the present embodiment, wherein a combination of the polycarbonate polyol, the polyester polyol and the polyether polyol of the present embodiment is preferred, and a combination of the polycarbonate polyol and the polyester polyol of the present embodiment is more preferred. (Polyisocyanate)

[0102] Polyisocyanates used in the production of water-based polyurethanes are not particularly limited; however, aromatic polyisocyanates such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimidated diphenylmethane polyisocyanate, etc., as well as polyisocyanates with aliphatic or alicyclic structures such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylene diisocyanate, tetramethylxylene diisocyanate, dimeric acid diisocyanate, norbornene diisocyanate, etc., are listed. These can be used individually or in combination of two or more types.

[0103] From the point of view of the durability of a urethane-cured product obtained using aqueous composition including aqueous polyurethanes, the use of polyisocyanates with an alicyclic structure is preferred, and the use of isophorone diisocyanate or dicyclohexylmethane diisocyanate is more preferred. (Compounds containing hydrophilic groups)

[0104] The isocyanate compounds used in the production of aqueous polyurethanes are not limited to the following; however, polyols with carboxyl groups such as 2,2'-dimethylolpropionic acid, 2,2'-dimethylolbutanoic acid, 2,2'-dimethylolbutyric acid, and 2,2'-dimethylolvaleric acid, as well as polyols with sulfonic acid groups such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5-[4-sulfophenoxy]isophthalic acid, are listed. These can be used individually or in combination of two or more types. (Chain extender)

[0105] Chain extenders used in the manufacture of aqueous polyurethanes are not limited to the following, however, diamines such as ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, and 1,4-cyclohexanediamine; diamines possessing a primary and a secondary amino group, such as N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, and N-methylaminopropylamine; polyamines such as diethylenetriamine, dipropylenetriamine, and triethylenetetramine; Hydrazines such as hydrazine, N,N'-dimethylhydrazine, and 1,6-hexamethylenebishydrazine; dihydrazides such as succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, and isophthalic acid dihydrazide;and semicarbazides such as β-semicarbazide propionic acid hydrazide, 3-semicarbazide propylcarbazide acid esters, and semicarbazide-3-semicarbazidomethyl-3,5,5-trimethylcyclohexane, etc. These can be used individually or in combination with two or more types. (Organic solvents)

[0106] Organic solvents can be used in the prepolymerization step of water-based polyurethane production, as needed. Examples of organic solvents that can be used in this prepolymerization step include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetate esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; and amides such as dimethylformamide and N-methylpyrrolidone. These can be used individually or in combination. [(C) component: hardening agent]

[0107] The aqueous composition of the present embodiment may contain a curing agent (C component) in addition to the above-mentioned water-dispersible polyol (A component) and aqueous polyurethane (B component).

[0108] The curing agent (C component) is not particularly restricted, provided it has reactive groups that can react with the hydroxyl groups of the water-dispersible polyol (A component) and / or the end groups and / or hydrophilic groups of the water-based polyurethane (B component), and it is preferred to use a compound having two or more such reactive groups.

[0109] Examples of compounds possessing such reactive groups include isocyanate compounds, carbodiimide compounds, and aziridine compounds, but this list is not limited to these. Isocyanate compounds are particularly favored among these.

[0110] The isocyanate compounds can be commercially available or synthesized using generally known methods.

[0111] Commercially available isocyanate compounds may be identical to those mentioned above, so a duplicate explanation is omitted here. (NCO / OH ratio)

[0112] When isocyanate is used as a curing agent, with regard to the content of the isocyanate compound in the aqueous composition, the ratio (mole count of the NCO group / mole count of the OH group) between the mole count of the hydroxyl group (OH group) contained in the (A) component, the mole count of the hydroxyl group (OH group) contained in the (B) component and the mole count of the isocyanate group (NCO group) contained in the (C) component is in the range of 0.2 to 7.0, preferably in the range of 0.5 to 5.0, more preferably in the range of 0.8 to 3.0, particularly preferably in the range of 0.8 to 2.5 and most preferably in the range of 0.8 to 2.0.

[0113] From the point of view of the durability of the urethane-cured product, it is preferred that the curing agent has a cyclic structure, and more preferably that it has an isocyanurate ring. [Hardenable composition]

[0114] The curable composition of the present embodiment contains the aqueous composition described above. The curable composition of the present embodiment can be prepared from the polycarbonate polyol of the present embodiment. Examples of curable compositions include paints, polyurethanes, and coatings containing the aqueous composition described above. The curable composition of the present embodiment is characterized by the inclusion of the aqueous composition described above, which tends to shorten the drying time, reduce the dilution of the cured product, increase flexibility, and provide high durability.

[0115] The curable composition of the present embodiment may contain further components in addition to the aqueous composition described above. Such other components are not particularly limited; however, examples include water-dispersible polyols such as polyhydric alcohol compounds, water-dispersible polyester polyols, acrylic polyol emulsions, water-dispersible polyether polyols, water-dispersible polyolefin polyols, and water-dispersible fluorinated polyols.

[0116] Furthermore, the curable composition of the present embodiment can additionally contain, for example, curing accelerators (catalysts), matting agents, anti-sedimenting agents, leveling agents, fillers, dispersants, flame retardants, dyes, organic or inorganic pigments, mold release agents, flow modifiers, plasticizers, antioxidants, UV absorbers, light stabilizers, defoamers, dyes, solvents, and other additives, depending on the various applications. By appropriately omitting these other additives, curable compositions with different properties, such as paint with a soft feel and clear paint, can be obtained. [Urethane-cured product]

[0117] The urethane-cured product of the present embodiment is obtained by curing the polycarbonate polyol and / or the curable composition of the present embodiment. Examples of urethane-cured products include urethane coatings, urethane films, and urethane resins. The urethane-cured products of the present embodiment, obtained from the polycarbonate polyol and / or the curable composition of the present embodiment, tend to be characterized by flexibility and high durability.

[0118] Furthermore, the present disclosure also provides a method for suppressing the odor of a polycarbonate polyol composition. That is, a method for suppressing the odor of a polycarbonate polyol composition, wherein the polycarbonate polyol composition comprises: a polycarbonate polyol with terminal hydroxyl groups, an (A) component: a compound represented by the following formula (A), and a (B) component: a compound represented by the following formula (B), wherein the mass ratio ((A) / (B)) of the (A) component to the (B) component is 0.0001 to 0.1000.

[0119] Furthermore, the present disclosure also provides a method for suppressing the odor of a urethane-cured product. That is, a method for suppressing the odor of a urethane-cured product comprising: selecting a polycarbonate polyol composition containing: a polycarbonate polyol with terminal hydroxyl groups, an (A) component: a compound represented by the following formula (A), and a (B) component: a compound represented by the following formula (B), wherein the mass ratio ((A) / (B)) of the (A) component to the (B) component is 0.0001 to 0.1000, and curing the polycarbonate polyol composition to produce a urethane-cured product.

