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

Abstract

Provided is a polycarbonate polyol composition and the like that can provide a polyurethane film having a long pot life, excellent handleability, good appearance, and excellent weather resistance. [Solution] A polycarbonate polyol composition comprising a polycarbonate polyol having a terminal hydroxy group, a compound represented by the following formula (A), and a compound represented by the following formula (B), wherein the mass ratio of the compound (A) to the compound (B), ((A) / (B)), is 0.0001 to 0.1000. JPEG0007827931000019.jpg10170 (In the above formula, R1 is hydrogen or an alkyl group having 1 to 12 carbon atoms, and R2 is an alkylene group having 1 to 12 carbon atoms.) JPEG0007827931000020.jpg11170 (In the above formula, R3 is an alkylene group having 2 to 12 carbon atoms, and may have a linear alkylene group, a divalent alicyclic hydrocarbon group, or a branched alkylene group.)

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate polyol composition, an adhesive composition, a water-based polyurethane, a water-based polyurethane, and a water-based polyurethane. The present invention relates to a dispersion composition, a polyurethane for synthetic leather, and synthetic leather. [Background technology]

[0002] Polycarbonate polyol is an effective raw material for urethane, which has both flexibility and toughness. It is known that soft materials such as polyurethane and thermoplastic elastomers are Among them, polycarbonate polyol is hydrolysis resistant. It is known as a material with excellent acid resistance. Various methods have been studied and are known so far.

[0003] For example, Patent Document 1 discloses a method for producing polyurethane elastomers and polyester elastomers. As a polycarbonate polyol that exhibits high polymerization reactivity and high polymerization rate in the reaction and a polycarbonate diol in which the ratio of primary terminal OH groups to all terminal groups is within a specific range. It has been disclosed.

[0004] In addition, Patent Document 2 describes a method for stabilizing the reaction and using it as a component material of paint. There is no roughness caused by fine gel-like substances or stickiness caused by low molecular weight substances, and Polycarbonate resin provides a coating film with a good balance of properties such as hydrolysis resistance and heat resistance. The polycarbonate diol disclosed has a specific range of primary terminal OH group ratio. It has been done. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 3874664 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-064140 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the polycarbonate diols disclosed in Patent Documents 1 and 2 Although the use of When mixed with isocyanate, the pot life is shortened and gelation occurs. As a result, it is difficult to obtain polyurethane with a good appearance, and the weather resistance of the polyurethane obtained is reduced. A new problem was discovered.

[0007] The present invention has been made in view of the above-mentioned problems. It has a long pot life when used as a polyurethane component for adhesives and synthetic leather, and is easy to handle. Polycarbonate polyolefin resins are excellent in heat resistance, appearance, and weather resistance. Another object of the present invention is to provide a polyol composition having excellent handling properties. Polycarbonate polyols that can provide polyurethanes with good appearance and excellent weather resistance. compositions, adhesive compositions, water-based polyurethanes, water-dispersed compositions, polyurethanes for synthetic leather, and and synthetic leather. [Means for solving the problem]

[0008] The present inventors have conducted extensive research in view of the above-mentioned problems. and a polycarbonate polyol containing the following component (A) and component (B): A polycarbonate resin having the following component (A) and component (B) in a content ratio within a specific range: The company has developed a new polycarbonate polyol composition, and by using this polycarbonate polyol composition, The present invention was completed based on the discovery that the above problems can be solved by the above method.

[0009] That is, the present invention provides various specific embodiments as shown below. <1> a polycarbonate polyol having terminal hydroxy groups; Component (A): a compound represented by the following formula (A), Component (B): a compound represented by the following formula (B), The mass ratio ((A) / (B)) of the component (A) to the component (B) is 0.0001 ~0.1000, Polycarbonate polyol compositions. [ka] (In formula (A), R1 is hydrogen or an alkyl group having 1 to 12 carbon atoms, and R2 is an alkyl group having 1 to 12 carbon atoms.) is an alkylene group having a carbon number of 1 to 12. [ka] (In formula (B), R3 is an alkylene group having 2 to 12 carbon atoms, and is a linear alkylene group, It may have a 2-valent alicyclic hydrocarbon group or a branched alkylene group.

[0010] <2> ICP(ICP-MS:Inductively Coupled Plasma M As measured by spectroscopy (ass spectrometry), titanium, ytterbium, and strontium Zinc, zirconium, magnesium, calcium, lithium, sodium, and manganese The content of at least one metal element selected from the group consisting of: 0% by mass, <1> The polycarbonate polyol composition according to claim 1.

[0011] <3> ICP(ICP-MS:Inductively Coupled Plasma M The phosphorus content measured by SS Spectrometry is 0.0001 to 0.050% by mass, <1> or <2> The polycarbonate polyol composition according to claim 1.

[0012] <4> In the compound represented by the formula (A) and the compound represented by the formula (B), R1 and R2 The sum of the total number of carbon atoms plus two carbon atoms is equal to the number of carbon atoms in R3. <1> ~ <3> The polycarbonate polyol composition according to any one of claims 1 to 10.

[0013] <5> The polycarbonate polyol having terminal hydroxy groups is 1,5-pentanedioic acid. and having repeating units derived from 1,6-hexanediol and / or 1,6-hexanediol, The compound represented by the formula (A) is a compound represented by the formula (A) in which R1 is a hydrogen atom and R2 is a carbon atom. a compound in which R1 in the formula (A) is an alkylene group having 4 or 3 carbon atoms; and R2 is an alkylene group having 3 or 2 carbon atoms, and is an alkylene group having 2 carbon atoms and R2 is an alkylene group having 2 or 1 carbon atoms. and one selected from the group consisting of The compound represented by the formula (A) has a total number of carbon atoms of R1 and R2 plus two carbon atoms. 5 or 6, which is equal to the number of carbon atoms in R3 of the compound represented by formula (B). <1> ~ <4> The polycarbonate polyol composition according to any one of claims 1 to 10.

[0014] <6> Further containing component (B'), The mass ratio of the component (B') to the component (B) ((B') / (B)) is 0.0001 to 1.000. <1> ~ <5> The polycarbonate polyol composition according to any one of claims 1 to 10. [ka] (In formula (B'), R4 is a group having 1 to 4 carbon atoms. Alkyl group )

[0015] <7> Polyol compounds having an ester repeating structure and / or an ether repeating structure further comprising: <1> ~ <6> The polycarbonate polyol composition according to any one of claims 1 to 10.

[0016] <8> the polycarbonate polyol and the ester repeating unit and / or ether Polyol compounds having a repeating structure and carbonate repeating structure: The total molar ratio of the ter repeating units and the ether repeating units is 20:80 to 80: 20 range, <7> The polycarbonate polyol composition according to claim 1.

[0017] <9> the mass ratio ((A) / (B)) is 0.0001 to 0.075; <1> ~ <8> The polycarbonate polyol composition according to any one of claims 1 to 10.

[0018] <10> the mass ratio ((A) / (B)) is 0.0001 to 0.069; <1> ~ <9> The polycarbonate polyol composition according to any one of claims 1 to 10.

[0019] <11> the mass ratio ((A) / (B)) is 0.0001 to 0.010; <1> ~ <10> The polycarbonate polyol composition according to any one of claims 1 to 10.

[0020] <12> the mass ratio ((A) / (B)) is 0.006 to 0.010; <1> ~ <11> The polycarbonate polyol composition according to any one of claims 1 to 10.

[0021] <13> The polycarbonate polyol having a terminal hydroxy group is represented by the following formula (P): having a structural unit <1> ~ <12> The polycarbonate polyol composition according to any one of claims 1 to 10. [ka] (In formula (P), R1 is any divalent aliphatic hydrocarbon group, and R2 is hydrogen or any and R3 is any divalent aliphatic hydrocarbon group.

[0022] <14> <1> ~ <13> The polycarbonate polyol composition according to any one of claims 1 to 4, Adhesive composition.

[0023] <15> <1> ~ <13> Using the polycarbonate polyol composition according to any one of To be produced, Water-based polyurethane.

[0024] <16> <1> ~ <13> Using the polycarbonate polyol composition according to any one of To be produced, Water dispersion composition.

[0025] <17> <1> ~ <13> Using the polycarbonate polyol composition according to any one of To be produced, Polyurethane for synthetic leather.

[0026] <18> <1> ~ <13> Using the polycarbonate polyol composition according to any one of To be produced, Synthetic leather.

[0027] <19> <1> ~ <13> Using the polycarbonate polyol composition according to any one of To be produced, Cured urethane.

[0028] <20> <18> The synthetic leather includes the synthetic leather described in Automotive interior materials.

[0029] <21> A method for controlling odor of a polycarbonate polyol composition, comprising: The carboxylate polyol composition is a polycarbonate polyol having terminal hydroxy groups; Component (A): a compound represented by the formula (A), (B) component: a compound represented by the formula (B), The mass ratio of the component (A) to the component (B) ((A) / (B)) is 0.0001 Let ~0.1000. method.

[0030] <22> A method for suppressing odor of a cured urethane product, comprising: a polycarbonate polyol having terminal hydroxy groups; Component (A): a compound represented by the formula (A), (B) component: a compound represented by the formula (B), The mass ratio ((A) / (B)) of the component (A) to the component (B) is 0.0001 Select a polycarbonate polyol composition having a viscosity of 0.1000 or less, The polycarbonate polyol composition is cured to produce a cured urethane product. include, method.

[0031] <23> A method for producing a polycarbonate polyol composition, comprising: The polycarbonate polyol composition comprises: a polycarbonate polyol having terminal hydroxy groups; Component (A): a compound represented by the formula (A), (B) component: a compound represented by the formula (B), The mass ratio of the component (A) to the component (B) ((A) / (B)) is 0.0001 Adjust to the range of ~0.1000, Manufacturing method.

[0032] <24> A method for producing a cured urethane product, comprising: a polycarbonate polyol having terminal hydroxy groups; Component (A): a compound represented by the formula (A), (B) component: a compound represented by the formula (B), The mass ratio ((A) / (B)) of the component (A) to the component (B) is 0.0001 Select a polycarbonate polyol composition having a viscosity of 0.1000 or less, curing the polycarbonate polyol composition. Manufacturing method.

[0033] <25> A method for producing synthetic leather, comprising: The method includes the steps of sequentially disposing an adhesive layer, an intermediate layer, and a skin layer on a substrate; Any of the surface layer, the intermediate layer, and the adhesive layer is made of a polycarbonate polyol. a urethane cured product of the composition, The polycarbonate polyol composition comprises: a polycarbonate polyol having terminal hydroxy groups; Component (A): a compound represented by the formula (A), (B) component: a compound represented by the formula (B), The mass ratio ((A) / (B)) of the component (A) to the component (B) is 0.0001 ~0.1000, Manufacturing method.

[0034] <26> A method for suppressing odor in synthetic leather, comprising: a polycarbonate polyol having terminal hydroxy groups; Component (A): a compound represented by the formula (A), (B) component: a compound represented by the formula (B), The mass ratio ((A) / (B)) of the component (A) to the component (B) is 0.0001 Select a polycarbonate polyol composition having a viscosity of 0.1000 or less, At least one of the adhesive layer, intermediate layer, and skin layer is made of the polycarbonate polyol composition. The method includes using a urethane cured product of the composition. [Effects of the Invention]

[0035] According to the present invention, the polyurethane may be used as a polyurethane component material for, for example, paints, adhesives, and synthetic leather. The polyurethane film has a long pot life, is easy to handle, has a good appearance, and is weather resistant. Furthermore, the present invention can provide a polycarbonate polyol composition and the like that can be realized. By using this polycarbonate polyol composition, it is possible to obtain products with excellent handling properties, good appearance, and weather resistance. Polycarbonate polyol composition and adhesive composition capable of producing polyurethane with excellent properties The present invention provides a water-based polyurethane, a water-dispersed composition, a polyurethane for synthetic leather, and synthetic leather. It can also be offered. [Brief explanation of the drawings]

[0036] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of a synthetic leather laminate using the polycarbonate polyol composition of the present embodiment. [Figure 2] FIG. 1 is a schematic diagram showing an example of a method for producing a synthetic leather laminate using the polycarbonate polyol composition of the present embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0037] Hereinafter, the embodiment for carrying out the present invention (hereinafter abbreviated as "the present embodiment") will be described in detail. The present invention is not limited to the following embodiments, and the gist of the invention will be described below. Various modifications can be made within the scope of the present invention.

[0038] <Polycarbonate polyol composition> The polycarbonate polyol composition of the present embodiment is a polycarbonate polyol having terminal hydroxyl groups. A carbonate polyol, component (A): a compound represented by the following formula (A), and component (B): and a compound represented by the following formula (B), wherein the mass ratio of the component (A) to the component (B) is The ratio ((A) / (B)) is characterized by being 0.0001 to 0.1000. [ka] (In formula (A), R1 is hydrogen or an alkyl group having 1 to 12 carbon atoms, and R2 is an alkyl group having 1 to 12 carbon atoms.) is an alkylene group having a carbon number of 1 to 12. [ka] (In formula (B), R3 is an alkylene group having 2 to 12 carbon atoms, and is not a linear alkylene group.) It may have a divalent alicyclic hydrocarbon group or a branched alkylene group.

[0039] <Polycarbonate polyol> The polycarbonate polyol composition of the present embodiment is a polycarbonate polyol having a terminal hydroxy group. Polycarbonate polyols having terminal hydroxy groups include There are no particular limitations on the type of hydroxyl group, as long as it has a carbonate repeating structure and two or more hydroxyl groups. Polycarbonate polyols having terminal hydroxyl groups are not specified. In addition to the repeating structure, for example, ester repeating structures, ether repeating structures, etc. Specific examples of polycarbonate polyols having terminal hydroxy groups include The aspects are described below.

[0040] In this embodiment, the number average of the polycarbonate polyol having a terminal hydroxy group The molecular weight (Mn) is not particularly limited, but is preferably 300 to 5000. The number average molecular weight of the polycarbonate polyol having a hydroxy group is 300 or more. As a result, the low-temperature properties of the resulting polyurethane tend to be improved. The number average molecular weight of the polycarbonate polyol having the formula: The resulting polyurethane tends to be less susceptible to deterioration in molding processability. From the appearance of the paint film, it is clear that the number average molecular weight of the polycarbonate polyol is between 300 and 3000. Preferably, the ratio is 350 to 2000, more preferably 500 It is more preferable that the number is not less than 2000.

