Composition, coating composition, aqueous polyurethane dispersion, polyurethane resin, and polyurea resin

Abstract

Provided are a composition, a coating composition, an aqueous polyurethane dispersion, a polyurethane resin, and a polyurea resin, the composition can provide a coating composition having excellent chemical resistance, abrasion resistance, scratch resistance, and soft texture, and little discoloration, and an aqueous polyurethane dispersion, a polyurethane resin, and a polyurea resin having excellent storage stability and little discoloration when used in a coating material, a coating agent, or the like. The composition contains (a) a curing agent and (b) a polycarbonate diol, the (a) curing agent is an organic polyisocyanate compound, the (b) polycarbonate diol is a polycondensate obtained by transesterification of a dihydroxy compound and a carbonate, the number average molecular weight of the (b) polycarbonate diol is 250-3000, and the number average molecular weight of the (b) polycarbonate diol is 100-200. (b) The polycarbonate diol contains at least one metal (M1) selected from the group consisting of Group 6, Group 7, Group 8, Group 9, Group 10, and Group 11 metals in a total amount of from 1 ppm to 25 ppm (inclusive) in the long-period periodic table.

Description

Technical Field

[0001] The invention relates to a composition, a coating composition, an aqueous polyurethane dispersion, a polyurethane resin and a polyurea resin. Background Art

[0002] In the past, polyurethane coatings or polyurethane resins and polyurea resins were used in a wide range of fields such as synthetic leather, artificial leather, adhesives, furniture coatings, and automotive coatings, and polyethers and polyesters were used as polyol components that react with isocyanates (for example, see Patent Documents 1 to 2). However, in recent years, requirements for heat resistance, weather resistance, hydrolysis resistance, mildew resistance, oil resistance, and other resistances of coatings and resins have gradually increased.

[0003] As a soft segment having excellent hydrolysis resistance, light resistance, resistance to oxidative degradation, heat resistance, etc., for example, Patent Documents 3 and 4 propose polycarbonate diols obtained by copolymerizing 1,6-hexanediol and 1,4-butanediol. The coating composition using these copolymerized polycarbonate diols described in Patent Document 3 can provide a coating film having excellent chemical resistance, abrasion resistance, and scratch resistance and having a soft touch. In addition, the polyurea resin using these copolymerized polycarbonate diols described in Patent Document 4 is also excellent in flexibility and low-temperature characteristics, and has attracted much attention in recent years.

[0004] As mentioned above, polyurethane resins have been used in a wide range of fields such as synthetic leather, artificial leather, adhesives, furniture coatings, and automotive coatings, and polyethers and polyesters have been used as polyol components that react with isocyanates. However, in recent years, requirements for heat resistance, weather resistance, hydrolysis resistance, oil resistance, chemical resistance, low-temperature flexibility, etc. have gradually increased. In addition, expectations for water-based polyurethane dispersions have been increasing from the perspective of environmental protection.

[0005] As a means for solving these problems, aqueous polyurethane dispersions using various polycarbonate diols having excellent heat resistance, weather resistance, hydrolysis resistance, oil resistance, and chemical resistance have been proposed.

[0006] For example, Patent Document 5 proposes an aqueous polyurethane dispersion containing polycarbonate diol formed using 2-methyl-1,3-propanediol. The aqueous polyurethane dispersion can be used for coatings, coating agents, adhesives, and adhesives that have excellent balance of physical properties such as chemical resistance, hydrolysis resistance, weather resistance, flexibility, and adhesion. Compared with the conventional polycarbonate diol formed using 1,6-hexanediol, the polycarbonate diol formed using 2-methyl-1,3-propanediol has low crystallinity at room temperature and therefore has excellent flexibility. In addition, the carbonate group concentration in the polycarbonate diol is high, so it has excellent chemical resistance and abrasion resistance.

[0007] In addition, for example, Patent Document 6 proposes an aqueous dispersion of a modified polycarbonate diol obtained by modifying a polycarbonate diol obtained by copolymerizing 1,5-pentanediol and 1,6-hexanediol with an isocyanate and a (meth)acrylate containing a hydroxyl group. The aqueous dispersion of the modified polycarbonate diol can be cured with ultraviolet light using a polymerization initiator to improve the above-mentioned chemical resistance and abrasion resistance.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Publication No. 2000-95836

[0011] Patent Document 2: Japanese Patent Application Publication No. 2001-123112

[0012] Patent Document 3: Japanese Patent Application Publication No. 2021-75632

[0013] Patent Document 4: Japanese Patent Application Publication No. 2021-88705

[0014] Patent Document 5: Japanese Patent Application Publication No. 2008-37987

[0015] Patent Document 6: Japanese Patent Application Publication No. 2013-82863 Summary of the invention

[0016] Problem that the invention aims to solve

[0017] On the other hand, the polycarbonate diol disclosed in Patent Document 3 uses titanium tetrabutoxide as a polymerization catalyst, so the coating composition containing the polycarbonate diol may be colored during storage due to the influence of the residual titanium tetrabutoxide residue, and there is room for improvement. In addition, as in Patent Document 3, such a coating composition may be discolored when used for automobile exterior clear coatings, automobile interior coatings, home appliance coatings, OA product coatings, leather surface treatment agents, synthetic leather surface treatment agents, etc., and there is room for improvement.

[0018] In addition, similarly, the polycarbonate diol disclosed in Patent Document 4 uses titanium tetrabutoxide as a polymerization catalyst, so the polyurea resin containing the polycarbonate diol may be colored during storage due to the influence of the residual titanium tetrabutoxide residue, and there is room for improvement. In addition, similarly to Patent Document 4, such a polyurea resin may be discolored when used for injection molded components (grip parts, steering wheels, airbag storage covers, watch bands, etc.), extrusion molded products (hoses, pipes, sheets, etc.), and synthetic leather adhesives dissolved in solvents, skin materials, surface treatment agents, fiber coating agents, various surface treatment agents, various adhesives, etc., and there is room for improvement.

[0019] In addition, the polycarbonate diol disclosed in Patent Document 5 uses lead acetate trihydrate as a polymerization catalyst. Therefore, the aqueous polyurethane dispersion containing this polycarbonate diol may be colored during storage due to the influence of the remaining lead acetate trihydrate residue, or may change color when used in paints, coatings, adhesives, adhesives, etc., and there is room for improvement.

[0020] In addition, the polycarbonate diol disclosed in Patent Document 6 uses titanium tetrabutoxide as a polymerization catalyst. Therefore, the aqueous polyurethane dispersion containing this polycarbonate diol may be colored during storage due to the influence of the remaining titanium tetrabutoxide residue, or may change color when used in paints, coatings, adhesives, adhesives, etc. as in Patent Document 1, and there is room for improvement.

[0021] Therefore, an object of the present invention is to provide a coating composition that can provide excellent chemical resistance, abrasion resistance, scratch resistance, soft touch and little discoloration, and a composition of an aqueous polyurethane dispersion, a polyurethane resin and a polyurea resin that has excellent storage stability and little discoloration when used in, for example, a paint or a coating agent.

[0022] Solutions for solving problems

[0023] The present inventors have repeatedly conducted intensive studies and, as a result, have found that by using a specific composition, a coating composition having excellent chemical resistance, abrasion resistance, scratch resistance, soft touch and little discoloration, as well as an aqueous polyurethane dispersion, a polyurethane resin and a polyurea resin having excellent storage stability and little discoloration when used in, for example, coatings and coating agents can be provided, thereby completing the present invention.

[0024] That is, the present invention includes the following aspects. [1]

[0026] A composition comprising (a) a curing agent and (b) a polycarbonate diol,

[0027] The curing agent (a) is an organic polyisocyanate compound.

[0028] The above-mentioned (b) polycarbonate diol is a polycondensate based on the transesterification reaction between a dihydroxy compound and a carbonate.

[0029] The number average molecular weight of the polycarbonate diol (b) is 250 or more and 3000 or less,

[0030] The (b) polycarbonate diol contains at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table in a total amount of 1 ppm to 25 ppm. [2]

[0032] A coating composition comprising the composition of [1],

[0033] The (a) curing agent is an organic polyisocyanate compound having 2.6 or more isocyanate groups in one molecule. [3]

[0035] The coating composition according to [2], wherein the metal (M1) is at least one metal selected from the group consisting of metals of Group 7 of the long-form periodic table. [4]

[0037] The coating composition according to [2], wherein the metal (M1) is manganese. [5]

[0039] The coating composition according to [2], wherein the polycarbonate diol (b) contains at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-form periodic table in a total amount of 0.1 ppm to 12.5 ppm. [6]

[0041] The coating composition according to [5], wherein the metal (M2) is lithium. [7]

[0043] The coating composition according to [2], wherein the (a) curing agent is a polyisocyanate derived from an aliphatic organic polyisocyanate compound and / or an alicyclic organic polyisocyanate compound. [8]

[0045] The coating composition according to [2], comprising 1 to 90% by mass of an inert organic solvent. [9]

[0047] The coating composition according to [2], comprising 1 to 80% by mass of a hydroxyl group-containing acrylic resin based on the total solid content.

[10]

[0049] The coating composition according to [9], wherein the number average molecular weight of the hydroxyl-containing acrylic resin is 500 to 10,000, and the hydroxyl value of the hydroxyl-containing acrylic resin is 50 to 300 mgKOH / g.

[11]

[0051] The coating composition according to [2], comprising 1 to 30% by mass of inorganic fine powder having an average particle size of 4 to 15 μm and / or polyurethane particles having an average particle size of 2 to 20 μm, based on the total solid content.

[12]

[0053] The coating composition according to [2], wherein the (b) polycarbonate diol has a Hazen color number of 50 or less as measured in accordance with JIS-K0071-1 (1998).

[13]

[0055] A coating-coated molded article, wherein the coating composition according to any one of [1] to

[12] is applied to the molded article.

[14]

[0057] An aqueous polyurethane dispersion comprising a water-dispersible polyurethane and water, wherein the water-dispersible polyurethane is a reaction product of the composition of [1] and (c) a polyol containing a carboxyl group and / or a sulfonic group or a salt thereof.

[15]

[0059] The aqueous polyurethane dispersion according to

[14] , wherein the metal (M1) is at least one metal selected from the group consisting of metals of Group 7 of the long-form periodic table.

[16]

[0061] The aqueous polyurethane dispersion according to

[14] , wherein the metal (M1) is manganese.

[17]

[0063] The aqueous polyurethane dispersion according to

[14] , wherein the (b) polycarbonate diol contains at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-form periodic table in a total amount of 0.1 ppm to 12.5 ppm.

[18]

[0065] The aqueous polyurethane dispersion according to

[17] , wherein the metal (M2) is lithium.

[19]

[0067] The aqueous polyurethane dispersion according to

[14] , wherein the organic polyisocyanate compound as the curing agent (a) is an aliphatic organic diisocyanate compound and / or an alicyclic organic diisocyanate compound.

[20]

[0069] The aqueous polyurethane dispersion according to

[14] , wherein the (b) polycarbonate diol has a Hazen color number of 50 or less as measured in accordance with JIS-K0071-1 (1998). [twenty one]

[0071] An aqueous coating composition comprising the aqueous polyurethane dispersion according to any one of

[14] to

[20] . [twenty two]

[0073] A polyurea resin which is a reaction product of the composition of [1] and a chain extender (d),

[0074] The chain extender (d) is a diamine compound,

[0075] The polyisocyanate compound as the curing agent (a) is an organic polyisocyanate compound having an average isocyanate group number of 2.5 or less in one molecule. [twenty three]

[0077] The polyurea resin according to

[22] , wherein the metal (M1) is at least one metal selected from the group consisting of metals of Group 7 of the long-form periodic table. [twenty four]

[0079] The polyurea resin according to

[22] , wherein the metal (M1) is manganese.

[25]

[0081] The polyurea resin according to

[22] , wherein the polycarbonate diol (b) contains at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-form periodic table in a total amount of 0.1 ppm to 12.5 ppm.

[26]

[0083] The polyurea resin according to

[25] , wherein the metal (M2) is lithium.

[27]

[0085] The polyurea resin according to

[22] , wherein the organic polyisocyanate compound as the curing agent (a) is an aliphatic organic diisocyanate compound and / or an alicyclic organic diisocyanate compound.

[28]

[0087] The polyurea resin according to

[22] , wherein the chain extender (d) is an alicyclic diamine.

[29]

[0089] The polyurea resin according to

[22] , wherein the Hazen color number of the polycarbonate diol (b) measured in accordance with JIS-K0071-1 (1998) is 50 or less.

[30]

[0091] A polyurethane resin, which is a reaction product of the composition of [1] and a chain extender (d),

[0092] The chain extender (d) is a dihydroxy compound,

[0093] The polyisocyanate compound as the curing agent (a) is an organic polyisocyanate compound having an average isocyanate group number of 2.5 or less in one molecule.

[31]

[0095] The polyurethane resin according to

[30] , wherein the metal (M1) is at least one metal selected from the group consisting of metals of Group 7 of the long-form periodic table.

[32]

[0097] The polyurethane resin according to

[30] , wherein the metal (M1) is manganese.

[33]

[0099] The polyurethane resin according to

[30] , wherein the polycarbonate diol (b) contains at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-form periodic table in a total amount of 0.1 ppm to 12.5 ppm.

[34]

[0101] The polyurethane resin according to

[33] , wherein the metal (M2) is lithium.

[35]

[0103] The polyurethane resin according to

[30] , wherein the organic polyisocyanate compound as the curing agent (a) is an aliphatic organic diisocyanate compound and / or an alicyclic organic diisocyanate compound.

[36]

[0105] The polyurethane resin according to

[30] , wherein the Hazen color number of the polycarbonate diol (b) measured in accordance with JIS-K0071-1 (1998) is 50 or less.

[37]

[0107] A film having a thickness of 10 μm to 500 μm obtained by molding the polyurea resin described in any one of

[22] to

[29] and / or the polyurethane resin described in any one of

[30] to

[36] into a film shape.

[38]

[0109] A synthetic leather using the polyurea resin described in any one of

[22] to

[29] and / or the polyurethane resin described in any one of

[30] to

[36] .

[0110] Effects of the Invention

[0111] According to the composition of the present invention, it is possible to provide a coating composition which has little coloration during storage, is excellent in chemical resistance, abrasion resistance, scratch resistance, has a soft touch and has little discoloration, as well as an aqueous polyurethane dispersion, polyurethane resin and polyurea resin which have little coloration during storage and have little discoloration when used in, for example, coatings, coating agents, adhesives, and binders. DETAILED DESCRIPTION

[0112] Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail. It should be noted that the present invention is not limited to the following embodiment, and various modifications can be made within the scope of the gist thereof.

[0113] <Composition>

[0114] The composition of this embodiment contains (a) a curing agent and (b) a polycarbonate diol.

[0115] The curing agent (a) is an organic polyisocyanate compound.

[0116] The above-mentioned (b) polycarbonate diol is a polycondensate based on the transesterification reaction between a dihydroxy compound and a carbonate.

[0117] The number average molecular weight of the polycarbonate diol (b) is 250 or more and 3000 or less,

[0118] The (b) polycarbonate diol contains at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table in a total amount of 1 ppm to 25 ppm.

[0119] The composition of this embodiment has such characteristics, and can provide a coating composition that has little coloration during storage, excellent chemical resistance, abrasion resistance, scratch resistance, soft touch and little discoloration, as well as an aqueous polyurethane dispersion, polyurethane resin and polyurea resin that has little coloration during storage and little discoloration when used for example in coatings, coating agents, adhesives, and binders.

[0120] <Coating composition>

[0121] The coating composition of the present embodiment is a coating composition containing the above-mentioned composition,

[0122] The (a) curing agent is an organic polyisocyanate compound having 2.6 or more isocyanate groups in one molecule.

[0123] Specifically, the coating composition of the present embodiment contains (a) a curing agent and (b) a polycarbonate diol.

[0124] The curing agent (a) is an organic polyisocyanate compound having 2.6 or more isocyanate groups in one molecule.

[0125] The above-mentioned (b) polycarbonate diol is a polycondensate based on the transesterification reaction between a dihydroxy compound and a carbonate.

[0126] The number average molecular weight of the polycarbonate diol (b) is 250 or more and 3000 or less,

[0127] The (b) polycarbonate diol contains at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table in a total amount of 1 ppm to 25 ppm.

[0128] The coating composition of the present embodiment has such characteristics, and is excellent in chemical resistance, abrasion resistance, scratch resistance, and soft touch, and has little discoloration.

[0129] The coating composition of the present embodiment preferably has a Hazen color number of the polycarbonate diol (b) measured in accordance with JIS-K0071-1 (1998) of 50 or less.

[0130] The coating composition of the present embodiment is not particularly limited, and can be suitably used, for example, for automobile exterior clear coatings, automobile interior coatings, home appliance coatings, OA product coatings, leather surface treatment agents, synthetic leather surface treatment agents, etc. The automobile exterior clear coatings, automobile interior coatings, home appliance coatings, OA product coatings, leather surface treatment agents, synthetic leather surface treatment agents, etc. produced using the coating composition of the present embodiment are characterized by little discoloration.

[0131] <(a) Curing agent>

[0132] The (a) curing agent used in the coating composition of the present embodiment is an organic polyisocyanate compound having 2.6 or more isocyanate groups in one molecule.

[0133] As the curing agent (a) used in the coating composition of the present embodiment, in particular, from the viewpoint of weather resistance, it is preferably a polyisocyanate derived from an aliphatic organic diisocyanate compound and / or an alicyclic organic diisocyanate compound, and specifically, although not particularly limited, examples thereof include polyisocyanates derived from aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI). Furthermore, a so-called blocked isocyanate curing agent in which these polyisocyanates are blocked with a known blocking agent such as butanol, 2-ethylhexanol, methyl ethyl ketone oxime, lactams, phenols, imidazoles, active methylene compounds, etc. can also be used. These polyisocyanate compounds are not particularly limited, and examples thereof include SUMIDUR 44S and 44V70 (both manufactured by Sumika Bayer Urethane Co., Ltd.), DESMODUR HL (manufactured by Sumika Bayer Urethane Co., Ltd.) which is a copolymer of TDI and HDI, and various DURANATEs manufactured by Asahi Kasei Corporation, namely, DURANATE 24A-100, DURANATE 22A-75PX, DURANATE 18H-70B, DURANATE 21S-75E, DURANATE THA-100, DURANATE TPA-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、DURANATEE-402-90T、DURANATE E-405-80T、DURANATE ME20-100、DURANATE 17B-60PX、DURANATETPA-B80X、DURANATE MF-B60X、DURANATE E-402-B80T ME20-B80S, DURANATEWB40-100, DURANATE WB40-80D, DURANATE WT20-100, DURANATE WT30-100, etc.From the viewpoint of improving the acid resistance, alkali resistance, alcohol resistance, oil resistance, abrasion resistance and scratch resistance of the cured coating film, the organic polyisocyanate compound is preferably a polyisocyanate derived from an aliphatic organic isocyanate compound and / or an alicyclic organic isocyanate compound having 2.6 or more isocyanate groups and / or blocked isocyanate groups in one molecule, and specifically, diisocyanate derivatives such as biuret, allophanate, uretdione and isocyanurate and polyol adduct types are more preferred.

[0134] In the organic polyisocyanate compound, the lower limit of the number of isocyanate groups in one molecule is 2.6, more preferably 2.8, and even more preferably 3.0, and the upper limit is preferably 8.0, more preferably 6.0, and even more preferably 4.0.

[0135] It should be noted that, in the present embodiment, the number of isocyanate groups (average number of functional groups) in one molecule of the organic polyisocyanate compound can be determined by the isocyanate group content (mass %) determined based on the method described in JIS K7301-1995 and the number average molecular weight of the organic polyisocyanate determined by measuring the number average molecular weight based on polystyrene by gel permeation chromatography (GPC) and by the following formula (I).

[0136] Average number of functional groups = number average molecular weight of organic polyisocyanate × isocyanate group content (mass %) / 100% / 42 (I)

[0137] In addition, the specific analysis method of the isocyanate group content and the number average molecular weight of the organic polyisocyanate is as follows.

[0138] (Physical Property 1) Isocyanate Group Content

[0139] The isocyanate group content was measured using the polyisocyanate composition as a sample according to the method described in JIS K7301-1995 (Testing methods for toluene diisocyanate prepolymers for thermosetting urethane elastomers). A more specific method for measuring the isocyanate group content is shown below.

[0140] (1) 1 g of a sample is placed in a 200 mL Erlenmeyer flask, and 20 mL of toluene is added to the flask to dissolve the sample.

[0141] (2) Then, 20 mL of a 2.0 N di-n-butylamine toluene solution was added to the flask, and the mixture was allowed to stand for 15 minutes.

[0142] (3) 70 mL of 2-propanol was added to the above flask and dissolved to obtain a solution.

[0143] (4) The solution obtained in the above (3) is titrated with 1 mol / L hydrochloric acid to determine the sample titration amount.

[0144] (5) When no sample is added, measurement is performed in the same manner as in (1) to (3) above to determine the blank titer.

[0145] The isocyanate group content was calculated by the following formula (II) from the sample titration and blank titration obtained as described above.

[0146] Isocyanate group content (mass %) = (blank titration - sample titration) × 42 / [sample mass (g) × 1,000] × 100%. (II)

[0147] (Physical Property 2) Number Average Molecular Weight of Organic Polyisocyanate

[0148] The polyisocyanate composition was used as a sample, and the number average molecular weight of the polyisocyanate including the modified polyisocyanate and the unreacted polyisocyanate in the polyisocyanate composition was measured by gel permeation chromatography (GPC) using the following apparatus and conditions.

[0149] Device: HLC-8120GPC (trade name) manufactured by Tosoh Corporation

[0150] Column: Tosoh Corporation TSKgelSuperH1000 (trade name) × 1 column, TSKgelSuperH2000 (trade name) × 1 column, TSKgelSuperH3000 (trade name) × 1 column,

[0151] Carrier: Tetrahydrofuran

[0152] Detection method: Differential refractometer

[0153] (Physical Property 3) Average Number of Isocyanate Functional Groups

[0154] The polyisocyanate composition is used as a sample, and the average isocyanate functional group number is the number of isocyanate functional groups statistically possessed by one molecule of polyisocyanate, which is calculated by the following formula (III) based on the number average molecular weight of the organic polyisocyanate measured in (Physical Property 2) and the isocyanate group content measured in (Physical Property 1).

[0155] Average number of functional groups = number average molecular weight of organic polyisocyanate × isocyanate group content (mass %) / 100% / 42 (III)

[0156] <2. (b) Polycarbonate diol>

[0157] The method for producing the (b) polycarbonate diol used in the coating composition of the present embodiment is not particularly limited, and for example, the following production method is preferred: a step of obtaining the polycarbonate diol by polycondensing a dihydroxy compound and a carbonate as raw material monomers through an ester exchange reaction in the presence of an ester exchange catalyst, wherein the ester exchange catalyst contains at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10, and Group 11 of the long-period periodic table. The method for producing the (b) polycarbonate diol used in the coating composition of the present embodiment uses an ester exchange catalyst containing a specific metal in this way, and the (b) polycarbonate diol used in the coating composition of the present embodiment can be efficiently produced. When used in the coating composition of the present embodiment, a coating composition with less coloring can be provided, and also when used in, for example, a clear coating for automobile exterior, a coating for automobile interior, a coating for home appliances, a coating for OA products, a leather surface treatment agent, a synthetic leather surface treatment agent, etc., is preferred.

[0158] In addition, the ester exchange catalyst comprises an ester exchange catalyst A1 containing at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table, and an ester exchange catalyst A2 containing at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-form periodic table, which is more efficient (specifically, for example, under milder reaction conditions and in a shorter time), and is more preferred.

[0159] The method for producing the (b) polycarbonate diol used in the coating composition of the present embodiment can efficiently produce the (b) polycarbonate diol used in the coating composition of the present embodiment by using at least two ester exchange catalysts containing a specific metal in this way. When used in the coating composition of the present embodiment, a coating composition with little coloring can be provided, and also with little discoloration when used in, for example, clear coatings for automobile exteriors, coatings for automobile interiors, coatings for home appliances, coatings for OA products, leather surface treatment agents, synthetic leather surface treatment agents, etc., and is therefore more preferred.

[0160] <2-1. Raw material monomer>

[0161] The method for producing the (b) polycarbonate diol used in the coating composition of the present embodiment uses a dihydroxy compound and a carbonate as raw material monomers.

[0162] <2-1-1. Dihydroxy compounds>

[0163] In the method for producing the (b) polycarbonate diol used in the coating composition of the present embodiment, the dihydroxy compound used as the raw material monomer is not particularly limited, and examples thereof include: linear terminal dihydroxy compounds such as ethylene glycol, 1,3-propylene glycol, 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, and 1,20-eicosandiol; and diethylene glycol, triethylene glycol, tetraethylene glycol, polypropylene glycol, and polytetramethylene glycol having an ether group. dihydroxy compounds; sulfide diols such as bishydroxyethyl sulfide; 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol and 2,4-diethyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (hereinafter sometimes referred to as neopentyl glycol), 2-ethyl-2-butyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol and 2-pentyl-2-propyl-1,3-propanediol and other 2,2-dialkyl-substituted 1,3-propanediols (hereinafter sometimes referred to as 2,2-dialkyl-1,3-propanediols).); tetraalkyl-substituted alkylene glycols such as 2,2,4,4-tetramethyl-1,5-pentanediol and 2,2,9,9-tetramethyl-1,10-decanediol, dihydroxy compounds containing cyclic groups such as 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane; 2,2-diphenyl-1,3-propanediol, 2,2-divinyl-1,3-propanediol, 2,2-diethynyl-1,3-propanediol, 2,2-dimethoxy-1,3-propanediol, bis(2-hydroxy-1,1-dimethylethyl) ether, bis(2-hydroxy-1,1-dimethylethyl) thioethers and dihydroxy compounds with branched chains such as 2,2,4,4-tetramethyl-3-cyano-1,5-pentanediol; dihydroxy compounds with cyclic groups in the molecule such as 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 4,4-dicyclohexyldimethylmethanediol, 2,2'-bis(4-hydroxycyclohexyl)propane, 1,4-dihydroxyethylcyclohexane, isosorbide, spirodiol, 2,5-bis(hydroxymethyl)tetrahydrofuran, 4,4'-isopropylidene dicyclohexanol and 4,4'-isopropylidene bis(2,2'-hydroxyethoxycyclohexane); 9,9-bis(4-(2-hydroxyethoxy)cyclohexane) dihydroxy compounds having an aromatic ring such as 9,9-bis(4-(2-hydroxyethoxy-2-methyl)phenyl)fluorene, diethanolamine, N-methyl-diethanolamine and other nitrogen-containing dihydroxy compounds; and bis(hydroxyethyl)sulfide and other sulfur-containing dihydroxy compounds; 2,2-bis(4-hydroxyphenyl)propane [= bisphenol A], 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2- Aromatic bisphenols such as bis(4-hydroxyphenyl)pentane, 2,4'-dihydroxy-diphenylmethane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone, bis(4-hydroxyphenyl)sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-2-methylphenyl)fluorene.

[0164] Among them, from the viewpoint of weather resistance of the coating composition containing the polycarbonate diol used in the present embodiment, the dihydroxy compound is preferably at least one compound selected from the group consisting of aliphatic dihydroxy compounds and alicyclic dihydroxy compounds represented by the following formula (1).

[0165] HO-R1-OH (1)

[0166] (In the formula, R1 represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 20 carbon atoms.)