[0120] Furthermore, the present disclosure also provides a process for preparing a polycarbonate polyol composition. That is, a process for preparing a polycarbonate polyol composition, wherein the polycarbonate polyol composition comprises: a polycarbonate polyol with terminal hydroxyl groups, an (A) component: a compound represented by the following formula (A), and a (B) component: a compound represented by the following formula (B), wherein the mass ratio ((A) / (B)) of the (A) component to the (B) component is adjusted to a range of 0.0001 to 0.1000.

[0121] Furthermore, the present disclosure also provides a method for producing a urethane-cured product. That is, a method for producing a urethane-cured product, comprising: selecting a polycarbonate polyol composition comprising: a polycarbonate polyol with terminal hydroxyl groups, an (A) component: a compound represented by the following formula (A), and a (B) component: a compound represented by the following formula (B), wherein the mass ratio ((A) / (B)) of the (A) component to the (B) component is 0.0001 to 0.1000, and curing the polycarbonate polyol composition.

[0122] Furthermore, the present disclosure also provides a method for producing artificial leather. That is, a method for producing artificial leather, comprising: a step for arranging an adhesive layer, an intermediate layer, and a surface layer on a base material in the specified order, wherein one of the surface layer, the intermediate layer, and the adhesive layer is a urethane-cured product of a polycarbonate polyol composition, and wherein the polycarbonate polyol composition comprises: a polycarbonate polyol with terminal hydroxyl groups, an (A) component: a compound represented by the following formula (A), and a (B) component: a compound represented by the following formula (B), wherein the mass ratio ((A) / (B)) of the (A) component to the (B) component is 0.0001 to 0.1000.

[0123] Furthermore, the present disclosure also provides a method for suppressing the odor of an artificial leather. That is, a method for suppressing the odor of an artificial leather, comprising: selecting a polycarbonate polyol composition comprising: a polycarbonate polyol with terminal hydroxyl groups, an (A) component: a compound represented by the following formula (A), and a (B) component: a compound represented by the following formula (B), wherein the mass ratio ((A) / (B)) of the (A) component to the (B) component is 0.0001 to 0.1000, and using a urethane-cured product of the polycarbonate polyol composition in at least one of the adhesive layer, the intermediate layer, and the surface layer. [Examples of implementation]

[0124] The present invention is explained in more detail below with reference to exemplary embodiments and comparative examples; however, the invention is not limited to these exemplary embodiments, provided that the core of the invention is not exceeded. In the following exemplary embodiments and comparative examples, the methods for analyzing and evaluating the physical properties of the individual components are as follows. With regard to the analytical peripherals, devices with the same performance can be used. [Analysis and evaluation of polycarbonate polyol composition]

[0125] The formulated composition of the polycarbonate polyol composition is shown in Table 1 and Table 2. <Hydroxylzahl von Polycarbonatpolyolzusammensetzung>

[0126] The measurement was performed according to JIS K1557-1. The numerical mean value of the molecular weight of the polycarbonate polyol composition was also calculated from the obtained hydroxyl number. <Analyse der in der Polycarbonatpolyolzusammensetzung enthaltenen Komponenten (ICP)>

[0127] The components contained in the polycarbonate polyol composition were analyzed as follows. First, the sample was weighed into a Teflon (registered trademark) decomposition vessel, high-purity nitric acid (manufactured by KANTO CHEMICAL CO., INC.) was added, and decomposition was carried out using a microwave decomposition apparatus (manufactured by Milestone General KK, ETHOS TC). The sample decomposed completely, yielding a colorless, transparent decomposition liquid. Pure water was added to the decomposition liquid to obtain the test solution. An inductively coupled plasma analyzer (manufactured by Thermo Fisher Scientific Inc., iCAP 6300 Duo) was used to analyze the obtained test solution, with quantification performed based on standard solutions for each element. <Analyse der (A)-Komponente und (B)-Komponente in der Polycarbonatpolyolzusammensetzung>

[0128] The analysis was performed using gas chromatography (GC). A GC-2014 gas chromatograph (manufactured by Shimadzu Corporation, Japan) equipped with a DB HeavyWAX column (manufactured by J&W, USA) was used for the GC analysis. Calibration curves were generated using the absolute calibration curve method with standards. A flame ionization detector (FID) was used as the detector, and a quantitative analysis of each component was performed. The column temperature rise profile included a holding time of 1 minute at 40°C, followed by a temperature increase at 10°C / min to 280°C, where the temperature was held for 10 minutes.

[0129] The following reagents were used as standards for creating the calibration curve.

[0130] 5-Hexen-1-ol: manufactured by Tokyo Chemical Industry Co., Ltd.

[0131] 4-Hexen-1-ol (cis-isomer): manufactured by Tokyo Chemical Industry Co., Ltd.

[0132] 4-Penten-1-ol: manufactured by Tokyo Chemical Industry Co., Ltd.

[0133] Ethylene glycol: manufactured by Tokyo Chemical Industry Co., Ltd.

[0134] 1,4-Butanediol: manufactured by Tokyo Chemical Industry Co., Ltd.

[0135] 1,5-Pentanediol: manufactured by Tokyo Chemical Industry Co., Ltd.

[0136] 1,6-Hexanediol: manufactured by Tokyo Chemical Industry Co., Ltd.

[0137] 2-Methyl-1,3-propanediol: manufactured by Tokyo Chemical Industry Co., Ltd.

[0138] 3-Methyl-1,5-pentanediol: manufactured by Tokyo Chemical Industry Co., Ltd. <Bestätigung der Eigenschaften der Polycarbonatpolyolzusammensetzung>

[0139] Polycarbonate polyol compositions heated to 60°C were placed in transparent sample vials, and the state after cooling to room temperature (23°C) was visually observed. Transparent samples that showed even slight flowability when the vial was tilted were classified as "liquid," and samples that were opaque, showed no change in state when the vial was tilted, or met both conditions, were classified as "solid." <Zusammensetzung (Copolymerisationsverhältnis) der Polycarbonatpolyolzusammensetzung>

[0140] One gram of the polycarbonate polyol composition was weighed into a 100-mL round-bottom flask, 30 g of ethanol and 4 g of potassium hydroxide were added, and the mixture was reacted at 100°C for one hour. After cooling the reaction solution to room temperature, two to three drops of phenolphthalein were added as an indicator, and the mixture was neutralized with hydrochloric acid. After cooling in a refrigerator for one hour, the precipitated salt was removed by filtration and analyzed by gas chromatography (GC). GC analysis was performed using a GC-2014 gas chromatograph (manufactured by Shimadzu Corporation, Japan) equipped with a DB-WAX column (manufactured by J&W, USA), using diethylene glycol diethyl ether as the internal standard and a flame ionization detector (FID) as the detector to quantitatively analyze each component.The temperature rise profile of the column included a 5-minute holding time at 60°C, followed by a temperature increase of 10°C / min to 250°C.