[0041] In this embodiment, the polycarbonate polyol having a terminal hydroxy group The number average molecular weight (Mn) can be measured by the method described in the Examples below.

[0042] In this embodiment, the hydroxyl group of the polycarbonate polyol having a terminal hydroxy group The OH value is not particularly limited, but the lower limit is preferably 20 mgKOH / g or more. It is preferable that the KOH / g is 30 mg KOH / g or more, and more preferable that the KOH / g is 50 mg KOH / g or more. It is more preferable that the pH is 60 mgKOH / g or more, and even more preferable that the pH is 60 mgKOH / g or more. It is particularly preferable that the pH is 0 mgKOH / g or more, and 74 mgKOH / g or more. The hydroxyl value of the polycarbonate polyol having terminal hydroxy groups is most preferred. The upper limit of the OH value is not particularly limited, but is preferably 700 mgKOH / g or less. Preferably, it is 500 mg KOH / g or less, more preferably 400 mg KOH / g or less. It is more preferable that the KOH / g is 350 mg KOH / g or less, and even more preferable that the KOH / g is 350 mg KOH / g or less. It is particularly preferable that the content is 300 mg KOH / g or less, and 230 mg KOH / g or less. It is most preferable that the hydroxyl group of the polycarbonate polyol having a terminal hydroxy group is By having the base value (OH value) within the above preferred range, the viscosity becomes low and handling becomes excellent. Polycarbonate polycarbonate having terminal hydroxy groups, which has excellent compatibility with inert organic solvents. In addition, polycarbonates having such terminal hydroxy groups tend to be easily obtained. By using a nate polyol, the stress, tensile elongation and chemical resistance of the resulting polyurethane are improved. There is a tendency for sex to increase.

[0043] In this embodiment, the hydroxyl group of the polycarbonate polyol having a terminal hydroxy group The method for controlling the value within the above range is not particularly limited, but for example, Controlled by adding and / or extracting alcohol compounds during the production of ester polyols. There are several ways to do this.

[0044] Polycarbonate polyols with terminal hydroxy groups are made by combining hydroxy compounds with carbon When a hydroxy compound (e.g., a polyfunctional dihydroxy compound) is used as a raw material, For example, "Po Transesterification reactions described in "Chemical Reviews, Vol. 9, pp. 9-20" It can be synthesized by

[0045] In this embodiment, the raw material for the polycarbonate polyol having a terminal hydroxy group is Examples of the hydroxy compound that can be used include diols. Specific examples include, but are not limited to, divalent aliphatic or alicyclic groups having 3 to 15 carbon atoms. Diols having an aromatic hydrocarbon skeleton are examples of diols. The diol has 3 or more carbon atoms. This makes it possible to keep the viscosity of the polycarbonate polyol composition low, and In addition to being able to reduce the amount of solvent used, the resulting synthetic leather tends to have improved flexibility and low-temperature properties. The diol compound has 15 or less carbon atoms, which improves the durability of the resulting synthetic leather. It tends to have excellent chemical properties. Specific examples include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10 -Decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1, 13-Tridecanediol, 1,14-tetradecanediol, 1,15-pentadecane Diols without side chains such as diols; 2-methyl-1,8-octanediol, 2- Ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl 2,4-dimethyl-1,5-pentanediol, 2,4 -Diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol diols with side chains such as 2,2-dimethyl-1,3-propanediol; ,4-Cyclohexanedimethanol, 2-bis(4-hydroxycyclohexyl)-propanol Examples of cyclic diols include cyclohexanediol, 1,4-cyclohexanediol, etc. These are not limited to the above. One or more of these may be used as a polymer having a terminal hydroxy group. It can be used as a raw material for carbonate polyol. Two or more diols can be used in combination. As a result, the regularity of the structural units of the resulting polycarbonate diol decreases, and the crystallinity decreases. By decreasing the temperature, it becomes easier to obtain liquid polycarbonate diol at room temperature (25°C). This tends to reduce the amount of inert organic solvent used.

[0046] From the viewpoint of increasing the chemical resistance and mechanical strength of the coating film, polycarbonate having a terminal hydroxyl group is used. As the raw material for carbonate polyol, one or more diols without side chains are used. More preferably, the linear diol is 1,3-propanediol. 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol , 1,7-heptanediol, 1,8-octanediol, and 1,9-nonanediol Among these, one or more kinds selected from the group consisting of raw materials are preferred. Diols include 1,4-butanediol, 1,5-pentanediol, and 1,6 and two diols selected from the group consisting of 1,5-hexanediol and 1,5-hexanediol are more preferred. Pentanediol and 1,6-hexanediol are more preferred.

[0047] In the production of polycarbonate polyol having terminal hydroxy groups, two or more When diols are used as raw materials, the proportion of the raw material diols is not particularly limited. The resulting polycarbonate polyol having terminal hydroxy groups is liquid at room temperature. It is preferable to appropriately set the ratio of the raw material diols used. When using diol as a raw material, the amount of diol charged should be set between 20:80 and 80:20 in molar ratio. It is preferable to set the temperature within this range. If the temperature is within this range, the crystallinity of the polycarbonate diol will not decrease. , and there is a tendency to obtain synthetic leather having high flexibility, good low-temperature properties, and good feel. The resulting polycarbonate polyol having terminal hydroxy groups tends to be liquid. This tends to make it easier to reduce the amount of inert organic solvent used. In a preferred embodiment, when ethanol is used as a raw material, the molar ratio is 30:70 or more. The molar ratio may be 40:60 or more, or may be 70:30 or less, and Since the mixture tends to be liquid even at temperatures below 0.degree. C., the molar ratio may be 60:40 or less.

[0048] Furthermore, the polycarbonate polyol composition of the present embodiment may be used within a range that does not excessively impair the performance of the polycarbonate polyol composition of the present embodiment. In the range of 1, compounds with three or more hydroxyl groups per molecule, such as trimethylolethane, Trimethylolpropane, hexanetriol, pentaerythritol, etc. are It can also be used as a raw material for polycarbonate polyols having hydroxy groups. As a raw material for polycarbonate polyols with terminal hydroxy groups, If too many compounds with hydroxyl groups are used, the polymerization of polycarbonate polyol will Therefore, if there are more than three hydroxy groups in one molecule, cross-linking may occur during the polymerization reaction, resulting in gelation. When a compound having a hydroxyl group is used as a raw material, the proportion of the compound used should be The total molar ratio of raw material diols used as raw materials for polycarbonate polyols having hydroxy groups The content is preferably 0.1 to 5 mol %, more preferably 0.1 to 1 mol %, based on the number of atoms.

[0049] In this embodiment, the raw material for the polycarbonate polyol having a terminal hydroxy group is Specific examples of carbonates that can be used as the carbonate include, but are not limited to, dimethyl carbonate. Carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate Dialkyl carbonates such as diphenyl carbonate; diaryl carbonates such as diphenyl carbonate ; Ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate , 1,2-butylene carbonate, 1,3-butylene carbonate, 1,2-pentylene These include alkylene carbonates such as carbonates. Two or more types are used as raw materials for polycarbonate polyol having terminal hydroxy groups. From the viewpoint of ease of acquisition and ease of setting polymerization reaction conditions, raw material carbon Carbonates include dimethyl carbonate, diethyl carbonate, and diphenyl carbonate. Preferred are ethylene carbonate, dibutyl carbonate, and / or ethylene carbonate.

[0050] In this embodiment, the synthesis of the polycarbonate polyol having a terminal hydroxy group is The reaction can be carried out by a method known in the art, and is not particularly limited. For example, the reaction can be carried out in the presence of a catalyst. From the viewpoint of reaction efficiency, synthesis can be carried out in the presence of a catalyst. As the catalyst, any catalyst known in the art can be appropriately used, and there are no particular limitations. Although not limited, examples include alkali metals such as lithium, sodium, and potassium; magnesium; Alcoholates of alkaline earth metals such as ammonium, calcium, strontium, and barium, Hydrides, oxides, amides, carbonates, hydroxides, nitrogen-containing borates, and salts of organic acids Examples of the catalyst include basic alkali metal salts and alkaline earth metal salts. For example, but not limited to, aluminum, titanium, vanadium, chromium, manganese, iron , cobalt, nickel, copper, zinc, gallium, germanium, zirconium, niobium, molybdenum Abdenum, ruthenium, rhodium, palladium, silver, indium, tin, antimony, titanium ungsten, rhenium, osmium, iridium, platinum, gold, thallium, lead, bismuth metals such as ytterbium, metal salts thereof, metal alkoxides thereof, organic compounds containing such metals These compounds can be used alone or in combination of two or more. This can be done.

[0051] Among these, lithium, sodium, potassium, magnesium, calcium, titanium Metals such as zinc, zirconium, tin, lead, manganese, ytterbium, and their metal salts and their When using one or more catalysts, polyalkoxides can be produced from metal alkoxides and organic compounds containing the metals. The polymerization of the recarbonate polyol is carried out satisfactorily, and the resulting polycarbonate polyol It is also preferable because it has little effect on the urethane reaction using The catalyst may be titanium, ytterbium, tin, zirconium, magnesium, or potassium. One metallic element selected from the group consisting of calcium, lithium, sodium, and manganese It is more preferable to use one or more catalysts containing titanium, ytterbium, a metal selected from the group consisting of tin, magnesium, calcium, lithium, and manganese It is more preferred to use one or more catalysts containing one or more elements, such as titanium, tin, Organic compounds containing magnesium, calcium, lithium and / or manganese are particularly preferred. I wish.

[0052] The polycarbonate polyol composition of the present embodiment contains a catalyst containing the above-mentioned metal element. In the polycarbonate polyol composition of the present embodiment, the catalyst may be contained. The amount was measured by ICP (Inductively Coupled Plasma Mass Spectroscopy) The content of metal elements measured using Mass Spectrometry (MS), It is preferable that the catalyst content is 0.0001 to 0.050 mass %. If the polycarbonate polyol is used, the polymerization of the polycarbonate polyol proceeds well, and the polycarbonate polyol composition In a preferred embodiment, the catalyst is contained in the urethane reaction product. The content of metal elements measured using ICP is 0.0005 mass% or more. It may be 0.020 mass % or less.

[0053] Method for producing polycarbonate polyol having terminal hydroxy groups according to the present embodiment One embodiment of the method is shown below. The polycarbonate polyol having terminal hydroxy groups can be produced by the following method. Although not particularly limited, for example, the transesterification reaction can be carried out in two steps according to the following procedure. It can be done.

[0054] Specifically, the diol and carbonate are mixed in a molar ratio (diol:carbonate), for example, For example, they are mixed in a ratio of 20:1 to 1:10, and are subjected to atmospheric or reduced pressure in the absence of an ester exchange catalyst. The first step of the reaction is carried out at 100-300°C in the presence or absence of dicarbonyl carbonate. When methyl carbonate is used, the resulting methanol is mixed with dimethyl carbonate. The resulting product can be removed to obtain a low molecular weight polycarbonate polyol. The alcohol derived from the carbonate (carbonic acid ester) is distilled off. When diethyl carbonate is used as the ethanol, the resulting ethanol is and a mixture thereof to obtain a low molecular weight polycarbonate polyol. For example, when ethylene carbonate is used as the carbonate, the resulting ethylene glycol The alcohol is removed as a mixture with ethylene carbonate to produce a low molecular weight polycarbonate. Then, in the second step, the reaction product of the first step is Then, the mixture is heated at 160-300°C under reduced pressure to remove unreacted diol and carbonate. Both are produced by condensing low molecular weight polycarbonate polyols to produce polycarbonates of a specified molecular weight. Carbonate polyols can be obtained.

[0055] In addition, the obtained polycarbonate polyol having terminal hydroxy groups may be treated with a different method from the above. A hydroxy compound having a skeleton corresponding to the hydroxy compound is added, and an ester exchange catalyst is added as needed, and the mixture is then heated at normal pressure or Further different structures can be introduced by carrying out the reaction under reduced pressure at 100-300°C. If necessary, the low boiling point hydroxy compound is removed by heating at 120 to 300°C under reduced pressure. At the same time, a low molecular weight polycarbonate polyol is condensed to obtain a polycarbonate having a predetermined molecular weight. Thus, a polycarbonate polyol having terminal hydroxy groups can be obtained.

[0056] In this embodiment, the polycarbonate polyol having a terminal hydroxy group is heated to 50°C. The melt viscosity at this temperature is not particularly limited, but is preferably 500 to 200,000 mPa·s. Preferably, the viscosity is 1,000 to 180,000 mPa·s, more preferably 1 ,500~165,000mPa·s. Melt viscosity at 50℃ is 500mPa·s By satisfying the above conditions, the stress, tensile elongation and chemical resistance of the resulting polyurethane are improved. The melt viscosity at 50°C is 180,000 mPa·s or less, This improves the wettability (contact efficiency) of the composition to be applied to the substrate, making it easier to achieve high adhesive strength. In addition, when used as a sealant raw material, the composition fills the fine details, resulting in high This allows for high insulation reliability.

[0057] In this embodiment, the polycarbonate polyol having a terminal hydroxy group is heated to 50°C. The method for controlling the melt viscosity at 2000 kJ / min to the above range is not particularly limited, but for example, For example, the number of carbon atoms in the diol may be adjusted to a small value. By adjusting the raw material type so that Similarly, the melt viscosity of the polymer tends to be high. When adjusted, the melt viscosity of the polycarbonate polyol having terminal hydroxy groups becomes high. This tends to be the case.

[0058] The method for measuring the melt viscosity in this embodiment is not particularly limited, but for example, the following device may be used: The viscosity can be measured using the Rotational viscometer: E-type viscometer (manufactured by Toki Sangyo Co., Ltd., TVE-22HT, cone: No. 6 )

[0059] The polycarbonate polyol composition of the present embodiment comprises a polycarbonate polyol, A polyol compound having an ester repeating structure and / or an ether repeating structure It may also contain.

[0060] Examples of polyol compounds having an ester repeating structure include polyester polyols. The diol used as a raw material for the polyester polyol is not particularly limited. However, for example, 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, 1,1 0-Decanediol, 1,11-Undecanediol, 1,12-Dodecanediol, 1 ,13-Tridecanediol, 1,14-Tetradecanediol, 1,15-Pentadecanediol Diols without side chains such as 2-methyl-1,8-octanediol, 2 -ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,3-propanediol 2,4-dimethyl-1,5-pentanediol, 2, 4-Diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propane diols, diols with side chains such as 2,2-dimethyl-1,3-propanediol; 1,4-Cyclohexanedimethanol, 2-bis(4-hydroxycyclohexyl)-propanol Examples of cyclic diols include cyclohexanediol and 1,4-cyclohexanediol. are ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4- butanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol. The diol may be one or two types. The above may be used as a raw material for polyester polyol.