[0167] Among such dihydroxy compounds, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 2-methyl-1,3-propylene glycol, 3-methyl-1,5-pentanediol, and 2-methyl-1,8-octanediol are particularly preferred as alicyclic dihydroxy compounds, and 1,4-cyclohexanedimethanol and tricyclodecanedimethanol are particularly preferred as alicyclic dihydroxy compounds. Among these dihydroxy compounds, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are more preferred because they can make the coating film obtained by applying the coating composition have excellent softness.

[0168] These dihydroxy compounds can be used alone or in combination of two or more, preferably in combination of multiple types to form a copolycarbonate diol, depending on the desired performance of the obtained polycarbonate diol. Copolycarbonate diols are generally inhibited from crystallizing and have higher fluidity than homopolycarbonate diols. They not only have excellent operability when processed into coating compositions, but also can impart flexibility and texture (soft feel) to the coating film using the coating composition.

[0169] Regarding the composition ratio of the copolymerization, for example, when two dihydroxy compounds are used, each dihydroxy compound is preferably used at 5 mol% or more, preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more relative to all dihydroxy compounds. When two or more dihydroxy compounds are used, it is more preferred to use at least two dihydroxy compounds selected from 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol because the coating film to which the coating composition is applied has excellent softness and texture (softness).

[0170] <2-1-2. Carbonate ester>

[0171] In the method for producing (b) polycarbonate diol used in the coating composition of the present embodiment, carbonates that can be used as raw material monomers are not limited unless the effects of the present invention are impaired, and examples thereof include dialkyl carbonates, diaryl carbonates, and alkylene carbonates.

[0172] Specific examples of dialkyl carbonates among carbonates that can be used in the method for producing the (b) polycarbonate diol used in the coating composition of the present embodiment are not particularly limited, and examples thereof include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diisobutyl carbonate, ethyl n-butyl carbonate, and ethyl isobutyl carbonate.

[0173] Examples of the diaryl carbonate include, but are not particularly limited to, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, and di-m-tolyl carbonate.

[0174] Examples of the alkylene carbonate include, but are not particularly limited to, ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 1,3-pentylene carbonate, 1,4-pentylene carbonate, 1,5-pentylene carbonate, 2,3-pentylene carbonate, 2,4-pentylene carbonate, and neopentyl carbonate.

[0175] These may be used alone or in combination of two or more.

[0176] Among these carbonates, dimethyl carbonate, diethyl carbonate, ethylene carbonate, and diphenyl carbonate are preferred because they are inexpensively available as industrial raw materials, have good reactivity, and produce a small amount of alcohol as a byproduct. Ethylene carbonate is particularly preferred because a coating film having excellent toughness can be obtained.

[0177] <2-1-3. Ratio of raw material monomers used>

[0178] In the method for producing (b) polycarbonate diol used in the coating composition of the present embodiment, the amount of carbonate used needs to be appropriately changed according to the target molecular weight of the polycarbonate diol, and is not particularly limited. Generally, the lower limit is 0.5, preferably 0.7, and more preferably 0.8, and the upper limit is 1.5, preferably 1.3, and more preferably 1.2, based on the molar ratio relative to 1 mole of the total dihydroxy compounds. When the amount of carbonate diester used is below the above upper limit, the proportion of the terminal groups of the obtained polycarbonate diol that are not hydroxyl groups can be suppressed or there is a tendency to produce the polycarbonate diol of the present embodiment with a molecular weight within a specified range. When it is above the above lower limit, there is a tendency to polymerize until the specified molecular weight.

[0179] <2-2. Transesterification catalyst>

[0180] In the method for producing the (b) polycarbonate diol used in the coating composition of the present embodiment, although not particularly limited, it is preferred that there is an ester exchange catalyst containing at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long period periodic table.

[0181] As one embodiment of the ester exchange catalyst containing at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table, at least one metal complex represented by the following formula (2) and / or a hydrate thereof is preferred.

[0182]

[0183] (In the formula, R2 and R4 each independently represent a monovalent hydrocarbon group having 1 to 10 carbon atoms, the hydrocarbon groups of R2 and R4 are optionally substituted with halogen atoms, and optionally have an oxygen atom, R3 represents hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, the hydrocarbon group of R3 is optionally substituted with halogen atoms, and optionally has an oxygen atom, M1 represents at least one metal selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long period periodic table, and n is 1, 2 or 3. In addition, the metal complex represented by formula (2) is optionally an association of multiple metals.)

[0184] The metal (M1) selected from the group consisting of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table is not particularly limited, but from the viewpoint of catalytic activity, molybdenum, manganese, iron, cobalt, nickel and copper are preferred, and among them, manganese is particularly preferred.

[0185] In addition, a transition metal compound and a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound may be used in combination with the transesterification catalyst represented by the formula (2).

[0186] In the present embodiment, the organometallic complex with these acetylacetone analogs used as the transesterification catalyst may be used in the form of a hydrate.

[0187] As another embodiment of the ester exchange catalyst containing at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table, it is preferred that the salt and / or hydrate thereof of at least one carboxylic acid represented by the following formula (3) and at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table.

[0188]

[0189] (In the formula, R5 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group of R5 may be substituted with a halogen atom and may have an oxygen atom.)

[0190] The carboxylic acid is not particularly limited, and examples thereof include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, palmitic acid, heptadecanoic acid, and stearic acid. Among these, acetic acid, propionic acid, and butyric acid are preferred, and acetic acid is particularly preferred.

[0191] The metal (M1) selected from the group consisting of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table is not particularly limited, but from the viewpoint of catalytic activity, molybdenum, manganese, iron, cobalt, nickel and copper are preferred, and among them, manganese is particularly preferred.

[0192] In addition, in the present embodiment, the salts of these carboxylic acids used as the transesterification catalyst may be used in the form of hydrates.

[0193] Regarding the amount of the transesterification catalyst used in the present embodiment, the total amount of the metal (M1) is preferably 0.5 ppm or more and 20 ppm or less, more preferably 0.5 ppm or more and 15 ppm or less, and further preferably 0.5 ppm or more and 10 ppm or less relative to the total amount of all dihydroxy compounds and carbonates, and preferably 1 ppm or more and 20 ppm or less, more preferably 3 ppm or more and 20 ppm or less, and further preferably 5 ppm or more and 20 ppm or less. When the amount of the transesterification catalyst used is 0.5 ppm or more, the reaction rate of the transesterification tends to be faster. In addition, when the amount of the transesterification catalyst used is 20 ppm or less in terms of the total amount as the metal (M1), the coloring of the obtained polycarbonate diol can be suppressed, and when used as a raw material for the coating composition of the present embodiment, there is a tendency for the curing reaction to be stable, and the coating composition of the present embodiment with little discoloration when used for, for example, clear coatings for automobile exteriors, coatings for automobile interiors, coatings for home appliances, coatings for OA products, leather surface treatment agents, synthetic leather surface treatment agents, etc. can be provided, which is more preferred.

[0194] The method for producing the (b) polycarbonate diol used in the coating composition of the present embodiment is not particularly limited, but a method using the above-mentioned transesterification catalyst A1 in combination with a transesterification catalyst A2 containing at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-form periodic table is more preferred.

[0195] The metal of the first group of the long-period periodic table is not particularly limited, and examples thereof include lithium, sodium, potassium, rubidium, cesium, and francium. Among these, lithium, sodium, and potassium are preferred due to their high catalytic activity. Lithium is particularly preferred because it has a particularly high activity and a small amount of ether bonds in the generated polycarbonate diol.

[0196] The form of the ester exchange catalyst A2 containing at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-form periodic table is not particularly limited, and examples thereof include salts with inorganic acids, salts with organic acids, alkoxides of various alcohols, and hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and titanium hydroxide.

[0197] Among them, an alkoxide of at least one alcohol represented by the following formula (4) and at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-form periodic table is preferred because of its high catalytic activity and little coloration.

[0198] R6-OH (4)

[0199] (In the formula, R6 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group of R6 may be substituted with a halogen atom and may have an oxygen atom.)

[0200] The alkoxide of at least one alcohol represented by formula (4) and a metal of Group 1 of the long-period periodic table is not particularly limited, and examples thereof include lithium methoxide (methoxylithium), lithium ethoxide (ethoxylithium), lithium propoxide, lithium butoxide, sodium methoxide (methoxysodium), sodium ethoxide (ethoxysodium), sodium propoxide, sodium butoxide, potassium methoxide (methoxypotassium), potassium ethoxide (ethoxypotassium), potassium propoxide, potassium butoxide, methoxyrubidium, ethoxyrubidium, methoxycesium, ethoxycesium, etc. Among these alkoxides, lithium methoxide, lithium ethoxide, sodium methoxide, and sodium ethoxide are preferred, and lithium methoxide and lithium ethoxide are particularly preferred, because they have high catalytic activity and produce a polycarbonate diol with a small amount of ether bonds and less coloration.

[0201] In the method for producing the (b) polycarbonate diol used in the coating composition of the present embodiment, although not particularly limited, when at least two transesterification catalysts, namely, a transesterification catalyst A1 containing at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long period periodic table and a transesterification catalyst A2 containing at least one metal (M2) selected from the group consisting of metals of Group 1 of the long period periodic table, are used in combination, the amount of the transesterification catalyst to be used is preferably 0.5 ppm or more and 20 ppm or less, more preferably 1 ppm or more and 20 ppm or less, based on the total amount of the metal (M1) relative to the total amount of all dihydroxy compounds and carbonates, and the amount of the transesterification catalyst A1 to be used is preferably 0.5 ppm or more and 20 ppm or less, more preferably 1 ppm or more and 20 ppm or less, and further preferably 2 ppm or more and 20 ppm or less, based on the total amount of the metal (M1). The total amount calculated based on the above-mentioned metal (M2) is preferably 0.5 ppm or more and 20 ppm or less, more preferably 0.5 ppm or more and 10 ppm or less, and further preferably 0.5 ppm or more and 7 ppm or less, relative to the total amount of all dihydroxy compounds and carbonates. The amount of the ester exchange catalyst A2 used is preferably 0.05 ppm or more and 10 ppm or less, more preferably 0.1 ppm or more and 10 ppm or less, and further preferably 1 ppm or more and 10 ppm or less, relative to the total amount of all dihydroxy compounds and carbonates. In addition, the amount of the ester exchange catalyst A2 used is preferably 0.05 ppm or more and 10 ppm or less, more preferably 0.05 ppm or more and 5 ppm or less, and further preferably 0.05 ppm or more and 3 ppm or less, relative to the total amount of all dihydroxy compounds and carbonates.

[0202] When the amount of the transesterification catalyst A1 used is 0.5 ppm or more in terms of the total amount calculated as the metal (M1), the reaction rate of the transesterification tends to be faster. In addition, when the amount of the transesterification catalyst is 20 ppm or less in terms of the total amount calculated as the metal (M1), the (b) polycarbonate diol used in the coating composition is less colored during storage, and a coating composition with less color change when used in, for example, automobile exterior clear coatings, automobile interior coatings, home appliance coatings, OA product coatings, leather surface treatment agents, synthetic leather surface treatment agents, etc., can be provided, which is more preferred.

[0203] In addition, when the amount of the transesterification catalyst A2 used is 0.05 ppm or more in terms of the total amount calculated as metal (M2), there is a tendency for the reaction rate of the transesterification to become faster. In addition, when the amount of the transesterification catalyst is 10 ppm or less in terms of the total amount calculated as metal (M2), the coloring of the obtained polycarbonate diol can be suppressed, and a coating composition with little discoloration when used for example in clear coatings for automobile exteriors, coatings for automobile interiors, coatings for home appliances, coatings for OA products, leather surface treatment agents, synthetic leather surface treatment agents, etc. can be provided, which is more preferred.

[0204] <2-3. (b) Method for producing polycarbonate diol>

[0205] In the coating composition of the present embodiment, it is preferred that polycarbonate diol is produced by subjecting one or more of the above-mentioned dihydroxy compounds to transesterification with one or more of the above-mentioned carbonates in the presence of the above-mentioned transesterification catalyst.

[0206] <2-3-1. Reaction conditions, etc.>

[0207] The feeding method of the reaction raw materials is not particularly limited and the feeding method can be freely selected, for example, a method in which the total amount of one or more dihydroxy compounds, carbonates and catalysts is simultaneously supplied to the feeding reaction; a method in which when the carbonate is a solid, the carbonate is first added and heated to melt it, and then the dihydroxy compounds and the catalyst are added; conversely, when the dihydroxy compound is a solid, the dihydroxy compound is first added and melted, and then the carbonate and the catalyst are added thereto; etc.

[0208] The reaction temperature during the transesterification reaction can be arbitrarily adopted as long as it is a temperature at which a practical reaction rate can be obtained. The temperature is not particularly limited, and the lower limit is preferably 80°C, more preferably 110°C, and further preferably 130°C. In addition, the upper limit of the reaction temperature is preferably 220°C, more preferably 200°C, further preferably 180°C, and particularly preferably 170°C. When the reaction temperature is above the above lower limit, there is a tendency for the transesterification reaction to proceed at a practical rate. In addition, when the reaction temperature is below the above upper limit, the coloring of the obtained polycarbonate diol can be suppressed, and there is a tendency for the quality to be improved, such as suppressing the formation of ether bonds and improving turbidity.

[0209] In particular, the method for producing the (b) polycarbonate diol used in the coating composition of the present embodiment can efficiently obtain the polycarbonate diol in a short time under mild reaction conditions, for example, at a low temperature of 160° C. or less (preferably 150° C. or less), by using an ester exchange catalyst containing a specific metal (M1) that is highly active compared to conventional methods.

[0210] The reaction can also be carried out under normal pressure, but the transesterification reaction is a balanced reaction, and the reaction can be made to tend to the generation system by distilling the generated monohydroxy compound or dihydroxy compound out of the system. Therefore, it is usually preferred to carry out the reaction while distilling off the monohydroxy compound or dihydroxy compound under reduced pressure in the second half of the reaction. Alternatively, the pressure can be gradually reduced from the middle of the reaction, and the reaction can be carried out while distilling off the generated monohydroxy compound or dihydroxy compound. When the pressure is gradually reduced from the middle of the reaction, there is the following tendency: the volatilization of low-boiling unreacted monomers can be suppressed, the yield can be increased, and a polycarbonate diol of a specified molecular weight can be obtained, or a polycarbonate diol of a specified copolymer composition ratio can be obtained in the case of copolymerization.

[0211] The pressure during the reaction can be appropriately selected according to the type of alcohol derived from carbonate to be distilled. For example, when the alcohol to be distilled is an alcohol with a lower boiling point such as methanol, the preferred pressure of the reactor is 5kPa to normal pressure, and more preferably 7kPa to 15kPa. In addition, when the alcohol to be distilled is an alcohol with a higher boiling point such as ethylene glycol, the preferred pressure of the reactor is 1 to 10kPa, and more preferably 3kPa to 7kPa.

[0212] Furthermore, from the perspective of preventing the distillation of the raw materials in the initial stage of these reactions, a distillation tower having a theoretical plate number of 10 or more, preferably 15 or more, and more preferably 20 or more can be installed in the reactor, so that the monohydroxy compound or dihydroxy compound generated by the reaction of the carbonate ester and the raw material carbonate ester and dihydroxy compound of the azeotropic reaction are refluxed and separated, and the monohydroxy compound or dihydroxy compound generated by the reaction of the carbonate ester is efficiently separated and distilled. In this case, the amount ratio of the reagent can be accurately matched without loss of the raw material monomer added.

[0213] In addition, at the end of the reaction, it is usually switched to simple distillation, and when the reduced pressure is increased to carry out the reaction, by-product alcohols and diols, monohydroxy compounds or dihydroxy compounds such as phenols, residual monomers such as carbonates, and cyclic carbonates (cyclic oligomers) that may cause turbidity can be efficiently distilled off, so it is preferred.

[0214] The reaction pressure at the end of the reaction is not particularly limited, and the upper limit is usually preferably 5 kPa, more preferably 2 kPa, further preferably 1 kPa or less, and further preferably 0.5 kPa or less. In order to effectively distill these low-boiling components, the reaction can also be carried out while passing a small amount of inert gas such as nitrogen, argon, helium into the reaction system.

[0215] When using carbonates or dihydroxy compounds with low boiling points during transesterification, the following method can also be used: react near the boiling point of carbonic acid diester or dihydroxy compounds in the initial stage of reaction, and further react by gradually raising the temperature as the reaction proceeds. In this case, it is preferred to prevent the distillation of unreacted carbonic acid diester or dihydroxy compounds in the initial stage of reaction.

[0216] <2-3-2. Polymerization reactor>

[0217] The polymerization reaction (polycondensation reaction) can be carried out intermittently or continuously. The device used can be any of a tank type, a tube type and a tower type, and various known polymerization tanks with stirring blades can be used. The atmosphere during the heating of the device is not particularly limited, and from the viewpoint of product quality, it is preferably carried out in an inert gas such as nitrogen at normal pressure or reduced pressure.

[0218] <2-3-3. Reaction time>

[0219] In the method for producing the (b) polycarbonate diol used in the coating composition of the present embodiment, the time required for the transesterification reaction (polymerization reaction or polycondensation reaction) varies greatly depending on the type and amount of the dihydroxy compound, carbonic acid diester, and transesterification catalyst used, and therefore cannot be generalized. Generally, the reaction time required to reach a specified molecular weight is preferably 30 hours or less, more preferably 20 hours or less, and further preferably 10 hours or less.

[0220] <2-3-4. Deactivation of Catalyst>

[0221] As mentioned above, when a transesterification catalyst is used during the transesterification reaction, the transesterification catalyst or its residue is usually left in the polycarbonate diol obtained, which sometimes causes the reaction to run away or causes coloration during the polyurethane reaction. In order to suppress the influence of the residual catalyst, a catalyst deactivator can be added in an amount almost equimolar to the transesterification catalyst used, such as a phosphorus-based or sulfur-based compound that is acidic or decomposes to become an acidic compound. Furthermore, when heat-treated as described later after addition, the transesterification catalyst can be efficiently deactivated. In addition, by deactivation, the color development from the transesterification catalyst can be reduced, and a polycarbonate diol having a Hazen color number of preferably less than 50, more preferably less than 30, and further preferably less than 20 as measured based on JIS-K0071-1 (1998) can be obtained.

[0222] Furthermore, by adding a catalyst deactivator, the coloration and property changes of the obtained polycarbonate diol composition caused by changes in the terminal structure and skeleton of the polycarbonate diol and the residual catalyst during storage and handling at high temperatures for a long time can be suppressed.

[0223] The compound for deactivating the transesterification catalyst (hereinafter sometimes referred to as a catalyst deactivator) is not particularly limited, and examples thereof include inorganic phosphoric acids such as phosphoric acid and phosphorous acid, organic phosphoric acid esters such as monobutyl phosphate, dibutyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, and triphenyl phosphite, sulfonic acid, sulfonic acid esters, etc. These may be used alone or in combination of two or more.

[0224] The amount of the catalyst deactivator used is not particularly limited, and may be almost equimolar to the transesterification catalyst used as described above. Specifically, relative to 1 mole of the transesterification catalyst used, the lower limit is preferably 0.8 mole, more preferably 1.0 mole, and the upper limit is preferably 5 moles, more preferably 2 moles.

[0225] The deactivation of the transesterification catalyst by adding a catalyst deactivator can be carried out at room temperature, but it is more efficient when heated. The temperature of the heat treatment is not particularly limited, and the lower limit is preferably 80°C, more preferably 100°C, and further preferably 110°C, and the upper limit is preferably 140°C, more preferably 130°C, and further preferably 120°C. When the temperature is above the lower limit, the time required for the deactivation of the transesterification catalyst becomes shorter, the efficiency is high, and the degree of deactivation is sufficient. On the other hand, when the temperature is below the upper limit, when a phosphorus compound is used as a deactivator, the decomposition of the phosphorus compound can be suppressed, and there is a tendency for the deactivation to proceed stably. Therefore, the coloring of the obtained polycarbonate diol can be suppressed, and when used as a coating composition, there is a tendency for the curing reaction to be stable.

[0226] The reaction time with the catalyst deactivator is not particularly limited, and is, for example, 1 to 5 hours.

[0227] <2-4. (b) Physical properties of polycarbonate diol>

[0228] The suitable physical properties of (b) the polycarbonate diol used in the coating composition of the present embodiment will be described below.

[0229] <2-4-1. Molecular weight and molecular weight distribution>

[0230] The lower limit of the number average molecular weight (Mn) of the (b) polycarbonate diol used in the coating composition of the present embodiment is 250, preferably 500, more preferably 750, and further preferably 1000. On the other hand, the upper limit of the number average molecular weight (Mn) of the (b) polycarbonate diol used in the coating composition of the present embodiment is 3000, preferably 2500, further preferably 2100, and particularly preferably 2000. When the number average molecular weight of the polycarbonate diol is above the above lower limit, the softness and texture (soft feel) of the coating film using the coating composition of the present embodiment are excellent, so it is more preferred. On the other hand, when the number average molecular weight of the polycarbonate diol is below the above upper limit, the viscosity of the polycarbonate diol decreases, and there is a tendency that the handling during the manufacture of the coating composition becomes easy.

[0231] The preferred range of the number average molecular weight (Mn) of the (b) polycarbonate diol used in the coating composition of the present embodiment is 250 to 3000, more preferably 500 to 2500, further preferably 750 to 2100, and particularly preferably 1000 to 2000.

[0232] Here, the number average molecular weight of the polycarbonate diol is determined from the hydroxyl value (average hydroxyl value) of the polycarbonate diol as described in Examples below.

[0233] The method for controlling the number average molecular weight (Mn) of the polycarbonate diol within the above range is not particularly limited, and examples thereof include a method for controlling the number average molecular weight (Mn) of the polycarbonate diol within the above range by adjusting the polycondensation reaction time of the polycarbonate diol, adjusting the amount of the dihydroxy compound extracted as a raw material monomer, and the like.

[0234] <2-4-2.APHA value>

[0235] The color of the (b) polycarbonate diol used in the coating composition of the present embodiment is preferably 50 or less, more preferably 40 or less, further preferably 30 or less, and particularly preferably 20 or less, in terms of the value expressed by the Hazen color number (based on JIS K0071-1: 1998), more preferably 30 or less, and particularly preferably 20 or less. The lower limit of the APHA value of the (b) polycarbonate diol is not particularly limited, and is, for example, 0 or more. When the APHA value of the (b) polycarbonate diol is 50 or less, the color tone of the coating composition obtained using the polycarbonate diol as a raw material becomes good, and there is a tendency that the commercial value is improved and the thermal stability becomes good. The preferred range of the APHA value of the (b) polycarbonate diol is 10 to 50, preferably 10 to 40, and further preferably 10 to 30.

[0236] The method for controlling the APHA value of the polycarbonate diol within the above range is not particularly limited, and examples thereof include a method in which the reaction temperature during the ester exchange reaction is within the above preferred temperature range, a method in which the time required for the ester exchange reaction (polymerization reaction or polycondensation reaction) is within the above preferred range, etc.

[0237] In addition, in this embodiment, the APHA value of the polycarbonate diol can be measured by the method described in the examples mentioned later.

[0238] <2-4-3. Metals contained in polycarbonate diol>

[0239] The (b) polycarbonate diol used in the coating composition of the present embodiment preferably contains, as a metal, at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10, and Group 11 of the long period periodic table. The metal (M1) is more preferably at least one metal selected from the group consisting of metals of Group 7 of the long period periodic table.

[0240] In the (b) polycarbonate diol used in the coating composition of the present embodiment, at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long period periodic table has a lower limit of 1 ppm, preferably 2 ppm, more preferably 5 ppm, and an upper limit of 25 ppm, preferably 20 ppm, more preferably 15 ppm, and even more preferably 10 ppm in terms of the total amount of the metals.

[0241] In the (b) polycarbonate diol used in the coating composition of the present embodiment, at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long period periodic table is preferably contained in an amount of 1 ppm or more and 25 ppm or less, more preferably 2 ppm or more and 25 ppm or less, further preferably 5 ppm or more and 25 ppm or less, and further preferably 1 ppm or more and 25 ppm or less, more preferably 2 ppm or more and 25 ppm or less, and further preferably 5 ppm or more and 25 ppm or less.

[0242] When the content of the metal (M1) in the (b) polycarbonate diol used in the coating composition of the present embodiment is 1 ppm or more in total, the APHA value becomes low, and when used as a raw material of the coating composition of the present embodiment, there is a tendency for the curing reaction rate to increase. In addition, when the content of the metal (M1) in the (b) polycarbonate diol used in the coating composition of the present embodiment is 25 ppm or less in total, the coloring of the (b) polycarbonate diol caused by heating can be suppressed, and the coloring during storage is small. In addition, a coating composition with little discoloration when used in, for example, a clear coating for automobile exterior, a coating for automobile interior, a coating for home appliances, a coating for OA products, a leather surface treatment agent, a synthetic leather surface treatment agent, etc. can be provided, which is more preferred.

[0243] The metal (M1) contained in the (b) polycarbonate diol used in the coating composition of the present embodiment is preferably at least one metal selected from molybdenum, manganese, iron, cobalt, nickel and copper. Among them, the metal (M1) is more preferably manganese.

[0244] The metal contained in the (b) polycarbonate diol may be present in the form of a polymerization catalyst residue, or may be intentionally added in a predetermined amount after production.

[0245] When the (b) polycarbonate diol used in the coating composition of the present embodiment contains at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-period periodic table, the lower limit of the total amount of the metals is preferably 0.1 ppm, more preferably 0.5 ppm, further preferably 0.7 ppm, particularly preferably 1 ppm, and the upper limit is preferably 12.5 ppm, more preferably 10 ppm, further preferably 5 ppm, particularly preferably 3 ppm.

[0246] When the (b) polycarbonate diol used in the coating composition of the present embodiment contains at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-period periodic table, the total amount thereof is preferably 0.1 ppm to 12.5 ppm, more preferably 0.5 ppm to 12.5 ppm, further preferably 0.7 ppm to 12.5 ppm, particularly preferably 1 ppm to 12.5 ppm, further preferably 0.1 ppm to 10 ppm, further preferably 0.1 ppm to 5 ppm, and particularly preferably 0.1 ppm to 3 ppm.

[0247] When the content of the metal (M2) in the (b) polycarbonate diol used in the coating composition of the present embodiment is 0.1 ppm or more in total, the APHA value becomes low, and when used as a raw material for coating, there is a tendency for the curing reaction rate to increase. In addition, when the content of the metal (M2) in the (b) polycarbonate diol used in the coating composition of the present embodiment is 12.5 ppm or less in total, the coloring of the (b) polycarbonate diol caused by heating can be suppressed, and the coloring during storage is small. In addition, a coating composition with little discoloration when used in, for example, clear coatings for automobile exteriors, coatings for automobile interiors, coatings for home appliances, coatings for OA products, leather surface treatment agents, synthetic leather surface treatment agents, etc. can be provided, and therefore it is more preferred.

[0248] The metal (M2) contained in the (b) polycarbonate diol used in the coating composition of the present embodiment is preferably at least one metal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and francium. Among them, at least one metal selected from the group consisting of lithium, sodium and potassium is more preferred, and lithium is particularly preferred.

[0249] The metal contained in these polycarbonate diols may be present in the form of a polymerization catalyst residue, or a predetermined amount may be intentionally added after production.

[0250] In addition, in this embodiment, the type and amount of the metal contained in the polycarbonate diol can be measured by the method described in the Examples mentioned later.

[0251] In the coating composition of the present embodiment, regarding the mixing ratio of (a) the curing agent (organic polyisocyanate compound) and (b) the polycarbonate diol, from the viewpoint of coating film performance, the lower limit of OH / NCO (equivalent ratio) is preferably 0.2, preferably 0.3, more preferably 0.5, and further preferably 0.7, and the upper limit is 5.0, preferably 3.0, more preferably 1.8, and further preferably 1.3.