[0141] From the molar ratios of each detected alcohol component from the above-mentioned analysis results, the composition (copolymerization ratio) of the polycarbonate polyol composition was determined in each case. <Carbonat-Wiederholungsstruktur: Gesamtmolverhältnis von Ester-Wiederholungsstruktur und Ether-Wiederholungsstruktur>

[0142] The carbonate repeat structure, the ester repeat structure, and the ether repeat structure were determined using 1 H-NMR and 13 ¹³C NMR was identified. The NMR measurements were performed using the following devices. 13 For the carbonate repeat structure, a peak at approximately 150–155 ppm (-OC=OO-, a specific peak for one carbon element originating from the carbonate group within the repeat unit), for the ester repeat structure, a peak at approximately 170–175 ppm (-C=OO-, a specific peak for two carbon elements originating from the ester group within the repeat unit), for the ether repeat structure, a peak at approximately 70 ppm, and for polytetramethylene glycol, a peak at approximately 70–77 ppm (-COC-, a specific peak for two carbon elements originating from the ether within the repeat unit) were used to calculate the molar ratio of the repeat units from the ratio of their signal intensities. If two or more carbon elements corresponded to a particular peak, the signal intensity was divided by the number of carbon elements to calculate the molar ratio of the repeat units.The device and measurement conditions were implemented according to the following specifications. 1 H-NMR

[0143] Device: “JEOL-ECZ500(SC)” (trade name), manufactured by JEOL Ltd.

[0144] Solvent: deuterated chloroform (containing 1 vol% tetramethylsilane) Number of additions: 120 Sample concentration: 10 wt. / vol.% Chemical shift reference: Tetramethylsilane set to 0.0 ppm. 13 C-NMR

[0145] Device: “JEOL-ECZ500(SC)” (trade name), manufactured by JEOL Ltd.

[0146] Solvent: deuterated chloroform (containing 1 vol% tetramethylsilane) Number of additions: 5120 Sample concentration: 30 wt. / vol.% Chemical shift reference: Dichloromethane set to 77.0 ppm. <Durchschnittliche Anzahl der funktionellen Gruppen der Polycarbonatpolyolzusammensetzung>

[0147] The average number of functional groups of the polycarbonate polyol composition synthesized exclusively using diol monomers as raw material was set at 2. When the raw materials contained polyfunctional monomers, the average number of functional groups was determined as follows. The number-mean molecular weight (Mn) of the polycarbonate polyol composition was determined by gel permeation chromatography (GPC) (see below for GPC apparatus and analytical conditions), with a calibration curve established using standard polystyrene of known molecular weight. The average number of functional groups per molecule (n) was calculated using formula (5), based on the separately analyzed hydroxyl number and the number-mean molecular weight (Mn) determined by GPC.

[0148] Average number of functional groups (n)=[Mn]×([OH−Number]×10−3 / 56,1) (GPC equipment and analysis conditions)

[0149] GPC device: HLC-8320, manufactured by Tosoh Corporation Column: TSKgel G4000H 1 piece G3000H 1 piece G2000H 2 pieces Eluant: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Column temperature: 40°C RI detector: RI (integrated in HLC-8320 device) <Messung der Topfzeit bei Urethanreaktion>

[0150] 60 g of the polycarbonate polyol composition synthesized in the exemplary embodiment and the comparative example were placed in a 200 ml wide-mouth glass bottle in each case. After sufficient nitrogen replacement, the bottle was heated in an oil bath set at 60°C. MDI was then added to achieve an NCO / OH ratio of 1.1. The viscosity increase behavior was checked using a torque-driven stirrer and determined according to the following evaluation criteria. <bewertungskriterien> ◯ (Very good): Stirring possible for 8 minutes △ (Good): Stirring no longer possible between 5 and 8 minutes × (Bad): Stirring is no longer possible within 5 minutes of addition. <Feststellung des Geruchs vonPolycarbonatpolyolzusammensetzung>

[0151] The odor of the polycarbonate polyol composition was evaluated by eight testers. 40 g of the polycarbonate polyol composition was weighed into a 50 ml glass bottle with a lid. After standing for one day at 23°C, the lid was opened, the odor was smelled, and an evaluation was performed. The evaluation results of the eight testers were classified according to the grading criteria listed below, and the average score was calculated. The final rating was then determined according to the same criteria. <benotungskriterien> 0: No smell or smell not perceptible 1: Faint odor perceptible 2: A distinct odor is noticeable 3: Strong odor noticeable <bewertungskriterien> △ (Very good): Average score of 1 or lower from eight examiners △ (Good): Average score from eight examiners greater than 1 and 2 or lower × (Bad): Average score of eight examiners greater than 2 and 3 or lower <Peroxidwert (POV)>

[0152] Samples of the polycarbonate polyol composition obtained in the embodiments and comparative examples described below were immersed in the test section of the POV test paper (SIBATA SCIENTIFIC TECHNOLOGY LTD), left for 3 minutes, and then washed with clean water. The POV test paper for the sample was compared to the standard color pattern, and the peroxide value (POV) in the sample was assessed as follows. [Assessment criteria] ◯ (Very good): 0 mEq / kg or more and 3 mEq / kg or less detected as 0 on the standard color pattern △ (Good): above 3 meq / kg and 10 meq / kg or less, according to standard colour pattern 10. × (Bad): above 10 meq / kg, and 40 meq / kg or less, according to standard colour pattern 30. [Production of polyurethane] (Raw materials used) • Main active ingredient: Polycarbonate polyol composition (PC-1 to 26), obtained in the exemplary embodiments and comparative examples • Curing agent: Diphenylmethane-4,4'-diisocyanate (MDI, NCO% = 33.5) • Catalyst: 1 wt% toluene solution of dibutyltin dilaurate (manufactured by FUJIFILM Wako Pure Chemical Corporation; dissolved in toluene to a 1 wt% solution) • Solvent: Methyl ethyl ketone (MEK, manufactured by FUJIFILM Wako Pure Chemical Corporation) (Manufacturing process)

[0153] In a nitrogen-sealed 200 mL mixing flask equipped with a stirring paddle, 30 g each of a polycarbonate polyol composition and a polyol composition (PC-1 to 26) preheated to 60°C, 0.3 g of a 1 wt% solution of dibutyltin dilaurate as a catalyst, MDI pre-dissolved at 80°C to achieve an NCO / OH ratio of 1.1, and methyl ethyl ketone (MEK) to achieve a solids concentration of 30 wt% were added. The mixture was stirred for 3 minutes at 60°C to obtain a polyurethane solution. The mixture was then applied with an applicator to a polypropylene resin film (width 100 mm, length 1200 mm, thickness 1 mm) with a width of 80 mm, a length of 100 mm and a thickness of 0.6 mm, was dried for 2 hours on a heating plate at a surface temperature of 60° C and then for 12 hours in an oven at 100° C.The polyurethane films were obtained by leaving them for at least 12 hours at a constant temperature and humidity of 23°C and 55% relative humidity. <Handhabungseigenschaften bei der Polyurethanherstellung>

[0154] The handling properties during polyurethane production were determined based on the following evaluation criteria. ◯ (Very good): A polyurethane solution was obtained, and the numerical mean molecular weight measured by GPC was 50,000 or more. △ (Good): A polyurethane solution was obtained, however, the mean molecular weight measured by GPC was 30,000 or less. × (Bad): No polyurethane solution could be obtained. <Messung des Molekulargewichts>