[0061] The dicarboxylic acid used as a raw material for the polyester polyol is not particularly limited, but examples thereof include: For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberin aliphatic dicarboxylic acids such as phthalic acid, isophthalic acid, tetracarboxylic ... Examples include aromatic dicarboxylic acids such as benzotricarboxylic acid and naphthalenedicarboxylic acid. More preferably, succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid One or more kinds of dicarboxylic acids can be used to prepare polyester polyols. It may also be used as a raw material for

[0062] A cyclic ester compound is used as a raw material for polyester polyol, and this is subjected to ring-opening polymerization. The cyclic ester compound is not particularly limited, but for example, β-propionyl lactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, β-butyrolactone lactone, γ-valerolactone, α-methyl-ε-caprolactone, β-methyl-ε- Caprolactone, γ-methyl-ε-caprolactone, β,δ-dimethyl-ε-caprolactone t, 3,3,5-trimethyl ε-caprolactone, enantholactone (7-heptanol) Examples of cyclic ester compounds having 3 to 12 carbon atoms include ε-caproate, etc. As the cyclic ester compound, one or more kinds of compounds may be used in the poly It may also be used as a raw material for ester polyol.

[0063] Examples of polyol compounds having an ether repeating structure include polyether polyols. The polyether polyol is not particularly limited, but examples thereof include polypropylene. Propylene glycol, polyethylene glycol, polytetramethylene glycol, propylene glycol Examples of the copolymer include ethylene oxide-ethylene oxide copolymers.

[0064] In the polyol composition, carbonate repeat units: ester repeat units and The molar ratio of the repeating ether structure is not particularly limited, but is preferably from 20:80 to 80:80. Preferably, the ratio is in the range of 30:70 to 75:35. The ratio is preferably in the range of 40:60 to 75:35, and more preferably 45: The ratio of carbonate repeating units to ester repeating units is in the range of 55 to 70:30. and / or the molar ratio of the repeating ether structure is 20:80 or more, The resulting polyol composition has a low melt viscosity and tends to be easy to handle. Structure: The molar ratio of the ester repeating structure and / or the ether repeating structure is 80: 20 or less, the chemical resistance of polyurethane obtained from the polyol composition is improved. This is desirable because it improves the resin functions such as

[0065] Carbonate repeating unit: Ester repeating unit and ether repeating unit The molar ratio of 13 Based on the integral ratio calculated by C-NMR measurement, the carbon structure of each structure was The polycarbonate polyol composition can be calculated by the elemental molar ratio. If necessary, differences in molecular weight and polarity can be used to separate each component using liquid phase chromatography, etc. In addition to the above analytical methods, NMR, IR, TOF- Identification can be performed by SIMS or the like.

[0066] <Component (A)> The polycarbonate polyol composition of the present embodiment contains a compound represented by the following formula (A): (A) component). [ka] (In formula (A), R1 is hydrogen or an alkyl group having 1 to 12 carbon atoms, and R2 is an alkyl group having 1 to 12 carbon atoms.) is an alkylene group having a carbon number of 1 to 12.

[0067] Specific examples of component (A) include 2-butene-1-ol, 3-butene-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 Hexen-1-ol, 2-hepten-1-ol, 3-hepten-1-ol, 4-hepten-1-ol 5-hepten-1-ol, 6-hepten-1-ol, 2-octenol 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-de decene-1-ol, 3-decene-1-ol, 4-decene-1-ol, 5-decene-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 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-dodecen-1 -ol, 7-dodecen-1-ol, 8-dodecen-1-ol, 9-dodecen-1- ol, 10-dodecen-1-ol, 11-dodecen-1-ol, etc. These may be used alone or in combination of two or more. If stereoisomers exist, they may be cis or trans. However, from the viewpoint of the effect on pot life and weather resistance, component (A) is 2-butene-1- ol, 3-buten-1-ol, 3-penten-1-ol, 4-penten-1-ol 5-hexen-1-ol and / or 4-hexen-1-ol are preferred. Preferably, it is 4-hexen-1-ol and / or 5-hexen-1-ol. These may cause odor, so the resulting polyurethane and synthetic leather From the viewpoint of suppressing the generation of odor, a low content is preferred.

[0068] The content of component (A) in the polycarbonate polyol composition is not particularly limited, but , the total mass of the (A) component relative to the total mass of the polycarbonate polyol composition is 0.01 It is more preferable that the content is not less than ppm (0.000001% by mass) and not more than 20% by mass. Preferably, the lower limit may be 0.1 ppm (0.00001 mass%) or more, and 0. It may be 5 ppm (0.00005 mass%) or more, and 1 ppm (0.0001 mass%) In a preferred embodiment, the upper limit may be 10% by mass or less. It may be 5% by mass or less, may be 1% by mass or less, or may be 0.5% by mass or less. When the value is within this preferred range, the production of the obtained polycarbonate polyol is easy. It tends to be less likely to discolor when heated to temperatures above 150°C. Furthermore, the coloring of the resulting polyurethane is suppressed and its stability against light is improved. The component (A) is a by-product produced during the synthesis of polycarbonate polyol. Alternatively, it may be a component added externally.

[0069] <(B) component> The polycarbonate polyol composition of the present embodiment contains a compound represented by the following formula (B): (B) component). [ka] (In formula (B), R3 is an alkylene group having 2 to 12 carbon atoms, and is a linear alkylene group, It may have a 2-valent alicyclic hydrocarbon group or a branched alkylene group.

[0070] Specific examples of component (B) 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. However, the present invention is not limited to these. These may be used alone or in combination. Among these, the most preferable one is selected from the viewpoint of the effect on pot life and weather resistance. From this point of view, component (B) is 1,5-pentanediol and / or 1,6-hexanediol. The alcohols are preferably 1,5-pentanediol and 1,6-hexanediol. It is more preferable that:

[0071] The content of component (B) in the polycarbonate polyol composition is not particularly limited, but , 1 ppm in total mass of component (B) relative to the total mass of the polycarbonate polyol composition It is preferable that the content is 0.0001% by mass or more and 40% by mass or less. The lower limit may be 10 ppm (0.001 mass%) or more, and 100 ppm ( In a preferred embodiment, the upper limit is 30% by mass. It may be 20% by mass or less, or 10% by mass or less. By keeping the viscosity within the preferred range, the viscosity of the resulting polycarbonate polyol can be kept within a good range. In addition, when it is reacted with isocyanate to form urethane, the reaction product of the formula (B) The component functions as a chain extender and acts as a hard segment, providing chemical resistance. The resin functions are improved, which is preferable. It may be a by-product produced during the synthesis of the polymer, or may be a component added externally.

[0072] <(B') component> The polycarbonate polyol composition of the present embodiment may further contain a compound (component (B')) represented by the following formula (B'): [ka] (In formula (B'), R4 is a group having 1 to 4 carbon atoms. Alkyl group )

[0073] Specific examples of the component (B') include methanol, ethanol, propanol, These may be used alone or in combination of two or more. Among these, from the viewpoint of the effect on pot life and weather resistance, (B') composition The solvent is preferably methanol and / or ethanol.

[0074] The content of component (B') in the polycarbonate polyol composition is not particularly limited. is the total mass of component (B') relative to the total mass of the polycarbonate polyol composition. It is preferably 1 ppm (0.00001 mass%) or more and 10 mass% or less. In one embodiment, the lower limit may be 1 ppm (0.0001 mass%) or more, and 10 ppm (0.001% by mass) or more. In a preferred embodiment, the upper limit is It may be 5% by mass or less, 3% by mass or less, or 1% by mass or less. By being within the preferred numerical range, the viscosity of the obtained polycarbonate polyol can be favorably controlled. In addition, when reacted with isocyanate to form urethane, the formula ( Component B' functions as a terminal terminator and suppresses gelation during urethane synthesis. The component (a) may be a by-product during the synthesis of polycarbonate polyol, or may be a separate external component. It may also be an added component.

[0075] The mass ratio of the component (B') to the component (B) ((B') / (B)) is particularly Although not limited to this, it is preferable that the value is 0.0001 to 1.000. By being within this range, the viscosity of the resulting polycarbonate polyol can be kept within a favorable range. In addition, when it is reacted with isocyanate to form urethane, the component of formula (B') is formed at the end. It functions as a terminal stopper and prevents gelation during urethane synthesis.

[0076] <Mass ratio of component (A) to component (B)> The content ratio of the aforementioned (B) component and (A) component is (A) to the total of the (B) component. The total mass ratio of the components ((A) / (B)) is preferably 0.0001 to 0.1000. , 0.0005 to 0.0800 is more preferable, and 0.0010 to 0.0700 is even more preferable. When the mass ratio ((A) / (B)) is within this preferred range, The pot life during the urethane reaction is within an appropriate range, and the polyurethane obtained The coloring of the composition is also suppressed, and the stability against light tends to be improved.

[0077] <Preferred mode> In one embodiment, the polycarbonate polyol having terminal hydroxy groups is Repeating units derived from 1,5-pentanediol and / or 1,6-hexanediol It is preferable that the compound represented by formula (A) has a unit, and that R1 in formula (A) is a compound in which R is a hydrogen atom and R2 is an alkylene group having 4 or 3 carbon atoms; a compound in which 1 is an alkylene group having 1 carbon atom and R2 is an alkylene group having 3 or 2 carbon atoms; In the formula (A), R1 is an alkylene group having 2 carbon atoms and R2 is an alkylene group having 2 or 1 carbon atoms. It is preferable that the compound contains one selected from the group consisting of compounds that are alkylene groups.

[0078] In addition, in the compound represented by formula (A) and the compound represented by formula (B), R1 and R2 It is preferable that the sum of the total number of carbon atoms is equal to the number of carbon atoms in R3. More specifically, The sum of the carbon numbers of R1 and R2 of the compound to be treated is 5 or 6 plus two carbon atoms, It is preferable that this is equal to the number of carbon atoms in R3 of the compound represented by formula (B).

[0079] <Optimal condition> In the preferred embodiment described above, a specific example of component (A) is 4-pentene-1-ol. 3-penten-1-ol, 4-hexen-1-ol and / or 5-hexen-1-ol -1-ol is preferred, and the raw material constituting the repeating unit of polycarbonate polyol is It is preferable that the diol contains 1,5-pentanediol and 1,6-hexanediol. Specific examples of the component include 1,5-pentanediol and 1,6-hexanediol. In this case, the mass ratio of the component (A) to the component (B) is preferably 0.0001. Preferably, it is 0.0001 to 0.075, and more preferably 0.0001 It is more preferably 0.0001 to 0.010, and more preferably 0.00 A range of 6 to 0.010 is particularly preferred.

[0080] The analytical method for the aforementioned components (A) and (B) is not particularly limited, but the analysis of trace components From an analytical perspective, gas chromatography (GC) and gas chromatography mass spectrometry (GC / MS) are used. The dissolution of the sample in the above analysis is performed by a person skilled in the art. For example, the injection sample is 2.0 g of the polycarbonate composition. The sample was collected in a 20 ml measuring flask, and dissolved in chloroform up to the mark. 1 μl can be collected and analyzed.

[0081] <Metal element content> In one embodiment, the polycarbonate polyol composition has a viscosity of 1000 ppm or less as measured by ICP. , titanium, ytterbium, tin, zirconium, magnesium, calcium, lithium , sodium, and manganese. The amount is not particularly limited, but it is preferably 0.00 based on the total amount of the polycarbonate polyol composition. It is preferably 0.01 to 0.050 mass%, more preferably 0.0005 to 0.020 mass%. In the polycarbonate polyol composition, when measured by ICP, Titanium, ytterbium, tin, magnesium, calcium, lithium, and Manganese is 0.0001 to 0.05 with respect to the total amount of the polycarbonate polyol composition. It is preferably 0 mass %, and more preferably 0.0005 to 0.020 mass %. It's nice.

[0082] In another embodiment, the polycarbonate polyol composition has a viscosity of 1000 ppm or less as measured by ICP. , titanium, tin, magnesium, calcium, lithium and / or manganese The content of at least one metal element selected from the group is not particularly limited. It is preferable that the content of the ester polyol is 0.0001 to 0.050% by mass relative to the total amount of the ester polyol composition. The content is preferably 0.0005 to 0.020 mass %, and more preferably 0.0005 to 0.020 mass %.

[0083] In this embodiment, the content of metal elements in the polycarbonate polyol composition can be measured by the method described in the Examples below.

[0084] <Phosphorus compounds> The polycarbonate polyol composition of the present embodiment can be used, for example, as a raw material for polyurethane. When used in the production of polycarbonate polyol, the catalyst used in the production of polycarbonate polyol is treated with a phosphorus compound. The phosphorus compound is not particularly limited, but examples thereof include trimethylphosphite. Phosphate, Triethyl Phosphate, Tributyl Phosphate, Di-2-ethylhexyl Phosphate, Triphenyl Phosphate, Tricresyl Phosphate, Cresyl Diphosphate Phosphate triesters such as phenyl phosphate; methyl acid phosphate, ethyl acetate Acid phosphate, propyl acid phosphate, isopropyl acid phosphate Acid phosphate, butyl acid phosphate, lauryl acid phosphate, stearyl acid Phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate Acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetraco Cyl acid phosphate, acetylene glycol acid phosphate, 2-hydroxy Ethyl methacrylate acid phosphate, dibutyl phosphate, monobutyl phosphate phosphate, monoisodecyl phosphate, bis(2-ethylhexyl) phosphate, etc. Acid phosphate esters; triphenyl phosphite, trisnonylphenyl phosphite, Tricresyl phosphite, triethyl phosphite, tris(2-ethylhexyl) phosphite Phosphite, tridecyl phosphite, trilauryl phosphite, tris(tridecyl ) phosphite, trioleyl phosphite, diphenyl mono (2-ethylhexyl) phosphite Phosphite, diphenyl monodecyl phosphite, diphenyl (monodecyl) phosphite phosphate, trilauryl phosphite, diethyl hydrogen phosphite, bis(2-ethyl Hexyl) Hydrogen Phosphite, Dilauryl Hydrogen Phosphite, Diolayl Diphenylhydrogen phosphite, diphenylhydrogen phosphite, tetraphenyldi Propylene glycol diphosphite, bis(decyl)pentaerythritol diphosphite phosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite , phosphite esters such as tris(2,4-di-tert-butylphenyl) phosphite further examples include, but are not limited to, phosphoric acid, phosphorous acid, hypophosphorous acid, etc. These may be used alone or in combination of two or more.