[0252] When NCO is 0.2 equivalents or more relative to OH1 equivalents, curing is sufficient, so chemical resistance, abrasion resistance, and scratch resistance can be obtained. When it is 5.0 equivalents or less relative to OH1 equivalents, the softness of the obtained coating film is improved. It should be noted that in this embodiment, softness means soft touch (softness).

[0253] <Hydryl-containing acrylic resin>

[0254] An acrylic resin containing hydroxyl groups may be added to the coating composition of the present embodiment. By adding an acrylic resin containing hydroxyl groups, chemical resistance, abrasion resistance, scratch resistance, and less discoloration performance can be maintained and the surface hardness can be adjusted. The acrylic resin containing hydroxyl groups used in the coating composition of the present embodiment is not particularly limited as long as it must contain a polymer containing a structural unit derived from an acrylic monomer having a hydroxyl group. It can be suitably a copolymer containing structural units derived from monomers such as acrylic monomers having carboxyl groups, other acrylic monomers, and copolymerizable acrylic monomers having ester groups, other vinyl monomers, and the types of structural units constituting the polymer are not particularly limited.

[0255] In the acrylic resin containing a hydroxyl group used in the coating composition of the present embodiment, the acrylic monomer having a hydroxyl group is not particularly limited, and examples thereof include 1-hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and ε-caprolactone adducts thereof, etc. These may be used alone or in combination of two or more as required.

[0256] The acrylic monomer having a carboxyl group is not particularly limited, and examples thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and anhydrides thereof, etc. These may be used alone or in combination of two or more as necessary.

[0257] The acrylic monomer having an ester group is not particularly limited, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate. These monomers may be used alone or in combination of two or more as required.

[0258] The other vinyl monomers are not particularly limited, and examples thereof include acrylamide monomers such as acrylamide, methacrylamide, N-methylol acrylamide, N,N-dimethyl acrylamide, and diacetone acrylamide; styrene, etc. These may be used alone or in combination of two or more as required.

[0259] The hydroxyl group-containing acrylic resin can be obtained by, for example, appropriately selecting a monomer from the above-mentioned acrylic monomers and vinyl monomers and polymerizing the monomers using a radical polymerization initiator, a chain transfer agent, and the like.

[0260] The hydroxyl value of the acrylic resin containing hydroxyl groups used in the coating composition of the present embodiment is not particularly limited, and is preferably 50 to 300 mgKOH / g, and more preferably 70 to 200 mgKOH / g. By making the hydroxyl value of the acrylic resin containing hydroxyl groups to be 50 mgKOH / g or more, there is a tendency that the coating hardness and coating strength of the coating obtained from the coating composition are further improved, and there is a tendency that the scratch resistance becomes better. In addition, by making the hydroxyl value of the acrylic resin containing hydroxyl groups to be 300 mgKOH / g or less, the crosslinking density of the coating obtained from the coating composition is adjusted to an appropriate range, and there is a tendency that the soft touch of the coating becomes better.

[0261] The number average molecular weight of the acrylic resin containing a hydroxyl group used in the coating composition of the present embodiment is not particularly limited, but is preferably 500 to 10,000, more preferably 1,500 to 8,000, and further preferably 2,000 to 6,000. By making the number average molecular weight of the acrylic resin containing a hydroxyl group 500 or more, there is a tendency that the soft touch of the coating film obtained by the coating composition becomes better. In addition, by making the number average molecular weight of the acrylic resin containing a hydroxyl group 10,000 or less, the viscosity of the coating composition is adjusted to a suitable range, and there is a tendency that the coating appearance becomes good and the scratch resistance becomes good.

[0262] The glass transition temperature of the hydroxyl group-containing acrylic resin used in the coating composition of the present embodiment is not particularly limited, but is preferably -20 to 60°C, and more preferably 0 to 40°C.

[0263] By making the glass transition temperature of the hydroxyl-containing acrylic resin used in the coating composition of the present embodiment to be -20°C or higher, the surface hardness of the coating film obtained from the coating composition becomes higher, and there is a tendency for the scratch resistance to become better. In addition, by making the glass transition temperature of the hydroxyl-containing acrylic resin to be 60°C or lower, the hardness of the coating film obtained from the coating composition is adjusted to an appropriate range, and there is a tendency for the soft touch and scratch resistance of the coating film to become better.

[0264] The hydroxyl-containing acrylic resin used in the coating composition of the present embodiment is not particularly limited, and for example, commercially available products can be used. Specifically, Setalux 1152, Setalux 1184, Setalux 1767 manufactured by Nuplex, LR-7606 manufactured by Mitsubishi Rayon Co., Ltd., SUPER LAC O-150Clear manufactured by Nippon Paint Co., Ltd., etc. can be suitably used.

[0265] The content of the hydroxyl-containing acrylic resin used in the coating composition of the present embodiment is preferably 1 to 80% by mass, more preferably 10 to 60% by mass, and even more preferably 30 to 50% by mass, based on the total solid content of the coating composition of the present embodiment.

[0266] By setting the content of the acrylic resin containing hydroxyl groups used in the coating composition of the present embodiment to 1% by mass or more, the surface hardness of the coating film obtained from the coating composition becomes higher, and there is a tendency for the scratch resistance to become better. In addition, by setting the content of the acrylic resin containing hydroxyl groups of the present embodiment to 80% by mass or less, the hardness of the coating film obtained from the coating composition is adjusted to a suitable range, and there is a tendency for the soft touch and scratch resistance of the coating film to become better.

[0267] When the hydroxyl-containing acrylic resin used in the coating composition of the present embodiment is added, regarding the blending ratio of the hydroxyl-containing acrylic resin of the present embodiment, (b) polycarbonate polyol, and (a) curing agent (organic polyisocyanate compound), from the viewpoint of the drying property and coating performance of the coating film, the equivalent ratio (OH group mole number / NCO group mole number) of the total number of moles of hydroxyl groups derived from the hydroxyl-containing acrylic resin of the present embodiment and the hydroxyl groups derived from the (b) polycarbonate polyol (hereinafter also referred to as "OH group mole number") to the number of moles of isocyanate groups contained in the (a) curing agent (hereinafter also referred to as "NCO group mole number") is preferably 1 / 0.5 to 1 / 2.0 (equivalent ratio), more preferably 1 / 0.7 to 1 / 1.3 (equivalent ratio), and further preferably 1 / 0.8 to 1 / 1.2 (equivalent ratio). When the number of OH groups is set to 1 equivalent, by making the number of NCO groups mole to be 0.5 equivalent or more, there is a tendency that the coating film properties become better. When the number of moles of NCO groups is 2.0 equivalents or less, based on the number of moles of OH groups being 1 equivalent, the curing rate can be made higher, and there is a tendency that the flexibility of the obtained coating film is more excellent.

[0268] <3. Inactive organic solvents>

[0269] In order to adjust the operability during coating, the coating composition of the present embodiment may contain an inactive organic solvent as required. Regarding the amount of the inactive organic solvent used, the lower limit is preferably 1% by mass, more preferably 10% by mass, and further preferably 20% by mass, relative to the total amount of the coating composition, and the upper limit is preferably 90% by mass, more preferably 70% by mass, and further preferably 50% by mass.

[0270] When the amount of the inactive organic solvent used is 1% by mass or more, the viscosity of the coating composition can be reduced and the workability of coating can be improved. In addition, when the amount of the inactive organic solvent used is 90% by mass or less, the drying time of the coating composition is shortened and the film thickness after coating becomes uniform, which is preferred.

[0271] The inactive organic solvent used is not particularly limited, but is preferably an organic solvent that is substantially inactive to the polyisocyanate compound and does not have active hydrogen. Examples thereof are not particularly limited, and examples thereof include hydrocarbons such as pentane, hexane, heptane, octane, decane, petroleum ether, petroleum benzine, volatile oil, petroleum spirit, cyclohexane, and methylcyclohexane; fluorine-based inactive liquids such as fluorinated oils such as trichlorofluoroethane, tetrachlorodifluoroethane, and perfluoroether; perfluorocyclohexane, perfluorobutyltetrahydrofuran, perfluorodecahydronaphthalene, perfluoro-n-butylamine, perfluoropolyether, dimethylpolysiloxane, etc., alone or in mixture. Also, examples thereof include single solvents or mixed solvents such as methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, toluene, and xylene.

[0272] <4. Additives>

[0273] <4-1. Inorganic fine powder>

[0274] In the coating composition of the present embodiment, in order to eliminate the gloss on the surface when making a coating film, produce a high-grade sense, preferably contain inorganic fine powder. In addition, by containing inorganic fine powder, the viscosity on the surface of the coating film obtained can be suppressed, and soft feel becomes good in addition, and is therefore preferred.

[0275] The inorganic fine powder is not particularly limited, and examples thereof include metal oxide fine powder, silicic acid compound fine powder, metal carbonate fine powder, nitride fine powder, gypsum fine powder, clay fine powder, talc fine powder, and natural mica fine powder.

[0276] There are no particular limitations on the metal oxide fine powder, and examples thereof include silicon oxide fine powder, titanium oxide fine powder, aluminum oxide fine powder, zirconium oxide fine powder, etc. There are no particular limitations on the silicic acid compound fine powder, and examples thereof include aluminum silicate fine powder, magnesium silicate fine powder, etc. There are no particular limitations on the metal carbonate fine powder, and examples thereof include calcium carbonate fine powder, barium carbonate fine powder, etc. There are no particular limitations on the nitride fine powder, and examples thereof include titanium nitride fine powder, silicon nitride fine powder, etc. These inorganic fine powders may be used alone or in combination of two or more.

[0277] The average particle size of these inorganic fine powders is preferably 4 to 15 μm, more preferably 6 to 13 μm, and further preferably 8 to 11 μm. When the average particle size of the inorganic fine powder is above the lower limit, the gloss elimination effect of the obtained soft-touch paint is fully exhibited, and the stickiness of the surface can be suppressed. In addition, when the average particle size of the inorganic fine powder is below the upper limit, the gloss of the obtained soft-touch paint is maintained well, and the wear resistance and scratch resistance of the coating film are improved.

[0278] In addition, about the content of these inorganic fine powders, relative to the total solid content of the coating composition, the lower limit is preferably 1 mass %, more preferably 3 mass %, further preferably 5 mass %, and the upper limit is preferably 30 mass %, more preferably 20 mass %, further preferably 10 mass %. When the content of inorganic fine powder is above the above lower limit, the gloss elimination effect of the obtained soft-feel coating is fully manifested, and the viscosity of the surface can be suppressed. In addition, when the content of inorganic fine powder is below the above upper limit, the gloss of the obtained soft-feel coating remains good, and the wear resistance and scratch resistance of the coating film are improved.

[0279] In addition, the content of these inorganic fine powders is preferably 1% by mass or more and 30% by mass or less, more preferably 1% by mass or more and 20% by mass or less, further preferably 1% by mass or more and 10% by mass or less, and further, preferably 3% by mass or more and 30% by mass or less, more preferably 5% by mass or more and 30% by mass or less, further preferably 10% by mass or more and 30% by mass or less.

[0280] As inorganic fine powder, silicon oxide fine powder is preferred. As silicon oxide fine powder, water-containing or anhydrous silicon dioxide fine powder can be exemplified. As such silicon dioxide fine powder, specifically, there is no particular limitation, and examples thereof include "ACEMATT OK 412 (trade name)", "ACEMATT OK 607 (trade name)", "ACEMATT OK 900 (trade name)", "ACEMATT TS100 (trade name)", "ACEMATT OK 520 (trade name)", "ACEMATT 3600 (trade name)", "ACEMATT 3300 (trade name)" etc. manufactured by Evonik.

[0281] <4-2. Polyurethane particles>

[0282] In order to further improve the softness of the obtained coating film, the coating composition of the present embodiment preferably contains polyurethane particles. As the polyurethane particles, there is no particular limitation, and for example, spherical polyurethane particles synthesized by the following methods can be cited: a method for manufacturing by dispersing a polyurethane prepolymer in water, cleaning, and drying in the presence of a suspension stabilizer (Japanese Patent Publication No. 1-185648), a method for emulsion polymerization of polyurethane in a non-aqueous inactive liquid in the presence of an emulsifier (Japanese Patent Publication No. 5-214054, Japanese Patent Publication No. 7-97425). In the case of using a difunctional or less isocyanate carbamate prepolymer in the synthesis of the polyurethane particles, thermoplastic carbamate particles can be obtained, and when using a terminal isocyanate carbamate prepolymer exceeding difunctional, three-dimensional crosslinked carbamate particles are obtained. As the polyurethane particles used in the present embodiment, in order to improve the acid resistance, alkali resistance, alcohol resistance, oil resistance, heat resistance, and abrasion resistance of the coating film obtained by the coating composition of the present embodiment, it is more suitable to use three-dimensional cross-linked urethane particles. The average particle size of the polyurethane particles used is preferably 2 to 20 μm, more preferably 4 to 15 μm, and further preferably 5 to 10 μm. When the average particle size of the polyurethane particles is above the above lower limit, the gloss of the obtained coating film is moderately suppressed, and not only a high-grade feel is obtained, but also a soft feel is improved. On the other hand, when the average particle size of the polyurethane particles is below the above upper limit, the abrasion resistance and scratch resistance of the obtained coating film are improved, and the soft feel of the surface is also obtained.

[0283] In the coating composition of the present embodiment, the content of the polyurethane particles is preferably 1% by mass, more preferably 3% by mass, and further preferably 5% by mass, with respect to the total solid content contained in the coating composition, and the upper limit is preferably 30% by mass, more preferably 20% by mass, and further preferably 10% by mass. When the content of the polyurethane particles is above the above lower limit, the obtained coating film can obtain a soft feel, and when the content of the polyurethane particles is below the above upper limit, the abrasion resistance of the obtained coating film is improved.

[0284] In addition, in this embodiment, the "average particle size" refers to the average particle size (volume average particle size) based on volume measured using a laser diffraction particle size distribution analyzer (for example, SALD2100 manufactured by Shimadzu Corporation).

[0285] <4-3. Other additives>

[0286] The coating composition of this embodiment may contain curing accelerators (catalysts), fillers, flame retardants, dyes, organic or inorganic pigments, release agents, fluidity regulators, plasticizers, antioxidants, ultraviolet absorbers, light stabilizers, defoamers, leveling agents, colorants, solvents, etc., depending on the application.

[0287] There are no particular limitations on the curing accelerator, and commonly used curing accelerators can be used, such as triethylamine and N,N-dimethylcyclohexylamine as monoamines, tetramethylethylenediamine as diamines, and triamines, cyclic amines, alcohol amines such as dimethylethanolamine, and ether amines. There are no particular limitations on the metal catalyst, and commonly used metal catalysts can be used, such as potassium acetate, potassium 2-ethylhexanoate, calcium acetate, lead octylate, dibutyltin dilaurate, tin octylate, bismuth neodecanoate, bismuth oxycarbonate, bismuth 2-ethylhexanoate, zinc octylate, zinc neodecanoate, phosphine, phosphazene, etc.

[0288] There are no particular limitations on fillers and pigments, and commonly used fillers and pigments can be used, such as woven fabrics, glass fibers, carbon fibers, polyamide fibers, mica, kaolin, bentonite, metal powder, azo pigments, carbon black, clay, silica, talc, gypsum, alumina white, barium carbonate, etc.

[0289] The release agent, fluidity adjuster, and leveling agent are not particularly limited, and for example, silicone, AEROSIL, wax, stearate, polysiloxane such as BYK-331 (manufactured by BYK Chemicals Co., Ltd.), etc. can be used.

[0290] As the additive used in the present embodiment, it is preferred to use at least an antioxidant, a light stabilizer and a heat stabilizer. As these antioxidants, there are no particular limitations, and phosphorus compounds such as aliphatic, aromatic or alkyl-substituted aromatic esters of phosphoric acid and phosphorous acid or hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonates, dialkyl pentaerythritol diphosphites, dialkyl bisphenol A diphosphites, etc. can be used; phenol derivatives, especially hindered phenol compounds, thioethers, dithiocarboxylates, mercaptobenzimidazoles, thiocarbanilides, thiodipropionates and other sulfur-containing compounds; tin compounds such as tin maleate and dibutyltin oxide. These can be used alone or in combination of two or more.

[0291] <5. Painting method>

[0292] The coating method of the coating composition of the present embodiment is not particularly limited, and for example, the following method can be used: the components are mixed just before coating, and then applied to the substrate using a spray, a roller, a brush, etc. The following method can also be used: the components other than the (a) component as a curing agent are mixed in advance, the (a) component is added just before coating and mixed evenly, and then the coating is performed. The drying time of the coating composition of the present embodiment is preferably 6 to 24 hours at room temperature, and preferably 30 minutes to 4 hours in a heated atmosphere below the deformation temperature of the plastic, i.e., 80°C.

[0293] <6. Application>

[0294] The coating composition of the present embodiment is excellent in abrasion resistance, scratch resistance, chemical resistance, soft feel and little discoloration, and is suitable for use as, for example, a clear coating for automobile exteriors and a coating for automobile interiors. In addition, it can be preferably used for household electrical appliances, OA products, leather surface treatment, synthetic leather surface treatment, etc.

[0295] <7. Paint-coated molded articles>

[0296] The paint-coated molded article of the present embodiment is a paint-coated molded article obtained by coating the above-mentioned paint composition on a molded article. Since the paint-coated molded article of the present embodiment is coated with the above-mentioned paint composition, it has the characteristics of excellent abrasion resistance, scratch resistance, chemical resistance, soft feel and little discoloration. Due to such characteristics, the paint-coated molded article of the present embodiment can be suitably used as a soft-feel paint-coated molded article.

[0297] <Waterborne polyurethane dispersion>

[0298] The aqueous polyurethane dispersion of the present embodiment contains a water-dispersible polyurethane which is a reaction product of the above composition and (c) a carboxyl group- and / or sulfonic group-containing polyol or a salt thereof, and water.

[0299] Specifically, the aqueous polyurethane dispersion of the present embodiment contains: a water-dispersible polyurethane which is a reaction product of (a) an organic polyisocyanate compound (preferably an organic polyisocyanate compound containing two or more isocyanate groups in one molecule) as a curing agent, (b) a polycarbonate diol, and (c) a polyol containing a carboxyl group and / or a sulfonic group or a salt thereof, and water, wherein the (b) polycarbonate diol is a polycondensate based on an ester exchange reaction between a dihydroxy compound and a carbonate, the (b) polycarbonate diol has a number average molecular weight of 250 to 3000, and the (b) polycarbonate diol contains at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long period periodic table in a total amount of 1 ppm to 25 ppm.

[0300] The aqueous polyurethane dispersion of the present embodiment has such characteristics, and is excellent in storage stability and rarely discolors when used in, for example, a paint, a coating agent, or the like.

[0301] The aqueous polyurethane dispersion of the present embodiment preferably has a Hazen color number of 50 or less as measured in accordance with JIS-K0071-1 (1998) for the polycarbonate diol (b).

[0302] The aqueous polyurethane dispersion of the present embodiment is not particularly limited and can be suitably used, for example, for synthetic leather, coatings, coatings, adhesives, and adhesives, etc. The synthetic leather, coatings, coatings, adhesives, and adhesives produced using the aqueous polyurethane dispersion of the present embodiment are characterized in that they undergo little discoloration.

[0303] <1. (a) Organic polyisocyanate compounds>

[0304] The organic polyisocyanate compound as the (a) curing agent used in the aqueous polyurethane dispersion of the present embodiment (hereinafter also referred to as “(a) organic polyisocyanate compound”) is not particularly limited as long as it contains two or more isocyanate groups in one molecule. (a) The organic polyisocyanate compound is not particularly limited, and examples thereof include aromatic, aliphatic, and alicyclic organic diisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, cyclohexane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate (HDI), trimethylhexane diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, 2,6-diisocyanatohexanoic acid methyl ester, isophorone diisocyanate (IPDI), methylcyclohexane-2,4- (or 2,6-) diisocyanate, and 4,4'-methylenebis (cyclohexyl isocyanate); or polymers containing polyfunctional isocyanate groups such as biuret bodies and isocyanurate bodies of these isocyanates, or these isocyanates alone or in mixtures thereof.

[0305] In particular, from the viewpoint of weather resistance, the (a) organic polyisocyanate compound is preferably an aliphatic organic diisocyanate compound and / or an alicyclic organic diisocyanate compound, and specifically, more preferably an aliphatic or alicyclic diisocyanate such as HDI, IPDI, dodecane diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, or a mixture of these isocyanates.

[0306] <2. (b) Polycarbonate diol>

[0307] The method for producing the polycarbonate diol (b) used in the aqueous polyurethane dispersion of the present embodiment is not particularly limited, and the following production method is preferred, for example: comprising a step of obtaining the polycarbonate diol by polycondensation through an ester exchange reaction using a dihydroxy compound and a carbonate as raw material monomers in the presence of an ester exchange catalyst, wherein the ester exchange catalyst contains at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10, and Group 11 of the long-period periodic table. The method for producing the polycarbonate diol (b) used in the aqueous polyurethane dispersion of the present embodiment is preferred because it can produce the polycarbonate diol efficiently (specifically, for example, under milder reaction conditions and in a short time) by using an ester exchange catalyst containing a specific metal in this way.

[0308] In addition, the ester exchange catalyst more preferably includes an ester exchange catalyst A1 containing at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table, and an ester exchange catalyst A2 containing at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-form periodic table.

[0309] The method for producing the polycarbonate diol (b) used in the aqueous polyurethane dispersion of the present embodiment can produce the polycarbonate diol efficiently (specifically, for example, under milder reaction conditions and in a short time) by using at least two transesterification catalysts containing a specific metal in this manner. The polycarbonate diol (b) used in the aqueous polyurethane dispersion has less coloration during storage, and can provide an aqueous polyurethane dispersion that has less color change when used in, for example, synthetic leather, paints, coatings, adhesives, binders, etc., and is therefore more preferred.

[0310] <2-1. Raw material monomer>

[0311] The method for producing the (b) polycarbonate diol used in the aqueous polyurethane dispersion of the present embodiment uses a dihydroxy compound and a carbonate as raw material monomers.

[0312] <2-1-1. Dihydroxy compounds>

[0313] In the method for producing the (b) polycarbonate diol used in the aqueous polyurethane dispersion of the present embodiment, the dihydroxy compound used as the raw material monomer is not particularly limited, and examples thereof include linear terminal dihydroxy compounds such as ethylene glycol, 1,3-propylene glycol, 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, and 1,20-eicosandiol; and ether-containing dihydroxy compounds such as diethylene glycol, triethylene glycol, tetraethylene glycol, polypropylene glycol, and polytetramethylene glycol. dihydroxy compounds containing 2-hydroxyl groups; thioether diols such as bishydroxyethyl sulfide; 2,2-dialkyl-substituted 1,3-propanediols such as 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol and 2,4-diethyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (hereinafter sometimes referred to as neopentyl glycol), 2-ethyl-2-butyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol and 2-pentyl-2-propyl-1,3-propanediol (hereinafter sometimes referred to as 2,2-dialkyl-1,3-propanediols).); tetraalkyl-substituted alkylene glycols such as 2,2,4,4-tetramethyl-1,5-pentanediol and 2,2,9,9-tetramethyl-1,10-decanediol, dihydroxy compounds containing cyclic groups such as 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane; 2,2-diphenyl-1,3-propanediol, 2,2-divinyl-1,3-propanediol, 2,2-diethynyl-1,3-propanediol, 2,2-dimethoxy-1,3-propanediol, bis(2-hydroxy-1,1-dimethylethyl) ether, bis(2-hydroxy-1,1-dimethylethyl) thioethers and dihydroxy compounds with branched chains such as 2,2,4,4-tetramethyl-3-cyano-1,5-pentanediol; dihydroxy compounds with cyclic groups in the molecule such as 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 4,4-dicyclohexyldimethylmethanediol, 2,2'-bis(4-hydroxycyclohexyl)propane, 1,4-dihydroxyethylcyclohexane, isosorbide, spirodiol, 2,5-bis(hydroxymethyl)tetrahydrofuran, 4,4'-isopropylidene dicyclohexanol and 4,4'-isopropylidene bis(2,2'-hydroxyethoxycyclohexane); 9,9-bis(4-(2-hydroxyethoxy) dihydroxy compounds having an aromatic ring such as 9,9-bis(4-(2-hydroxyethoxy-2-methyl)phenyl)fluorene, diethanolamine, N-methyl-diethanolamine and other nitrogen-containing dihydroxy compounds; and bis(hydroxyethyl)sulfide and other sulfur-containing dihydroxy compounds; 2,2-bis(4-hydroxyphenyl)propane [= bisphenol A], 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2- Aromatic bisphenols such as bis(4-hydroxyphenyl)pentane, 2,4'-dihydroxy-diphenylmethane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone, bis(4-hydroxyphenyl)sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-2-methylphenyl)fluorene.

[0314] Among them, from the viewpoint of weather resistance of a polyurethane obtained using the polycarbonate diol, the dihydroxy compound is preferably at least one compound selected from the group consisting of aliphatic dihydroxy compounds and alicyclic dihydroxy compounds represented by the following formula (1).

[0315] HO-R1-OH (1)

[0316] (In the formula, R1 represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 20 carbon atoms.)

[0317] Among such dihydroxy compounds, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 2-methyl-1,3-propylene glycol, 3-methyl-1,5-pentanediol, and 2-methyl-1,8-octanediol are particularly preferred as alicyclic dihydroxy compounds, and 1,4-cyclohexanedimethanol and tricyclodecanedimethanol are particularly preferred as alicyclic dihydroxy compounds. Among these dihydroxy compounds, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are more preferred because they can provide excellent flexibility to the obtained water-based polyurethane.

[0318] These dihydroxy compounds can be used alone or in combination according to the desired properties of the obtained polycarbonate diol, preferably in combination to form a copolycarbonate diol. Copolycarbonate diols are generally inhibited from crystallizing and have higher fluidity than homopolycarbonate diols, and not only have excellent operability when processed into polyurethanes, but also can impart softness and texture to polyurethanes.

[0319] Regarding the composition ratio of the copolymerization, for example, when two dihydroxy compounds are used, each dihydroxy compound is preferably used at 5 mol% or more, preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more relative to the total dihydroxy compounds. When two or more dihydroxy compounds are used, it is more preferred to use at least two dihydroxy compounds selected from 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol because the obtained water-based polyurethane has excellent flexibility.

[0320] <2-1-2. Carbonate ester>

[0321] In the method for producing the (b) polycarbonate diol used in the aqueous polyurethane dispersion of the present embodiment, carbonates that can be used as raw material monomers are not limited unless the effects of the present invention are impaired, and examples thereof include dialkyl carbonates, diaryl carbonates, and alkylene carbonates.

[0322] Specific examples of dialkyl carbonates among carbonates that can be used in the method for producing the (b) polycarbonate diol used in the aqueous polyurethane dispersion of the present embodiment are not particularly limited, and examples thereof include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diisobutyl carbonate, ethyl n-butyl carbonate, and ethyl isobutyl carbonate.

[0323] Examples of the diaryl carbonate include, but are not particularly limited to, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, and di-m-tolyl carbonate.

[0324] Examples of the alkylene carbonate include, but are not particularly limited to, ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 1,3-pentylene carbonate, 1,4-pentylene carbonate, 1,5-pentylene carbonate, 2,3-pentylene carbonate, 2,4-pentylene carbonate, and neopentyl carbonate.