[0155] A portion of each of the above-mentioned polyurethane films was cut out, an N,N-dimethylacetamide solution was prepared such that the polyurethane concentration was 0.1 wt%, and the GPC apparatus [Tosoh Corporation, trade name “HLC-8320” (columns: Tskgel SuperHM-H, 4 pieces) using a solution of 2.6 g lithium bromide dissolved in 1 L dimethylacetamide as eluant] was used to measure the number mean molecular weight (Mn) and weight mean molecular weight (Mw), respectively, converted to standard polystyrene. [Analysis and evaluation of polyurethane coatings]<Herstellung von Polyurethanbeschichtungen> (Raw materials used) • Main active ingredient: Polycarbonate polyol composition (PC-1 to 26), obtained in the exemplary embodiments and comparative examples • Hardening agent: Duranate TPA-100 (manufactured by Asahi Kasei Co., NCO% = 23.1) • Catalyst: 1 wt% toluene solution of dibutyltin dilaurate (manufactured by FUJIFILM Wako Pure Chemical Corporation; dissolved in toluene to a 1 wt% solution) • Solvent: Butyl acetate (manufactured by FUJIFILM Wako Pure Chemical Corporation) (Color composition)

[0156] The raw materials (main active ingredient, hardening agent, catalyst, solvent) were weighed into a plastic container according to the formulation conditions mentioned below, stirred with a stirrer and the respective color compositions were obtained. (Formulation conditions) • NCO / OH: 1,2 • Solids content of the paint: 40% by mass • Catalyst: 1% by mass based on the total amount of the main active ingredient and the hardening agent (Manufacturing process)

[0157] The main active ingredient and the catalyst were weighed into a plastic container under the formulation conditions specified above. The solvent was added to achieve a solids content of 20 wt% for the color composition, and the mixture was stirred until uniform distribution was achieved. The curing agent was then weighed into the same plastic container to achieve an NCO / OH ratio of 1.25, and the color compositions were each prepared by stirring until uniform distribution was achieved. (Coating step)

[0158] Each obtained color composition was applied to a polycarbonate sheet (“Takiron PC-1600” (trade name), 2 mm × 70 mm × 150 mm) so that the dry film thickness was 40 µm. (Drying step)

[0159] The color compositions applied to the polycarbonate sheet were baked on at 60°C to obtain polyurethane coatings.

[0160] Various physical properties were evaluated for each polyurethane coating obtained. The evaluation results are shown in Table 3. <Bewertung des Aussehens von Polyurethanbeschichtungen>

[0161] The surface appearance of the polyurethane films produced in the manner described above was visually assessed according to the following criteria. ◯ (Very good): Surface is smooth △ (Good): Slight streaks visible on the surface in the direction of the applicator's movement. × (Bad): Numerous streaks visible on the surface in the direction of the applicator's movement. <Chemische Beständigkeit>

[0162] 3 cm × 3 cm samples were cut from the polyurethane coating. After measuring the mass of each sample with a precision balance, they were placed in 250 ml glass bottles containing 50 ml of oleic acid as a test solvent. The bottles were then incubated for 16 hours in a constant-temperature bath at 80°C under a nitrogen atmosphere. After the test, the samples were removed, their front and back surfaces were lightly wiped with a paper towel, and their mass was measured with a precision balance. The rate of mass change relative to the mass before the test (increase rate: swelling rate for oleic acid resistance) was calculated for each sample and evaluated according to the following criteria. (Evaluation criteria) ◯ (Very good): Mass increase rate of less than 6% △ (Good): Mass increase rate of 6% or more and less than 20% × (Bad): Mass increase rate of 20% or more, or no rating possible <Wetterbeständigkeit>

[0163] Using the same procedure as above, the plate was coated with the applicator to a dry film thickness of 200 µm and left to stand for 168 hours at 23°C and 50% humidity to obtain urethane films (polyisocyanate-cured products). The resulting polyisocyanate-cured products were each placed in a super-xenon weather station (irradiance: 60 W / m²). 2 The following conditions were given: For the weather resistance test, the temperature of the black plate during light exposure was set to 65°C and the humidity to 50%. After 102 minutes, an 18-minute cycle was repeated at 95% humidity with water injection. The L*a*b* values ​​(CIE 1976) of the polyisocyanate-cured product before the weather resistance test and after 2000 hours were measured with a colorimeter. The weather resistance was then evaluated according to the following criteria, based on the color difference (δE), which was calculated using the following color difference formula. δE={(δL*)2+(δa*)2+(δb*)2}1 / 2

[0164] (δL*, δa*, δb* are the differences between the L*, a*, b* values ​​measured before the weather resistance test and after 2000 hours) (Evaluation criteria) ◯ (Very good): δE less than 5 △ (Good): δE equal to or greater than 5 and less than 10 × (Bad): δE equal to or greater than 10 (Production examples 1 to 3)

[0165] The hexen-1-ol solutions (1) to (3) were prepared as follows.

[0166] H1: 4-Hexen-1-ol (trans isomer): manufactured by Aldrich Co.

[0167] H2: 4-Hexen-1-ol (cis-isomer): manufactured by Tokyo Chemical Industry Co., Ltd.

[0168] H3: 5-Hexen-1-ol: manufactured by Tokyo Chemical Industry Co., Ltd.

[0169] The above-mentioned H1, H2 and H3 were mixed in a mass ratio of 1:1:2 to obtain a hexen-1-ol solution (1).

[0170] The above-mentioned H2 and H3 were mixed in a mass ratio of 1:4 to obtain a hexen-1-ol solution (2).

[0171] The above-mentioned H2 and H3 were mixed in a mass ratio of 1:20 to obtain a hexen-1-ol solution (3). (Example 1)

[0172] In a 2 L glass flask equipped with a distillation column containing standard packing material and a stirring device, 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 placed. 0.33 g of titanium tetrabutoxide was added to the flask as a catalyst. The reaction was carried out for 12 hours at a temperature of 140–160°C, during which time the pressure was reduced from 10 kPa to 2 kPa, and the resulting mixture of ethylene glycol and ethylene carbonate was distilled off. The reaction was then converted to single distillation, and the mixture was subjected to a gradual reduction of the vacuum to 0.5 kPa for 4 hours at 180°C to distill off the monomer.Subsequently, 0.37 g of 2-ethylhexyl phosphate, as a phosphorus compound, was added to the aforementioned flask. The mixture in the flask was heated to 120°C for 5 hours, after which 0.09 g of hexen-1-ol solution (1) was added to obtain the polycarbonate polyol composition. The analytical results of the obtained polycarbonate polyol composition are given in Table 1. This polycarbonate polyol composition is abbreviated as PC-1. The quantification of components (A) and (B) in the obtained polycarbonate polyol composition was carried out using the procedure described above, and their ratio is given in Table 1. The amounts of titanium and phosphorus measured using the procedure described above are also given in Table 1. (Example 2)

[0173] Using the same apparatus as in embodiment 1, the same procedures were carried out as in embodiment 1, except that 0.07 g of hexen-1-ol solution (2) was added, and a polycarbonate polyol composition was obtained. This polycarbonate polyol composition is abbreviated as PC-2. The analysis results of PC-2 are given in Table 1. (Example 3)