[0085] The polycarbonate polyol composition of the present embodiment may contain a phosphorus compound. In the polycarbonate polyol composition of the present embodiment, the content of the phosphorus compound is, in particular, Although not limited thereto, the content of phosphorus (P) measured using ICP is It is preferable that the content of the polyol component is 0.0001 to 0.050% by mass relative to the total amount of the polyol composition. In the polycarbonate polyol composition of the present embodiment, the content of the phosphorus compound is If the value is within the desired range, when the material is used as a raw material for polyurethane, the polyurethane The influence of the catalyst used in the production of the polycarbonate polyol composition on the production reaction of the polycarbonate polyol was investigated. Furthermore, phosphorus compounds can be used in polyurethane manufacturing reactions and reaction products. The polycarbonate polyol composition also tends to have less effect on the physical properties of the composition. In the composition, the content of phosphorus (P) measured by ICP is It is more preferable that the content of the polyol is 0.0005 to 0.020% by mass relative to the total amount of the polyol composition. I wish.

[0086] The polycarbonate polyol of this embodiment has a structure represented by the above formula (A) at its terminal. The unit may be a structural unit represented by the following formula (P) in which the units are bonded. [ka] (In formula (P), R1 is any divalent aliphatic hydrocarbon group, and R2 is hydrogen or any R3 is any divalent aliphatic hydrocarbon group, (A) R1 to R3 are the same as R1 to R3.)

[0087] In the polycarbonate polyol of this embodiment, The terminal group other than the hydroxyl group is not particularly limited, but examples thereof include alkyl groups, vinyl groups, and the like. Examples of the alkyl group include an alkyl group and an aryl group.

[0088] In this embodiment, the amount of hydroxyl groups in the terminal groups is measured using the method described below. This can be done.

[0089] Hydroxyl group terminal purity The hydroxyl-terminated purity can be calculated by the following formula. [1] Hydroxyl-terminated purity = [[[2] Amount of terminal hydroxyl groups of polycarbonate polyol]] / [[[3]] Amount of terminal groups of polycarbonate polyol [2] Amount of terminal hydroxyl groups of polycarbonate polyol = [[[4] Total amount of hydroxyl groups]] - [[[5] Remaining Hydroxyl group amount of hydroxy compound [4] Total amount of hydroxyl groups: The amount of hydroxyl groups calculated from the hydroxyl value (the total of the terminal hydroxyl group amount of polycarbonate polyol and the hydroxyl group amount of the remaining hydroxy compound) [5] Hydroxyl group amount of remaining hydroxy compound: The total hydroxyl group amount of each free hydroxy compound measured in b below [3] Amount of terminal groups of polycarbonate polyol = [[[2] Amount of terminal hydroxyl groups of polycarbonate polyol]] + [[[6] Amount of monohydroxy groups in the backbone of polycarbonate polyol]] [6] Amount of monohydroxy groups in the backbone of polycarbonate polyol = [[[7] Total amount of monohydroxy groups]] - [[[8] Amount of free monohydroxy groups]] [7] Total amount of monohydroxy groups: The hydroxyl group amount of all monohydroxy compounds measured in a below [8] Amount of free monohydroxy groups: The hydroxyl group amount of all free monohydroxy compounds measured in b below

[0090] [a. Analysis of all hydroxy compounds constituting polycarbonate polyol] The ratio of the constituent units of polycarbonate polyol can be measured by the following method. Take 1 g of polycarbonate polyol into a 100 mL eggplant flask and add an internal standard As a substance, 0.1 g of diethylene glycol diethyl ether, further 30 g of ethanol and 4 g of potassium hydroxide are added, and a hydrolysis reaction is carried out at 100 °C for 1 hour. After cooling to room temperature, 2 to 3 drops of phenolphthalein are added to the eggplant flask as an indicator, and neutralized with hydrochloric acid to do. After cooling the eggplant flask in a refrigerator for 1 hour, the precipitated salt is removed by filtration, a composition analysis solution is obtained. The obtained composition analysis solution is analyzed for the hydroxy compound components contained in the polycarbonate polyol by gas chromatography (GC). Each hydroxy compound concentration can create a calibration curve from each hydroxy compound known in advance as a standard substance, and the mass% can be calculated from the area ratio obtained by gas chromatography (GC). <b. Analysis of residual hydroxy compounds in polycarbonate polyol>

[0091] 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 the residual hydroxy compound is measured by GC analysis.

[0092] <Water content> In the polycarbonate polyol composition of the present embodiment, the water content is not particularly limited, but it is preferably 10 to 500 ppm with respect to the total amount of the polycarbonate polyol composition. If the water content of the polycarbonate polyol composition of the present embodiment is 500 ppm or less, it is preferable because clouding due to the reaction between water and isocyanate tends to be difficult to occur. Also, if the water content of the polycarbonate polyol composition of the present embodiment is 10 ppm or more, side reactions during urethanization are suppressed, and a urethane coating film excellent in yellowing is easily obtained.

[0093] In the polycarbonate polyol composition, the water content is The content of the polycarbonate polyol is preferably 15 to 200 ppm relative to the total amount of the polycarbonate polyol composition. More preferable.

[0093] <Other additives> When a polyurethane is produced using the polycarbonate polyol composition of this embodiment, In some cases, curing accelerators (catalysts), fillers, flame retardants, dyes, organic or inorganic additives may be added depending on the application. Pigments, release agents, flow control agents, plasticizers, antioxidants, UV absorbers, light stabilizers, antifoaming agents, Belling agents, colorants, foaming agents, etc. may be added.

[0094] The curing accelerator is not particularly limited, but examples thereof include amines and metal catalysts. can be. The amine effect accelerator is not particularly limited, but for example, triamine, which is a monoamine, Ethylamine, N,N-dimethylcyclohexylamine, diamine tetramethyl ethylamine ethylenediamine, other triamines, cyclic amines, amines such as dimethylethanolamine Examples of the metal catalyst include alcoholamines and etheramines. For example, potassium acetate, potassium 2-ethylhexanoate, calcium acetate, octyl Lead nitrate, dibutyltin dilaurate, stannous octoate, bismuth neodecanoate, bismuth octoate Bismuth carbonate, bismuth 2-ethylhexanoate, zinc octylate, zinc neodecanoate Examples thereof include noate, phosphine, and phospholine.

[0095] The fillers and pigments are not particularly limited, but examples thereof include woven fabric, glass fiber, carbon fiber, Polyamide fiber, mica, kaolin, bentonite, metal powder, azo pigment, carbon black , clay, silica, talc, gypsum, alumina white, barium carbonate, calcium carbonate, etc. can be done.

[0096] The release agent, flow control agent, and leveling agent are not particularly limited, but examples thereof include silicone. Aerosil, wax, stearate, BYK-331 (BYK Chemicals) Examples of suitable polysiloxanes include polysiloxanes such as:

[0097] When a polyurethane is produced using the polycarbonate polyol composition of this embodiment, In this case, additives that are preferably used include antioxidants, light stabilizers, heat stabilizers, and flame retardants. I wish.

[0098] The antioxidant is not particularly limited, but examples thereof include phosphoric acid, phosphorous acid, aliphatic, aromatic or or alkyl-substituted aromatic esters, hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphine Sphinic acid, diphenylphosphonic acid, polyphosphonate, dialkylpentaerythritol Phosphorus compounds such as alkyl diphosphite, dialkyl bisphenol A diphosphite; phenol derivatives, especially hindered phenol compounds, thioethers, dithioate salts, mercury Ions such as benzimidazoles, thiocarbanilides, and thiodipropionates Compounds containing tin; tin compounds such as tin maleate and dibutyltin monoxide These may be used alone or in combination of two or more.

[0099] <Inert organic solvent> The polycarbonate polyol composition of the present embodiment is a polyol having a viscosity of 1000 to 15000 MPa, and is a polyol having a viscosity of 1000 to 1500 MPa. In order to achieve this, an inert organic solvent may be contained as necessary. The content of the inert organic solvent is The amount of the polycarbonate polyol is preferably 40% by mass or less, more preferably 50% by mass or less, based on the total amount of the polycarbonate polyol composition. Preferably, the content is 3% by mass or more and 30% by mass or less, and more preferably 5% by mass or more and 20% by mass or less. It reduces the viscosity of the polycarbonate polyol composition and improves the workability during the production of synthetic leather. In order to further improve the appearance of the resulting synthetic leather, it is necessary to add an inert organic solvent. However, the solvents used in the process are expensive and require expensive solvent recovery equipment. It is released into the atmosphere after the drying process, so it is subject to VOC (Volatile Organic Compounds) The content of inert organic solvents may increase. To reduce the environmental impact, the amount of solvent used should be kept low, or ideally, no solvent should be used at all. preferable.

[0100] The inert organic solvent is particularly any organic solvent that is substantially inert to polyisocyanates. The inert organic solvent is not limited to the above, and is preferably one that does not have active hydrogen. Examples of the solvent include, but are not limited to, pentane, hexane, heptane, octane, decane, Petroleum ether, petroleum benzine, ligroin, petroleum spirit, cyclohexane, methyl cyclohexane hydrocarbons such as hexane; trichlorofluoroethane, tetrachlorodifluoroethane fluorinated inert liquids such as perfluoroether and other fluorinated oils; perfluorocyclohexyl; perfluorobutyltetrahydrofuran, perfluorodecalin, perfluoro-n -butylamine, perfluoropolyether, dimethylpolysiloxane, etc. These may be used alone or in combination. These include methyl ethyl ketone (also written as MEK), acetone, ethyl acetate, and butyl acetate. , toluene, xylene, dimethylformamide (DMF), dimethylacetamide (DM Ac), dimethyl sulfoxide, diethylformamide, dimethylacetamide, N-methyl N-ethylpyrrolidone, N-ethylpyrrolidone, tetrahydrofuran (THF), dioxane, etc. The above solvents may be used singly or in combination.

[0101] In this specification, the term "active hydrogen" refers to an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, or the like. It means a hydrogen atom bonded to a hydrogen atom or the like, and a hydrogen atom of a terminal methine group. "Active hydrogen" includes, for example, an -OH group, a -C(=O)OH group, a -C(=O)H group, and a -SH group. , -SO3H group, -SO2H group, -SOH group, -NH2 group, -NH- group, -SiH group, -C ≡ refers to hydrogen contained in an atomic group such as a CH group.

[0102] The polycarbonate polyol composition of the present embodiment may be a curable composition, By this reaction, polyurethane can be formed. The resulting polyurethane can be used as synthetic leather. In addition to synthetic leather that uses knitted or woven fabric as the base fabric, "synthetic leather" in The concept includes the artificial leather used. When hardening, isopropyl alcohol may be used as a hardener if necessary. Cyanates may also be used. Such isocyanates are not particularly limited. However, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and its mixtures, diphenylmethane-4,4'-diisocyanate (MDI), naphthalene NDI, 3,3'-dimethyl-4,4'-biphenylene Diisocyanate (TODI), Polymethylene Polyphenylene Polyisocyanate (PM Aromatic diisocyanates such as xylylene diisocyanate (XDI), phenylene Aromatic aliphatic diisocyanates such as 4,4'-methylenebiscyclohexane Xyl diisocyanate (hydrogenated MDI), hexamethylene diisocyanate isophorone diisocyanate (HDI), isophorone diisocyanate (IPDI), cyclohexane diisocyanate Aliphatic diisocyanates such as diisocyanates (hydrogenated diisocyanates); etc. Use polyisocyanate with an average of 2.1 or more isocyanate groups per molecule. Polyisocyanate with an average of 2.1 or more isocyanate groups per molecule Examples include aromatic polyisocyanates such as crude MDI and crude TDI; HDI and IPDI. Derivatives of aliphatic isocyanates such as biuret, allophanate, uretidine, etc. Diisocyanate derivatives such as isocyanurates and polyhydric alcohol adducts In addition, commercially available isocyanates include, for example, Sumidur 44S, 44V70 (both manufactured by Sumika Bayer Urethane), copolymer of TDI and HDI Dismodur HL (manufactured by Sumika Bayer Urethane), which is a Duranate, namely Duranate 24A-100, Duranate 22A-75PX, Duranate 18H-70B, Duranate 21S-75E, Duranate THA-100 , Duranate TPA-100, Duranate TKA-100, Duranate TLA-1 00, 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 Duranate ME20-B80S, Duranate WB40-100, Duranate WB40-8 0D, Duranate WT20-100, Duranate WT30-100, etc. are available. do.

[0103] <Method for producing polycarbonate polyol composition> The polycarbonate polyol composition of the present embodiment is produced using a method generally used in industry. It can be produced by the method.

[0104] The polycarbonate polyol composition of the present embodiment may be, for example, a polyol having a terminal hydroxy group. Polycarbonate polyol, inert organic solvents and additives as needed, are all mixed together. It can be produced by a method of mixing and reacting (hereinafter referred to as the "one-shot method"). In addition, the polycarbonate polyol composition of the present embodiment can be, for example, Isocyanate-terminated prepolyols derived from polycarbonate polyols containing hydroxy groups. or hydroxyl-terminated polycarbonate polyols. Hydroxyl-terminated prepolymers were prepared in advance, and these prepolymers were mixed with isocyanates. The esters and / or polyols are mixed with an inert organic solvent and additives as required. It can be produced by a method of reacting a Here, one type of prepolymer may be used, or two or more types may be used.