[0325] These may be used alone or in combination of two or more.

[0326] Among these carbonates, dimethyl carbonate, diethyl carbonate, ethylene carbonate, and diphenyl carbonate are particularly preferred because they are available as industrial raw materials at low cost, have good reactivity, and produce a small amount of alcohol as a by-product.

[0327] <2-1-3. Ratio of raw material monomers used>

[0328] In the method for producing the polycarbonate diol (b) of the aqueous polyurethane dispersion used in the present embodiment, the amount of carbonate used needs to be appropriately changed according to the target molecular weight of the polycarbonate diol, and is not particularly limited. Generally, the lower limit is preferably 0.5, more preferably 0.7, and further preferably 0.8, and the upper limit is generally 1.5, preferably 1.3, and more preferably 1.2, based on the molar ratio relative to 1 mole of the total dihydroxy compounds. When the amount of carbonate diester used is below the above upper limit, there is a tendency to suppress the proportion of the terminal groups of the obtained polycarbonate diol that are not hydroxyl groups or to produce the polycarbonate diol (b) used in the present embodiment with a molecular weight within a specified range. When it is above the above lower limit, there is a tendency to carry out polymerization until the specified molecular weight.

[0329] <2-2. Transesterification catalyst>

[0330] In the method for producing the (b) polycarbonate diol of the aqueous polyurethane dispersion of the present embodiment, although not particularly limited, it is preferred that there is an ester exchange catalyst containing at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table.

[0331] As one embodiment of the ester exchange catalyst containing at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table, at least one metal complex represented by the following formula (2) and / or a hydrate thereof is preferred.

[0332]

[0333] (In the formula, R2 and R4 each independently represent a monovalent hydrocarbon group having 1 to 10 carbon atoms, the hydrocarbon groups of R2 and R4 are optionally substituted with halogen atoms, and optionally have an oxygen atom, R3 represents hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, the hydrocarbon group of R3 is optionally substituted with halogen atoms, and optionally has an oxygen atom, M1 represents at least one metal selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long period periodic table, and n is 1, 2 or 3. In addition, the metal complex represented by formula (2) is optionally an association of multiple metals.)

[0334] The metal (M1) selected from the group consisting of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table is not particularly limited, but from the viewpoint of catalytic activity, molybdenum, manganese, iron, cobalt, nickel and copper are preferred, and among them, manganese is particularly preferred.

[0335] In addition, a transition metal compound and a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound may be used in combination with the transesterification catalyst represented by the formula (2).

[0336] In the present embodiment, the organometallic complex with these acetylacetone analogs used as the transesterification catalyst may be used in the form of a hydrate.

[0337] As another embodiment of the ester exchange catalyst containing at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table, it is preferred that the salt and / or hydrate thereof of at least one carboxylic acid represented by the following formula (3) and at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table.

[0338]

[0339] (In the formula, R5 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group of R5 may be substituted with a halogen atom and may have an oxygen atom.)

[0340] The carboxylic acid is not particularly limited, and examples thereof include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, palmitic acid, heptadecanoic acid, and stearic acid. Among these, acetic acid, propionic acid, and butyric acid are preferred, and acetic acid is particularly preferred.

[0341] The metal (M1) selected from the group consisting of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table is not particularly limited, but from the viewpoint of catalytic activity, molybdenum, manganese, iron, cobalt, nickel and copper are preferred, and among them, manganese is particularly preferred.

[0342] In addition, in the present embodiment, the salts of these carboxylic acids used as the transesterification catalyst may be used in the form of hydrates.

[0343] Regarding the amount of the transesterification catalyst used in the present embodiment, according to the total amount calculated by the above-mentioned metal (M1), the total amount relative to all dihydroxy compounds and carbonates is preferably 0.5ppm or more and 20ppm or less, more preferably 0.5ppm or more and 15ppm or less, further preferably 0.5ppm or more and 10ppm or less, and preferably 1ppm or more and 20ppm or less, more preferably 3ppm or more and 20ppm or less, and further preferably 5ppm or more and 20ppm or less. When the amount of the transesterification catalyst is 0.5ppm or more, the reaction rate of the transesterification tends to be faster. In addition, when the amount of the transesterification catalyst is 20ppm or less, the coloring of the obtained polycarbonate diol can be suppressed, and when used as a raw material for an aqueous polyurethane dispersion, there is a tendency for the urethane reaction to be stable, and an aqueous polyurethane dispersion with less discoloration when used for, for example, synthetic leather, coatings, coating agents, adhesives, adhesives, etc. can be provided, so it is more preferred.

[0344] The method for producing the (b) polycarbonate diol used in the aqueous polyurethane dispersion of the present embodiment is not particularly limited, but a method using the above-mentioned transesterification catalyst A1 in combination with a transesterification catalyst A2 containing at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-form periodic table is more preferred.

[0345] The metal of the first group of the long-period periodic table is not particularly limited, and examples thereof include lithium, sodium, potassium, rubidium, cesium, and francium. Among these, lithium, sodium, and potassium are preferred due to their high catalytic activity. Lithium is particularly preferred because it has a particularly high activity and a small amount of ether bonds in the generated polycarbonate diol.

[0346] The form of the ester exchange catalyst A2 containing at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-form periodic table is not particularly limited, and examples thereof include salts with inorganic acids, salts with organic acids, alkoxides of various alcohols, and hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and titanium hydroxide.

[0347] Among them, an alkoxide of at least one alcohol represented by the following formula (4) and at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-form periodic table is preferred because of its high catalytic activity and little coloration.

[0348] R6-OH (4)

[0349] (In the formula, R6 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group of R6 may be substituted with a halogen atom and may have an oxygen atom.)

[0350] The alkoxide of at least one alcohol represented by formula (4) and a metal of Group 1 of the long-period periodic table is not particularly limited, and examples thereof include lithium methoxide (methoxylithium), lithium ethoxide (ethoxylithium), lithium propoxide, lithium butoxide, sodium methoxide (methoxysodium), sodium ethoxide (ethoxysodium), sodium propoxide, sodium butoxide, potassium methoxide (methoxypotassium), potassium ethoxide (ethoxypotassium), potassium propoxide, potassium butoxide, methoxyrubidium, ethoxyrubidium, methoxycesium, ethoxycesium, etc. Among these alkoxides, lithium methoxide, lithium ethoxide, sodium methoxide, and sodium ethoxide are preferred, and lithium methoxide and lithium ethoxide are particularly preferred, because they have high catalytic activity and produce a polycarbonate diol with a small amount of ether bonds and less coloration.

[0351] In the method for producing the (b) polycarbonate diol of the aqueous polyurethane dispersion of the present embodiment, it is preferred that at least two transesterification catalysts are present: an ester exchange catalyst A1 containing at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-period periodic table, and an ester exchange catalyst A2 containing at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-period periodic table.

[0352] Compared with using the ester exchange catalyst A1 or the ester exchange catalyst A2 alone, the combined use of the ester exchange catalyst A1 and the ester exchange catalyst A2 can obtain higher catalytic activity, can efficiently produce polycarbonate diol, and the (b) polycarbonate diol used for the obtained aqueous polyurethane dispersion has less coloration during storage. In addition, an aqueous polyurethane dispersion with less discoloration when used for example in synthetic leather, paint, coating agent, adhesive, binder, etc. can be provided, which is more preferred.

[0353] In the method for producing the (b) polycarbonate diol used in the aqueous polyurethane dispersion of the present embodiment, although not particularly limited, when at least two transesterification catalysts are used in combination, namely, a transesterification catalyst A1 containing at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long period periodic table and a transesterification catalyst A2 containing at least one metal (M2) selected from the group consisting of metals of Group 1 of the long period periodic table, the amount of the transesterification catalyst to be used is preferably 0.5 ppm or more and 20 ppm or less, more preferably 1 ppm or more and 20 ppm or less, based on the total amount of the above-mentioned metals (M1) relative to the total amount of all dihydroxy compounds and carbonates, and the amount of the transesterification catalyst A1 is preferably 0.5 ppm or more and 20 ppm or less, more preferably 1 ppm or more and 20 ppm or less, and further preferably 2 ppm or more and 20 ppm or less. The total amount of (M1) is preferably 0.5 ppm or more and 20 ppm or less, more preferably 0.5 ppm or more and 10 ppm or less, and further preferably 0.5 ppm or more and 7 ppm or less, and the amount of the ester exchange catalyst A2 is preferably 0.25 ppm or more and 10 ppm or less, more preferably 0.5 ppm or more and 10 ppm or less, and further preferably 1 ppm or more and 10 ppm or less, relative to the total amount of all dihydroxy compounds and carbonates, and the total amount of the ester exchange catalyst A2 is preferably 0.25 ppm or more and 10 ppm or less, more preferably 0.25 ppm or more and 5 ppm or less, and further preferably 0.25 ppm or more and 3 ppm or less, relative to the total amount of all dihydroxy compounds and carbonates, according to the total amount of the above-mentioned metal (M2).

[0354] When the amount of the transesterification catalyst A1 is 0.5 ppm or more in terms of the total amount calculated as the metal (M1), the reaction rate of the transesterification tends to be faster. In addition, when the amount of the transesterification catalyst is 20 ppm or less in terms of the total amount calculated as the metal (M1), the polycarbonate diol (b) used in the aqueous polyurethane dispersion is less colored during storage, and an aqueous polyurethane dispersion with less color change when used in, for example, synthetic leather, paint, coating agent, adhesive, binder, etc. can be provided, which is more preferred.

[0355] When the amount of the transesterification catalyst A2 is 0.25 ppm or more based on the total amount of the metal (M2), the reaction rate of the transesterification tends to be faster. In addition, when the amount of the transesterification catalyst is 10 ppm or less based on the total amount of the metal (M2), the coloring of the obtained polycarbonate diol can be suppressed, the number of ether bonds is reduced, and when used as a urethane raw material, the urethane formation reaction tends to be stable, the color tone of the obtained urethane tends to be good, and the heat resistance tends to be improved.

[0356] <2-3. Method for producing polycarbonate diol>

[0357] In the present embodiment, it is preferred that the polycarbonate diol is produced by subjecting one or more of the above-mentioned dihydroxy compounds to transesterification with one or more of the above-mentioned carbonates in the presence of the above-mentioned transesterification catalyst.

[0358] <2-3-1. Reaction conditions, etc.>

[0359] The feeding method of the reaction raw materials is not particularly limited and the feeding method can be freely selected, for example, a method in which the total amount of one or more dihydroxy compounds, carbonates and catalysts is simultaneously supplied to the feeding reaction; a method in which when the carbonate is a solid, the carbonate is first added and heated to melt it, and then the dihydroxy compounds and the catalyst are added; conversely, when the dihydroxy compound is a solid, the dihydroxy compound is first added and melted, and then the carbonate and the catalyst are added thereto; etc.

[0360] The reaction temperature during the transesterification reaction can be arbitrarily adopted as long as it is a temperature at which a practical reaction rate can be obtained. The temperature is not particularly limited, and the lower limit is preferably 80°C, more preferably 110°C, and further preferably 130°C. In addition, the upper limit of the reaction temperature is preferably 220°C, more preferably 200°C, further preferably 180°C, and particularly preferably 170°C. When the reaction temperature is above the above lower limit, there is a tendency for the transesterification reaction to proceed at a practical rate. In addition, when the reaction temperature is below the above upper limit, the coloring of the obtained polycarbonate diol can be suppressed, and there is a tendency for the quality to be improved, such as suppressing the formation of ether bonds or improving turbidity.

[0361] In particular, the method for producing the (b) polycarbonate diol used in the aqueous polyurethane dispersion of the present embodiment can efficiently obtain the polycarbonate diol in a short time under mild reaction conditions, for example, at a low temperature of 160° C. or less (preferably 150° C. or less), by using an ester exchange catalyst containing a specific metal (M1) that is highly active compared to conventional methods.

[0362] The reaction can also be carried out under normal pressure, but the transesterification reaction is a balanced reaction, and the reaction can be made to tend to the generation system by distilling the generated monohydroxy compound or dihydroxy compound out of the system. Therefore, it is usually preferred to carry out the reaction while distilling off the monohydroxy compound or dihydroxy compound under reduced pressure in the second half of the reaction. Alternatively, the pressure can be gradually reduced from the middle of the reaction, and the reaction can be carried out while distilling off the generated monohydroxy compound or dihydroxy compound. When the pressure is gradually reduced from the middle of the reaction, there is the following tendency: the volatilization of low-boiling unreacted monomers can be suppressed, the yield can be increased, and a polycarbonate diol of a specified molecular weight can be obtained, or a polycarbonate diol of a specified copolymer composition ratio can be obtained in the case of copolymerization.

[0363] The pressure during the reaction can be appropriately selected according to the type of alcohol derived from carbonate to be distilled. For example, when the alcohol to be distilled is an alcohol with a lower boiling point such as methanol, the preferred pressure of the reactor is 5kPa to normal pressure, and more preferably 7kPa to 15kPa. In addition, when the alcohol to be distilled is an alcohol with a higher boiling point such as ethylene glycol, the preferred pressure of the reactor is 1 to 10kPa, and more preferably 3kPa to 7kPa.

[0364] Furthermore, from the perspective of preventing the distillation of the raw materials in the initial stage of these reactions, a distillation tower having a theoretical plate number of 10 or more, preferably 15 or more, and more preferably 20 or more can be installed in the reactor, so that the monohydroxy compound or dihydroxy compound generated by the reaction of the carbonate ester and the raw material carbonate ester and dihydroxy compound of the azeotropic reaction are refluxed and separated, and the monohydroxy compound or dihydroxy compound generated by the reaction of the carbonate ester is efficiently separated and distilled. In this case, the amount ratio of the reagent can be accurately matched without loss of the raw material monomer added.

[0365] In addition, at the end of the reaction, it is usually switched to simple distillation, and when the reduced pressure is increased to carry out the reaction, by-product alcohols and diols, monohydroxy compounds or dihydroxy compounds such as phenols, residual monomers such as carbonates, and cyclic carbonates (cyclic oligomers) that may cause turbidity can be efficiently distilled off, so it is preferred.

[0366] The reaction pressure at the end of the reaction is not particularly limited, and the upper limit is usually preferably 5 kPa, more preferably 2 kPa, further preferably 1 kPa or less, and further preferably 0.5 kPa or less. In order to effectively distill these low-boiling components, the reaction can also be carried out while passing a small amount of inert gas such as nitrogen, argon, helium into the reaction system.

[0367] When using carbonates or dihydroxy compounds with low boiling points during transesterification, the following method can also be used: react near the boiling point of carbonic acid diester or dihydroxy compounds in the initial stage of reaction, and further react by gradually raising the temperature as the reaction proceeds. In this case, it is preferred to prevent the distillation of unreacted carbonic acid diester or dihydroxy compounds in the initial stage of reaction.

[0368] <2-3-2. Polymerization reactor>

[0369] The polymerization reaction (polycondensation reaction) can be carried out in batches or continuously. The continuous reaction is excellent in terms of the stability of the quality of the product, such as the molecular weight. The device used can be any of a tank type, a tube type, and a tower type, and various known polymerization tanks with stirring blades can be used. The atmosphere during the heating of the device is not particularly limited. From the perspective of the quality of the product, it is preferably carried out in an inert gas such as nitrogen at normal pressure or reduced pressure.

[0370] <2-3-3. Reaction time>

[0371] In the method for producing the (b) polycarbonate diol of the aqueous polyurethane dispersion of the present embodiment, the time required for the transesterification reaction (polymerization reaction or polycondensation reaction) varies greatly depending on the types and amounts of the dihydroxy compound, carbonic acid diester, and transesterification catalyst used, and therefore cannot be generalized. Generally, the reaction time required to reach a specified molecular weight is preferably 30 hours or less, more preferably 20 hours or less, and further preferably 10 hours or less.

[0372] <2-3-4. Deactivation of Catalyst>

[0373] As mentioned above, when a transesterification catalyst is used during the transesterification reaction, the transesterification catalyst or its residue is usually left in the polycarbonate diol obtained, which sometimes causes the reaction to run away or causes coloration during the polyurethane reaction. In order to suppress the influence of the residual catalyst, a catalyst deactivator can be added in an amount almost equimolar to the transesterification catalyst used, such as a phosphorus-based or sulfur-based compound that is acidic or decomposes to become an acidic compound. Furthermore, when heat-treated as described later after addition, the transesterification catalyst can be efficiently deactivated. In addition, by deactivation, the color development from the transesterification catalyst can be reduced, and a polycarbonate diol having a Hazen color number of preferably less than 50, more preferably less than 30, and further preferably less than 20 as measured based on JIS-K0071-1 (1998) can be obtained.

[0374] Furthermore, by adding a catalyst deactivator, the coloration and property changes of the obtained polycarbonate diol composition caused by changes in the terminal structure and skeleton of the polycarbonate diol and the residual catalyst during storage and handling at high temperatures for a long time can be suppressed.

[0375] The compound for deactivating the transesterification catalyst (hereinafter sometimes referred to as a catalyst deactivator) is not particularly limited, and examples thereof include inorganic phosphoric acids such as phosphoric acid and phosphorous acid, organic phosphoric acid esters such as monobutyl phosphate, dibutyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, and triphenyl phosphite, sulfonic acid, sulfonic acid esters, etc. These may be used alone or in combination of two or more.

[0376] The amount of the catalyst deactivator used is not particularly limited, and may be almost equimolar to the transesterification catalyst used as described above. Specifically, the upper limit is preferably 5 moles, more preferably 2 moles, and the lower limit is preferably 0.8 moles, more preferably 1.0 moles, relative to 1 mole of the transesterification catalyst used.

[0377] The deactivation of the transesterification catalyst by adding a catalyst deactivator can be carried out at room temperature, but it is more efficient when heated. The temperature of the heat treatment is not particularly limited, and the upper limit is preferably 140°C, more preferably 130°C, and further preferably 120°C, and the lower limit is preferably 80°C, more preferably 100°C, and further preferably 110°C. When the temperature is above the above lower limit, the time required for the deactivation of the transesterification catalyst becomes shorter, the efficiency is high, and the degree of deactivation is sufficient. On the other hand, when the temperature is below 140°C, when a phosphorus compound is used as a deactivator, the decomposition of the phosphorus compound can be suppressed, and there is a tendency for the deactivation to proceed stably. Therefore, the coloring of the obtained polycarbonate diol can be suppressed, and when used as a polyurethane raw material, there is a tendency for the urethanization reaction to be stable.

[0378] The reaction time with the catalyst deactivator is not particularly limited, and is, for example, 1 to 5 hours.

[0379] <2-4. Physical properties of polycarbonate diol>

[0380] The suitable physical properties of the (b) polycarbonate diol used in the aqueous polyurethane dispersion of the present embodiment will be described below.

[0381] <2-4-1. Molecular weight and molecular weight distribution>

[0382] The lower limit of the number average molecular weight (Mn) of the (b) polycarbonate diol used in the aqueous polyurethane dispersion of the present embodiment is 250, preferably 500, more preferably 750, and further preferably 1000. On the other hand, the upper limit of the number average molecular weight (Mn) of the (b) polycarbonate diol used in the aqueous polyurethane dispersion of the present embodiment is 3000, preferably 2500, further preferably 2100, and particularly preferably 2000. When the number average molecular weight of the polycarbonate diol is above the lower limit, the flexibility and the like tend to be good when the polyurethane is prepared. On the other hand, when the number average molecular weight of the polycarbonate diol is below the upper limit, the viscosity of the polycarbonate diol decreases, and the handling tends to be easy when the polyurethane is formed. As the preferred range of the number average molecular weight (Mn) of the (b) polycarbonate diol used in the aqueous polyurethane dispersion of the present embodiment, 250 to 3000, more preferably 500 to 2500, further preferably 750 to 2100, and particularly preferably 1000 to 2000 can be cited.

[0383] Here, the number average molecular weight of the polycarbonate diol is determined from the hydroxyl value (average hydroxyl value) of the polycarbonate diol as described in Examples below.

[0384] The method for controlling the number average molecular weight (Mn) of the polycarbonate diol within the above range is not particularly limited, and examples thereof include a method for controlling the number average molecular weight (Mn) of the polycarbonate diol within the above range by adjusting the polycondensation reaction time of the polycarbonate diol, adjusting the amount of the dihydroxy compound extracted as a raw material monomer, and the like.

[0385] <2-4-2.APHA value>

[0386] The color of the (b) polycarbonate diol used in the aqueous polyurethane dispersion of the present embodiment is preferably 50 or less, more preferably 40 or less, further preferably 30 or less, and particularly preferably 20 or less, in terms of the value expressed by the Hazen color number (based on JIS K0071-1:1998) (hereinafter referred to as "APHA value"). The lower limit of the APHA value of the (b) polycarbonate diol is not particularly limited, and is, for example, 0 or more. When the APHA value of the (b) polycarbonate diol is 50 or less, the color tone of the polyurethane obtained using the polycarbonate diol as a raw material becomes good, and there is a tendency that the commercial value is improved or the thermal stability becomes good. The preferred range of the APHA value of the (b) polycarbonate diol is 10 to 50, preferably 10 to 40, and further preferably 10 to 30.

[0387] The method for controlling the APHA value of the polycarbonate diol within the above range is not particularly limited, and examples thereof include a method in which the reaction temperature during the ester exchange reaction is within the above preferred temperature range, a method in which the time required for the ester exchange reaction (polymerization reaction or polycondensation reaction) is within the above preferred range, etc.

[0388] In addition, in this embodiment, the APHA value of the polycarbonate diol can be measured by the method described in the examples mentioned later.

[0389] <2-4-3. Metals contained in polycarbonate diol>

[0390] The (b) polycarbonate diol used in the aqueous polyurethane dispersion of the present embodiment preferably contains, as a metal, at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10, and Group 11 of the long period periodic table. The metal (M1) is more preferably at least one metal selected from the group consisting of metals of Group 7 of the long period periodic table.

[0391] The (b) polycarbonate diol used in the aqueous polyurethane dispersion of the present embodiment preferably contains at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long period periodic table in an amount of 1 ppm or more and 25 ppm or less, more preferably 2 ppm or more and 25 ppm or less, further preferably 5 ppm or more and 25 ppm or less, further preferably 1 ppm or more and 20 ppm or less, more preferably 2 ppm or more and 15 ppm or less, further preferably 5 ppm or more and 10 ppm or less.

[0392] In the (b) polycarbonate diol used in the aqueous polyurethane dispersion of the present embodiment, the lower limit of the content of at least one metal (M1) is 1 ppm, preferably 2 ppm, and more preferably 5 ppm, and the upper limit is 25 ppm, preferably 20 ppm, more preferably 15 ppm, and further preferably 10 ppm, in terms of the total amount.

[0393] When the content of the metal (M1) in the (b) polycarbonate diol used in the aqueous polyurethane dispersion of the present embodiment is 1 ppm or more in total, the APHA value becomes low, and when used as a raw material of the aqueous polyurethane dispersion, the reaction rate of urethanization tends to increase. In addition, when the content of the metal (M1) in the (b) polycarbonate diol used in the aqueous polyurethane dispersion of the present embodiment is 25 ppm or less in total, the coloring of the (b) polycarbonate diol caused by heating can be suppressed, the coloring during storage is small, and an aqueous polyurethane dispersion with little discoloration when used for synthetic leather, paint, coating agent, adhesive, adhesive, etc. can be provided, which is more preferred.

[0394] The metal (M1) contained in the (b) polycarbonate diol used in the aqueous polyurethane dispersion of the present embodiment is preferably at least one metal selected from molybdenum, manganese, iron, cobalt, nickel and copper. Among them, the metal (M1) is more preferably manganese.

[0395] The metal contained in these polycarbonate diols may be present in the form of a polymerization catalyst residue, or a predetermined amount may be intentionally added after production.

[0396] When the (b) polycarbonate diol used in the aqueous polyurethane dispersion of the present embodiment contains at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-period periodic table, the total amount thereof is preferably 0.1 ppm to 12.5 ppm, more preferably 0.5 ppm to 12.5 ppm, further preferably 0.7 ppm to 12.5 ppm, particularly preferably 1 ppm to 12.5 ppm, further preferably 0.5 ppm to 10 ppm, further preferably 0.5 ppm to 5 ppm.

[0397] In the (b) polycarbonate diol used in the aqueous polyurethane dispersion of the present embodiment, the lower limit of the content of at least one metal (M2) is preferably 0.1 ppm, more preferably 0.5 ppm, further preferably 0.7 ppm, and particularly preferably 1 ppm, and the upper limit is preferably 12.5 ppm, more preferably 10 ppm, and further preferably 5 ppm, in terms of the total amount.

[0398] When the content of the metal (M2) in the (b) polycarbonate diol used in the aqueous polyurethane dispersion of the present embodiment is 0.1 ppm or more in total, the APHA value becomes low, and when used as a raw material for urethane, the reaction rate of urethanization tends to increase. In addition, when the content of the metal (M2) in the (b) polycarbonate diol used in the aqueous polyurethane dispersion of the present embodiment is 12.5 ppm or less in total, the coloring of the (b) polycarbonate diol caused by heating can be suppressed, the coloring during storage is small, and an aqueous polyurethane dispersion with little discoloration when used for, for example, synthetic leather, paint, coating agent, adhesive, adhesive, etc. can be provided, which is more preferred.

[0399] The metal (M2) contained in the (b) polycarbonate diol used in the aqueous polyurethane dispersion of the present embodiment is preferably at least one metal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and francium. Among them, at least one metal selected from the group consisting of lithium, sodium and potassium is more preferred, and lithium is particularly preferred.

[0400] The metal contained in these polycarbonate diols may be present in the form of a polymerization catalyst residue, or a predetermined amount may be intentionally added after production.

[0401] In addition, in this embodiment, the type and amount of the metal contained in the polycarbonate diol can be measured by the method described in the Examples mentioned later.

[0402] <3. (c) Polyols containing carboxyl groups and / or sulfonic groups or their salts>

[0403] The polyol or its salt containing carboxyl and / or sulfonic group used in the aqueous polyurethane dispersion of the present embodiment (c) is a component used to introduce a carboxylate group or a sulfonate group to make the water-dispersible polyurethane self-emulsified in water and to impart dispersion stability to the aqueous polyurethane dispersion. As the polyol containing a carboxyl group, there is no particular limitation, and examples thereof include 2,2-dimethylol propionic acid (DMPA), 2,2-dimethylol butyric acid, 2,2-dimethylol heptanoic acid, 2,2-dimethylol octanoic acid, etc. In addition, as the polyol containing a sulfonic group, examples thereof include sulfonic acid diol {3-(2,3-dihydroxypropoxy)-1-propanesulfonic acid} and aminosulfonic acid diol {N,N-bis(2-hydroxy)aminosulfonic acid} and its alkylene oxide adducts, etc. The salts of these polyols containing a carboxyl group and / or a sulfonic group are not particularly limited, and examples thereof include ammonium salts, amine salts [salts of primary amines having 1 to 12 carbon atoms (primary monoamines, such as methylamine, ethylamine, propylamine, and octylamine), salts of secondary monoamines (dimethylamine, diethylamine, and dibutylamine), salts of tertiary monoamines (aliphatic tertiary monoamines such as trimethylamine, triethylamine triethanolamine, N-methyldiethanolamine, and N,N-dimethylethanolamine; heterocyclic tertiary monoamines such as N-methylpiperidine and N-methylmorpholine; tertiary monoamines containing aromatic rings such as benzyldimethylamine, α-methylbenzyldimethylamine, and N-dimethylaniline)], salts of alkali metals (sodium, potassium, and lithium cations), and combinations of two or more thereof.