[0174] Using the same apparatus as in embodiment 1, the same procedures were carried out as in embodiment 1, except that 0.18 g of titanium tetrabutoxide, 0.20 g of 2-ethylhexyl phosphate, and 0.01 g of hexen-1-ol solution (3) were added, and a polycarbonate polyol composition was obtained. This polycarbonate polyol composition is abbreviated as PC-3. The analytical results of PC-3 are given in Table 1. (Example 4)

[0175] Using the same apparatus as in embodiment 1, the same procedures were carried out as in embodiment 1, except that 0.18 g of titanium tetrabutoxide, 0.20 g of 2-ethylhexyl phosphate, and 0.003 g of hexen-1-ol solution (2) were added, the distillation was changed to single distillation, and the reaction was carried out for 7 hours at 180°C while the pressure was gradually reduced to 0.5 kPa to distill off the monomer, and a polycarbonate polyol composition was obtained. This polycarbonate polyol composition is abbreviated as PC-4. The analytical results of PC-4 are given in Table 1. (Example 5)

[0176] Using the same apparatus as in embodiment 1, the same procedures were carried out, except that 0.01 g of hexen-1-ol solution (3) was added, the distillation was changed to single distillation, and the reaction was carried out for 3 hours at 180°C while the pressure was gradually reduced to 0.5 kPa to distill off the monomer, and a polycarbonate polyol composition was obtained. This polycarbonate polyol composition is abbreviated as PC-5. The analytical results of PC-5 are given in Table 1. (Example 6)

[0177] Using the same apparatus as in embodiment 1, the same procedures were carried out, except that 0.06 g of hexen-1-ol solution (3) was added, the distillation was changed to single distillation, and the reaction was carried out for 1.5 hours at 180°C while the pressure was gradually reduced to 0.5 kPa to distill off the monomer, and a polycarbonate polyol composition was obtained. This polycarbonate polyol composition is abbreviated as PC-6. The analytical results of PC-6 are listed in Table 1. (Example 7)

[0178] Using the same apparatus as in embodiment 1, the same procedures were carried out as in embodiment 1, except that 0.01 g of 4-penten-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and a polycarbonate polyol composition was obtained. This polycarbonate polyol composition is abbreviated PC-7. The analytical results of PC-7 are given in Table 1. (Example 8)

[0179] Using the same apparatus as in embodiment 1, the same procedures were carried out as in embodiment 1, except that 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 given, and 0.01 g of hexen-1-ol solution (3) were added, and a polycarbonate polyol composition was obtained. This polycarbonate polyol composition is abbreviated as PC-8. The analytical results of PC-8 are given in Table 1. (Example 9)

[0180] Using the same apparatus as in embodiment 1, the same procedures were carried out as in embodiment 1, except that 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 given, and 0.01 g of hexen-1-ol solution (3) were added, and a polycarbonate polyol composition was obtained. This polycarbonate polyol composition is abbreviated as PC-9. The analytical results of PC-9 are listed in Table 1. (Example 10)

[0181] Using the same apparatus as in embodiment 1, the same procedures were carried out as in embodiment 1, except that 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 given, 0.003 g of hexen-1-ol solution (2) was added, and the reaction was carried out for 24 hours while the mixture of ethylene glycol and ethylene carbonate was distilled off, and the reaction was carried out for 5 hours at 180°C to distill off the monomer, and a polycarbonate polyol composition was obtained. This polycarbonate polyol composition is abbreviated PC-10. The analytical results of PC-10 are listed in Table 1. (Example 11)

[0182] Using the same apparatus as in embodiment 1, the same procedures were carried out as in embodiment 1, except that 766 g (8.7 mol) of ethylene carbonate and 1038 g (8.8 mol) of 1,6-hexanediol were added, and 0.13 g of hexen-1-ol solution (3) were added, and a polycarbonate polyol composition was obtained. This polycarbonate polyol composition is abbreviated as PC-11. The analytical results of PC-11 are given in Table 1. (Example 12)

[0183] Using the same apparatus as in embodiment 1, the same procedures as in embodiment 4 were carried out, except that 0.02 g of hexen-1-ol solution (2) was added, and a polycarbonate polyol composition was obtained. This polycarbonate polyol composition is abbreviated as PC-12. The analytical results of PC-12 are given in Table 1. (Example 13)

[0184] Using the same apparatus as in embodiment 1, the same procedures as in embodiment 4 were carried out, except that 0.003 g of hexen-1-ol solution (2) and 0.01 g of methanol were added, and a polycarbonate polyol composition was obtained. This polycarbonate polyol composition is abbreviated as PC-13. The analytical results of PC-13 are given in Table 1. (Example 14)

[0185] Using the same apparatus as in embodiment 1, the same procedures were carried out as in embodiment 1, except that 0.26 g of hexen-1-ol solution (3) was added, and a polycarbonate polyol composition was obtained. This polycarbonate polyol composition is abbreviated as PC-14. The analytical results of PC-14 are given in Table 2. (Example 15)

[0186] Using the same apparatus as in embodiment 1, the same procedures were carried out as in embodiment 1, except that 0.50 g of hexen-1-ol solution (3) was added, and a polycarbonate polyol composition was obtained. This polycarbonate polyol composition is abbreviated as PC-15. The analytical results of PC-15 are given in Table 2. (Example 16)

[0187] Using the same apparatus as in embodiment 1, the same procedures as in embodiment 4 were carried out, except that 0.18 g of hexen-1-ol solution (2) was added, and a polycarbonate polyol composition was obtained. This polycarbonate polyol composition is abbreviated as PC-16. The analytical results of PC-16 are given in Table 2. (Example 17)

[0188] 50 g of the polycarbonate polyol composition (PC-4) obtained in embodiment 4 were weighed and mixed with 50 g of polyester polyol (Teslac, 2460, molecular weight 2000, liquid polyol) produced by Resonac to obtain a polycarbonate polyol composition (PC-17). Calculations based on the integral ratio of carbonate repeats to ester repeats determined by 13C-NMR measurement yielded a carbonate repeat to ester repeat ratio of 41:59 (molar ratio). The analytical results for PC-17 are given in Table 2. (Example 18)

[0189] 50 g of the polycarbonate polyol composition (PC-4) obtained in embodiment 4 were weighed and mixed with 50 g of polyester polyol (Kuraray polyol, P-2010, molecular weight 2000, liquid polyol) manufactured by KURARAY to obtain a polycarbonate polyol composition (PC-18). Calculations based on the integral ratio of carbonate repeats to ester repeats determined by 13C-NMR measurement yielded a carbonate repeat to ester repeat ratio of 46:54 (molar ratio). The analytical results for PC-18 are given in Table 2. (Example 19)

[0190] 50 g of the polycarbonate polyol composition (PC-4) obtained in embodiment 4 were weighed and mixed with 50 g of polytetramethylene ether glycol (PTMG2000), manufactured by Mitsubishi Chemical, to obtain a polycarbonate polyol composition (PC-19). Calculations based on the 13 C-NMR measurements determined the integral ratio of carbonate repeat structure to ether repeat structure to yield a ratio of carbonate repeat structure to ether repeat structure of 24:76 (mol ratio).