[0105] <Manufacturing method for synthetic leather> A method for producing polyurethane using the polycarbonate polyol composition of the present embodiment By applying this method, synthetic leather can be produced. The method for producing synthetic leather using the oil composition is not particularly limited, but for example, The polyurethane produced using the polycarbonate polyol composition of this embodiment is A wet method in which the material (base fabric) is coated or impregnated with the material and wet-set. The polyurethane produced using the polyol composition is applied to release paper or a substrate (fabric). Furthermore, methods for producing synthetic leather include the dry method, which involves drying the leather using release paper. The polyurethane produced using the polycarbonate polyol composition of this embodiment was After the surface material is formed by coating, the polycarbonate polyol composition of the present embodiment is applied thereon. The polyurethane produced using this material is used as an adhesive layer to bond the base material (fabric). Transfer coating (a type of dry method) is used, in which the release paper is removed after the coating is applied. That is, the composition of the present embodiment can be used in an adhesive layer for synthetic leather. The polycarbonate polyol composition of the present embodiment can reduce the amount of inert organic solvent used. Therefore, the dry method (transfer coating method) is preferably used.

[0106] From the above, a preferred embodiment of the polycarbonate polyol composition of the present embodiment is In addition, the polycarbonate polyol composition of the present embodiment may be an adhesive composition. A preferred embodiment is a water-based polyurethane. A preferred embodiment of the polyol composition may be a water-dispersed composition.

[0107] The method for producing polyurethane for synthetic leather and synthetic leather will be explained below using the dry method as an example. As the substrate (base fabric), various materials can be used, and there is no particular limitation. For example, fibrous The fibrous substrate is not particularly limited, but for example, a fiber substrate such as a nonwoven fabric A fiber aggregate in the form of a woven fabric, a mesh fabric, a buffed fabric, or the like, or a fiber aggregate Examples of such fibers include those in which the fibers are bonded together with an elastic polymer. The fibers that can be used are not particularly limited, but include, for example, natural fibers such as cotton, linen, and wool; Regenerated or semi-synthetic fibers such as yon, acetate, polyamide, polyester, polyacrylonitrile Examples include synthetic fibers such as nitrile, polyvinyl alcohol, and polyolefin. The fibers may be either single spun fibers or mixed spun fibers. However, for example, paper, release paper, polyester or polyolefin plastic filler Examples of the substrate include a metal plate such as aluminum, and a glass plate.

[0108] The polycarbonate polyol composition of the present embodiment is useful for adhesive compositions, compositions for synthetic leather, or polyurethane for synthetic leather, and apply it in a manner commonly used The coating method is not particularly limited, but for example, a floating knife coating method can be used. Knife over roll coater, reverse roll coater, roll doctor coater Examples of the coater include a gravure roll coater and a kiss roll coater.

[0109] <Synthetic leather> The resulting synthetic leather can be used as is. Alternatively, the synthetic leather can be further processed. In order to give them various properties, polyurethane resin, vinyl chloride resin, cellulose resin, etc. The polymer solution or emulsion may be applied to synthetic leather. Synthetic leather is obtained by drying the above polymer solution or emulsion that has been applied to a separate release paper. After laminating the coated film, the release paper can be peeled off to obtain a laminate. The synthetic leather obtained from the polycarbonate polyol composition of this embodiment has excellent handling properties. In a more preferred embodiment, the composition further has little odor and is weather resistant. It is possible to achieve a product with an excellent balance of chemical properties.

[0110] The present embodiment will be described below with reference to the drawings. The above is one example of the present embodiment, and the present embodiment is not limited to this example.

[0111] FIG. 1 is a schematic cross-sectional view of a synthetic leather laminate produced by the dry method shown in FIG. The structure of the layered body is a surface layer 2 on a base material (polyester woven fabric) 4 via an adhesive layer 3. The outermost layer has release paper 1 attached, which was used during manufacturing, but it is peeled off before use. .

[0112] FIG. 2 shows a polycarbonate polyol produced using the polycarbonate polyol composition of the present embodiment. FIG. 1 is a schematic diagram showing one method for producing a dry synthetic leather laminate sheet using urethane. In the production method, first, the polycarbonate polymer of the present embodiment, which has been previously prepared at a predetermined temperature, is heated. The raw materials of the all-composition are mixed in the mixing head 5 to obtain a polycarbonate polyol. The coating composition (for the surface layer) is poured onto a release paper 1 (usually having a leather-like pattern).

[0113] When the one-shot method is applied, the polycarbonate polyol composition of this embodiment Inert organic solvents and additives, if necessary, are added separately or together in the mixing head. The polyol component is continuously fed to the polyol feeder 5, mixed, and then dropped onto the release paper 1. Alternatively, two or more types may be used simultaneously.

[0114] When the prepolymer method is applied, the polycarbonate polyol composition of this embodiment The derivatized isocyanate-terminated prepolymer and polyols, or the polyols of this embodiment, Hydroxyl-terminated prepolymers derived from carbonate polyol compositions and isocyanates The mixture of an anate and, if necessary, an inert organic solvent and additives is poured into the mixing head. The mixture is continuously fed into the mold 5, mixed, and then allowed to flow down onto the release paper 1.

[0115] Before mixing, the components are usually heated to a temperature of 20 to 80°C, preferably 30 to 70°C, and more preferably The temperature of the mixing head 5 is adjusted to 40 to 60°C. The temperature is adjusted to preferably 30 to 70°C, more preferably 40 to 60°C. The temperature of each component and the temperature of the mixing head 5 are 20°C or higher. The viscosity of the raw materials is reduced and the flow rate tends to be stable. The temperature of the kissing head 5 is 80° C. or less, so that the polycarbonate of this embodiment The curing rate of the polyol composition is appropriately controlled, and the rapid curing of the polycarbonate polyol composition is This tends to prevent a sudden increase in viscosity and result in a uniform thickness of synthetic leather.

[0116] Thereafter, the mixture is passed through a coating roll 8 to form a sheet of a certain thickness, and then passed through a dryer 11. The synthetic leather surface layer 2 is formed by hardening and drying the inert organic solvent. The temperature is usually set to 60 to 150°C, preferably 70 to 130°C, and more preferably 80 to 110°C. The drying time is usually 2 to 15 minutes, preferably 3 to 10 minutes, more preferably 10 to 20 minutes. is 4 to 7 minutes.

[0117] Next, the polycarbonate polyol composition of the present embodiment prepared in advance is heated to a predetermined temperature. The polycarbonate of this embodiment is obtained by mixing the raw materials in a mixing head 6 (for adhesive layer). The nate polyol composition is then poured down to form the adhesive layer 3. The adhesive layer is produced by the one-shot method. When applied, the polycarbonate polyol composition of this embodiment and, if necessary, Active organic solvents and additives are continuously fed into the mixing head 6 separately or simultaneously. When the prepolymer method is used to manufacture the adhesive layer, A prepolymer composition, a non-prepolymerized polyol, and an inert solvent, if necessary. The organic solvent and additives are fed separately or simultaneously into a mixing head 6 continuously. Mix and pour onto the epidermal layer.

[0118] Before mixing, the components are usually heated to a temperature of 20 to 60°C, preferably 30 to 50°C, and more preferably The temperature of the mixing head 6 is usually adjusted to 35 to 45°C. The temperature is adjusted to preferably 30 to 50°C, more preferably 35 to 45°C. The temperature of the ingredients and the temperature of the mixing head 6 are 20°C or higher. The viscosity of the raw materials is reduced and the flow rate tends to be stable. The temperature of the kissing head 6 is 60° C. or less, so that the polycarbonate of this embodiment The curing rate of the polyol composition is appropriately controlled, and the rapid curing of the polycarbonate polyol composition is This tends to prevent a sudden increase in viscosity and result in a uniform thickness of synthetic leather.

[0119] Thereafter, the mixture is passed through a coating roll 8 to form a sheet of a certain thickness, and then passed through a dryer 11. After hardening and drying of the inert organic solvent, the adhesive layer 3 of the synthetic leather is formed. The adhesive layer 4 and the adhesive layer 3 are superimposed and pressed together by a pressing roll 9, and then a sheet structure 7 is obtained and wound up. The desired synthetic leather laminate is obtained by winding it up on a roll 10. The temperature of the dryer 11 is usually 50 to 1 The temperature is set to 10°C, preferably 60 to 100°C, and more preferably 70 to 90°C. The time is usually 2 to 15 minutes, preferably 3 to 10 minutes, and more preferably 4 to 7 minutes.

[0120] In Figure 2, an example of the production of synthetic leather including three layers, a skin layer, an adhesive layer, and a substrate, is shown. The synthetic leather laminate, which includes the two layers of skin layer / substrate, can also be manufactured using the same equipment. The adhesiveness between the skin layer and the substrate can be controlled by adjusting the curing state of the polycarbonate polyol composition. Specifically, the polycarbonate polyol composition of the present embodiment is This can be obtained by pressing the substrate in a state where the cured film is not completely cured. The curing temperature is 50 to 110°C, preferably 60 to 100°C, and more preferably 70 to 90°C. The drying time is usually set to 2 to 15 minutes, preferably 3 to 10 minutes, and more preferably is set to 4 to 7 minutes.

[0121] A surface treatment agent may be applied to the surface layer, and the structure of surface treatment agent / surface layer / adhesive layer / substrate may be used. It may be a synthetic leather laminate including four layers, or a synthetic leather including three layers of surface treatment agent / surface layer / substrate. It may also be a leather laminate.

[0122] <Application> Polyurethane / polyurethanes produced using the polycarbonate polyol composition of this embodiment Synthetic leather obtained using urethane cured products is used for automobile interior materials such as car seats, It can be used for furniture such as cars, clothing, shoes, bags, and other miscellaneous goods, especially in automobiles. It can be suitably used as synthetic leather (polyurethane for synthetic leather) for decorative materials. Polyurethanes produced using the polycarbonate polyol compositions of the present invention are useful in adhesive compositions. It is also used as a laminating adhesive for various films and as a surface protective agent. Water-based polyurethane / water-based composition prepared using the polycarbonate polyol composition of the embodiment The dispersion composition is used as a material for various purposes, such as paints and coating agents, in addition to the synthetic leather described above. It is possible.

[0123] [Method of producing water-based polyurethane] The method for producing the water-based polyurethane of this embodiment is not particularly limited, and a known method can be used. For example, a mixture of a polyol, a polyisocyanate, and a hydrophilic group-containing compound can be used. By reacting the two, a urethane prepolymer having an isocyanate group at the end is produced. a step (prepolymer step), and a step of reacting the urethane prepolymer with a chain extender. It can be produced by undergoing a chain elongation step.

[0124] (Polyol) The polycarbonate polyol of this embodiment can be used to produce water-based polyurethane. In addition to the polycarbonate polyol of this embodiment, other polycarbonate polyols are also available, including but not limited to the following: However, polyester polyol, acrylic polyol, polyether polyol, polyole Fin polyols, fluorine polyols, etc. can be used alone or in combination of two or more types. It is possible.

[0125] Among these, the flexibility of the cured urethane obtained using an aqueous composition containing water-based polyurethane is In terms of the properties and durability, in addition to the polycarbonate polyol of this embodiment, polyester Polyols, polyether polyols, and fluorine polyethers can be preferably used. The polycarbonate polyol, polyester polyol, and polyether polyol of this embodiment A combination of a terpolyol is more preferred, and the polycarbonate polyol of this embodiment and polyester polyol combinations are more preferred.

[0126] (Polyisocyanate) Polyisocyanates used in the production of water-based polyurethanes are limited to the following: However, phenylene diisocyanate, tolylene diisocyanate, diphenyl methacrylate Diisocyanate, Naphthalene diisocyanate, Polymethylene polyphenyl polyisocyanate aromatic polyisocyanates such as cyanates and carbodiimidized diphenylmethane polyisocyanates cyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexyl San diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate anate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, da Aliphatic or alicyclic structures such as mer diisocyanate and norbornene diisocyanate These may be used alone or in combination of two or more. They can be used in combination.

[0127] Among these, urethane curing agents obtained using an aqueous composition containing water-based polyurethane are From the viewpoint of durability of the product, it is preferable to use a polyisocyanate having an alicyclic structure. Instead, use isophorone diisocyanate or dicyclohexylmethane diisocyanate. It is more preferable that

[0128] (Hydrophilic group-containing compound) The isocyanate compounds used in the production of water-based polyurethane are limited to the following: Not specified, but 2,2'-dimethylolpropionic acid, 2,2'-dimethylolbutanoic acid 2,2'-dimethylol butyric acid, 2,2'-dimethylol valeric acid, etc. Polyols that contain 5-sulfoisophthalic acid, sulfoterephthalic acid, and 4-sulfophthalic acid and polyols having a sulfonic acid group such as 5[4-sulfophenoxy]isophthalic acid. These can be used alone or in combination of two or more.

[0129] (Chain extender) Chain extenders used in the production of waterborne polyurethanes include, but are not limited to: , ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, Perazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexyl Silmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine diamines such as 1,4-cyclohexanediamine; N-hydroxymethylaminoethyl Amines, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropyl 1 unit of N-propylamine, N-ethylaminoethylamine, N-methylaminopropylamine, etc. Diamines containing one primary amino group and one secondary amino group; diethylenetriamine, di Polyamines such as propylenetriamine and triethylenetetramine; hydrazine, N,N hydrazines such as '-dimethylhydrazine and 1,6-hexamethylenebishydrazine; Cinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid Dihydrazides such as dihydrazide, isophthalic acid dihydrazide; β-semicarbazide proton Pionic acid hydrazide, 3-semicarbazido-propyl-carbazic acid ester, semica Semicarbazid-3-semicarbazidmethyl-3,5,5-trimethylcyclohexane, etc. These may be used alone or in combination of two or more. It can be used.

[0130] (organic solvent) If necessary, an organic solvent may be used in the prepolymer process when producing water-based polyurethane. Examples of organic solvents that can be used in the prepolymerization process include acetone, methyl ... Ketones such as ethyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetic acid Acetate esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; dimethylformamide These may be used alone, Alternatively, two or more types can be used in combination.

[0131] [Component (C): Curing agent] The aqueous composition of this embodiment comprises the water-dispersible polyol (component A) and the water-dispersible polyurethane. In addition to the tan (component B), a curing agent (component C) may also be contained.

[0132] The curing agent (component C) is a compound that reacts with the hydroxyl groups of the water-dispersible polyol (component A) and / or the above-mentioned water-dispersible polyol. It has reactive groups that can react with the terminal groups and / or hydrophilic groups of the polyurethane (component B). There are no particular limitations on the type, provided that it has such a reactive group, but it is preferable to use one having two or more reactive groups.

[0133] Examples of compounds having such reactive groups include isocyanate compounds and carbodiimides. Examples of the compound include, but are not limited to, imide compounds and aziridine compounds. Among these, isocyanate compounds are preferred.

[0134] The isocyanate compound may be a commercially available product or may be synthesized by a known method. good.