[0404] Among the salts, amine salts are preferred, aliphatic tertiary monoamine salts are more preferred, and triethylamine salts are particularly preferred.

[0405] When the (c) polyol is not a salt but a polyol containing a carboxyl group and / or a sulfonic group, the carboxyl group and / or the sulfonic group may be neutralized with a neutralizing agent to form a carboxylate group and / or a sulfonic acid salt group.

[0406] The neutralizing agent is not particularly limited, and examples thereof include alkaline compounds that form cations listed as the counterions. Specifically, there are no particular limitations, and examples thereof include ammonia, amines [primary amines having 1 to 12 carbon atoms (primary monoamines, such as methylamine, ethylamine, propylamine, and octylamine), secondary monoamines (dimethylamine, diethylamine, and dibutylamine), tertiary monoamines (aliphatic tertiary monoamines such as trimethylamine, triethylamine triethanolamine, N-methyldiethanolamine, and N,N-dimethylethanolamine; heterocyclic tertiary monoamines such as N-methylpiperidine and N-methylmorpholine; benzyldimethylamine, α-methylbenzyldimethylamine; and tertiary monoamines containing aromatic rings such as N-dimethylaniline)], alkali metals (sodium, potassium, and lithium cations), alkali metal hydroxides, and combinations of two or more thereof.

[0407] Among these, amines are preferred, aliphatic tertiary monoamines are more preferred, and triethylamine is particularly preferred.

[0408] (c) The amount of the polyol or its salt containing carboxyl and / or sulfonic group is preferably such that the carboxyl and / or sulfonic group is 0.01 to 10% by mass relative to the water-dispersible polyurethane. The ratio of carboxyl and / or sulfonic group to water-dispersible polyurethane is more preferably 0.1 to 10% by mass, and more preferably 0.5 to 10% by mass. In addition, the ratio of carboxyl and / or sulfonic group to water-dispersible polyurethane is more preferably 0.1 to 7% by mass, and more preferably 0.1 to 5% by mass. By making the carboxyl and / or sulfonic group 0.01% by mass or more, there is a tendency for the emulsion stability to be more excellent. In addition, by being 10% by mass or less, there is a tendency for the water resistance of the obtained coating film to be more excellent.

[0409] In addition, appropriate surfactants, such as anionic surfactants represented by higher fatty acids, resin acids, acidic fatty alcohols, sulfates, higher alkyl sulfonates, alkyl aryl sulfonates, sulfonated castor oils, sulfosuccinates, etc., or nonionic surfactants represented by known reaction products of ethylene oxide with long-chain fatty alcohols or phenols, etc. can be used in combination to maintain emulsion stability. Among these, nonionic surfactants are preferred.

[0410] <4. Method for producing aqueous polyurethane dispersion>

[0411] The method for producing the aqueous polyurethane dispersion of the present embodiment is not particularly limited, and the following method can be cited. In the presence or absence of an organic solvent that does not contain an active hydrogen group in the molecule (e.g., acetone, methyl ethyl ketone, tetrahydrofuran, N,N-dimethylformamide, etc.), (a) an organic polyisocyanate containing two or more isocyanate groups in one molecule, (b) a polycarbonate diol, and (c) a polyol containing a carboxyl group and / or a sulfonic group or a salt thereof are mixed at an equivalent ratio (NCO group / OH group) of preferably 0.5 to 1.5, more preferably 0.8 to 1.5, and even more preferably 0.9 to 1.5, or (a) an organic polyisocyanate containing two or more isocyanate groups in one molecule, (b) a polycarbonate diol, and (c) a polyol containing a carboxyl group and / or a sulfonic group or a salt thereof. An organic polyisocyanate having two or more isocyanate groups, (b) a polycarbonate diol, and (c) a polyol containing a carboxyl group and / or a sulfonic group or a salt thereof are subjected to a urethanization reaction in a range of preferably 0.5 to 1.2, more preferably 0.8 to 1.1, at an equivalent ratio (NCO group / OH group) by a one-step method or a multi-step method to synthesize a polyurethane, the polyurethane is neutralized with a neutralizing agent as needed, and then the obtained reaction solution is vigorously stirred, and water is added dropwise at this time. After the addition is completed, the solvent is removed as needed to obtain an aqueous polyurethane dispersion.

[0412] Alternatively, the obtained reaction solution may be added to water while being stirred to disperse the mixture, and then the solvent may be removed as necessary to obtain an aqueous polyurethane dispersion.

[0413] By setting the (NCO group / OH group) equivalent ratio to 0.5 or more, the molecular weight of the obtained polyurethane can be increased, and there is a tendency to obtain a more stable aqueous polyurethane dispersion, and further, there is a tendency to further improve the strength and softness of the coating film formed by the soft-touch coating composition containing the aqueous polyurethane dispersion as a constituent component. In addition, by setting the (NCO group / OH group) equivalent ratio to 1.5 or less, the molecular weight of the obtained polyurethane can be increased, and there is a tendency to obtain a more stable aqueous polyurethane dispersion, and further, there is a tendency to further improve the strength and softness of the coating film formed by the aqueous soft-touch coating composition containing the aqueous polyurethane dispersion as a constituent component.

[0414] In addition, as a method for producing the aqueous polyurethane dispersion of the present embodiment, a prepolymer may be synthesized in advance from (a) an organic polyisocyanate containing two or more isocyanate groups in one molecule, (b) a polycarbonate diol, and (c) a polyol containing a carboxyl group and / or a sulfonic group or a salt thereof under the condition of an excess of isocyanate, and after dispersing the prepolymer in water, a chain extender is added to prepare the aqueous polyurethane dispersion.

[0415] The chain extender is not particularly limited, and examples thereof include short-chain diols such as water, ethylene glycol, 1,3-propylene glycol, and 1,4-butylene glycol; and polyamines such as hydrazine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, hexamethylenediamine, and cyclohexanediamine. The amount of the chain extender added is usually 0.1 to 2.0 mol, preferably 0.6 to 2.0 mol, relative to 1 mol of the isocyanate group of the urethane prepolymer, and is also 0.6 to 1.5 mol, preferably 0.6 to 1.2 mol, relative to 1 mol of the isocyanate group of the urethane prepolymer.

[0416] In the process of manufacturing the aqueous polyurethane dispersion of the present embodiment, a known urethanization reaction catalyst may be used as needed. The urethanization reaction catalyst is not particularly limited, and examples thereof include amine catalysts, and specifically, although not particularly limited, examples thereof include triethylamine, N-ethylmorpholine, triethylenediamine, etc.; tin catalysts, such as dibutyltin dilaurate, dioctyltin dilaurate, and tin octoate; and titanium catalysts, such as tetrabutyl titanate, etc.

[0417] The solid content of the aqueous polyurethane dispersion of the present embodiment is preferably 10 to 70% by mass, more preferably 20 to 70% by mass. The solid content of the aqueous polyurethane dispersion is preferably 10 to 60% by mass, more preferably 10 to 50% by mass.

[0418] In addition, the average particle size of the polyurethane in the aqueous polyurethane dispersion of the present embodiment is preferably 500 nm or less, more preferably 200 nm or less, and further preferably 150 nm or less. The lower limit of the average particle size is not particularly limited, and is, for example, 30 nm. When the average particle size of the polyurethane is 500 nm or less, the appearance, strength, and abrasion resistance of the coating film of the aqueous soft-touch coating composition containing the aqueous polyurethane dispersion tend to be more excellent, which is preferred.

[0419] In addition, the average particle diameter of the polyurethane in the aqueous polyurethane dispersion of the present embodiment can be measured by the method described in the Examples described later.

[0420] <5. Aqueous coating composition>

[0421] The aqueous coating composition of the present embodiment contains the aqueous polyurethane dispersion described above.

[0422] The water-based coating composition of the present embodiment is not particularly limited, and can be suitably used for example synthetic leather, coating, coating agent, adhesive and adhesive etc. The synthetic leather, coating, coating agent, adhesive and adhesive etc. made using the water-based coating composition of the present embodiment are characterized in that discoloration is small.

[0423] In the aqueous coating composition of the present embodiment, the content of the aqueous polyurethane dispersion is preferably 5 to 65% by mass, more preferably 10 to 65% by mass, or 20 to 65% by mass, and the content of the aqueous polyurethane dispersion is more preferably 5 to 55% by mass, and even more preferably 5 to 50% by mass.

[0424] Fillers, flame retardants, dyes, organic or inorganic pigments, release agents, fluidity regulators, plasticizers, antioxidants, ultraviolet absorbers, light stabilizers, defoamers, leveling agents, colorants, solvents, etc. can be added to the aqueous coating composition of this embodiment according to various uses.

[0425] There are no particular limitations on fillers and pigments, and commonly used fillers and pigments such as woven fabrics, glass fibers, carbon fibers, polyamide fibers, mica, kaolin, bentonite, metal powder, azo pigments, carbon black, clay, silica, talc, gypsum, alumina white, barium carbonate, and resin particles can be used.

[0426] The release agent, fluidity adjuster, and leveling agent are not particularly limited, and for example, silicone, AEROSIL, wax, stearate, polysiloxane such as BYK-331 (manufactured by BYK Chemicals Co., Ltd.), etc. can be used.

[0427] As the additive used in the aqueous coating composition of the present embodiment, it is preferred to use at least an antioxidant, a light stabilizer and a heat stabilizer. As these antioxidants, there is no particular limitation, and examples thereof include phosphorus compounds such as aliphatic, aromatic or alkyl-substituted aromatic esters of phosphoric acid and phosphorous acid or hypophosphorous acid derivatives, phenylsulfonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonates, dialkyl pentaerythritol diphosphites, and dialkyl bisphenol A diphosphites; phenol derivatives, especially hindered phenol compounds, thioethers, and dithiocarboxylates; sulfur-containing compounds such as mercaptobenzimidazoles, thiocarbanilides, and thiodipropionates; tin compounds such as tin maleate and dibutyltin oxide. These can be used alone or in combination of two or more.

[0428] The coating method of the aqueous coating composition of the present embodiment is not particularly limited, and examples thereof include a method in which various additive components are mixed with the aqueous polyurethane dispersion and then applied to a substrate by spraying, rolling, brushing, or the like.

[0429] <Polyurethane resin and / or polyurea resin>

[0430] The polyurethane resin of this embodiment is a reaction product of the above composition and a chain extender (d), wherein the chain extender (d) is a diamine compound, and the polyisocyanate compound as the curing agent (a) is an organic polyisocyanate compound having an average isocyanate group number of 2.5 or less in one molecule.

[0431] Specifically, the polyurethane resin of the present embodiment is a reaction product of a polyisocyanate compound (a) as a curing agent, a polycarbonate diol (b), and a chain extender (d).

[0432] The chain extender (d) is a diamine compound,

[0433] The polyisocyanate compound (a) is an organic polyisocyanate compound having an average isocyanate group number of 2.5 or less in one molecule.

[0434] The above-mentioned (b) polycarbonate diol is a polycondensate based on the transesterification reaction between a dihydroxy compound and a carbonate.

[0435] The number average molecular weight of the polycarbonate diol (b) is 250 or more and 3000 or less,

[0436] The (b) polycarbonate diol contains at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table in a total amount of 1 ppm to 25 ppm.

[0437] The polyurethane resin of the present embodiment has such characteristics, and is excellent in storage stability and rarely discolors when used in, for example, paints, coating agents, and the like.

[0438] The polyurethane resin of the present embodiment preferably has a Hazen color number of the polycarbonate diol (b) measured in accordance with JIS-K0071-1 (1998) of 50 or less.

[0439] The polyurea resin of this embodiment is a reaction product of the above composition and a chain extender (d), wherein the chain extender (d) is a dihydroxy compound, and the polyisocyanate compound as the curing agent (a) is an organic polyisocyanate compound having an average isocyanate group number of 2.5 or less in one molecule.

[0440] Specifically, the polyurea resin of the present embodiment is a reaction product of a polyisocyanate compound (a) as a curing agent, a polycarbonate diol (b), and a chain extender (d).

[0441] The chain extender (d) is a dihydroxy compound,

[0442] The polyisocyanate compound (a) is an organic polyisocyanate compound having an average isocyanate group number of 2.5 or less in one molecule.

[0443] The above-mentioned (b) polycarbonate diol is a polycondensate based on the transesterification reaction between a dihydroxy compound and a carbonate.

[0444] The number average molecular weight of the polycarbonate diol (b) is 250 or more and 3000 or less,

[0445] The (b) polycarbonate diol contains at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table in a total amount of 1 ppm to 25 ppm.

[0446] The polyurea resin of the present embodiment has such characteristics, and is excellent in storage stability and rarely discolors when used in, for example, paints, coating agents, and the like.

[0447] The polyurea resin of the present embodiment preferably has a Hazen color number of the polycarbonate diol (b) measured in accordance with JIS-K0071-1 (1998) of 50 or less.

[0448] <(a) Polyisocyanate compound>

[0449] The component (a) as a curing agent for the polyurethane resin and / or polyurea resin of the present embodiment (hereinafter also referred to as "organic polyisocyanate compound" or "polyisocyanate compound (a)") is an organic polyisocyanate compound having an average isocyanate group number of 2.5 or less in one molecule. Specific examples of such organic polyisocyanate compounds are not particularly limited, and examples thereof include well-known aromatic diisocyanates such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and a mixture thereof (TDI), diphenylmethane-4,4'-diisocyanate (MDI), naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-biphenyl diisocyanate, crude TDI, polymethylene polyphenyl isocyanate, and crude MDI. ; xylylene diisocyanate (XDI), phenylene diisocyanate and other well-known aromatic alicyclic diisocyanates; 4,4'-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), cyclohexane diisocyanate (hydrogenated XDI) and other well-known aliphatic diisocyanates; and these isocyanates are modified by isocyanurate, carbodiimide, biuret, etc. The organic polyisocyanate compound used for the polyurethane resin and / or polyurea resin of the present embodiment is preferably an aliphatic organic diisocyanate compound and / or an alicyclic organic diisocyanate compound. Among them, the polyisocyanate compound (a) used for the polyurethane resin and / or polyurea resin of the present embodiment is preferably an alicyclic polyisocyanate. When it is an alicyclic polyisocyanate, there is a tendency that the strength, wear resistance and chemical resistance of the obtained polyurea resin are excellent. From the viewpoint of the strength and abrasion resistance of the obtained polyurea resin, diphenylmethane-4,4'-diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and 4,4'-methylenebiscyclohexyl diisocyanate (hydrogenated MDI) are particularly preferred. Among them, isophorone diisocyanate (IPDI) and 4,4'-methylenebiscyclohexyl diisocyanate (hydrogenated MDI) are particularly preferred because they have excellent weather resistance.

[0450] In addition, regarding the organic polyisocyanate compound, the lower limit of the average number of isocyanate groups in one molecule is preferably 1.9, more preferably 2.0, and the upper limit is 2.5, more preferably 2.3. Regarding the organic polyisocyanate compound, the preferred range of the average number of isocyanate groups in one molecule is, for example, 1.9 to 2.5, more preferably 2.0 to 2.3.

[0451] It should be noted that, in the present embodiment, the average number of isocyanate groups (average number of functional groups) in one molecule of the organic polyisocyanate compound can be obtained by using the following formula (i) from the isocyanate group content (mass %) obtained by the method described in JIS K7301-1995 and the number average molecular weight of the organic polyisocyanate obtained by measuring the number average molecular weight based on polystyrene by gel permeation chromatography (GPC).

[0452] Average number of functional groups = number average molecular weight of organic polyisocyanate × isocyanate group content (mass %) / 100% / 42 (i)

[0453] In addition, the specific analysis method of the isocyanate group content and the number average molecular weight of the organic polyisocyanate is as follows.

[0454] (Physical Property 1) Isocyanate Group Content

[0455] The isocyanate group content was measured using the polyisocyanate composition as a sample according to the method described in JIS K7301-1995 (Testing methods for toluene diisocyanate prepolymers for thermosetting urethane elastomers). A more specific method for measuring the isocyanate group content is shown below.

[0456] (1) 1 g of a sample is placed in a 200 mL Erlenmeyer flask, and 20 mL of toluene is added to the flask to dissolve the sample.

[0457] (2) Then, 20 mL of a 2.0 N di-n-butylamine toluene solution was added to the flask, and the mixture was allowed to stand for 15 minutes.

[0458] (3) 70 mL of 2-propanol was added to the above flask and dissolved to obtain a solution.

[0459] (4) The solution obtained in the above (3) is titrated with 1 mol / L hydrochloric acid to determine the sample titration amount.

[0460] (5) When no sample is added, measurement is performed in the same manner as in (1) to (3) above to determine the blank titer.

[0461] The isocyanate group content was calculated by the following formula (II) from the sample titration and blank titration obtained as described above.

[0462] Isocyanate group content (mass %) = (blank titration - sample titration) × 42 / [sample mass (g) × 1,000] × 100%. (ii)

[0463] (Physical Property 2) Number Average Molecular Weight of Organic Polyisocyanate

[0464] The polyisocyanate composition was used as a sample, and the number average molecular weight of the polyisocyanate including the modified polyisocyanate and the unreacted polyisocyanate in the polyisocyanate composition was measured by gel permeation chromatography (GPC) using the following apparatus and conditions.

[0465] Device: HLC-8120GPC (trade name) manufactured by Tosoh Corporation

[0466] Column: Tosoh Corporation TSKgelSuperH1000 (trade name) × 1 column, TSKgelSuperH2000 (trade name) × 1 column, TSKgelSuperH3000 (trade name) × 1 column,

[0467] Carrier: Tetrahydrofuran

[0468] Detection method: Differential refractometer

[0469] (Physical Property 3) Average Number of Isocyanate Functional Groups

[0470] The polyisocyanate composition is used as a sample, and the average isocyanate functional group number is the number of isocyanate functional groups statistically possessed by one molecule of polyisocyanate, which is calculated by the following formula (III) based on the number average molecular weight of the organic polyisocyanate measured in (Physical Property 2) and the isocyanate group content measured in (Physical Property 1).

[0471] Average number of functional groups = number average molecular weight of organic polyisocyanate × isocyanate group content (mass %) / 100% / 42 (iii)

[0472] <2. (b) Polycarbonate diol>

[0473] The method for producing the polycarbonate diol (b) used in the polyurethane resin and / or polyurea resin of the present embodiment is not particularly limited, and the following production method is preferred, for example: it includes a step of obtaining the polycarbonate diol by polycondensing a dihydroxy compound and a carbonate as raw material monomers through an ester exchange reaction in the presence of an ester exchange catalyst, wherein the ester exchange catalyst contains at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10, and Group 11 of the long-period periodic table. The method for producing the polycarbonate diol (b) used in the polyurethane resin and / or polyurea resin of the present embodiment is preferred because it can efficiently produce the polycarbonate diol by using an ester exchange catalyst containing a specific metal as described above.

[0474] In addition, the ester exchange catalyst comprises an ester exchange catalyst A1 containing at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table, and an ester exchange catalyst A2 containing at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-form periodic table, which is more efficient (specifically, for example, under milder reaction conditions and in a shorter time), and is more preferred.

[0475] The method for producing (b) polycarbonate diol for the polyurethane resin and / or polyurea resin of the present embodiment can efficiently produce polycarbonate diol by using at least two ester exchange catalysts containing specific metals in this way, and can provide a polyurethane resin and / or polyurea resin that is less colored when used for the polyurethane resin and / or polyurea resin of the present embodiment and less discolored when used for, for example, synthetic leather, paints, coatings, adhesives, binders, etc., and is therefore more preferred.

[0476] <2-1. Raw material monomer>

[0477] The method for producing (b) polycarbonate diol used for the polyurethane resin and / or polyurea resin of the present embodiment uses a dihydroxy compound and a carbonate as raw material monomers.

[0478] <2-1-1. Dihydroxy compounds>

[0479] In the method for producing the polyurethane resin and / or polyurea resin (b) polycarbonate diol used in the present embodiment, the dihydroxy compound used as the raw material monomer is not particularly limited, and examples thereof include linear terminal dihydroxy compounds such as ethylene glycol, 1,3-propylene glycol, 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, and 1,20-eicosandiol; and polyhydroxy compounds such as diethylene glycol, triethylene glycol, tetraethylene glycol, polypropylene glycol, and polytetramethylene glycol. Dihydroxy compounds having an ether group; thioether diols such as bishydroxyethyl sulfide; 2,2-dialkyl-substituted 1,3-propanediols such as 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 2,4-diethyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (hereinafter sometimes referred to as neopentyl glycol), 2-ethyl-2-butyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol and 2-pentyl-2-propyl-1,3-propanediol (hereinafter sometimes referred to as 2,2-dialkyl-1,3-propanediols).); tetraalkyl-substituted alkylene glycols such as 2,2,4,4-tetramethyl-1,5-pentanediol and 2,2,9,9-tetramethyl-1,10-decanediol, dihydroxy compounds containing cyclic groups such as 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane; 2,2-diphenyl-1,3-propanediol, 2,2-divinyl-1,3-propanediol, 2,2-diethynyl-1,3-propanediol, 2,2-dimethoxy-1,3-propanediol, bis(2-hydroxy-1,1-dimethylethyl) ether, bis(2-hydroxy-1,1-dimethylethyl) thioethers and dihydroxy compounds with branched chains such as 2,2,4,4-tetramethyl-3-cyano-1,5-pentanediol; dihydroxy compounds with cyclic groups in the molecule such as 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 4,4-dicyclohexyldimethylmethanediol, 2,2'-bis(4-hydroxycyclohexyl)propane, 1,4-dihydroxyethylcyclohexane, isosorbide, spirodiol, 2,5-bis(hydroxymethyl)tetrahydrofuran, 4,4'-isopropylidene dicyclohexanol and 4,4'-isopropylidene bis(2,2'-hydroxyethoxycyclohexane); 9,9-bis(4-(2-hydroxyethoxy) dihydroxy compounds having an aromatic ring such as 9,9-bis(4-(2-hydroxyethoxy-2-methyl)phenyl)fluorene, diethanolamine, N-methyl-diethanolamine and other nitrogen-containing dihydroxy compounds; and bis(hydroxyethyl)sulfide and other sulfur-containing dihydroxy compounds; 2,2-bis(4-hydroxyphenyl)propane [= bisphenol A], 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2- Aromatic bisphenols such as bis(4-hydroxyphenyl)pentane, 2,4'-dihydroxy-diphenylmethane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone, bis(4-hydroxyphenyl)sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-2-methylphenyl)fluorene.

[0480] Among them, from the viewpoint of weather resistance of a polyurethane resin or polyurea resin obtained by using the (b) polycarbonate diol, the dihydroxy compound is preferably at least one compound selected from the group consisting of aliphatic dihydroxy compounds and alicyclic dihydroxy compounds represented by the following formula (1).

[0481] HO-R1-OH (1)

[0482] (In the formula, R1 represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 20 carbon atoms.)

[0483] Among such dihydroxy compounds, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 2-methyl-1,3-propylene glycol, 3-methyl-1,5-pentanediol, and 2-methyl-1,8-octanediol are particularly preferred as alicyclic dihydroxy compounds, and 1,4-cyclohexanedimethanol and tricyclodecanedimethanol are particularly preferred as alicyclic dihydroxy compounds. Among these dihydroxy compounds, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are more preferred because they can make the obtained water-based polyurethane resin and polyurea resin excellent in flexibility.

[0484] These dihydroxy compounds can be used alone or in combination of two or more, preferably in combination of multiple types to form copolycarbonate diols, depending on the desired properties of the obtained polycarbonate diols. Copolycarbonate diols are generally inhibited from crystallizing and have higher fluidity than homopolycarbonate diols. They not only have excellent operability when processed into polyurethane resins and polyurea resins, but also can impart softness and texture to polyurethane resins and polyurea resins.

[0485] Regarding the composition ratio of the copolymerization, for example, when two dihydroxy compounds are used, each dihydroxy compound is preferably used at 5 mol% or more, preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more relative to the total dihydroxy compounds. When two or more dihydroxy compounds are used, it is more preferred to use at least two dihydroxy compounds selected from 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol because the obtained water-based polyurethane resin and polyurea resin have excellent flexibility.

[0486] <2-1-2. Carbonate ester>

[0487] In the method for producing (b) polycarbonate diol for use in the polyurethane resin and / or polyurea resin of the present embodiment, carbonates that can be used as raw material monomers are not limited unless the effects of the present invention are impaired, and examples thereof include dialkyl carbonates, diaryl carbonates, and alkylene carbonates.

[0488] There are no particular limitations on specific examples of dialkyl carbonates among carbonates that can be used in the method for producing the (b) polycarbonate diol used for the polyurethane resin and / or polyurea resin of the present embodiment, and examples thereof include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diisobutyl carbonate, ethyl n-butyl carbonate, and ethyl isobutyl carbonate.

[0489] Examples of the diaryl carbonate include, but are not particularly limited to, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, and di-m-tolyl carbonate.

[0490] Specific examples of the alkylene carbonate are not particularly limited, and examples thereof include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 1,3-pentylene carbonate, 1,4-pentylene carbonate, 1,5-pentylene carbonate, 2,3-pentylene carbonate, 2,4-pentylene carbonate, and neopentyl carbonate.

[0491] These may be used alone or in combination of two or more.

[0492] Among these carbonates, dimethyl carbonate, diethyl carbonate, ethylene carbonate, and diphenyl carbonate are particularly preferred because they are available as industrial raw materials at low cost, have good reactivity, and produce a small amount of alcohol as a by-product.

[0493] <2-1-3. Ratio of raw material monomers used>

[0494] In the method for producing (b) polycarbonate diol of the polyurethane resin and / or polyurea resin of the present embodiment, the amount of carbonate used needs to be appropriately changed according to the target molecular weight of the polycarbonate diol, and is not particularly limited. Generally, the lower limit is preferably 0.5, more preferably 0.7, and further preferably 0.8, and the upper limit is generally 1.5, preferably 1.3, and more preferably 1.2, based on the molar ratio relative to 1 mole of the total dihydroxy compounds. When the amount of carbonate diester used is below the above upper limit, the proportion of the terminal groups of the obtained polycarbonate diol that are not hydroxyl groups can be suppressed or there is a tendency to produce the (b) polycarbonate diol used in the present embodiment with a molecular weight within a specified range. When it is above the above lower limit, there is a tendency to polymerize until the specified molecular weight.

[0495] <2-2. Transesterification catalyst>

[0496] In the method for producing the (b) polycarbonate diol of the polyurethane resin and / or polyurea resin of the present embodiment, although not particularly limited, it is preferred that there is an ester exchange catalyst containing at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table.

[0497] As one embodiment of the ester exchange catalyst containing at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table, at least one metal complex represented by the following formula (2) and / or a hydrate thereof is preferred.

[0498]

[0499] (In the formula, R2 and R4 each independently represent a monovalent hydrocarbon group having 1 to 10 carbon atoms, the hydrocarbon groups of R2 and R4 are optionally substituted with halogen atoms, and optionally have an oxygen atom, R3 represents hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, the hydrocarbon group of R3 is optionally substituted with halogen atoms, and optionally has an oxygen atom, M1 represents at least one metal selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long period periodic table, and n is 1, 2 or 3. In addition, the metal complex represented by formula (2) is optionally an association of multiple metals.)

[0500] The metal (M1) selected from the group consisting of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table is not particularly limited, but from the viewpoint of catalytic activity, molybdenum, manganese, iron, cobalt, nickel and copper are preferred, and among them, manganese is particularly preferred.

[0501] In addition, a transition metal compound and a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound may be used in combination with the transesterification catalyst represented by the formula (2).