[0191] The analysis results for PC-19 are given in Table 2. (Example 20)

[0192] 70 g of the polycarbonate polyol composition (PC-4) obtained in embodiment 4 were weighed and mixed with 30 g of polyester polyol (Teslac, 2460, molecular weight 2000, liquid polyol) produced by Resonac to obtain a

[0193] to obtain the polycarbonate polyol composition (PC-20). Calculations based on the integral ratio determined by 13C-NMR measurement. 13 ¹³C NMR measurements determined the integral ratio of the carbonate repeat structure to the ester repeat structure, yielding a carbonate repeat to ether repeat ratio of 67:33 (molar ratio). The analysis results for PC-20 are given in Table 2. (Example 21)

[0194] 70 g of the polycarbonate polyol composition (PC-4) obtained in embodiment 4 were weighed and mixed with 30 g of polyester polyol (Kuraray polyol, P-2010) manufactured by KURARAY to obtain a polycarbonate polyol composition (PC-21). Calculations based on the 13 The integral ratio of the carbonate repeat structure to the ester repeat structure determined by 13C NMR measurement yielded a carbonate repeat to ester repeat ratio of 67:33 (molar ratio). The analysis results for PC-21 are given in Table 2. (Example 22)

[0195] 20 g of the polycarbonate polyol composition (PC-4) obtained in embodiment 4 were weighed and mixed with 30 g of the polycarbonate polyol composition (PC-6) obtained in embodiment 6 and 50 g of polyester polyol (Teslac, 2460) from embodiment 6 to obtain a polycarbonate polyol composition (PC-22). Calculations based on the 13 The integral ratio of carbonate repeats to ester repeats determined by 13C NMR measurement yielded a ratio of 44:56 (molar ratio). The analysis results for PC-22 are given in Table 2. (Example 23)

[0196] 20 g of the polycarbonate polyol composition (PC-4) obtained in embodiment 4 were weighed and mixed with 30 g of the polycarbonate polyol composition (PC-6) obtained in embodiment 6 and 50 g of polyester polyol (Kuraray Polyol, P-2010), manufactured by KURARAY, to obtain a polycarbonate polyol composition (PC-23). ​​Calculations based on the 13 The integral ratio of carbonate repeats to ester repeats determined by 13C NMR measurement yielded a ratio of 44:56 (molar ratio). The analysis results for PC-23 are given in Table 2. (Comparative example 1)

[0197] Using the same apparatus as in the above-mentioned embodiment 1, the same procedures were carried out as in embodiment 1, except that 2.4 g of hexen-1-ol solution (1) were added, and a polycarbonate polyol composition was obtained. This polycarbonate polyol composition is abbreviated as PC-24. The analytical results of PC-24 are given in Table 2. (Comparative example 2)

[0198] Using the same apparatus as in the above-mentioned embodiment 1, the same procedures were carried out as in embodiment 1, except that 1.2 g of hexen-1-ol solution (1) was added, and a polycarbonate polyol composition was obtained. This polycarbonate polyol composition is abbreviated as PC-25. The analytical results of PC-25 are given in Table 2. (Comparative example 3)