[0135] As commercially available isocyanate compounds, the same ones mentioned above can be used. , and a duplicated explanation will be omitted here.

[0136] (NCO / OH ratio) When using isocyanate as a curing agent, the content of the isocyanate compound in the aqueous composition In view of the durability of the urethane cured product obtained using the aqueous composition, the component (A) The number of moles of hydroxyl groups (OH groups) contained in the component (B) is The ratio of the number of moles of isocyanate groups (NCO groups) contained in the component (C) to the number of moles of isocyanate groups (NCO groups) contained in the component (C) (NC The ratio (moles of O groups / moles of OH groups) is preferably 0.2 to 7.0, and more preferably 0.5 to 5. It is more preferable that the ratio is 0, and further more preferable that the ratio is 0.8 to 3.0. It is particularly preferred that it is 0.5, and most preferred that it is 0.8 to 2.0.

[0137] From the viewpoint of durability of the urethane cured product, it is preferable that the curing agent has a cyclic structure. It is more preferable that the alkyl group has a socyanurate ring.

[0138] [Curable composition] The curable composition of this embodiment includes the above-described aqueous composition. The curable composition can be produced from the polycarbonate polyol of this embodiment. Examples of the water-based composition include paints, polyurethanes, coating agents, etc. The curable composition of the present embodiment contains the above-mentioned aqueous composition, and therefore, the curable composition can be dried in a short time. The cured product tends to be thinner, more flexible, and more durable.

[0139] The curable composition of the present embodiment may contain other components in addition to the above-described aqueous composition. The other components are not particularly limited, but examples thereof include polyhydric alcohol compounds, water-dispersible polymers, Ester polyol, acrylic polyol emulsion, water-dispersible polyether polyol water-dispersible polyols such as polyolefin polyols, water-dispersible fluorine polyols, etc. An example is an oar.

[0140] In addition to the above, the curable composition of the present embodiment may further contain, for example, a curing accelerator depending on various applications. Accelerator (catalyst), matting agent, anti-settling agent, leveling agent, filler, dispersant, flame retardant, dye, Organic or inorganic pigments, release agents, flow control agents, plasticizers, antioxidants, UV absorbers, light stabilizers Other additives such as antifoaming agents, colorants, solvents, etc. may be added. By adding an appropriate amount, it is possible to create paints with different properties, such as soft feel paints and clear paints. A curable composition can be obtained.

[0141] [Cured urethane] The cured urethane product of the present embodiment is a polycarbonate polyol and / or Alternatively, the cured urethane product can be obtained by curing the curable composition of the present embodiment. Examples of the material include a urethane coating, a urethane film, and a urethane resin. The urethane cured product is the polycarbonate polyol of this embodiment and / or the polycarbonate polyol of this embodiment. Since the curable composition is obtained from such a curable composition, the curable composition tends to have excellent flexibility and high durability.

[0142] The present disclosure also provides a method for suppressing the odor of a polycarbonate polyol composition. That is, it is a method for suppressing the odor of a polycarbonate polyol composition. Therefore, the polycarbonate polyol composition is a polycarbonate having a terminal hydroxy group. a carboxylate polyol, component (A): a compound represented by the formula (A), and component (B): and a compound represented by formula (B), wherein the mass ratio of component (A) to component (B) is This is a method in which the ratio ((A) / (B)) is set to 0.0001 to 0.1000.

[0143] The present disclosure also provides a method for suppressing the odor of a cured urethane product. That is, a method for suppressing the odor of a cured urethane product, comprising the steps of: a carbonate polyol, component (A): a compound represented by the formula (A), and component (B): and a compound represented by the formula (B), and the quality of the component (A) relative to the component (B) is Polycarbonate polyol with a ratio ((A) / (B)) of 0.0001 to 0.1000 A polycarbonate polyol composition is selected, and the polycarbonate polyol composition is cured to form a urethane cured product. It is a method that includes making an object.

[0144] Furthermore, the present disclosure does not provide a method for producing a polycarbonate polyol composition. That is, there is provided a method for producing a polycarbonate polyol composition, comprising the steps of: The carbonate polyol composition comprises a polycarbonate polyol having a terminal hydroxy group. Component (A): a compound represented by the formula (A); and component (B): a compound represented by the formula (B). a compound, and a mass ratio of the component (A) to the component (B) ((A) / (B) ) is adjusted to the range of 0.0001 to 0.1000.

[0145] The present disclosure also provides a method for producing a cured urethane product. A method for producing a cured product of a polycarbonate polyol having terminal hydroxy groups Component (A): a compound represented by the formula (A); and component (B): a compound represented by the formula (B). and a compound containing the component (A) in a ratio by mass of the component (A) to the component (B), )) is selected from a polycarbonate polyol composition having a value of 0.0001 to 0.1000, and curing the polycarbonate polyol composition.

[0146] Furthermore, the present disclosure also provides a method for producing synthetic leather. The method includes the steps of sequentially disposing an adhesive layer, an intermediate layer, and a surface layer on a substrate. and any one of the surface layer, the intermediate layer, and the adhesive layer is made of polycarbonate polyol. The polycarbonate polyol composition is a urethane cured product of the polycarbonate polyol composition, a polycarbonate polyol having an hydroxy group, and component (A): a polycarbonate polyol represented by the formula (A) and (B) component: a compound represented by the formula (B), and The mass ratio of the component (A) ((A) / (B)) is 0.0001 to 0.1000. , a manufacturing method.

[0147] The present disclosure also provides a method for suppressing odor in synthetic leather, namely: A method for suppressing odor in synthetic leather, comprising the step of: a component (A): a compound represented by the formula (A); and a component (B): a compound represented by the formula (B). and a compound represented by the following formula (1): ) / (B)) is 0.0001 to 0.1000. and at least one of the adhesive layer, intermediate layer, and skin layer is made of the polycarbonate polyol. The method includes using a urethane cured product of the polyurethane foam composition. [Example]

[0148] The present invention will be described in more detail below with reference to examples and comparative examples. The present invention is not limited to these examples as long as it does not exceed the scope of the present invention. In the comparative examples, the methods for analyzing and evaluating the physical properties of each component are as follows: Regarding the above, it can be implemented using a device with equivalent performance.

[0149] [Analysis and Evaluation of Polycarbonate Polyol Compositions] The formulations of the polycarbonate polyol compositions are shown in Tables 1 and 2. <Hydroxyl value of polycarbonate polyol composition> Measurement was carried out in accordance with JIS K1557-1. The number average molecular weight of the polycarbonate polyol composition was also calculated from the hydroxyl value of the polycarbonate polyol composition. .

[0150] <Analysis of components contained in polycarbonate polyol compositions (ICP)> Each component contained in the polycarbonate polyol composition was analyzed as follows. The sample was weighed into a Teflon (registered trademark) decomposition vessel and high-purity nitric acid (Kanto Chemical) was added. Additionally, a microwave decomposition device (Milestone General, ETHOS TC) was used. The sample was completely decomposed, and the resulting decomposition liquid was colorless and transparent. The test solution was analyzed by an inductively coupled plasma analyzer (Thermophor A Fischer Scientific iCAP6300 Duo was used to measure the standard of each element. Quantitative determination was carried out based on the semi-liquid.

[0151] <Analysis of Components (A) and (B) in Polycarbonate Polyol Composition> The analysis was carried out using gas chromatography (GC). Gas chromatograph GC-2014 ( A calibration curve was prepared using the absolute calibration curve method using a standard sample. A ionization detector (FID) was used as the detector, and quantitative analysis of each component was carried out. The temperature profile of the system was 40°C for 1 minute, then increased to 280°C at 10°C / min. and held for 10 minutes. The following reagents were used as standards for preparing the calibration curve. 5-Hexen-1-ol: Tokyo Chemical Industry Co., Ltd. 4-Hexene-1-ol (cis form): manufactured by Tokyo Chemical Industry Co., Ltd. 4-Penten-1-ol: Tokyo Chemical Industry Co., Ltd. Ethylene glycol: Tokyo Chemical Industry Co., Ltd. 1,4-Butanediol: Tokyo Chemical Industry Co., Ltd. 1,5-Pentanediol: Tokyo Chemical Industry Co., Ltd. 1,6-Hexanediol: Tokyo Chemical Industry Co., Ltd. 2-Methyl-1,3-propanediol: Tokyo Chemical Industry Co., Ltd. 3-Methyl-1,5-pentanediol: Tokyo Chemical Industry Co., Ltd.

[0152] <Confirmation of the properties of the polycarbonate polyol composition> The polycarbonate polyol composition heated to 60°C was placed in each transparent sample bottle. The samples were visually inspected after being cooled to room temperature (23°C). If there is even a slight amount of fluidity when tilting the pull bottle, it is considered "liquid" and if it is opaque or the sample bottle is Either or both cases where the state does not change even when tilted are designated as "solid."

[0153] <Composition of Polycarbonate Polyol Composition (Copolymerization Ratio)> Weigh 1 g of the polycarbonate polyol composition sample into a 100 mL eggplant flask. 30 g of ethanol and 4 g of potassium hydroxide were added and reacted at 100°C for 1 hour. After cooling the reaction solution to room temperature, add 2-3 drops of phenolphthalein as an indicator and neutralize with hydrochloric acid. After cooling in a refrigerator for 1 hour, the precipitated salt was removed by filtration and analyzed by gas chromatography ( The GC analysis was carried out using a DB-WAX column (J&M, USA). A gas chromatograph GC-2014 (Shimadzu Corporation, Japan) equipped with a Diethylene glycol diethyl ether was used as an internal standard and a hydrogen flame ionization detector (F The column temperature profile was also used. The tube was held at 60°C for 5 minutes and then heated to 250°C at a rate of 10°C / min. From the molar ratio of each alcohol component detected in the above analysis, polycarbonate polyol The composition (copolymerization ratio) of each copolymer was determined.

[0154] <Carbonate repeating unit: Sum of ester repeating units and ether repeating units Molar ratio of > The carbonate repeating unit, the ester repeating unit and the ether repeating unit are 1 H -NMR and 13 The NMR measurements were carried out using the following equipment: And went. 13 In C-NMR, the carbonate repeating structure is at 150-155 ppm Nearby peak (-O- C =OO-, Carbon element 1 derived from carbonate group in the repeating structural unit The ester repeating structure has a peak around 170-175 ppm (- C =OO-, two specific peaks of C elements derived from the ester group in the repeating structural unit) The repeating terephthalate structure is represented by a peak at around 70 ppm in the case of polytetramethylene glycol, In the case of polypropylene glycol, the peak around 77-70 ppm (- C -O- C -, repeat Using the two specific peaks of ether-derived C elements in the repeating structural unit, the signal intensity The molar ratio of the repeating structural unit was calculated from the ratio of the C element corresponding to a specific peak. If there are two or more C atoms, the signal intensity is divided by the number of C atoms to obtain the moles of repeating structural units. The ratio was calculated. The measurement was carried out using the following equipment and under the following conditions. 1 H-NMR Device: JEOL “JEOL-ECZ500(SC)” (product name) Solvent: deuterated chloroform (containing 1 vol% tetramethylsilane) Accumulation count: 120 times Sample concentration: 10 wt / vol% Chemical shift standard: tetramethylsilane was set as 0.0 ppm. 13 C-NMR Device: JEOL “JEOL-ECZ500(SC)” (product name) Solvent: deuterated chloroform (containing 1 vol% tetramethylsilane) Accumulation count: 5120 times Sample concentration: 30 wt / vol% Chemical shift standard: deuterated chloroform was used as 77.0 ppm.

[0155] <Average Functional Group Number of Polycarbonate Polyol Composition> Polycarbonate polyol composition synthesized using only diol monomers as raw materials The average number of functional groups of the material was set to 2. When a polyfunctional monomer is included as a raw material, the average The number of functional groups was determined by gel permeation analysis using a calibration curve prepared using standard polystyrenes with known molecular weights. By gel permeation chromatography (GPC) analysis (see below for GPC equipment and analysis conditions), The number average molecular weight (Mn) of the polycarbonate polyol composition was determined. The number average molecular weight (Mn) determined by GPC and the base value are calculated by formula (5) to obtain the The average number of functional groups (n) was calculated. Average number of functional groups (n) = [Mn] × ([OH value] × 10 -3 / 56.1) (5)

[0156] (GPC equipment and analysis conditions) GPC equipment: Tosoh HLC-8320 Column: TSKgel G4000H 1 piece G3000H 1 piece G2000H 2 pieces Eluent: tetrahydrofuran (THF) Flow rate: 1.0mL / min Column temperature: 40℃ RI detector: RI (built-in in the device HLC-8320)

[0157] <Measurement of urethane reaction pot life> The polycarbonate polysulfones synthesized in the Examples and Comparative Examples were placed in a 200 mL wide-mouth glass bottle. 60g of each composition was charged, and after sufficient nitrogen substitution, the oil temperature was set at 60°C. After that, MDI was added so that the NCO / OH ratio was 1.1, and torque was applied. The viscosity increase behavior of each sample was confirmed using a stirrer, and the results were determined according to the following evaluation criteria. <Evaluation criteria> 〇 (Very Good): Stirring was possible for 8 minutes △(Good): Stirring became impossible within 5 to 8 minutes × (Bad): Stirring became impossible within 5 minutes after addition

[0158] <Odor Confirmation of Polycarbonate Polyol Composition> The odor evaluation of the polycarbonate polyol composition was carried out by eight testers using 50 mL lidded bottles. 40 g of the polycarbonate polyol composition was weighed out and placed in a glass bottle, and left to stand at 23°C for a day. After that, the lid was opened and the smell was evaluated. The evaluation results of eight inspectors were rated based on the following criteria: The average value was then calculated and the evaluation criteria were determined as follows: <Score criteria> 0: No or no odor 1: A faint odor is detected 2: A clear odor is detected 3: Strong odor <Evaluation criteria> 〇 (Very Good): The average value of 8 inspectors is 1 or less △ (Good): The average value of 8 inspectors is greater than 1 and less than 2 × (Bad): The average value of 8 inspectors is greater than 2 and less than 3

[0159] <Peroxide Value (POV)> The polycarbonate polyol composition samples obtained in the examples and comparative examples described below were used as P The test portion of OV test paper (Shibata Scientific Co., Ltd.) was immersed in the solution, left for 3 minutes, and then washed with pure water. The POV test paper of the sample is compared with the standard color sample to determine the peroxide value (P OV) was determined as follows: [Judgment criteria] ○ (Very Good): 0 meq / kg or more and 3 meq / kg or more, which is detected as 0 on the standard color sample under △ (Good): Over 3 meq / kg and up to 10 meq / kg, equivalent to standard color sample 10 × (Bad): Over 10 meq / kg and 40 meq / kg or less, equivalent to 30 of the standard color sample

[0160] [Preparation of polyurethane] (Raw materials used) Base: Polycarbonate polyol compositions (PC-1 to PC-26) obtained in the examples and comparative examples ) Curing agent: Diphenylmethane-4,4'-diisocyanate (MDI, NCO%=33. 5) Catalyst: Dibutyltin dilaurate 1% by mass toluene solution (Fujifilm Wako Pure Chemical Industries, Ltd.) (Manufactured by the company, dissolved in toluene to make a 1% by mass solution) Solvent: Methyl ethyl ketone (MEK, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (Production method) In a nitrogen-sealed 200 mL separable flask equipped with a stirring blade, add preheated polymer solution to 60°C. 30 g of the recarbonate polyol composition (PC-1 to 26) and dibutyltin as a catalyst 0.3 g of a 1% by mass solution of dilaurate was added to MDI pre-dissolved at 80°C. 1.1, and methyl ethyl ketone (MEK) was added to a solids concentration of 30% by mass. The polyurethane solutions were mixed at 60°C for 3 minutes. Then, a polypropylene resin sheet (width 100 mm, length 1 200mm, thickness 1mm) and apply with a width of 80mm, length of 100mm and thickness of 0.6mm. , on a hot plate at a surface temperature of 60°C for 2 hours, followed by 12 hours in an oven at 100°C. The polyurethane film was dried by leaving it to stand for 12 hours or more under constant temperature and humidity of 23°C and 55% RH. Each of them obtained the same results.