[0502] In the present embodiment, the organometallic complex with these acetylacetone analogs used as the transesterification catalyst may be used in the form of a hydrate.

[0503] As another embodiment of the ester exchange catalyst containing at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table, it is preferred that the salt and / or hydrate thereof of at least one carboxylic acid represented by the following formula (3) and at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table.

[0504]

[0505] (In the formula, R5 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group of R5 may be substituted with a halogen atom and may have an oxygen atom.)

[0506] The carboxylic acid is not particularly limited, and examples thereof include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, palmitic acid, heptadecanoic acid, and stearic acid. Among these, acetic acid, propionic acid, and butyric acid are preferred, and acetic acid is particularly preferred.

[0507] The metal (M1) selected from the group consisting of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table is not particularly limited, but from the viewpoint of catalytic activity, molybdenum, manganese, iron, cobalt, nickel and copper are preferred, and among them, manganese is particularly preferred.

[0508] In addition, in the present embodiment, the salts of these carboxylic acids used as the transesterification catalyst may be used in the form of hydrates.

[0509] Regarding the amount of the transesterification catalyst used in the present embodiment, according to the total amount calculated by the above-mentioned metal (M1), relative to the total amount of all dihydroxy compounds and carbonates, the lower limit is 0.5ppm, preferably 1ppm, more preferably 2ppm, and the upper limit is 20ppm, preferably 10ppm, more preferably 7ppm. When the amount of the transesterification catalyst is calculated as 0.5ppm or more in terms of the total amount calculated by the metal (M1), there is a tendency for the reaction rate of the transesterification to become faster. In addition, when the amount of the transesterification catalyst is calculated as 20ppm or less in terms of the total amount calculated by the metal (M1), the coloring of the obtained polycarbonate diol can be suppressed, and when used as the raw material of the polyurethane resin and / or polyurea resin of the present embodiment, there is a tendency for the carbamate reaction to be stable, and the polyurethane resin and / or polyurea resin of the present embodiment with less discoloration when used for synthetic leather, coatings, coatings, adhesives, adhesives, etc. can be provided, so it is more preferred.

[0510] The method for producing the (b) polycarbonate diol used for the polyurethane resin and / or polyurea resin of the present embodiment is not particularly limited, but a production method using the above-mentioned transesterification catalyst A1 in combination with a transesterification catalyst A2 containing at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-form periodic table is more preferred.

[0511] The metal of the first group of the long-period periodic table is not particularly limited, and examples thereof include lithium, sodium, potassium, rubidium, cesium, and francium. Among these, lithium, sodium, and potassium are preferred due to their high catalytic activity. Lithium is particularly preferred because it has a particularly high activity and a small amount of ether bonds in the generated polycarbonate diol.

[0512] The form of the ester exchange catalyst A2 containing at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-form periodic table is not particularly limited, and examples thereof include salts with inorganic acids, salts with organic acids, alkoxides of various alcohols, and hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and titanium hydroxide.

[0513] Among them, an alkoxide of at least one alcohol represented by the following formula (4) and at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-form periodic table is preferred because of its high catalytic activity and little coloration.

[0514] R6-OH (4)

[0515] (In the formula, R6 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group of R6 may be substituted with a halogen atom and may have an oxygen atom.)

[0516] The alkoxide of at least one alcohol represented by formula (4) and a metal of Group 1 of the long-period periodic table is not particularly limited, and examples thereof include lithium methoxide (methoxylithium), lithium ethoxide (ethoxylithium), lithium propoxide, lithium butoxide, sodium methoxide (methoxysodium), sodium ethoxide (ethoxysodium), sodium propoxide, sodium butoxide, potassium methoxide (methoxypotassium), potassium ethoxide (ethoxypotassium), potassium propoxide, potassium butoxide, methoxyrubidium, ethoxyrubidium, methoxycesium, ethoxycesium, etc. Among these alkoxides, lithium methoxide, lithium ethoxide, sodium methoxide, and sodium ethoxide are preferred, and lithium methoxide and lithium ethoxide are particularly preferred, because they have high catalytic activity and produce a polycarbonate diol with a small amount of ether bonds and less coloration.

[0517] In the method for producing the (b) polycarbonate diol used for the polyurethane resin and / or polyurea resin of the present embodiment, although not particularly limited, when at least two transesterification catalysts, namely, a transesterification catalyst A1 containing at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-period periodic table and a transesterification catalyst A2 containing at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-period periodic table, are used in combination, the amount of the transesterification catalyst to be used is preferably 0.5 ppm, more preferably 1 ppm, and even more preferably 2 ppm in lower limit, and preferably 20 ppm, more preferably 10 ppm, and even more preferably 7 ppm in upper limit, in terms of the total amount of the above-mentioned metal (M1) relative to the total amount of all dihydroxy compounds and carbonates.

[0518] In addition, the amount of the ester exchange catalyst A2 is preferably 0.05 ppm, more preferably 0.2 ppm, further preferably 0.5 ppm, and particularly preferably 1 ppm in terms of the total amount of the above-mentioned metal (M2) relative to the total amount of all dihydroxy compounds and carbonates, and the upper limit is preferably 10 ppm, more preferably 5 ppm, and further preferably 3 ppm.

[0519] When the amount of the transesterification catalyst A1 is 0.5 ppm or more in terms of the total amount calculated as the metal (M1), the reaction rate of the transesterification tends to be faster. In addition, when the amount of the transesterification catalyst is 20 ppm or less in terms of the total amount calculated as the metal (M1), the (b) polycarbonate diol used in the polyurethane resin and / or polyurea resin is less colored during storage, and a polyurethane resin and / or polyurea resin with less color change when used in, for example, synthetic leather, coatings, coating agents, adhesives, and binders can be provided, which is more preferred.

[0520] When the amount of the transesterification catalyst A2 is 0.05 ppm or more based on the total amount of the metal (M2), the reaction rate of the transesterification tends to be faster. When the amount of the transesterification catalyst is 10 ppm or less based on the total amount of the metal (M2), the coloring of the obtained polycarbonate diol can be suppressed, the number of ether bonds decreases, and when used as a urethane raw material, the urethane reaction tends to be stable, the color tone of the obtained urethane tends to be good, and the heat resistance tends to be improved.

[0521] <2-3. Method for producing polycarbonate diol>

[0522] The polyurethane resin and / or polyurea resin of the present embodiment is preferably prepared by transesterifying one or more of the above-mentioned dihydroxy compounds with one or more of the above-mentioned carbonates in the presence of the above-mentioned transesterification catalyst to produce polycarbonate diol.

[0523] <2-3-1. Reaction conditions, etc.>

[0524] The feeding method of the reaction raw materials is not particularly limited and the feeding method can be freely selected, for example, a method in which the total amount of one or more dihydroxy compounds, carbonates and catalysts is simultaneously supplied to the feeding reaction; a method in which when the carbonate is a solid, the carbonate is first added and heated to melt it, and then the dihydroxy compounds and the catalyst are added; conversely, when the dihydroxy compound is a solid, the dihydroxy compound is first added and melted, and then the carbonate and the catalyst are added thereto; etc.

[0525] The reaction temperature during the transesterification reaction can be arbitrarily adopted as long as it is a temperature at which a practical reaction rate can be obtained. The temperature is not particularly limited, and the lower limit is preferably 80°C, more preferably 110°C, and further preferably 130°C. In addition, the upper limit of the reaction temperature is preferably 220°C, more preferably 200°C, further preferably 180°C, and particularly preferably 170°C. When the reaction temperature is above the above lower limit, there is a tendency for the transesterification reaction to proceed at a practical rate. In addition, when the reaction temperature is below the above upper limit, the coloring of the obtained polycarbonate diol can be suppressed, and there is a tendency for the quality to be improved, such as suppressing the formation of ether bonds or improving turbidity.

[0526] In particular, the method for producing the (b) polycarbonate diol used for the polyurethane resin and / or polyurea resin of the present embodiment can efficiently obtain the polycarbonate diol in a short time under mild reaction conditions, for example, at a low temperature of 160° C. or less (preferably 150° C. or less), by using an ester exchange catalyst containing a specific metal (M1) that is highly active compared to conventional methods.

[0527] The reaction can also be carried out under normal pressure, but the transesterification reaction is a balanced reaction, and the reaction can be made to tend to the generation system by distilling the generated monohydroxy compound or dihydroxy compound out of the system. Therefore, it is usually preferred to carry out the reaction while distilling off the monohydroxy compound or dihydroxy compound under reduced pressure in the second half of the reaction. Alternatively, the pressure can be gradually reduced from the middle of the reaction, and the reaction can be carried out while distilling off the generated monohydroxy compound or dihydroxy compound. When the pressure is gradually reduced from the middle of the reaction, there is the following tendency: the volatilization of low-boiling unreacted monomers can be suppressed, the yield can be increased, and a polycarbonate diol of a specified molecular weight can be obtained, or a polycarbonate diol of a specified copolymer composition ratio can be obtained in the case of copolymerization.

[0528] The pressure during the reaction can be appropriately selected according to the type of alcohol derived from carbonate to be distilled. For example, when the alcohol to be distilled is an alcohol with a lower boiling point such as methanol, the preferred pressure of the reactor is 5kPa to normal pressure, and more preferably 7kPa to 15kPa. In addition, when the alcohol to be distilled is an alcohol with a higher boiling point such as ethylene glycol, the preferred pressure of the reactor is 1 to 10kPa, and more preferably 3kPa to 7kPa.

[0529] Furthermore, from the perspective of preventing the distillation of the raw materials in the initial stage of these reactions, a distillation tower having a theoretical plate number of 10 or more, preferably 15 or more, and more preferably 20 or more can be installed in the reactor, so that the monohydroxy compound or dihydroxy compound generated by the reaction of the carbonate ester and the raw material carbonate ester and dihydroxy compound of the azeotropic reaction are refluxed and separated, and the monohydroxy compound or dihydroxy compound generated by the reaction of the carbonate ester is efficiently separated and distilled. In this case, the amount ratio of the reagent can be accurately matched without loss of the raw material monomer added.

[0530] In addition, at the end of the reaction, it is usually switched to simple distillation, and when the reduced pressure is increased to carry out the reaction, by-product alcohols and diols, monohydroxy compounds or dihydroxy compounds such as phenols, residual monomers such as carbonates, and cyclic carbonates (cyclic oligomers) that may cause turbidity can be efficiently distilled off, so it is preferred.

[0531] The reaction pressure at the end of the reaction is not particularly limited, and the upper limit is usually preferably 5 kPa, more preferably 2 kPa, further preferably 1 kPa or less, and further preferably 0.5 kPa or less. In order to effectively distill these low-boiling components, the reaction can also be carried out while passing a small amount of inert gas such as nitrogen, argon, helium into the reaction system.

[0532] When using carbonates or dihydroxy compounds with low boiling points during transesterification, the following method can also be used: react near the boiling point of carbonic acid diester or dihydroxy compounds in the initial stage of reaction, and further react by gradually raising the temperature as the reaction proceeds. In this case, it is preferred to prevent the distillation of unreacted carbonic acid diester or dihydroxy compounds in the initial stage of reaction.

[0533] <2-3-2. Polymerization reactor>

[0534] The polymerization reaction (polycondensation reaction) can be carried out intermittently or continuously. The device used can be any of a tank type, a tube type and a tower type, and various known polymerization tanks with stirring blades can be used. The atmosphere during the heating of the device is not particularly limited, and from the viewpoint of product quality, it is preferably carried out in an inert gas such as nitrogen at normal pressure or reduced pressure.

[0535] <2-3-3. Reaction time>

[0536] In the method for producing (b) polycarbonate diol of the polyurethane resin and / or polyurea resin of the present embodiment, the time required for the transesterification reaction (polymerization reaction or polycondensation reaction) varies greatly depending on the type and amount of the dihydroxy compound, carbonic acid diester, and transesterification catalyst used, and therefore cannot be generalized. Generally, the reaction time required to reach a specified molecular weight is preferably 30 hours or less, more preferably 20 hours or less, and even more preferably 10 hours or less.

[0537] <2-3-4. Deactivation of Catalyst>

[0538] As mentioned above, when a transesterification catalyst is used during the transesterification reaction, the transesterification catalyst or its residue is usually left in the polycarbonate diol obtained, which sometimes causes the reaction to run away or causes coloration during the polyurethane reaction. In order to suppress the influence of the residual catalyst, a catalyst deactivator can be added in an amount almost equimolar to the transesterification catalyst used, such as a phosphorus-based or sulfur-based compound that is acidic or decomposes to become an acidic compound. Furthermore, when heat-treated as described later after addition, the transesterification catalyst can be efficiently deactivated. In addition, by deactivation, the color development from the transesterification catalyst can be reduced, and a polycarbonate diol having a Hazen color number of preferably less than 50, more preferably less than 30, and further preferably less than 20 as measured based on JIS-K0071-1 (1998) can be obtained.

[0539] Furthermore, by adding a catalyst deactivator, the coloration and property changes of the obtained polycarbonate diol composition caused by changes in the terminal structure and skeleton of the polycarbonate diol and the residual catalyst during storage and handling at high temperatures for a long time can be suppressed.

[0540] The compound for deactivating the transesterification catalyst (hereinafter sometimes referred to as a catalyst deactivator) is not particularly limited, and examples thereof include inorganic phosphoric acids such as phosphoric acid and phosphorous acid, organic phosphoric acid esters such as monobutyl phosphate, dibutyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, and triphenyl phosphite, sulfonic acid, sulfonic acid esters, etc. These may be used alone or in combination of two or more.

[0541] The amount of the catalyst deactivator used is not particularly limited, and may be almost equimolar to the transesterification catalyst used as described above. Specifically, the upper limit is preferably 5 moles, more preferably 2 moles, and the lower limit is preferably 0.8 moles, more preferably 1.0 moles, relative to 1 mole of the transesterification catalyst used.

[0542] The deactivation of the transesterification catalyst by adding a catalyst deactivator can be carried out at room temperature, but it is more efficient when heated. The temperature of the heat treatment is not particularly limited, and the upper limit is preferably 140°C, more preferably 130°C, and further preferably 120°C, and the lower limit is preferably 80°C, more preferably 100°C, and further preferably 110°C. When the temperature is above the above lower limit, the time required for the deactivation of the transesterification catalyst becomes shorter, the efficiency is high, and the degree of deactivation is sufficient. On the other hand, when the temperature is below 140°C, when a phosphorus compound is used as a deactivator, the decomposition of the phosphorus compound can be suppressed, and there is a tendency for the deactivation to proceed stably. Therefore, the coloring of the obtained polycarbonate diol can be suppressed, and when used as a carbamate raw material, there is a tendency for the carbamate reaction to be stable.

[0543] The reaction time with the catalyst deactivator is not particularly limited, and is, for example, 1 to 5 hours.

[0544] <2-4. (b) Physical properties of polycarbonate diol>

[0545] The following describes suitable physical properties of (b) the polycarbonate diol used for the polyurethane resin and / or polyurea resin of the present embodiment.

[0546] <2-4-1. Molecular weight and molecular weight distribution>

[0547] The lower limit of the number average molecular weight (Mn) of the polycarbonate diol (b) used in the polyurethane resin and / or polyurea resin of the present embodiment is 250, preferably 500, more preferably 750, and further preferably 1000. On the other hand, the upper limit of the number average molecular weight (Mn) of the polycarbonate diol (b) used in the polyurethane resin and / or polyurea resin of the present embodiment is 3000, preferably 2500, further preferably 2100, and particularly preferably 2000. When the number average molecular weight of the polycarbonate diol is above the above lower limit, there is a tendency that the softness and the like become good when the polyurethane resin and / or polyurea resin is made. On the other hand, when the number average molecular weight of the polycarbonate diol (b) is below the above upper limit, the viscosity of the polycarbonate diol decreases, and there is a tendency that the handling becomes easy during polyurethane formation. The number average molecular weight (Mn) of the (b) polycarbonate diol used in the polyurethane resin and / or polyurea resin of the present embodiment preferably ranges from 250 to 3,000, more preferably from 500 to 2,500, further preferably from 750 to 2,100, and particularly preferably from 1,000 to 2,000.

[0548] Here, the number average molecular weight of the polycarbonate diol is determined from the hydroxyl value (average hydroxyl value) of the polycarbonate diol as described in Examples below.

[0549] The method for controlling the number average molecular weight (Mn) of the polycarbonate diol within the above range is not particularly limited, and examples thereof include a method for controlling the number average molecular weight (Mn) of the polycarbonate diol within the above range by adjusting the polycondensation reaction time of the polycarbonate diol, adjusting the amount of the dihydroxy compound extracted as a raw material monomer, and the like.

[0550] <2-4-2.APHA value>

[0551] The color of the (b) polycarbonate diol used for the polyurethane resin and / or polyurea resin of the present embodiment is preferably 50 or less, more preferably 40 or less, further preferably 30 or less, and particularly preferably 20 or less in terms of the value expressed by the Hazen color number (based on JIS K0071-1:1998), more preferably 40 or less, further preferably 30 or less, and particularly preferably 20 or less. The lower limit of the APHA value of the (b) polycarbonate diol is not particularly limited, and is, for example, 0 or more. When the APHA value of the (b) polycarbonate diol is 50 or less, the color tone of the polyurethane resin and / or polyurea resin obtained using the polycarbonate diol as a raw material becomes good, and there is a tendency that the commercial value is improved and the thermal stability becomes good. The preferred range of the APHA value of the (b) polycarbonate diol is 10 to 50, preferably 10 to 40, and further preferably 10 to 30.

[0552] The method for controlling the APHA value of the (b) polycarbonate diol to be within the above range is not particularly limited, and examples thereof include a method in which the reaction temperature during the ester exchange reaction is within the above preferred temperature range, a method in which the time required for the ester exchange reaction (polymerization reaction or polycondensation reaction) is within the above preferred range, etc.

[0553] In addition, in this embodiment, the APHA value of the polycarbonate diol can be measured by the method described in the examples mentioned later.

[0554] <2-4-3. Metals contained in polycarbonate diol>

[0555] The (b) polycarbonate diol used for the polyurethane resin and / or polyurea resin of the present embodiment preferably contains at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10, and Group 11 of the long period periodic table. The metal (M1) is more preferably at least one metal selected from the group consisting of metals of Group 7 of the long period periodic table.

[0556] In the (b) polycarbonate diol used for the polyurethane resin and / or polyurea resin of the present embodiment, at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-period periodic table has a lower limit of 1 ppm, preferably 2 ppm, more preferably 5 ppm, and an upper limit of 25 ppm, preferably 20 ppm, more preferably 15 ppm, and even more preferably 10 ppm in terms of the total amount of the metals.

[0557] When the content of the metal (M1) in the (b) polycarbonate diol used in the polyurethane resin and / or polyurea resin of the present embodiment is 1 ppm or more in total, the APHA value becomes low, and when used as a raw material for the polyurethane resin and / or polyurea resin, there is a tendency for the urethanization reaction rate to increase. In addition, when the content of the metal (M1) in the (b) polycarbonate diol used in the polyurethane resin and / or polyurea resin of the present embodiment is 25 ppm or less in total, the coloring of the (b) polycarbonate diol caused by heating can be suppressed, and the coloring during storage is small. In addition, a polyurethane resin and / or polyurea resin with little discoloration when used in, for example, synthetic leather, coatings, coating agents, adhesives, adhesives, etc. can be provided, and therefore it is more preferred.

[0558] The metal (M1) contained in the polycarbonate diol (b) used for the polyurethane resin and / or polyurea resin of the present embodiment is preferably at least one metal selected from molybdenum, manganese, iron, cobalt, nickel and copper. Among them, the metal (M1) is more preferably manganese.

[0559] The metal contained in these polycarbonate diols may be present in the form of a polymerization catalyst residue, or a predetermined amount may be intentionally added after production.

[0560] When the (b) polycarbonate diol used for the polyurethane resin and / or polyurea resin of the present embodiment contains at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-period periodic table, the lower limit of the total amount of the metals is preferably 0.1 ppm, more preferably 0.5 ppm, further preferably 0.7 ppm, particularly preferably 1 ppm, and the upper limit is preferably 12.5 ppm, more preferably 10 ppm, further preferably 5 ppm, particularly preferably 3 ppm.

[0561] When the content of the metal (M2) in the (b) polycarbonate diol used in the polyurethane resin and / or polyurea resin of the present embodiment is 0.1 ppm or more in total, the APHA value becomes low, and when used as a raw material for carbamate, there is a tendency for the reaction rate of carbamate formation to increase. In addition, when the content of the metal (M2) in the (b) polycarbonate diol used in the polyurethane resin and / or polyurea resin of the present embodiment is 12.5 ppm or less in total, the coloring of the (b) polycarbonate diol caused by heating can be suppressed, the coloring during storage is small, and the polyurethane resin and / or polyurea resin with little discoloration when used for, for example, synthetic leather, coatings, coating agents, adhesives, adhesives, etc. can be provided, and therefore it is more preferred.

[0562] The metal (M2) contained in the polycarbonate diol (b) used for the polyurethane resin and / or polyurea resin of the present embodiment is preferably at least one metal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and francium. Among them, at least one metal selected from the group consisting of lithium, sodium and potassium is more preferred, and lithium is particularly preferred.

[0563] The metal contained in these polycarbonate diols may be present in the form of a polymerization catalyst residue, or a predetermined amount may be intentionally added after production.

[0564] In addition, in this embodiment, the type and amount of the metal contained in the polycarbonate diol can be measured by the method described in the Examples mentioned later.

[0565] <3.(d) Chain Extender>

[0566] As the (d) chain extender used for the polyurethane resin and / or polyurea resin of the present embodiment, for example, a dihydroxy compound and a diamine compound are preferably used.

[0567] As the dihydroxy compound, aliphatic dihydroxy compounds and alicyclic dihydroxy compounds are preferred. Specifically, the dihydroxy compound is not particularly limited, and examples thereof include linear terminal dihydroxy compounds such as ethylene glycol, 1,3-propylene glycol, 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, and 1,20-eicosandiol; dihydroxy compounds having an ether group such as diethylene glycol, triethylene glycol, tetraethylene glycol, polypropylene glycol, and polytetramethylene glycol; thioether diols such as bishydroxyethyl sulfide; 2-ethyl-1,6 2,2-dialkyl-substituted 1,3-propanediols (hereinafter sometimes referred to as 2,2-dialkyl-1,3-propanediols) such as 2-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol and 2,4-diethyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (hereinafter sometimes referred to as neopentyl glycol), 2-ethyl-2-butyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol and 2-pentyl-2-propyl-1,3-propanediol; 2,2,4,4-tetramethyl-1,5-pentanediol and 2 , 2,9,9-tetramethyl-1,10-decanediol and other tetraalkyl-substituted alkylene glycols, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane and other dihydroxy compounds containing cyclic groups; 2,2-diphenyl-1,3-propanediol, 2,2-divinyl-1,3-propanediol, 2,2-diethynyl-1,3-propanediol, 2,2-dimethoxy-1,3-propanediol, bis(2-hydroxy-1,1-dimethylethyl) ether, bis(2-hydroxy-1,1-dimethylethyl) sulfide and 2,2,4, Dihydroxy compounds having a branched chain such as 4-tetramethyl-3-cyano-1,5-pentanediol; dihydroxy compounds having a cyclic group in the molecule such as 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 4,4-dicyclohexyldimethylmethanediol, 2,2'-bis(4-hydroxycyclohexyl)propane, 1,4-dihydroxyethylcyclohexane, isosorbide, spirodiol, 2,5-bis(hydroxymethyl)tetrahydrofuran, 4,4'-isopropylidene dicyclohexanol and 4,4'-isopropylidene bis(2,2'-hydroxyethoxycyclohexane), 4,4'-bicyclohexanediol, etc.

[0568] From the viewpoint of obtaining a polyurethane resin having excellent tensile strength at break, abrasion resistance, chemical resistance and weather resistance, the chain extender (d) is more preferably a short-chain linear aliphatic diol such as ethylene glycol, 1,3-propylene glycol and 1,4-butanediol, and an alicyclic diol such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and 4,4'-bicyclohexanediol.

[0569] Specific examples of the diamine compound include, but are not particularly limited to, diamines such as ethylenediamine, propylenediamine, hexamethylenediamine, toluenediamine, xylylenediamine, diphenyldiamine, diaminodiphenylmethane, 4,4'-methylenebis(cyclohexylamine), piperazine, isophoronediamine (IPDA), and 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA).

[0570] From the viewpoint of obtaining a polyurea resin having excellent tensile strength at break, abrasion resistance, chemical resistance and weather resistance, the chain extender (d) is more preferably an alicyclic diamine, and specifically, 4,4'-methylenebis(cyclohexylamine), isophoronediamine (IPDA) and 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA) are preferred.

[0571] <4. Synthesis method of polyurethane resin and polyurea resin>

[0572] In the method for synthesizing the polyurethane resin and / or polyurea resin of the present embodiment, a method of simultaneously reacting three compounds, namely, a polyisocyanate compound (a), a polycarbonate diol (b), and a chain extender (d), and a method of reacting a polyisocyanate compound (a) and a polycarbonate diol (b) in advance to form a prepolymer and then adding a chain extender (d) to extend the chain are used.

[0573] It should be noted that, as the synthetic raw materials for the polyurethane resin and / or polyurea resin of the present embodiment, in addition to the above-mentioned (a), (b) and (d) components, other components may be used in combination within the range that does not impair the effects of the present invention, for example, the polyol (e) containing a carboxyl group and / or a sulfonic group or its salt and known polyols described later.

[0574] When the three kinds of (a) polyisocyanate compound, (b) polycarbonate diol and (d) chain extender are reacted simultaneously, the compounding ratio is preferably (the total equivalent of hydroxyl group and amino group) / NCO equivalent = 1 / 0.5 to 1 / 1.5, and more preferably (the total equivalent of hydroxyl group and amino group) / NCO equivalent = 1 / 0.8 to 1 / 1.2, in terms of the total equivalent of hydroxyl group and / or amino group of (b) polycarbonate diol and (d) chain extender to the NCO equivalent of (a) polyisocyanate compound. When the three kinds of (a) polyisocyanate compound, (b) polycarbonate diol and (d) chain extender are reacted simultaneously, the compounding amount of (d) chain extender is preferably 3 to 40% by mass, and more preferably 5 to 25% by mass, relative to the total mass of (a) polyisocyanate compound and (b) polycarbonate diol.

[0575] In the case of using a method in which (a) the polyisocyanate compound and (b) the polycarbonate diol are reacted in advance to form a prepolymer and then the chain extension is performed by adding the chain extender (d), the prepolymer is synthesized by preferably making the (b) polycarbonate diol and the (a) polyisocyanate compound have a mixing ratio of OH / NCO (equivalent ratio) of 1 / 1.5 to 2.5, more preferably a mixing ratio of OH / NCO (equivalent ratio) of 1 / 1.8 to 2.2, and then the chain extension is performed by adding the chain extender (d) in an amount of preferably 0.5 to 1.5, more preferably 0.8 to 1.2, of hydroxyl and / or amino group equivalents relative to 1 equivalent of NCO of the obtained prepolymer.

[0576] Furthermore, a known polyol may be used in combination with the polycarbonate diol (b) used in the present embodiment within the range that does not impair the effects of the present invention. Examples of known polyols include known polyesters, polyethers, and the like described in Yoshio Imai, Polyurethane Foam Polymer Publishing Association, 1987, pp. 12-23.

[0577] The method for producing the polyurethane resin and / or polyurea resin of the present embodiment is not particularly limited, and conventionally known urethanization reaction techniques and urea reaction techniques can be used. For example, the polyurethane resin and / or polyurea resin of the present embodiment can be produced by reacting (b) polycarbonate diol, (a) polyisocyanate compound, and (d) chain extender at room temperature to 200°C.