[0199] Using the same apparatus as in the above-mentioned embodiment 1, the same procedures were carried out as in embodiment 1, except that 0.001 g of hexen-1-ol solution (3) was added, the distillation was changed to single distillation, and the reaction was carried out for 7 hours at 180°C while the pressure was gradually reduced to 0.5 kPa to distill off the monomer, and a polycarbonate polyol composition was obtained. To the obtained polycarbonate polyol composition, 17 g of 1,5-pentanediol and 18 g of 1,6-hexanediol were added. This polycarbonate polyol composition is abbreviated as PC-26. The analytical results of PC-26 are given in Table 2. [Table 1] Look Hydroxyl number mg KOH / g Numerical mean of the molecular weight Ti P (A) component (B) component Relationship Salary (mass-%) Salary (ppm) Salary (ppm) Mass % (AWAY) Example implementation 1PC-1 fluid 112.0 1002 0.011 0.010 4-hexen-1-ol 5-hexen-1-ol solution (1) 7883 1,6-Hexanediol 1,5-Pentanediol 90007000 0.90.7 0.0101 sum 161 sum 16000 1.6 Example implementation 2PC-2 fluid 112.3 999 0.010 0.010 4-hexen-1-ol 5-hexen-1-ol solution (2) 27101 1,6-Hexanediol 1,5-Pentanediol 90008000 0.90.8 0.0075 sum 128 sum 17000 1.7 Example implementation 3PC-3 fluid 112.9 994 0.005 0.006 4-hexen-1-ol 5-hexen-1-ol solution (3) 119 1,6-Hexanediol 1,5-Pentanediol 80007000 0.80.7 0.0013 sum 20 sum 15000 1.5 Example 4PC-4 fluid 56.2 1996 0.006 0.006 4-hexen-1-ol 5-hexen-1-ol solution (2) 0.35 1,6-Hexanediol 1,5-Pentanediol 20002000 0.20.2 0.0013 sum 5.3 sum 4000 0.4 Example implementation 5PC-5 fluid 143.7 781 0.008 0.009 4-hexen-1-ol 5-hexen-1-ol solution (3) 1.225 1,6-Hexanediol 1,5-Pentanediol 1600014000 1.61.4 0.0009 sum 26.2 sum 30000 3.0 Example implementation 6PC-6 fluid 226.1 496 0.010 0.010 4-hexen-1-ol 5-hexen-1-ol solution (3) 11220 1,6-Hexanediol 1,5-Pentanediol 3300034000 3.33.4 0.0034 sum 231 sum 67000 6.7 Example 7PC-7 fluid 112.3 999 0.010 0.010 4-Penten-1-ol 25 1,6-Hexanediol 1,5-Pentanediol 80007000 0.807 0.0017 sum 25 sum 15000 1.5 Example 8PC-8 fluid 113.1 992 0.010 0.009 4-hexen-1-ol 5-hexen-1-ol solution (3) 124 1,6-Hexanediol 1,4-Butanediol 80007000 0.80.7 0.0017 sum 25 sum 15000 1.5 Example implementation 9PC-9 fluid 112.8 995 0.010 0.010 4-hexen-1-ol 5-hexen-1-ol solution (3) 122 1,6-Hexanediol 1,5-Pentanediol 80007000 0.80.7 0.0015 sum 23 sum 15000 1.5 Example 10 fluid 56.9 1972 0.015 0.014 4-hexen-1-ol 5-hexen-1-ol solution (2) 16 2-Methyl-1,3-Propanediol1,4-Butanediol 20002000 0.20.2 0.0018 PC-10 sum sum 4000 0.4 Example 11 fluid 112.8 995 0.010 0.009 4-hexen-1-ol 5-hexen-1-ol solution (3) 10200 1,6-Hexanediol 3000 0.3 0.0700 PC-11 sum 210 sum 3000 0.3 Example 12 fluid 56.4 1989 0.009 0.010 4-hexen-1-ol 5-hexen-1-ol solution (2) 931 1,6-Hexanediol 1,5-Pentanediol 20002000 0.20.2 0.0100 PC-12 sum 40 sum 4000 0.4 Example 13 fluid 56.2 1996 0.008 0.009 4-hexen-1-ol 5-hexen-1-ol solution (2) 0.75 1,6-Hexanediol 1,5-Pentanediol 20002000 0.20.2 0.0014 PC-13 sum 5.7 sum 4000 0.4 [Table 2] Look Hydroxyl number mg KOH / g Numerical mean of the molecular weight Ti P (A) component (B) component Relationship Salary (mass-%) Salary (ppm) Salary (ppm) Mass % (AWAY) Example 14 fluid 112.3 999 0.011 0.010 4-hexen-1-ol 5-hexen-1-ol solution (3) 22407 1,6-Hexanediol 1,5-Pentanediol 90008000 0.90.8 0.0252 PC-14 sum 429 sum 17000 1.7 Example 15 fluid 114.7 978 0.010 0.010 4-hexen-1-ol 5-hexen-1-ol solution (3) 37788 1,6-Hexanediol 1,5-Pentanediol 90008000 0.90.8 0.0485 PC-15 sum 825 sum 17000 1.7 Example 16 fluid 57.1 1965 0.010 0.010 4-hexen-1-ol 5-hexen-1-ol solution (2) 61257 1,6-Hexanediol 1,5-Pentanediol 20002000 0.20.2 0.0795 PC-16 sum 318 sum 4000 0.4 Example 17PC-17 fluid 55.8 2011 0.009 0.010 4-hexen-1-ol 5-hexen-1-ol solution (2) 0.33 Ethylene glycol1,4-butanediol1,6-hexanediol1,5-pentanediol 4000500010001000 0.40.50.10.1 0.0003 sum 3.3 sum 11000 1.1 Example 18 fluid 56.6 1982 0.010 0.009 4-hexen-1-ol 5-hexen-1-ol solution (2) 0.23 3-Methyl-1,5-pentanediol1,6-hexanediol1,5-pentanediol 600010001000 0.60.10.1 0.0004 PC-18 sum 3.2 sum 8000 0.8 Example 19 firmly 56.7 1979 0.006 0.007 4-hexen-1-ol 5-hexen-1-ol solution (2) 0.35 1,6-Hexanediol 1,5-Pentanediol 10001000 0.10.1 0.0027 PC-19 sum 5.3 sum 2000 0.2 Example 20PC-20 fluid 56.7 1979 0.010 0.009 4-hexen-1-ol 5-hexen-1-ol solution (3) 0.64 Ethylene glycol1,4-butanediol1,6-hexanediol1,5-pentanediol 2400300014001400 0.240.300.140.14 0.0007 PC-20 sum 4.6 sum 6800 0.68 Example 21 fluid 57.1 1965 0.011 0.010 4-hexen-1-ol 5-hexen-1-ol solution (2) 0.24 3-Methyl-1,5-pentanediol1,6-hexanediol1,5-pentanediol 340013001300 0.340.130.13 0.0007 PC-21 sum 4.2 sum 6000 0.60 Example 22PC-22 fluid 111.2 1009 0.010 0.010 4-hexen-1-ol 5-hexen-1-ol solution (2),(3) 6.570 Ethylene glycol1,4-butanediol1,6-hexanediol1,5-pentanediol 400050001000010000 0.40.51.01.0 0.0026 sum 76.5 sum 29000 2.9 Example 23 fluid 108.8 1031 0.009 0.010 4-hexen-1-ol 5-hexen-1-ol solution (2),(3) 5.867 3-Methyl-1,5-pentanediol1,6-hexanediol1,5-pentanediol 60001000011000 0.61.01.1 0.0027 PC-23 sum 72.8 sum 27000 2.7 Comparative example 1 fluid 112.9 994 0.011 0.010 4-hexen-1-ol 5-hexen-1-ol solution (1) 20151997 1,6-Hexanediol 1,5-Pentanediol 90008000 0.90.8 0.2360 PC-24 sum 4012 sum 17000 1.7 Comparison example 2PC-25 fluid 112.2 1000 0.010 0.010 4-hexen-1-ol 5-hexen-1-ol solution (1) 1001995 1,6-Hexanediol 1,5-Pentanediol 80008000 0.80.8 0.1248 sum 1996 sum 16000 1.6 Comparison example 3PC-26 fluid 56.3 1993 0.010 0.010 4-hexen-1-ol 5-hexen-1-ol solution (1) 11 1,6-Hexanediol 1,5-Pentanediol 3000030000 3.03.0 0.00003 sum 2 60000 6.0 [Table 3] Measurement of pot life in urethane reaction Handling properties in polyurethane production Appearance of polyurethane coating Colorfastness Peroxide value POV chemical resistance Determination of the odor of polycarbonate polyol Weather resistance Example 1 PC-1 ◯ ◯ ◯ ◯ ◯ ◯ △ ◯ Example 2 PC-2 ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Example 3 PC-3 ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Example 4 PC-4 ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Execution example 5 PC-5 ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Example 6 PC-6 ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Example 7 PC-7 ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Example 8 PC-8 ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Execution example 9 PC-9 ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Example 10 PC-10 ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Example 11 PC-11 ◯ △ △ △ ◯ △ △ △ Example 12 PC-12 ◯ ◯ ◯ △ ◯ ◯ ◯ ◯ Example 13 PC-13 ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Example 14 PC-14 ◯ ◯ ◯ △ ◯ ◯ △ ◯ Example 15 PC-15 ◯ △ △ △ ◯ ◯ △ ◯ Example 16 PC-16 ◯ △ △ △ ◯ ◯ △ △ Example 17 PC-17 ◯ ◯ ◯ △ ◯ △ ◯ ◯ Example 18 PC-18 ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Example 19 PC-19 ◯ ◯ ◯ △ ◯ △ ◯ △ Example 20 PC-20 ◯ ◯ ◯ ◯ ◯ △ ◯ ◯ Example 21 PC-21 ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Example 22 PC-22 ◯ ◯ ◯ ◯ ◯ △ ◯ ◯ Example 23 PC-23 ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Comparative example 1 PC-24 ◯ × △ × × × × × Comparative example 2 PC-25 △ × △ × × △ × × Comparison 3 PC-26 I △ × × ◯ ◯ ◯ ◯ ◯ Industrial applicability

[0200] The polycarbonate polyol composition of the present invention can provide a polyurethane film with a long pot life, excellent handling properties, good appearance and excellent weather resistance, and can therefore be widely and effectively used as a component for, e.g., paints, paint compositions, adhesives, adhesive compositions, water-based polyurethanes, water dispersion compositions, polyurethane for artificial leather, artificial leather, etc. Explanation of reference symbols 1 Form release paper 2 Surface layer 3 adhesive layers 4 base material (polyester fabric) 5 Mixing head (surface layer) 6 Mixing head (adhesive layer) 7 Foil structure (dry synthetic leather product) 8 coating roller 9 Press roller 10 winding roller 11 dryers QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] JP 3874664 B [0003, 0005] JP 2013-064140 A [0004, 0005] Cited non-patent literature

[0000] Polymer Reviews, Volume 9, pp. 9 - 20

[0017] < / bewertungskriterien> < / benotungskriterien> < / bewertungskriterien> < / anwendungen> < / kunstleder> < / wassermenge> < / phosphorverbindung> < / metallelementgehalt> < / polycarbonatpolyol> < / polycarbonatpolyolzusammensetzung>