[0161] <Handling during polyurethane production> The handling properties of the polyurethane during production were determined according to the following evaluation criteria. ◯ (Very Good): A polyurethane solution can be obtained. The number average molecular weight measured by GPC is 50,000 or more △ (Good): A polyurethane solution was obtained, but The number average molecular weight measured by GPC is 30,000 or less. × (Bad): No polyurethane solution was obtained

[0162] <Molecular weight measurement> A portion of each of the polyurethane films was cut out and the polyurethane concentration was measured. A solution of N,N-dimethylacetamide was prepared to give a concentration of 100% by volume. Manufacturer: HLC-8320 (column: Tskgel SuperHM-H, 4 columns) The eluent was a solution of 2.6 g of lithium bromide dissolved in 1 L of dimethylacetamide. The number average molecular weight (Mn) and weight average molecular weight (Mn) are calculated using standard polystyrene equivalents. (Mw) of each was measured.

[0163] [Analysis and evaluation of polyurethane coatings] <Preparation of polyurethane coating film> (Raw materials used) Base: Polycarbonate polyol compositions (PC-1 to PC-26) obtained in the examples and comparative examples ) Hardener: Duranate TPA-100 (Asahi Kasei Corporation, NCO%=23.1) Catalyst: Dibutyltin dilaurate 1% by mass toluene solution (Fujifilm Wako Pure Chemical Industries, Ltd.) (Manufactured by the company, dissolved in toluene to make a 1 wt% solution) Solvent: Butyl acetate (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0164] (Paint composition) According to the paint formulation conditions below, weigh the raw materials (main agent, hardener, catalyst, solvent) into a plastic container. The mixture was collected and stirred using a stirrer to obtain each coating composition. (Combination conditions) NCO / OH: 1.2 ·Paint solid content: 40% by mass Catalyst: 1% by mass based on the total amount of base agent and curing agent (Preparation method) Weigh out the main agent and catalyst in a polyethylene container to achieve the above-mentioned blending conditions, and measure the solid content of the paint composition. After adding the solvent to a concentration of 20 wt %, the mixture was stirred with a stirrer until it was uniformly dispersed. Then, weigh out the curing agent into the plastic container so that the NCO / OH ratio becomes 1.25, and mix. The mixture was stirred using a mixer until uniformly dispersed to obtain each coating composition.

[0165] (Coating process) Each of the resulting coating compositions was used to coat a polycarbonate plate ("TAKIRON PC-1600") (product name), 2mm x 70mm x 150mm) so that the dry film thickness is 40μm were applied to each.

[0166] (drying process) The coating composition applied to the polycarbonate plate was baked at 60°C to form a polycarbonate coating. A urethane coating was obtained for each.

[0167] The resulting polyurethane coating films were evaluated for various physical properties. is shown in Table 3.

[0168] <Appearance evaluation of polyurethane coating film> The surface appearance of the polyurethane film prepared above was visually inspected according to the following criteria: The decision was made. ○ (Very Good): The surface is smooth △(Good): A few streaks are observed on the surface in the direction of applicator movement. × (Bad): Many streaks are observed on the surface in the direction of applicator movement.

[0169] <Chemical resistance> Test pieces measuring 3cm x 3cm were cut out from the polyurethane coating. Tested using a precision balance. After measuring the mass of the piece, place it in a 250 mL gas tank containing 50 mL of oleic acid as the test solvent. The samples were placed in glass bottles and left to stand in a constant temperature bath under a nitrogen atmosphere at 80°C for 16 hours. After that, the test piece was taken out and lightly wiped on both sides with a paper wiper, and then the mass was measured using a precision balance. The mass change rate from before the test (increase rate: oleic acid swelling rate) was calculated and the following was obtained. The evaluation was based on the following criteria. (Evaluation criteria) ○ (Very Good): Mass increase rate is less than 6% △ (Good): Mass increase rate is 6% or more but less than 20% × (Bad): Mass increase rate is 20% or more, or evaluation is not possible

[0170] <Weather resistance> Using the same method as above, apply the paint to the panel using an applicator until the thickness after drying is 200μ The coating was applied so that the thickness was 100 mm, and the coating was left to cure for 168 hours at 23°C and 50% humidity. The obtained polyisocyanate cured materials were Super Xenon Weather Meter (Irradiance: 60W / m 2 ) were added to each. The weather resistance test conditions were set at a black panel temperature of 65°C and humidity of 50% during light irradiation. After 102 minutes, the cycle was repeated for 18 minutes at 95% humidity with water spray. L*a*b* (CIE1) of the cured polyisocyanate before the test and after 2000 hours 976) was measured using a color difference meter. The color difference (Δ E) and evaluated the weather resistance according to the following evaluation criteria. ΔE={(ΔL * ) 2 +(Δa * ) 2 +(Δb * ) 2} 1 / 2 (ΔL * , Δa * , Δb * L * , a * , b * Before the start of each weather resistance test and at 2000 hours (This is the difference between the measured values ​​after a certain period of time.) (Evaluation criteria) ○ (Very Good): ΔE is less than 5 △(Good): ΔE is 5 or more and less than 10 × (Bad): ΔE is 10 or more

[0171] (Manufacturing Examples 1 to 3) Hexen-1-ol solutions (1) to (3) were prepared as follows. H1: 4-Hexene-1-ol (trans form): Aldrich H2: 4-Hexene-1-ol (cis form): manufactured by Tokyo Chemical Industry Co., Ltd. H3: 5-Hexene-1-ol: manufactured by Tokyo Chemical Industry Co., Ltd. The above H1, H2, and H3 were mixed in a mass ratio of 1:1:2, and hexene-1 -ol solution (1) was obtained. The above H2 and H3 were mixed in a mass ratio of 1:4, and the hexene-1-ol solution was Liquid (2) was obtained. The above H2 and H3 were mixed in a mass ratio of 1:20, and hexen-1-ol was obtained. A solution (3) was obtained.

[0172] Example 1 Ethylene was added to a 2 L glass flask equipped with a rectification column packed with structured packing and a stirrer. 766g (8.7mol) of ethylenediamine carbonate and 450g (4 520 g (4.4 mol) of 1,6-hexanediol was added. 0.33g of titanium tetrabutoxide was added as a catalyst to the Lasco, and the reaction temperature was adjusted to 140-160°C. At 0°C, the pressure is reduced from 10 kPa to 2 kPa, and the ethylene glycol produced The reaction was carried out for 12 hours while distilling off the mixture of ethylene carbonate and ethylene carbonate. The pressure was gradually reduced to 0.5 kPa while the reaction was carried out at 180°C for 4 hours. After that, 2-ethylhexyl acid phosphate was added to the flask as a phosphorus compound. 0.37 g of phosphate was added, and the mixture in the flask was heated at 120°C for 5 hours. Furthermore, 0.09 g of hexen-1-ol solution (1) was added to the polycarbonate. The polycarbonate polyol composition obtained was analyzed as follows: The results are shown in Table 1. This polycarbonate polyol composition is abbreviated as PC-1. The amounts of components (A) and (B) in the carbonate polyol composition were determined by the above-mentioned method. The ratios are shown in Table 1. The amounts of titanium and phosphorus measured by the above method were also The results are listed in Table 1.

[0173] Example 2 Using the same apparatus as in Example 1, 0.07 g of hexen-1-ol solution (2) was added. Except for this, the same procedure as in Example 1 was carried out to obtain a polycarbonate polyol composition. This polycarbonate polyol composition is abbreviated as PC-2. The results of analyzing PC-2 are as follows: The results are listed in Table 1.

[0174] Example 3 Using the same apparatus as in Example 1, 0.18 g of titanium tetrabutoxide and 2-ethylhexyl 0.20 g of xyl acid phosphate, 0.01 g of hexen-1-ol solution (3) The same procedure as in Example 1 was carried out except that g of polycarbonate polyol composition was added. This polycarbonate polyol composition is referred to as PC-3. The results are shown in Table 1.

[0175] Example 4 Using the same apparatus as in Example 1, 0.18 g of titanium tetrabutoxide and 2-ethylhexyl 0.20 g of xyl acid phosphate, 0.00 g of hexen-1-ol solution (2) After adding 3g, switch to simple distillation and gradually reduce the pressure to 0.5kPa while heating at 180℃. The same procedure as in Example 1 was carried out except that the reaction was carried out for 7 hours and the monomer was distilled off. This polycarbonate polyol composition was used as PC-4. The results of the analysis of PC-4 are shown in Table 1.

[0176] Example 5 Using the same apparatus as in Example 1, 0.01 g of hexen-1-ol solution (3) was added. Then, switch to simple distillation, gradually reduce the pressure to 0.5 kPa, and react at 180°C for 3 hours. The same procedure as in Example 1 was carried out except that the monomer was distilled off by stirring. A polyol composition was obtained, and this polycarbonate polyol composition is abbreviated as PC-5. The analysis results of PC-5 are shown in Table 1.

[0177] Example 6 Using the same apparatus as in Example 1, 0.06 g of hexen-1-ol solution (3) was added. Switch to simple distillation, gradually reduce the pressure to 0.5 kPa, and keep at 180°C for 1.5 hours. The same procedure as in Example 1 was carried out except that the reaction was carried out and the monomer was distilled off, and polycarbonate was obtained. This polycarbonate polyol composition is abbreviated as PC-6. The analysis results for PC-6 are shown in Table 1.

[0178] Example 7 Using the same apparatus as in Example 1, 4-penten-1-ol: manufactured by Tokyo Chemical Industry Co., Ltd. The same procedure as in Example 1 was carried out except that 0.01 g of This polycarbonate polyol composition is referred to as PC-7. The results of the analysis of 7 are shown in Table 1.

[0179] Example 8 Using the same apparatus as in Example 1, 766 g (8.7 mol) of ethylene carbonate 390g (4.3mol) of 1,4-butanediol and 52g of 1,6-hexanediol 0g (4.4mol) of hexen-1-ol solution (3) was added. Other than this, the same procedure as in Example 1 was carried out to obtain a polycarbonate polyol composition. The polycarbonate polyol composition is abbreviated as PC-8. The analysis results of PC-8 are shown in Table 1. It is stated in.

[0180] Example 9 Using the same apparatus as in Example 1, 766 g (8.7 mol) of ethylene carbonate, 1 ,5-pentanediol 355g (3.4mol), 1,6-hexanediol 366g (3.1 mol), 378 g (2.2 mol) of 1,10-decanediol were charged, and The same procedure as in Example 1 was carried out except that 0.01 g of sen-1-ol solution (3) was added. Thus, a polycarbonate polyol composition was obtained. The results of the analysis of PC-9 are shown in Table 1.

[0181] Example 10 Using the same apparatus as in Example 1, 766 g (8.7 mol) of ethylene carbonate 450g (4.3mol) of 1,5-pentanediol and 5g of 1,6-hexanediol 20g (4.4mol) of hexen-1-ol solution (2) was added. The mixture of ethylene glycol and ethylene carbonate produced was distilled off for 24 hours. The reaction was carried out in the same manner as in Example 1, except that the reaction was carried out at 180°C for 5 hours and the monomer was distilled off. The same procedure was carried out to obtain a polycarbonate polyol composition. The entire composition is abbreviated as PC-10. The analysis results of PC-10 are shown in Table 1.

[0182] Example 11 Using the same apparatus as in Example 1, 766 g (8.7 mol) of ethylene carbonate 1,6-hexanediol 1038g (8.8mol) was charged, and hexen-1-ol The same procedure as in Example 1 was carried out except that 0.13 g of solution (3) was added. This polycarbonate polyol composition was abbreviated as PC-11. The analysis results of PC-11 are shown in Table 1.

[0183] Example 12 Using the same apparatus as in Example 1, 0.02 g of hexen-1-ol solution (2) was added. Except for this, the same procedure as in Example 4 was carried out to obtain a polycarbonate polyol composition. This polycarbonate polyol composition is abbreviated as PC-12. The results are shown in Table 1.

[0184] Example 13 Using the same apparatus as in Example 1, 0.003 g of hexen-1-ol solution (2) and methyl The same procedure as in Example 4 was carried out except that 0.01 g of ethanol was added. This polycarbonate polyol composition is abbreviated as PC-13. The results of the analysis of PC-13 are shown in Table 1.

[0185] Example 14 Using the same apparatus as in Example 1, 0.26 g of hexen-1-ol solution (3) was added. Except for this, the same procedure as in Example 1 was carried out to obtain a polycarbonate polyol composition. This polycarbonate polyol composition is abbreviated as PC-14. The results are shown in Table 2.