[0578] In the production of these, known polymerization catalysts represented by tertiary amines and organic metal salts of tin, titanium, etc. can also be used, such as "described in Yoshida Keiji (Polyurethane Resin) Japan Industrial News Publishing Co., Ltd., pp. 23-32 (1969)". In addition, these reactions can be carried out using a solvent, and preferred solvents include dimethylformamide, diethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, methyl isobutyl ketone, dioxane, cyclohexanone, benzene, toluene, ethyl cellosolve, etc.

[0579] In addition, when manufacturing the polyurethane resin and / or polyurea resin of the present embodiment, compounds containing only one active hydrogen that reacts with an isocyanate group, such as monohydric alcohols such as ethanol and propanol, primary amines such as n-propylamine, n-butylamine, n-pentylamine, and n-hexylamine, and secondary amines such as diethylamine and di-n-propylamine, can also be used as end-capping agents.

[0580] As additives for the polyurethane resin and / or polyurea resin of the present embodiment, stabilizers such as heat stabilizers and light stabilizers can be preferably cited. As heat stabilizers, there are no particular limitations, and phosphorus compounds such as phosphoric acid, aliphatic, aromatic or alkyl-substituted aromatic esters of phosphoric acid and phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonic acid esters, dialkyl pentaerythritol diphosphites, dialkyl bisphenol A diphosphites, etc.; sulfur compounds such as phenol derivatives, especially hindered phenol compounds, thioethers, dithiocarboxylates, mercaptobenzimidazoles, thiocarbanilides, and thiodipropionates can be used; tin compounds such as tin maleate and dibutyltin oxide can be used.

[0581] Preferred hindered phenol compounds include Irganox 1010 (trade name: manufactured by Ciba-Geigy), Irganox 1520 (trade name: manufactured by Ciba-Geigy), etc. Preferred phosphorus compounds as secondary antioxidants include PEP-36, PEP-24G, HP-10 (all trade names: manufactured by Asahi Denka), and Irgafos 168 (trade name: manufactured by Ciba-Geigy). Preferred sulfur compounds include sulfide compounds such as dilauryl thiopropionate (DLTP) and distearyl thiopropionate (DSTP).

[0582] The light stabilizer is not particularly limited, and examples thereof include benzotriazole-based and benzophenone-based compounds, etc. In addition, a radical scavenging light stabilizer such as a hindered amine compound can also be suitably used.

[0583] These stabilizers may be used alone or in combination of two or more. The amount of these stabilizers added is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and even more preferably 0.2 to 2 parts by mass, based on 100 parts by mass of the polyurethane resin and / or polyurea resin.

[0584] Furthermore, the polyurethane resin and / or polyurea resin of the present embodiment may also be added with a plasticizer as needed. Examples of the plasticizer are not particularly limited, and examples thereof include phthalates such as dioctyl phthalate, dibutyl phthalate, diethyl phthalate, butyl benzyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate, di(undecyl) phthalate, and diisononyl phthalate; phosphates such as tricresyl phosphate, triethyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, tri(methylhexyl) phosphate, tri(chloroethyl) phosphate, and tri(dichloropropyl) phosphate; and trimellitic acid octyl ester, Isodecyl trimellitate, trimellitate esters, dipentaerythritol esters, dioctyl adipate, dimethyl adipate, di(2-ethylhexyl) azelaic acid, dioctyl azelaic acid, dioctyl sebacate, di(2-ethylhexyl) sebacate, methyl acetyl ricinoleate and other fatty acid esters: octyl pyromellitic acid and other pyromellitic acid esters; epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid alkyl esters and other epoxy plasticizers; adipate ether esters, polyethers and other polyethers; liquid rubbers such as liquid NBR, liquid acrylic rubber, liquid polybutadiene; non-aromatic paraffin oil, etc.

[0585] These plasticizers may be used alone or in combination of two or more. The amount of the plasticizer added is appropriately selected depending on the required hardness and physical properties, and is preferably 0 to 50 parts by mass based on 100 parts by mass of the polyurethane resin and / or polyurea resin of the present embodiment.

[0586] In addition, inorganic fillers, lubricants, colorants, silicone oils, foaming agents, flame retardants, etc. may be added to the polyurethane resin and / or polyurea resin of the present embodiment. The inorganic fillers are not particularly limited, and examples thereof include calcium carbonate, talc, magnesium hydroxide, mica, barium sulfate, silicic acid (white carbon), titanium oxide, carbon black, etc.

[0587] <Application>

[0588] The polyurethane resin and / or polyurea resin of the present embodiment can be used for injection molded components (grip parts, steering wheels, airbag storage covers, watch straps, etc.), extrusion molded products (hoses, pipes, sheets, etc.), synthetic leather binders dissolved in solvents, surface materials, surface treatment agents, fiber coating agents, various surface treatment agents, and various adhesives, etc. In particular, the polyurethane resin and / or polyurea resin of the present embodiment is preferably used for synthetic leather.

[0589] <Film>

[0590] The film of the present embodiment is a film having a thickness of 10 μm to 500 μm obtained by molding the above-mentioned polyurethane resin and / or polyurea resin into a film shape.

[0591] Specific examples of the film of the present embodiment are not particularly limited, and examples thereof include extrusion-molded films of the above-mentioned polyurethane resin and / or polyurea resin, and cast films obtained by dissolving the above-mentioned polyurethane resin and / or polyurea resin in a solvent and applying and drying. The film of the present embodiment has excellent flexibility, strength, abrasion resistance, chemical resistance, and low-temperature characteristics, and has little discoloration, and is therefore particularly suitable for use as a surface material or surface treatment agent for synthetic leather that requires an appearance.

[0592] Example

[0593] The present embodiment will be described in more detail below using examples and the like, but the present embodiment is not limited to these examples at all. The analysis methods and physical property evaluations in the following examples and comparative examples were carried out according to the following test methods.

[0594] <Test method>

[0595] [(b) Determination of Hydroxyl (OH) Value of Polycarbonate Diol]

[0596] Prepare the acetylating agent by making the volume of 12.5 g of acetic anhydride with 50 mL of pyridine. Accurately weigh 2.5-5.0 g of the sample into a 100 mL eggplant-shaped flask. After adding 5 mL of the acetylating agent and 10 mL of toluene to the above-mentioned eggplant-shaped flask using a full-volume pipette, install a condenser, and stir and heat the solution in the above-mentioned eggplant-shaped flask at 100°C for 1 hour. Add 2.5 mL of distilled water to the above-mentioned eggplant-shaped flask using a full-volume pipette, and further heat and stir the solution in the above-mentioned eggplant-shaped flask for 10 minutes. After cooling the solution in the above-mentioned eggplant-shaped flask for 2-3 minutes, add 12.5 mL of ethanol. After adding 2-3 drops of phenolphthalein as an indicator to the above-mentioned eggplant-shaped flask, the solution in the above-mentioned eggplant-shaped flask is titrated with 0.5 mol / L ethanolic potassium hydroxide.

[0597] As a blank test, 5 mL of acetylating agent, 10 mL of toluene and 2.5 mL of distilled water were added to a 100 mL eggplant flask, heated and stirred for 10 minutes, and then titrated in the same manner as above. Based on the results, the hydroxyl (OH) value of the polycarbonate diol was calculated using the following formula (IV).

[0598] OH value (mg-KOH / g) = {(ba) × 28.05 × f} / e (IV)

[0599] a: Titration of sample (mL)

[0600] b: Blank test titration (mL)

[0601] e: Sample mass (g)

[0602] f: factor of the titrant

[0603] [Number average molecular weight (Mn)]

[0604] The number average molecular weight of the polycarbonate diol was determined by the following formula (V).

[0605] Number average molecular weight = 2 / (OH value × 10 -3 / 56.11)(V)

[0606] [Determination of APHA value]

[0607] The Hazen color number (APHA value) is measured by comparison with a standard solution in a colorimetric tube according to JIS K0071-1. A polycarbonate diol that is solid at room temperature is heated to 70°C to dissolve it and the APHA value is measured. The smaller the APHA value, the less coloration is evaluated.

[0608] [Residual Catalyst Amount in Polycarbonate Diol]

[0609] About 0.1 g of polycarbonate diol was measured and dissolved in 4 mL of acetonitrile to obtain a solution. Afterwards, 20 mL of pure water was added to the obtained solution to precipitate the polycarbonate diol, and the precipitated polycarbonate diol was removed by filtration. Then, the filtered solution was diluted with pure water to a specified concentration. The metal ion concentration in the diluted solution was analyzed by ion chromatography. It should be noted that the metal ion concentration of acetonitrile used as a solvent was measured as a blank value, and the value obtained by subtracting the metal ion concentration of the solvent from the metal ion concentration of the above-mentioned diluted solution was used as the metal ion concentration of the polycarbonate diol product. The measurement conditions are as follows. Using the pre-made standard curves of various metals, the concentrations of various metals remaining in the polycarbonate diol were calculated.

[0610] High performance liquid chromatography (HPCL) conditions

[0611] Installation: Waters2690

[0612] Column: IonPac CS12A

[0613] Flow rate: 1.0ml / min

[0614] Injection volume: 1.5ml

[0615] Pressure: 950-980 psi

[0616] Column temperature: 35°C

[0617] Detector sensitivity: RANGE 200μS

[0618] Suppressor: CSRS 60mA

[0619] Eluent: 20mmol / l methanesulfonic acid aqueous solution

[0620] <Evaluation method of coating film>

[0621] [Pendulum hardness]

[0622] The coating solution prepared in the examples and comparative examples was evenly applied on a glass plate with an applicator so that the coating thickness after drying reached 40 μm. After drying at room temperature for 15 minutes, it was then dried in an oven at 80°C for 2 hours, and the obtained coating was taken out of the oven. The obtained coating was placed in a constant temperature room at 23°C for 24 hours and then evaluated for pendulum hardness.

[0623] The pendulum hardness was measured using a pendulum hardness tester (using a Koenig oscillator) manufactured by BYK-Gardner. Specifically, the coating sample was placed in the device, and the time (t) from the moment when the amplitude reached 5° to the moment when the amplitude reached 2° was measured. The same measurement was performed on the uncoated glass plate, and the time (t0) from the moment when the amplitude reached 5° to the moment when the amplitude reached 2° was measured. The pendulum hardness (X) was calculated using the following formula (VI).

[0624] Pendulum hardness: X = t / t0 (VI)

[0625] [Room temperature tensile test]

[0626] The coating film (film) was prepared by the same method as in the above <Pendulum hardness> except that the film thickness was set to 0.5 mm, and a strip test piece having a width of 10 mm, a length of 100 mm, and a thickness of about 0.5 mm was obtained using the prepared coating film (film) in accordance with JIS K6301 (2010). The obtained test piece was subjected to a tensile test using a tensile testing machine (manufactured by ORIENTEC, product name "TENSILON, model RTE-1210") at a distance between the clamps of 20 mm and a tensile speed of 100 mm / min at a temperature of 23°C (relative humidity of 55%), and the stress (100% modulus) at the time when the test piece was elongated 100%, the breaking point strength, and the breaking point elongation were measured.

[0627] [Scratch resistance]

[0628] A coating film is formed on glass in the same manner as used in the pendulum hardness test. On the coated surface, a 4-row brass brush manufactured by Industry Kowa is used to make scratches by reciprocating 20 times in parallel with the handle with a load of 600 g, a stroke speed of 30 cm / second, and a stroke width of 5 cm. Immediately after the scratches are made, the gloss (gloss) at an angle of 60 degrees is measured on the scratched portion using a variable angle gloss meter manufactured by Suga Test Instruments Co., Ltd: G1. The initial gloss (gloss) at the same position before the scratch test is set to G0, and the scratch resistance is evaluated by the decrease in gloss according to the following formula (VII).

[0629] Gloss retention (%) = (G1 / G0) × 100 (VII)

[0630] The higher the gloss retention rate, the better the scratch resistance was evaluated to be.

[0631] [Abrasion resistance]

[0632] A coating film having a thickness of 40 μm was formed on an acrylonitrile-butadiene-styrene (ABS) resin plate in the same manner as used in the pendulum hardness measurement. The obtained coating film was subjected to a wear resistance measurement using a cone abrasion tester in accordance with the method of JIS K5600-5-8. The mass change of the coated plate mass before the abrasion test and the coated plate mass after the abrasion test (500 revolutions) was measured.

[0633] [Evaluation of oleic acid resistance]

[0634] The coating solution prepared in the examples and comparative examples was applied to a glass plate, and heated at 80°C for 2 hours to prepare a coating film (film) with a film thickness of 0.5 mm. The coating film (film) was peeled off from the glass plate, cut off about 3 cm × 3 cm, and then the mass of the coating film (film) before immersion was weighed. The coating film (film) was put into a 250 mL glass bottle containing 50 ml of oleic acid as a test solvent, and allowed to stand in a thermostatic bath under a nitrogen atmosphere at 80°C for 16 hours. After the test, the coating film (film) was taken out, and after gently wiping the surface and back with a paper towel, the mass was measured with a precision balance, and the mass change rate (increase rate (%)) compared to before the test was calculated.

[0635] [Softness]

[0636] The coating solutions prepared in the examples and comparative examples were applied to acrylonitrile-butadiene-styrene (ABS) resin plates at a thickness of 40 μm to obtain coated plates. The softness was evaluated by touching the surface of the obtained coated plates with hands. The evaluation results were represented by the following symbols.

[0637] ◎: Very good softness

[0638] ○: Good softness

[0639] △: Good softness

[0640] ×: No softness is felt.

[0641] [Chemical resistance]

[0642] A coating film (thin film) was prepared by the same method as in the above <Pendulum hardness>, and a cotton ball with a diameter of 10 mm impregnated with various solvents (ethanol (EtOH), methyl ethyl ketone (MEK), xylene) was placed on the obtained coating film for 1 minute, and the coating film state after removing the solvent remaining on the surface was observed. The determination method is as follows.

[0643] ○: Transparent, no dents

[0644] △: Slightly cloudy or slightly concave

[0645] ×: cloudy or sunken

[0646] [Weather resistance test]

[0647] The coating solutions prepared in the examples and comparative examples were stirred after adding 0.2 mass % of IRGANOX 1076 and 0.2 mass % of TINUVIN 765 to prepare coating solutions for weather resistance test. These were applied on a white acrylonitrile-butadiene-styrene (ABS) resin plate with an applicator, and then heated and cured at 80° C. for 2 hours to obtain a coating film for weather resistance test with a film thickness of 40 μm.

[0648] The obtained coating film for weather resistance test was measured using DPWL-5R manufactured by Suga Test Instruments Co., Ltd. (black panel temperature 60° C., irradiance 30 w / m 2 , Cycle conditions: irradiation at 60°C for 4 hours, humidity at 40°C for 4 hours, UV fluorescent lamp: SUGA-FS-40) Implement a 1-month weathering test.

[0649] The L value, a value, and b value of the coating film before and after the weather resistance test were measured, and the color difference was calculated by the following ΔE calculation method.

[0650] ΔE={(L1-L2) 2 +(a1-a2) 2 +(b1-b2) 2} 1 / 2

[0651] In the above formula, L1, a1, and b1 represent the L value, a value, and b value of the coating film before the weather resistance test, and L2, a2, and b2 represent the L value, a value, and b value of the coating film after the weather resistance test.

[0652] The lower the ΔE value, the less coloring was evaluated.

[0653] 〔Abbreviation of compound〕

[0654] The abbreviations of the compounds in the following Examples and Comparative Examples are as follows.

[0655] Mn(OAc)2·4H2O: Manganese(II) acetate tetrahydrate

[0656] Mn(acac)2·2H2O: Manganese(II) acetylacetonate dihydrate

[0657] Mn(acac)3: Manganese(III) acetylacetonate

[0658] Mn(tBuCOCH2COtBu)2·2H2O: 2,2,6,6-Tetramethyl-3,5-heptanedione manganese(II) dihydrate

[0659] Mn(CF3COCH2COCF3)2·2H2O:Manganese hexafluoroacetylacetonate dihydrate

[0660] [Mo(acac)]2: Molybdenum(II) acetylacetonate dimer

[0661] Fe(acac)3: Iron(III) acetylacetonate

[0662] Co(acac)2·2H2O: Cobalt(II) acetylacetonate dihydrate

[0663] Ni(acac)2·2H2O: Nickel(II) acetylacetonate dihydrate

[0664] Cu(acac)2: Copper(II) acetylacetonate

[0665] Ti(OBu)4:Tetrabutyl titanate

[0666] Ti(acac)2(OiPr)2: Bis(acetylacetonato)diisopropyl titanate(IV)

[0667] Mg(acac)2·2H2O: Magnesium(II) acetylacetonate dihydrate

[0668] Li-OMe: Lithium Methanol

[0669] Na-OMe: Sodium Methanol

[0670] K-OMe: Potassium Methanol

[0671] Li-t-OBu: Lithium tert-butylate

[0672] EC: Ethylene carbonate

[0673] DEC: Diethyl carbonate

[0674] 14BDO: 1,4-Butanediol

[0675] 15PDO: 1,5-pentanediol

[0676] 16HDO: 1,6-Hexanediol

[0677] [Synthesis Example 1 of Polycarbonate Diol]

[0678] Into a 1L separable flask equipped with a stirrer, a thermometer, and an Oldershaw (theoretical plate number 15 plates) with a reflux head on the top and a vacuum jacket, 355 g (3.00 mol) of 1,6-hexanediol and 264 g (3.00 mol) of ethylene carbonate as raw material monomers were added, and 13.8 mg (5 ppm in terms of metal amount relative to the total amount of all dihydroxy compounds and carbonates) of manganese (II) acetate tetrahydrate as a catalyst was added. The raw materials in the flask were heated in an oil bath set at 160°C, and the raw material monomers were polycondensed by transesterification reaction for 5 hours while a portion of the fraction was removed from the reflux head at an internal temperature of the flask of 140°C and a vacuum degree of 3 kPa, to obtain a polycarbonate diol.

[0679] After that, the mixture was switched to simple distillation. The temperature of the oil bath was set to 175°C while the pressure was slowly reduced to 0.1 kPa. The mixture was reacted for 3 hours at an internal temperature of 160°C in the flask to distill off the monomers and obtain polycarbonate diol. After nitrogen was introduced into the flask to restore the normal pressure, the temperature of the oil bath was set to 125°C and the internal temperature of the flask was set to 110-120°C. Monobutyl phosphate was added as a catalyst deactivator in an amount equimolar to the amount of catalyst added, and the mixture was stirred at a temperature of 110-120°C for 3 hours. The analysis results of the obtained polycarbonate diol are shown in Table 1. This polycarbonate polyol is referred to as PC1.

[0680] [Synthesis Examples 2 to 10 of Polycarbonate Diol]

[0681] Polycarbonate diols were obtained by polycondensation of the raw monomers by transesterification reaction in the same manner as in Synthesis Example 1 except that the type and amount of the added catalyst were those described in Table 1. The analysis results are shown in Table 1. The obtained polycarbonate diols are referred to as PC2 to PC10.

[0682] [Synthesis Examples 11 to 13 of Polycarbonate Diol]

[0683] The raw material monomers were polycondensed by transesterification reaction in the same manner as in Synthesis Example 1, except that the time for taking out a part of the fraction from the reflux head at a vacuum degree of 3 kPa was set to 12 hours and the type and amount of the added catalyst were set to the type and amount described in Table 1, to obtain polycarbonate diols. The analysis results are shown in Table 1. The obtained polycarbonate diols are referred to as PC11 to PC13.

[0684]

Table 1

[0685]

[0686] [Synthesis Example 14]

[0687] 355 g (3.00 mol) of 1,6-hexanediol and 264 g (3.00 mol) of ethylene carbonate were added to a 1L separable flask equipped with a stirrer, a thermometer, a reflux head on the top and a vacuum jacket, and 13.8 mg of manganese (II) acetate tetrahydrate and 6.7 mg of lithium methoxide were added as catalysts. The raw materials in the flask were heated in an oil bath set at 170° C., and the raw material monomers were polycondensed by transesterification reaction for 4 hours at an internal temperature of 135° C. and a vacuum degree of 3 kPa while a portion of the fraction was removed from the reflux head to obtain a polycarbonate diol.

[0688] After that, the mixture was switched to simple distillation. The temperature of the oil bath was set to 165°C while the pressure was slowly reduced to 0.1 kPa. The mixture was reacted for 2 hours at an internal temperature of 150°C in the flask to distill off the monomers and obtain polycarbonate diol. After nitrogen was introduced to restore the normal pressure, the temperature of the oil bath was set to 125°C and the internal temperature of the flask was set to 110-120°C. Monobutyl phosphate was added as a catalyst deactivator in an amount equimolar to the amount of catalyst added, and the mixture was stirred at a temperature of 110-120°C for 3 hours. The analysis results of the obtained polycarbonate diol are shown in Table 2. This polycarbonate diol is referred to as PC14.

[0689] [Synthesis Examples 15 to 26 of Polycarbonate Diol]

[0690] The raw material monomers were polycondensed by transesterification reaction in the same manner as in Synthesis Example 14 except that the type and amount of the added catalyst were those shown in Table 2 to obtain polycarbonate diols. The analysis results are shown in Table 2. The obtained polycarbonate diols are referred to as PC15 to PC26.

[0691] [Synthesis Examples 27 to 29 of Polycarbonate Diol]

[0692] The raw material monomers were polycondensed by transesterification reaction in the same manner as in Synthesis Example 14, except that the time for taking out a part of the fraction from the reflux head at a vacuum degree of 3 kPa was set to 12 hours and the type and amount of the added catalyst were set to the type and amount described in Table 2, to obtain polycarbonate diols. The analysis results are shown in Table 2. The obtained polycarbonate diols are referred to as PC27 to PC29.

[0693]

Table 2

[0694]

[0695] [Synthesis Examples 30 to 33]

[0696] The raw material monomers were polycondensed by transesterification reaction in the same manner as in Synthesis Example 14 except that the dihydroxy compound and carbonate used were the types and amounts shown in Table 3 to obtain polycarbonate diols. The properties of the obtained polycarbonate diols are shown in Table 3. The obtained polycarbonate diols are referred to as PC30 to PC33, respectively.

[0697] [Synthesis Example 34]

[0698] The raw material monomers were polycondensed by transesterification reaction in the same manner as in Synthesis Example 14, except that the dihydroxy compound and carbonate used were the types and amounts shown in Table 3 and the reaction time after switching to simple distillation was 0.5 hours, to obtain a polycarbonate diol. The properties of the obtained polycarbonate diol are shown in Table 3. The obtained polycarbonate diol is referred to as PC34.

[0699] [Synthesis Example 35]

[0700] The raw material monomers were polycondensed by transesterification reaction in the same manner as in Synthesis Example 14, except that the dihydroxy compound and carbonate used were the types and amounts shown in Table 3 and the reaction time after switching to simple distillation was 3 hours, to obtain a polycarbonate diol. The properties of the obtained polycarbonate diol are shown in Table 3. The obtained polycarbonate diol is referred to as PC35.

[0701] [Synthesis Examples 36 to 39]

[0702] The raw material monomers were polycondensed by transesterification reaction in the same manner as in Synthesis Example 14 except that the dihydroxy compound and carbonate used were the types and amounts shown in Table 3 to obtain polycarbonate diols. The properties of the obtained polycarbonate diols are shown in Table 3. The obtained polycarbonate diols are referred to as PC36 to PC39, respectively.

[0703]

Table 3

[0704]

[0705] [Example 1]

[0706] 200 g (0.1 mol) of polycarbonate diol PC1, 2.06 g of leveling agent BYK-331 (manufactured by BYK Chemicals), 0.8 g of dibutyltin dilaurate (manufactured by Air Products) and 356 g of a mixed solvent of xylene / butyl acetate (70 / 30) as a diluent were added and stirred to obtain a coating base. 38.2 g of DURANATE TPA-100 (manufactured by Asahi Kasei Chemicals: hexamethylene diisocyanate-based isocyanurate-type curing agent, NCO content = 23.1 mass %, isocyanate groups in 1 molecule: 3.0) as a curing agent was added thereto and mixed to prepare a coating solution (coating composition). This was applied on a glass plate with an applicator and then cured by heating at 80°C for 2 hours to obtain a coating film. Various physical properties of the coating film and thin film obtained from the coating solution (coating composition) using PC1 are shown in Table 4.

[0707] [Examples 2 to 10]

[0708] Coating solutions (coating compositions) were prepared in the same manner as in Example 1 except that PC2 to PC10 were used as polycarbonate diols as shown in Table 4, and various physical properties of coating films and thin films obtained from the coating solutions (coating compositions) were evaluated. The evaluation results are shown in Table 4.

[0709] [Comparative Examples 1 to 3]

[0710] Coating solutions (coating compositions) were prepared in the same manner as in Example 1 except that PC11 to PC13 were used as polycarbonate diols as shown in Table 4, and various physical properties of coating films and thin films obtained from the coating solutions (coating compositions) were evaluated.

[0711]

Table 4

[0712]

[0713] [Examples 11 to 23, Comparative Examples 4 to 6]

[0714] As shown in Table 5, PC14, PC15, PC16, PC17, PC18, PC19, PC20, PC21, PC22, PC23, PC24, PC25, PC26, PC27, PC28, and PC29 were used instead of polycarbonate diol PC1. The coating solution (coating composition) was prepared in the same manner as in Example 1, and various physical properties of the coating film and film obtained from each coating solution (coating composition) were evaluated. The evaluation results are shown in Table 5.

[0715]

Table 5

[0716]

[0717] [Examples 24 to 33]

[0718] As shown in Table 6, PC30, PC31, PC32, PC33, PC34, PC35, PC36, PC37, PC38, and PC39 were used instead of polycarbonate diol PC1. The coating solution (coating composition) was prepared in the same manner as in Example 1, and various physical properties of the coating film and film obtained from each coating solution (coating composition) were evaluated. The evaluation results are shown in Table 6.

[0719]

Table 6

[0720]

[0721] [Example 34]

[0722] 200 g of polycarbonate diol PC32, 2.06 g of leveling agent BYK-331 (manufactured by BYK Chemicals), 0.8 g of dibutyltin dilaurate (manufactured by Air Products), 25 g of fine powdered silica (ACEMATT TS100, manufactured by EVONIK, average particle size: 9.5 μm), and 356 g of a mixed solvent of xylene / butyl acetate (70 / 30) as a diluent were added and stirred to obtain a coating base. 38.2 g of DURANATE TPA-100 (manufactured by Asahi Kasei Chemicals: hexamethylene diisocyanate-based isocyanurate type curing agent, NCO content = 23.1 mass %, isocyanate groups per molecule: 3.0) as a curing agent was added thereto and mixed to prepare a coating solution (coating composition). The solution was applied onto an acrylonitrile-butadiene-styrene (ABS) resin plate and then cured by heating at 80°C for 2 hours to obtain a coating film having a thickness of 40 μm. Table 7 shows various physical properties of the coating film and thin film obtained from the coating solution (coating composition).

[0723] [Example 35]

[0724] 200 g of polycarbonate diol PC32, 2.06 g of leveling agent BYK-331 (manufactured by BYK Chemical Co., Ltd.), 0.8 g of dibutyltin dilaurate (manufactured by Air Products Co., Ltd.), 25 g of fine powdered silica (ACEMATT TS100, manufactured by EVONIK Co., Ltd., average particle size: 9.5 μm), and 356 g of a mixed solvent of xylene / butyl acetate (70 / 30) as a diluent were added and stirred to obtain a coating base. 37.5 g of DURANATE 24A-100 (manufactured by Asahi Kasei Co., Ltd.: hexamethylene diisocyanate-based biuret type curing agent, NCO content = 23.5 mass%, isocyanate groups per molecule: 3.5) as a curing agent was added thereto and mixed to prepare a coating solution (coating composition). The solution was applied onto an acrylonitrile-butadiene-styrene (ABS) resin plate and then cured by heating at 80°C for 2 hours to obtain a coating film having a thickness of 40 μm. Table 7 shows various physical properties of the coating film and thin film obtained from the coating solution (coating composition).