Claims

[1] Polycarbonate polyol composition, containing: Polycarbonate polyol with terminal hydroxyl groups, a (A) component: a compound represented by the following formula (A), and a (B)-component: a compound represented by the following formula (B), characterized by , that the mass ratio ((A) / (B)) of the (A) component to the (B) component is 0.0001 to 0.1000, where R1 is hydrogen or an alkyl group with 1 to 12 carbon atoms and R2 is an alkylene group with 1 to 12 carbon atoms, and where R3 is an alkylene group with 2 to 12 carbon atoms, which may have a straight-chain alkylene group, a divalent alicyclic hydrocarbon group or a branched alkylene group. [2] Polycarbonate polyol composition according to claim 1, wherein, when measured by ICP (ICP-MS: Inductively Coupled Plasma Mass Spectrometry), the content of at least one metal element selected from the group consisting of titanium, ytterbium, tin, zirconium, magnesium, calcium, lithium, sodium and manganese, is 0.0001 to 0.050 wt%. [3] Polycarbonate polyol composition according to claim 1, wherein, when measured by ICP (ICP-MS: Inductively Coupled Plasma Mass Spectrometry), the phosphorus content is 0.0001 to 0.050 wt%. [4] Polycarbonate polyol composition according to claim 1, wherein, in the compound represented by formula (A) and the compound represented by formula (B), a number obtained by adding two carbon atoms to the sum of the total number of carbon atoms of R1 and R2 corresponds to the number of carbon atoms of R3. [5] Polycarbonate polyol composition according to claim 1, wherein the polycarbonate polyol with terminal hydroxyl groups has repeating units derived from 1,5-pentanediol and / or 1,6-hexanediol, wherein the compound represented by formula (A) contains a compound selected from the group consisting of a compound in which R1 in formula (A) is a hydrogen atom and R2 is an alkylene group with 4 or 3 carbon atoms, a compound in which R1 in formula (A) is an alkylene group with 1 carbon atom and R2 is an alkylene group with 3 or 2 carbon atoms, and a compound in which R1 in formula (A) is an alkylene group with 2 carbon atoms and R2 is an alkylene group with 2 or 1 carbon atoms, and wherein a number obtained by adding two carbon atoms to the sum of the total number of carbon atoms of R1 and R2 of the compound represented by formula (A) is 5 or 6, and this corresponds to the number of carbon atoms of R3 of the compound represented by formula (B). [6] Polycarbonate polyol composition according to claim 1, further comprising a (B') component, characterized by , that the mass ratio ((B') / (B)) of the (B') component to the (B) component is 0.0001 to 1.000, where R4 is an alkylene group with 1 to 4 carbon atoms. [7] Polycarbonate polyol composition according to claim 1, further comprising a polyol compound having an ester repeat structure and / or an ether repeat structure. [8] Polycarbonate polyol composition according to claim 7, wherein the total molar ratio of carbonate repeat structure:ester repeat structure and ether repeat structure contained in the polycarbonate polyol and the polyol compound with the ester repeat structure and / or the ether repeat structure is in the range of 20:80 to 80:

20. [9] Polycarbonate polyol composition according to claim 1, wherein the mass ratio ((A) / (B)) is 0.0001 to 0.0075. [10] Polycarbonate polyol composition according to claim 1, wherein the mass ratio ((A) / (B)) is 0.0001 to 0.

069. [11] Polycarbonate polyol composition according to claim 1, wherein the mass ratio ((A) / (B)) is 0.0001 to 0.

010. [12] Polycarbonate polyol composition according to claim 1, wherein the mass ratio ((A) / (B)) is 0.006 to 0.

010. [13] Polycarbonate polyol composition according to claim 1, wherein the polycarbonate polyol with terminal hydroxyl groups comprises a constitutional unit represented by the following formula (P), wherein 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] Adhesive composition comprising a polycarbonate polyol composition according to any one of claims 1 to 13. [15] Water-based polyurethane produced using a polycarbonate polyol composition according to any one of claims 1 to 13. [16] Water dispersion composition prepared using a polycarbonate polyol composition according to any one of claims 1 to 13. [17] Polyurethane for artificial leather produced using a polycarbonate polyol composition according to any one of claims 1 to 13. [18] Artificial leather produced using a polycarbonate polyol composition according to any one of claims 1 to 13. [19] Urethane-cured product produced using a polycarbonate polyol composition according to any one of claims 1 to 13. [20] Interior trim material of a vehicle, comprising an artificial leather according to claim 18. [21] Method for suppressing the odor of a polycarbonate polyol composition, wherein the polycarbonate polyol composition contains: a polycarbonate polyol with terminal hydroxyl groups, a (A) component: a compound represented by the following formula (A), and a (B)-component: a compound represented by the following formula (B), where the mass ratio ((A) / (B)) of the (A) component to the (B) component is 0.0001 to 0.1000. [22] Method for suppressing the odor of a urethane-cured product, comprising: Selecting a polycarbonate polyol composition that contains: a polycarbonate polyol with terminal hydroxyl groups, a (A) component: a compound represented by the following formula (A), and a (B)-component: a compound represented by the following formula (B), where the mass ratio ((A) / (B)) of the (A) component to the (B) component is 0.0001 to 0.1000, and Curing the polycarbonate polyol composition to produce a urethane-cured product. [23] Method for producing a polycarbonate polyol composition, wherein the polycarbonate polyol composition contains: a polycarbonate polyol with terminal hydroxyl groups, a (A) component: a compound represented by the following formula (A), and a (B)-component: a compound represented by the following formula (B), where the mass ratio ((A) / (B)) of the (A) component to the (B) component is set to a range of 0.0001 to 0.1000. [24] Method for producing a urethane-cured product, comprising: Selecting a polycarbonate polyol composition that contains: a polycarbonate polyol with terminal hydroxyl groups, a (A) component: a compound represented by the following formula (A), and a (B)-component: a compound represented by the following formula (B), where the mass ratio ((A) / (B)) of the (A) component to the (B) component is 0.0001 to 0.1000, and Curing of the polycarbonate polyol composition. [25] Method for producing artificial leather, comprising: a step to arrange an adhesive layer, an intermediate layer and a surface layer on a base material in the specified order, wherein one of the surface layer, the intermediate layer and the adhesive layer is a urethane-cured product of a polycarbonate polyol composition, and the polycarbonate polyol composition contains: a polycarbonate polyol with terminal hydroxyl groups, a (A) component: a compound represented by the following formula (A), and a (B)-component: a compound represented by the following formula (B), where the mass ratio ((A) / (B)) of the (A) component to the (B) component is 0.0001 to 0.1000. [26] Method for suppressing the odor of an artificial leather, comprising: Selecting a polycarbonate polyol composition that contains: a polycarbonate polyol with terminal hydroxyl groups, a (A) component: a compound represented by the following formula (A), and a (B)-component: a compound represented by the following formula (B), where the mass ratio ((A) / (B)) of the (A) component to the (B) component is 0.0001 to 0.1000, and Using a urethane-cured product of the polycarbonate polyol composition in at least one of the adhesive layer, the intermediate layer and the surface layer.

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