[0186] Example 15 Using the same apparatus as in Example 1, 0.50 g of hexen-1-ol solution (3) was added. Except for this, the same procedure as in Example 1 was carried out to obtain a polycarbonate polyol composition. This polycarbonate polyol composition is abbreviated as PC-15. The results are shown in Table 2.

[0187] Example 16 Using the same apparatus as in Example 1, 0.18 g of hexen-1-ol solution (2) was added. Except for this, the same procedure as in Example 4 was carried out to obtain a polycarbonate polyol composition. This polycarbonate polyol composition is abbreviated as PC-16. The results are shown in Table 2.

[0188] Example 17 50 g of the polycarbonate polyol composition (PC-4) obtained in Example 4 was weighed and resorcinolated. NAC polyester polyol (Teslac, 2460, molecular weight 2000, liquid polyol) The mixture was mixed with 50 g of 100% ethanol to obtain a polycarbonate polyol composition (PC-17). Carbonate repeating units and ester repeating units calculated by 3C-NMR measurements Calculation based on the integral ratio of carbonate repeating structure: ester repeating structure = 4 The molar ratio was 1:59. The analysis results of PC-17 are shown in Table 2.

[0189] Example 18 50 g of the polycarbonate polyol composition (PC-4) obtained in Example 4 was weighed out and Kuraray Polyester Polyol (Kuraray Polyol, P-2010, molecular weight 2000, liquid Polycarbonate polyol composition (PC-18) was obtained by mixing with 50 g of the above-mentioned polyol. The carbonate repeating structure and ester repeating structure calculated by 13C-NMR measurement The ratio of repeating carbonate structures to repeating ester structures was calculated based on the integral ratio of the repeating carbonate structures to repeating ester structures. The molar ratio of PC-18 was 46:54. The analysis results of PC-18 are shown in Table 2.

[0190] Example 19 50 g of the polycarbonate polyol composition (PC-4) obtained in Example 4 was weighed and Mix with 50g of chemical polytetramethylene ether glycol (PTMG2000) As a result, a polycarbonate polyol composition (PC-19) was obtained. 13 For C-NMR measurements Calculated based on the integral ratio of carbonate repeating units and ether repeating units calculated from The carbonate repeating unit:ether repeating unit ratio was 24:76 (molar ratio). The results of the analysis of PC-19 are shown in Table 2.

[0191] Example 20 70 g of the polycarbonate polyol composition (PC-4) obtained in Example 4 was weighed and resorcinolated. NAC polyester polyol (Teslac, 2460, molecular weight 2000, liquid polyol) The mixture was mixed with 30 g of a polycarbonate polyol (PC-20) to obtain a polycarbonate polyol composition. 1 3 Carbonate repeating units and ester repeating units calculated by C-NMR measurement Calculation based on the integral ratio of carbonate repeating structure: ester repeating structure = 6 The molar ratio was 7:33. The analysis results of PC-20 are shown in Table 2.

[0192] Example 21 70 g of the polycarbonate polyol composition (PC-4) obtained in Example 4 was weighed and Mix with 30g of Kuraray Polyester Polyol (Kuraray Polyol, P-2010) to form a polyol. A recarbonate polyol composition (PC-21) was obtained. 13 Calculated by C-NMR measurement The ratio was calculated based on the integral ratio of the carbonate repeating structure and the ester repeating structure. The carbonate repeating unit:ester repeating unit ratio was 67:33 (molar ratio). The analysis results of PC-21 are shown in Table 2.

[0193] Example 22 20 g of the polycarbonate polyol composition (PC-4) obtained in Example 4 was weighed out and 30 g of the polycarbonate polyol composition (PC-6) obtained in Example 6 and 30 g of Resonac polyol Mix with 50g of ester polyol (Teslac, 2460) to make polycarbonate poly. A thiol composition (PC-22) was obtained. 13 Carbonate calculated by C-NMR measurement Calculations based on the integral ratio of the repeating structure and the ester repeating structure showed that the carbonate The repeating unit:ester repeating unit ratio was 44:56 (molar ratio). The analysis results are shown in Table 2.

[0194] Example 23 20 g of the polycarbonate polyol composition (PC-4) obtained in Example 4 was weighed out and 30 g of the polycarbonate polyol composition (PC-6) obtained in Example 6 and Kuraray Polyester Mix with 50g of terpolyol (Kuraray Polyol, P-2010) to make polycarbonate. A carboxylate polyol composition (PC-23) was obtained. 13 Carbon calculated by C-NMR measurement Calculations based on the integral ratio of the repeating ester structure and the repeating ester structure showed that The molar ratio of repeating ester units to repeating ester units was 44:56. The results of the analysis of 3 are shown in Table 2.

[0195] (Comparative Example 1) Using the same apparatus as in Example 1, 2.4 g of hexen-1-ol solution (1) was added. Other than this, the same procedure as in Example 1 was carried out to obtain a polycarbonate polyol composition. This polycarbonate polyol composition is abbreviated as PC-24. Analysis results of PC-24 are listed in Table 2.

[0196] (Comparative Example 2) Using the same apparatus as in Example 1, 1.2 g of hexen-1-ol solution (1) was added. Other than this, the same procedure as in Example 1 was carried out to obtain a polycarbonate polyol composition. The polycarbonate polyol composition is abbreviated as PC-25. Analysis results of PC-25 are listed in Table 2.

[0197] (Comparative Example 3) Using the same apparatus as in Example 1, 0.001 g of hexen-1-ol solution (3) was added. After that, the reaction mixture was switched to simple distillation, and the pressure was gradually reduced to 0.5 kPa while the reaction mixture was reacted at 180°C for 7 hours. The same procedure as in Example 1 was carried out except that the reaction was carried out and the monomer was distilled off. The resulting polycarbonate polyol composition was mixed with 1,5-pentaerythritol, and the ... 17g of hexanediol and 18g of 1,6-hexanediol were added. The nate polyol composition is abbreviated as PC-26. The analysis results for PC-26 are shown in Table 2. did.

[0198] [Table 1]

[0199] [Table 2]

[0200] [Table 3] [Industrial Applicability]

[0201] The polycarbonate polyol composition of the present invention has a long pot life, is easy to handle, and is suitable for external use. Since it is possible to provide a polyurethane film with good appearance and excellent weather resistance, it is suitable for use in, for example, paints, paint compositions, etc. Adhesive, adhesive composition, water-based polyurethane, water-dispersed composition, polyurethane for synthetic leather The present invention can be widely and effectively used as a constituent material for synthetic leather and the like. [Explanation of symbols]

[0202] 1...Release paper 2... Epidermal layer 3...Adhesive layer 4. Base material (polyester woven fabric) 5. Mixing head (surface layer) 6. Mixing head (adhesive layer) 7. Seat structure (dry synthetic leather product) 8. Coating roll 9. Crimping roll 10. Winding roll 11...Dryer

Claims

1. a polycarbonate polyol having terminal hydroxy groups; Component (A): a compound represented by the following formula (A), Component (B): a compound represented by the following formula (B): the content of the component (A) is 1 ppm or more and 0.5 mass % or less relative to the total mass of the polycarbonate polyol composition, and the mass ratio of the component (A) to the component (B) ((A) / (B)) is 0.0001 to 0.1000; Polycarbonate polyol compositions. 【Chemistry 1】 (In formula (A), R 1 is hydrogen or an alkyl group having 1 to 12 carbon atoms, and R 2 is an alkylene group having 1 to 12 carbon atoms. 【Chemistry 2】 (In formula (B), R 3 is an alkylene group having 2 to 12 carbon atoms, and may have a linear alkylene group, a divalent alicyclic hydrocarbon group, or a branched alkylene group.

2. 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% when measured by ICP (ICP-MS: Inductively Coupled Plasma Mass Spectrometry), The polycarbonate polyol composition of claim 1 .

3. The phosphorus content measured by ICP (ICP-MS: Inductively Coupled Plasma Mass Spectrometry) is 0.0001 to 0.050% by mass, The polycarbonate polyol composition of claim 1 .

4. Among the compounds represented by the formula (A) and the compounds represented by the formula (B), R 1 and R 2 The sum of the total number of carbon atoms plus two carbon atoms is R 3 The number of carbon atoms is equal to The polycarbonate polyol composition of claim 1 .

5. The polycarbonate polyol having a terminal hydroxy group has repeating units derived from 1,5-pentanediol and / or 1,6-hexanediol, The compound represented by the formula (A) is 1 is a hydrogen atom and R 2 is an alkylene group having 4 or 3 carbon atoms, 1 is an alkylene group having 1 carbon atom, and R 2 is an alkylene group having 3 or 2 carbon atoms, and 1 is an alkylene group having 2 carbon atoms, and R 2 is an alkylene group having 2 or 1 carbon atoms, R of the compound represented by formula (A) 1 and R 2 The sum of the total carbon atoms of the above groups plus two carbon atoms is 5 or 6, and this is R of the compound represented by formula (B). 3 The number of carbon atoms is equal to The polycarbonate polyol composition of claim 1 .

6. Further containing component (B'), a mass ratio of the component (B') to the component (B) ((B') / (B)) of 0.0001 to 1.000; The polycarbonate polyol composition of claim 1 . 【Transformation 3】 (In formula (B'), R 4 is an alkyl group having 1 to 4 carbon atoms.

7. Further comprising a polyol compound having an ester repeating unit and / or an ether repeating unit, The polycarbonate polyol composition of claim 1 .

8. the molar ratio of carbonate repeating units to the total of ester repeating units and ether repeating units contained in the polycarbonate polyol and the polyol compound having an ester repeating unit and / or an ether repeating unit is in the range of 20:80 to 80:20; The polycarbonate polyol composition of claim 7.

9. the mass ratio ((A) / (B)) is 0.0001 to 0.075; The polycarbonate polyol composition of claim 1 .

10. the mass ratio ((A) / (B)) is 0.0001 to 0.069; The polycarbonate polyol composition of claim 1 .

11. the mass ratio ((A) / (B)) is 0.0001 to 0.010; The polycarbonate polyol composition of claim 1 .

12. the mass ratio ((A) / (B)) is 0.006 to 0.010; The polycarbonate polyol composition of claim 1 .

13. The polycarbonate polyol having a terminal hydroxy group has a structural unit represented by the following formula (P): The polycarbonate polyol composition of claim 1 . 【Chemistry 4】 (In formula (P), R 1 is any divalent aliphatic hydrocarbon group, and R 2 is hydrogen or any monovalent aliphatic hydrocarbon group, and R 3 is any divalent aliphatic hydrocarbon group.

14. The polycarbonate polyol composition according to any one of claims 1 to 13, Adhesive composition.

15. A polycarbonate polyol composition according to any one of claims 1 to 13, Water-based polyurethane.

16. A polycarbonate polyol composition according to any one of claims 1 to 13, Water dispersion composition.

17. A polycarbonate polyol composition according to any one of claims 1 to 13, Polyurethane for synthetic leather.

18. A polycarbonate polyol composition according to any one of claims 1 to 13, Synthetic leather.

19. A polycarbonate polyol composition according to any one of claims 1 to 13, Cured urethane.

20. The synthetic leather according to claim 18, Automotive interior materials.

21. A method for suppressing odor of a polycarbonate polyol composition, the polycarbonate polyol composition comprising: a polycarbonate polyol having terminal hydroxy groups; Component (A): a compound represented by the formula (A), (B) component: a compound represented by the formula (B), the content of the component (A) is 1 ppm or more and 0.5 mass % or less relative to the total mass of the polycarbonate polyol composition, and the mass ratio of the component (A) to the component (B) ((A) / (B)) is 0.0001 to 0.1000; method.

22. A method for suppressing odor of a cured urethane product, comprising: a polycarbonate polyol having terminal hydroxy groups; Component (A): a compound represented by the formula (A), Component (B): a compound represented by the formula (B), selecting a polycarbonate polyol composition in which the content of the component (A) is 1 ppm or more and 0.5 mass % or less relative to the total mass of the polycarbonate polyol composition, and the mass ratio of the component (A) to the component (B) ((A) / (B)) is 0.0001 to 0.1000; and curing the polycarbonate polyol composition to produce a urethane cured product. method.

23. A method for producing a polycarbonate polyol composition, comprising: The polycarbonate polyol composition comprises: a polycarbonate polyol having terminal hydroxy groups; Component (A): a compound represented by the formula (A), (B) component: a compound represented by the formula (B), the content of the component (A) is 1 ppm or more and 0.5 mass % or less relative to the total mass of the polycarbonate polyol composition, and the mass ratio of the component (A) to the component (B) ((A) / (B)) is adjusted to the range of 0.0001 to 0.1000; Manufacturing method.

24. A method for producing a cured urethane product, comprising: a polycarbonate polyol having terminal hydroxy groups; Component (A): a compound represented by the formula (A), Component (B): a compound represented by the formula (B), selecting a polycarbonate polyol composition in which the content of the component (A) is 1 ppm or more and 0.5 mass % or less relative to the total mass of the polycarbonate polyol composition, and the mass ratio of the component (A) to the component (B) ((A) / (B)) is 0.0001 to 0.1000; curing the polycarbonate polyol composition. Manufacturing method.

25. A method for producing synthetic leather, comprising: The method includes the steps of sequentially disposing an adhesive layer, an intermediate layer, and a skin layer on a substrate; any one of the surface layer, the intermediate layer, and the adhesive layer is a urethane cured product of a polycarbonate polyol composition; The polycarbonate polyol composition comprises: a polycarbonate polyol having terminal hydroxy groups; Component (A): a compound represented by the formula (A), (B) component: a compound represented by the formula (B), the content of the component (A) is 1 ppm or more and 0.5 mass % or less relative to the total mass of the polycarbonate polyol composition, and the mass ratio of the component (A) to the component (B) ((A) / (B)) is 0.0001 to 0.1000; Manufacturing method.

26. A method for suppressing odor in synthetic leather, comprising: a polycarbonate polyol having terminal hydroxy groups; Component (A): a compound represented by the formula (A), Component (B): a compound represented by the formula (B), selecting a polycarbonate polyol composition in which the content of the component (A) is 1 ppm or more and 0.5 mass % or less relative to the total mass of the polycarbonate polyol composition, and the mass ratio of the component (A) to the component (B) ((A) / (B)) is 0.0001 to 0.1000; A method comprising using a urethane-cured product of the polycarbonate polyol composition in at least one of an adhesive layer, an intermediate layer, and a skin layer.

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