[0725] [Example 36]

[0726] 200 g of polycarbonate diol PC32, 2.06 g of leveling agent BYK-331 (manufactured by BYK Chemicals), 0.8 g of dibutyltin dilaurate (manufactured by Air Products), 25 g of polyurethane particles (ART PEAR, C-800, average particle size: 6 μm, manufactured by Negami Industries Co., Ltd.), and 356 g of a mixed solvent of xylene / butyl acetate (70 / 30) as a diluent were added and stirred to obtain a coating base. 38.2 g of DURANATE TPA-100 (manufactured by Asahi Kasei Chemicals: hexamethylene diisocyanate-based isocyanurate type curing agent, NCO content = 23.1 mass %, isocyanate groups per molecule: 3.0) as a curing agent was added thereto and mixed to prepare a coating solution (coating composition). The solution was applied on an acrylonitrile-butadiene-styrene (ABS) resin plate and then cured by heating at 80° C. for 2 hours to obtain a coating film having a film thickness of 40 μm. Table 7 shows various physical properties of the coating film and thin film obtained from the coating solution (coating composition).

[0727]

Table 7

[0728]

[0729] It should be noted that, in the present example, the average particle diameter of the inorganic fine powder and the polyurethane particles was measured by preparing a 0.25 mass % aqueous solution (aqueous dispersion) using a particle size distribution measuring instrument SALD-2100 manufactured by Shimadzu Corporation.

[0730] [Example 37]

[0731] 20 g of polycarbonate diol PC32, 131 g of Setalux 1152 manufactured by Nuplex as a hydroxyl-containing acrylic resin (xylene / methoxypropyl acetate mixed solution, solid content 61% by mass, solid content-equivalent hydroxyl value 139 mgKOH / g, number average molecular weight of hydroxyl-containing acrylic resin 3000), 1.06 g of a leveling agent BYK-331 (manufactured by BYK Chemical Co., Ltd.), 0.8 g of dibutyltin dilaurate (manufactured by Air Products Co., Ltd.) and 200 g of a mixed solvent of xylene / butyl acetate (70 / 30) as a diluent were added and stirred to obtain a coating base. 42.1 g of DURANATE TKA-100 (manufactured by Asahi Kasei Corporation: hexamethylene diisocyanate isocyanurate curing agent, NCO content = 21.8 mass %, isocyanate groups in 1 molecule: 3.0) was added thereto as a curing agent and mixed to prepare a coating solution (coating composition). The coating solution was applied on an acrylonitrile-butadiene-styrene (ABS) resin plate and then heated and cured at 80°C for 2 hours to obtain a coating film with a film thickness of 20 μm. Various physical properties of the coating film obtained from the coating solution (coating composition) are shown in Table 8.

[0732] [Example 38]

[0733] 60 g of polycarbonate diol PC32, 65.6 g of Setalux 1152 manufactured by Nuplex as a hydroxyl-containing acrylic resin (xylene / methoxypropyl acetate mixed solution, solid content 61 mass %, solid content equivalent hydroxyl value 139 mgKOH / g, number average molecular weight of hydroxyl-containing acrylic resin 3000), 0.8 g of leveling agent BYK-331 (manufactured by BYK Chemical Co., Ltd.), 0.7 g of dibutyltin dilaurate (manufactured by Air Products Co., Ltd.) and 150 g of a mixed solvent of xylene / butyl acetate (70 / 30) as a diluent were added and stirred to obtain a coating base. 30.7 g of DURANATE TKA-100 (manufactured by Asahi Kasei Corporation: hexamethylene diisocyanate isocyanurate curing agent, NCO content = 21.8 mass %, isocyanate groups in 1 molecule: 3.0) was added thereto as a curing agent and mixed to prepare a coating solution (coating composition). After coating it on an acrylonitrile-butadiene-styrene (ABS) resin plate, it was heated and cured at 80°C for 2 hours to obtain a coating film with a film thickness of 20 μm. Various physical properties of the coating film obtained from the coating solution (coating composition) are shown in Table 8.

[0734] [Example 39]

[0735] A coating solution (coating composition) was prepared by the same method as in Example 38, except that polycarbonate polyol PC34 was used instead of polycarbonate polyol PC32 in Example 38 and the addition amount of polycarbonate polyol PC34 was set to 30 g, and various physical properties of the coating film obtained from the coating solution (coating composition) were evaluated. The evaluation results are shown in Table 8.

[0736] [Comparative Example 7]

[0737] A coating solution (coating composition) was prepared in the same manner as in Example 38, except that polycarbonate polyol PC11 was used instead of polycarbonate polyol PC32 of Example 38, and various physical properties of the coating film obtained from the coating solution (coating composition) were evaluated. The evaluation results are shown in Table 8.

[0738]

Table 8

[0739]

[0740] The present invention (particularly the aqueous polyurethane dispersion) will be described in further detail using the following examples, etc., but the present invention is not limited to these examples. The analysis methods and evaluation of coating film properties in the following examples and comparative examples were carried out according to the following test methods.

[0741] [Average particle size of aqueous polyurethane dispersion]

[0742] The number average particle size (nm) of the aqueous polyurethane dispersion was measured using a particle size analyzer Nanotrac 150 (manufactured by Microtrac).

[0743] [Number average molecular weight and molecular weight distribution of aqueous polyurethane dispersion]

[0744] The number average molecular weight and molecular weight distribution of the aqueous polyurethane dispersion were obtained by gel permeation chromatography (GPC). The GPC device was a HLC-8220GPC device manufactured by Tosoh, and four TSK gel Super HM-H were used therein, and the detection was performed with an RI detector. The developing solvent was dimethylformamide (DMF), the flow rate was 0.5 mL / min, the operating temperature was 40°C, and the results were obtained by polystyrene conversion.

[0745] [Tensile strength and elongation at break]

[0746] A specified amount of aqueous polyurethane dispersion was injected into an aluminum dish, placed at room temperature for 24 hours, and then heat treated at 60°C for 24 hours to produce a sheet with a thickness of 500 μm. A polyurethane resin film sample with a width of 6.6 mm and a length of 60 mm was cut out from the sheet. In a constant temperature room at 23°C, the tensile breaking strength (MPa) and elongation at break (%) of the above-mentioned sample film were measured using a Universal Testing Machine (manufactured by Zwick Corp.) at a clamp spacing of 20 mm and a tensile speed of 5 mm / min. It should be noted that the sample film is also used to evaluate (low temperature) flexibility and oil resistance.

[0747] [Softness]

[0748] The test was conducted by the method described in the above [Tensile Strength at Break and Elongation at Break], and the stress (MPa) at 50% elongation (at 25 mm elongation) was measured. The lower the stress, the higher the flexibility was evaluated.

[0749] [Oil resistance]

[0750] The sample film prepared in the above [Tensile Strength at Break and Elongation at Break] was immersed in oleic acid at 23° C. for one week and its swelling ratio was measured. The swelling ratio was determined using the following mathematical formula (4).

[0751] Swelling ratio (%) = {(mass after test - mass before test) / mass before test} × 100 (4)

[0752] The lower the swelling ratio, the better the oil resistance was evaluated to be.

[0753] [Abrasion resistance of waterborne polyurethane dispersion]

[0754] The sheet obtained by the same operation as in the above [tensile breaking strength and breaking elongation] was evaluated according to the JIS K5600 abrasion wheel method (abrasion wheel CS-10, weight 500 g, 500 revolutions). The measurement result (mg) of the mass lost during the test is shown as the evaluation of wear resistance.

[0755] [Evaluation of colorability of aqueous polyurethane dispersion]

[0756] The sheet was prepared by the same operation as in the above [tensile strength at break and elongation at break]. The sheet was placed in a thermostatic chamber at 60°C for 1 month. The color difference of the sheet surface was measured using a spectrophotometer (CM-3700A) manufactured by Konica Minolta. The b obtained in this measurement was ＊ The smaller the value, the more excellent the storage stability and the less coloration were evaluated.

[0757] [Surface Hardness of Coating Film of Aqueous Polyurethane Dispersion Coating Composition]

[0758] The aqueous coating composition (aqueous soft-touch coating composition) containing an aqueous polyurethane dispersion was applied on a polycarbonate plate having a thickness of about 2 mm using an applicator so that the film thickness after curing was about 40 μm, and dried at room temperature for 24 hours to obtain a coating film. The obtained coating film was measured and evaluated for pencil hardness according to JIS K-5400.

[0759] [Abrasion resistance of coating films of aqueous polyurethane dispersion coating compositions]

[0760] The coating film obtained by the same operation as in the above [Film Surface Hardness] was evaluated according to the JIS K5600 abrasion wheel method (abrasion wheel CS-10, weight 500 g, 500 revolutions). The measurement result (mg) of the mass lost during the test is shown as the evaluation of the wear resistance.

[0761] [Evaluation of Colorability of Coating Films of Aqueous Polyurethane Dispersion Coating Compositions]

[0762] The coating film was prepared by the same operation as in the above [Film Surface Hardness]. The coating film was placed in a constant temperature oven at 60°C for 1 month. The color difference of the coating film surface was measured using a spectrophotometer (CM-3700A) manufactured by Konica Minolta. The b obtained in this measurement ＊ The smaller the value, the more excellent the storage stability and the less coloration were evaluated.

[0763] [Example 40]

[0764] In a 1000 ml four-necked flask equipped with a stirrer, a condenser, a nitrogen inlet tube, and a thermometer, 33.3 g (0.15 mol) of isophorone diisocyanate (IPDI), 100 g (0.05 mol) of polycarbonate diol PC1, 6.7 g (0.05 mol) of dimethylol propionic acid (DMPA), 6.1 g (0.05 mol) of triethylamine (TEA), and 30 ml of methyl ethyl ketone (MEK) were added under a nitrogen atmosphere, and reacted at 80° C. for 2.5 hours to obtain a prepolymer solution with an NCO terminal. Next, 342 g of deionized water was added, and the mixture was mixed with the prepolymer solution at 35° C. to obtain a prepolymer dispersion. A solution containing 1.5 g (0.0025 mol) of ethylenediamine (EDA) in 2.0 g of deionized water was added to the prepolymer dispersion, and stirred at 30° C. for 1 hour. Next, the mixture was heated to 80° C. to remove MEK, thereby obtaining an aqueous polyurethane dispersion having a solid content of 30% by mass. Table 9 summarizes the properties of the obtained aqueous polyurethane dispersion (PUD1) and the physical properties of a sheet produced using the aqueous polyurethane.

[0765] [Examples 41 to 49, Comparative Examples 8 to 10]

[0766] As shown in Table 9, PC2, PC3, PC4, PC5, PC6, PC7, PC8, PC9, PC10, PC11, PC12, PC13 were used instead of polycarbonate diol PC1, and the reaction was carried out in the same manner as in Example 40 to obtain an aqueous polyurethane dispersion. The properties of the obtained aqueous polyurethane dispersions (PUD2, PUD3, PUD4, PUD5, PUD6, PUD7, PUD8, PUD9, PUD10, PUD11, PUD12, PUD13) and the physical properties of the sheet produced using the aqueous polyurethane are summarized in Table 9.

[0767]

Table 9

[0768]

[0769] [Examples 50 to 62, Comparative Examples 11 to 13]

[0770] As shown in Table 10, the reaction was carried out in the same manner as in Example 40, except that PC14, PC15, PC16, PC17, PC18, PC19, PC20, PC21, PC22, PC23, PC24, PC25, PC26, PC27, PC28, and PC29 were used instead of the polycarbonate diol PC1, to obtain an aqueous polyurethane dispersion. The properties of the obtained aqueous polyurethane dispersions (PUD14, PUD15, PUD16, PUD17, PUD18, PUD19, PUD20, PUD21, PUD22, PUD23, PUD24, PUD25, PUD26, PUD27, PUD28, and PUD29) and the physical properties of the sheet produced using the aqueous polyurethane are summarized in Table 10.

[0771]

Table 10

[0772]

[0773] [Examples 63 to 66]

[0774] As shown in Table 11, the reaction was carried out in the same manner as in Example 40, except that PC30, PC31, PC32, and PC33 were used instead of polycarbonate diol PC1. The properties of the obtained aqueous polyurethane dispersions (PUD30, PUD31, PUD32, and PUD33) and the physical properties of the sheets produced using the aqueous polyurethane are summarized in Table 11.

[0775] [Example 67]

[0776] The same reaction as in Example 40 was performed except that PC34 was used instead of polycarbonate diol PC1 and the amount of polycarbonate diol was changed to 200 g to obtain an aqueous polyurethane dispersion. The properties of the obtained aqueous polyurethane dispersion (PUD34) and the physical properties of a sheet produced using the aqueous polyurethane are summarized in Table 11.

[0777] [Example 68]

[0778] An aqueous polyurethane dispersion was obtained by reacting in the same manner as in Example 40 except that PC35 was used instead of polycarbonate diol PC1 and the amount of polycarbonate diol was changed to 50 g. The properties of the obtained aqueous polyurethane dispersion (PUD35) and the physical properties of a sheet produced using the aqueous polyurethane are summarized in Table 11.

[0779] [Examples 69 to 72]

[0780] As shown in Table 11, the reaction was carried out in the same manner as in Example 40, except that PC36, PC37, PC38, and PC39 were used instead of polycarbonate diol PC1. The properties of the obtained aqueous polyurethane dispersions (PUD36, PUD37, PUD38, and PUD39) and the physical properties of the sheets produced using the aqueous polyurethane are summarized in Table 11.

[0781]

Table 11

[0782]

[0783] [Example 73]

[0784] (Evaluation of coating composition using aqueous polyurethane dispersion)

[0785] 300 g of aqueous polyurethane dispersion of PUD1, 2.06 g of aqueous leveling agent BYK-3455 (manufactured by BYK Chemical Co., Ltd.), and 35 g of polyurethane particles (ART PEAR, C-800, average particle size = 6 μm, manufactured by Negami Industries Co., Ltd.) were mixed and stirred to obtain an aqueous soft-touch coating composition. After coating it on an acrylonitrile-butadiene-styrene (ABS) resin plate, it was heated and dried at 80°C for 2 hours to obtain a coating film with a film thickness of 30 to 40 μm. Its various physical properties are shown in Table 12. In Table 12, the softness was evaluated by the touch when the surface of the coated plate was touched by hand. The judgment results are represented by the following symbols.

[0786] ○: It feels like natural leather and has a good soft feel.

[0787] △: It feels like natural leather and is relatively soft.

[0788] ×: No natural leather-like feel, no softness

[0789] [Examples 74 to 78, Comparative Example 14]

[0790] As shown in Table 12, PUD30, PUD31, PUD32, PUD34, PUD35, and PUD11 were used instead of PUD1 to obtain an aqueous soft-touch coating composition in the same manner as in Example 73. Various physical properties thereof are shown in Table 12.

[0791]

Table 12

[0792]

[0793] The present invention (particularly polyurethane resin and polyurea resin) will be described in further detail using the following examples, etc., but the present invention is not limited to these examples. The analysis methods and physical property evaluations in the following examples and comparative examples were carried out according to the following test methods.

[0794] <Evaluation method of polyurethane and / or polyurea resin film>

[0795] [Tensile strength and elongation at break]

[0796] A N,N-dimethylformamide (DMF) solution of a polyurea resin having a solid content of 20% by mass was applied to a glass plate and heated at 80°C for 2 hours to produce a film with a thickness of 40 μm. After being placed at room temperature for 24 hours, a sample with a width of 6.6 mm and a length of 60 mm was cut out from the film as a sample film. In a constant temperature chamber at 23°C, using Universal Testing Machine (manufactured by Zwick Corp.), under the conditions of a clamp spacing of 20 mm and a tensile speed of 10 mm / min, the tensile breaking strength (MPa) and the elongation at break (%) of the above sample film were measured. The stress at 100% stretching (100% modulus: MPa) was obtained. The lower the stress at 100% stretching, the softer it is evaluated to be, and the better the flexibility.

[0797] [Chemical resistance]

[0798] The film prepared by the same operation as in the above [Tensile Strength and Elongation at Break] was immersed in oleic acid at 23°C for one week and the swelling ratio was measured. The swelling ratio was calculated using the following mathematical formula (III). The lower the swelling ratio (%), the better the chemical resistance was evaluated.

[0799] Swelling ratio (%) = {(mass after test - mass before test) / mass before test} × 100 (III)

[0800] [Abrasion resistance]

[0801] For the film produced by the same operation as the above [tensile strength at break and elongation at break], the wear resistance was measured using a cone abrasion tester according to the method of JIS K5600-5-8. The mass change (mg) between the mass of the coated plate before the abrasion test and the mass of the coated plate after the abrasion test (500 turns) was measured and marked. The less the mass change (mg), the better the wear resistance was evaluated.

[0802] [Colorability Evaluation]

[0803] The film was prepared by the same operation as in the above [tensile strength at break and elongation at break]. The film was placed in a thermostatic chamber at 60°C for 1 month. The color difference of the film surface was measured using a spectrophotometer (CM-3700A) manufactured by Konica Minolta. The b obtained in this measurement was ＊ The smaller the value, the more excellent the storage stability and the less coloration were evaluated.

[0804] [Example 79]

[0805] 15.74 g (0.06 mol) of 4,4'-methylenebiscyclohexyl diisocyanate (hydrogenated MDI, average number of isocyanate groups in one molecule: 2.0) and 100 g of N,N-dimethylformamide (DMF) were added to a 500 mL separable flask sealed with nitrogen and equipped with a stirrer, and heated to 40°C to obtain a solution. While stirring the above solution, 140 g of N,N-dimethylformamide (DMF) and 40 g (0.02 mol) of polycarbonate polyol PC1 to which 0.0029 g of dibutyltin dilaurate as a catalyst were added dropwise to the above flask over 30 minutes. The mixture was reacted at 50°C with stirring for 2 hours to obtain a prepolymer of terminal isocyanate. The temperature of the solution in the flask was lowered to room temperature, and then 6.8 g (0.04 mol) of isophorone diamine as a chain extender was added. After reacting at room temperature for 1 hour, 0.5 g of ethanol as a reaction terminator was added to obtain a DMF solution of a polyurea resin (solid content of about 20% by mass). The obtained N,N-dimethylformamide (DMF) solution of a polyurea resin with a solid content of 20% by mass was coated on a glass plate and heated at 80°C for 2 hours to prepare a polyurea resin film with a film thickness of 40 μm. After being left at room temperature for 24 hours, various physical properties were evaluated. The evaluation results are shown in Table 13.

[0806] [Examples 80 to 88]

[0807] As shown in Table 13, a polyurea resin film was obtained in the same manner as in Example 79 except that PC2 to PC10 were used as polycarbonate diols, and various physical properties were evaluated. The evaluation results are summarized in Table 13.

[0808] [Comparative Examples 15 to 17]

[0809] As shown in Table 13, a polyurea resin film was obtained in the same manner as in Example 79 except that PC11 to PC13 were used as polycarbonate diols, and various physical properties were evaluated. The evaluation results are summarized in Table 13.

[0810]

Table 13

[0811]

[0812] [Examples 89 to 101, Comparative Examples 18 to 20]

[0813] As shown in Table 14, PC14, PC15, PC16, PC17, PC18, PC19, PC20, PC21, PC22, PC23, PC24, PC25, PC26, PC27, PC28, and PC29 were used instead of polycarbonate diol PC1. The reaction was carried out in the same manner as in Example 79 to obtain a polyurea resin film, which was then evaluated for various physical properties. The physical properties of the obtained polyurea resin are summarized in Table 14.

[0814]

Table 14

[0815]

[0816] [Examples 102 to 111]

[0817] As shown in Table 15, PC30, PC31, PC32, PC33, PC34, PC35, PC36, PC37, PC38, and PC39 were used instead of polycarbonate diol PC1, and the reaction was carried out in the same manner as in Example 79 to obtain a polyurea resin film, which was then evaluated for various physical properties. The physical properties of the obtained polyurea resin are summarized in Table 15.

[0818]

Table 15

[0819]

[0820] [Examples 112 to 117]

[0821] Films of polyurethane resin and polyurea resin were obtained in the same manner as in Example 79 except that PC32 was used as the polycarbonate diol, the isocyanate described in Table 16, and the chain extender described in Table 16 were used, and various physical properties were evaluated. The evaluation results are shown in Table 16. It should be noted that polyurethane resins were synthesized in Examples 114 and 115 using diol as a chain extender. In addition, polyurea resins were synthesized in Examples 112, 113, 116, and 117 using diamine as a chain extender.

[0822]

Table 16

[0823]

[0824] Hydrogenated MDI: 4,4'-methylenebiscyclohexyl diisocyanate

[0825] IPDI: Isophorone diisocyanate

[0826] HDI: Hexamethylene diisocyanate

[0827] IPDA: Isophorone diamine

[0828] CHA 4,4'-methylenebis(cyclohexylamine)

[0829] EDA: Ethylenediamine

[0830] CHDO 4,4'-Bicyclohexanediol

[0831] BDO: 1,4-Butanediol

[0832] Industrial Applicability

[0833] The coating composition of the present invention has excellent various physical properties and excellent coloring stability, and therefore can provide a coating composition that has little discoloration when used in clear coatings for automobile exteriors, coatings for automobile interiors, coatings for home appliances, coatings for OA products, leather surface treatment agents, synthetic leather surface treatment agents, and the like.

[0834] Furthermore, the aqueous polyurethane dispersion of the present invention can provide an aqueous polyurethane dispersion that is less discolored when used for, for example, synthetic leather, paints, coating agents, adhesives, pressure-sensitive adhesives, and the like.

[0835] In addition, the polyurea resin and polyurethane resin of the present invention are excellent in various physical properties and coloring stability, and therefore can be used, for example, in injection molded components (grip parts, steering wheels, airbag storage covers, watch straps, etc.), extrusion molded products (hoses, pipes, sheets, etc.), and solvent-soluble synthetic leather binders, surface materials, surface treatment agents, fiber coating agents, various surface treatment agents and various adhesives.

Claims

1. A composition comprising (a) a curing agent and (b) a polycarbonate diol, The (a) curing agent is an organic polyisocyanate compound, The (b) polycarbonate diol is a polycondensate based on the transesterification reaction of a dihydroxy compound and a carbonate. The number average molecular weight of the (b) polycarbonate diol is 250 or more and 3000 or less, The (b) polycarbonate diol contains at least one metal (M1) selected from the group consisting of metals of Group 6, Group 7, Group 8, Group 9, Group 10 and Group 11 of the long-form periodic table in a total amount of 1 ppm to 25 ppm.

2. A coating composition comprising the composition according to claim 1, The (a) curing agent is an organic polyisocyanate compound having 2.6 or more isocyanate groups in one molecule.

3. The coating composition according to claim 2, in, The metal (M1) is at least one metal selected from the group consisting of metals of Group 7 of the long-period periodic table.

4. The coating composition according to claim 2, in, The metal (M1) is manganese.

5. The coating composition according to claim 2, in, The (b) polycarbonate diol contains at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-form periodic table in a total amount of 0.1 ppm to 12.5 ppm.

6. The coating composition according to claim 5, in, The metal (M2) is lithium.

7. The coating composition according to claim 2, in, The (a) curing agent is a polyisocyanate derived from an aliphatic organic polyisocyanate compound and / or an alicyclic organic polyisocyanate compound.

8. The coating composition according to claim 2, comprising 1 to 90% by mass of an inert organic solvent.

9. The coating composition according to claim 2, in, The hydroxyl group-containing acrylic resin is contained in an amount of 1 to 80% by mass based on the total solid content.

10. The coating composition according to claim 9, in, The number average molecular weight of the acrylic resin containing a hydroxyl group is 500 to 10,000, and the hydroxyl value of the acrylic resin containing a hydroxyl group is 50 to 300 mgKOH / g.

11. The coating composition according to claim 2, in, The present invention contains 1 to 30% by mass of inorganic fine powder having an average particle size of 4 to 15 μm and / or polyurethane particles having an average particle size of 2 to 20 μm based on the total solid content.

12. The coating composition according to claim 2, in, The (b) polycarbonate diol has a Hazen color number of 50 or less as measured in accordance with JIS-K0071-1 (1998). 13 . A paint-coated molded product, wherein the paint composition according to claim 1 is applied to the molded product.

14. An aqueous polyurethane dispersion comprising a water-dispersible polyurethane and water, wherein the water-dispersible polyurethane is a reaction product of the composition according to claim 1 and (c) a polyol containing a carboxyl group and / or a sulfonic group or a salt thereof.

15. The aqueous polyurethane dispersion according to claim 14, in, The metal (M1) is at least one metal selected from the group consisting of metals of Group 7 of the long-period periodic table.

16. The aqueous polyurethane dispersion according to claim 14, in, The metal (M1) is manganese.

17. The aqueous polyurethane dispersion according to claim 14, in, (b) The polycarbonate diol contains at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-form periodic table in a total amount of 0.1 ppm to 12.5 ppm.

18. The aqueous polyurethane dispersion according to claim 17, in, The metal (M2) is lithium.

19. The aqueous polyurethane dispersion according to claim 14, in, The organic polyisocyanate compound as the (a) curing agent is an aliphatic organic diisocyanate compound and / or an alicyclic organic diisocyanate compound.

20. The aqueous polyurethane dispersion according to claim 14, in, The (b) polycarbonate diol has a Hazen color number of 50 or less as measured in accordance with JIS-K0071-1 (1998). 21 . An aqueous coating composition comprising the aqueous polyurethane dispersion according to claim 14 .

22. A polyurea resin, which is a reaction product of the composition of claim 1 and a chain extender (d), The chain extender (d) is a diamine compound, The polyisocyanate compound as the (a) curing agent is an organic polyisocyanate compound having an average isocyanate group number of 2.5 or less in one molecule.

23. The polyurea resin according to claim 22, in, The metal (M1) is at least one metal selected from the group consisting of metals of Group 7 of the long-period periodic table.

24. The polyurea resin according to claim 22, in, The metal (M1) is manganese.

25. The polyurea resin according to claim 22, in, The (b) polycarbonate diol contains at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-form periodic table in a total amount of 0.1 ppm to 12.5 ppm.

26. The polyurea resin according to claim 25, in, The metal (M2) is lithium.

27. The polyurea resin according to claim 22, in, The organic polyisocyanate compound as the (a) curing agent is an aliphatic organic diisocyanate compound and / or an alicyclic organic diisocyanate compound.

28. The polyurea resin according to claim 22, in, The chain extender (d) is an alicyclic diamine.

29. The polyurea resin according to claim 22, in, The (b) polycarbonate diol has a Hazen color number of 50 or less as measured in accordance with JIS-K0071-1 (1998).

30. A polyurethane resin, which is a reaction product of the composition of claim 1 and a chain extender (d), The chain extender (d) is a dihydroxy compound, The polyisocyanate compound as the (a) curing agent is an organic polyisocyanate compound having an average isocyanate group number of 2.5 or less in one molecule.

31. The polyurethane resin according to claim 30, in, The metal (M1) is at least one metal selected from the group consisting of metals of Group 7 of the long-period periodic table.

32. The polyurethane resin according to claim 30, in, The metal (M1) is manganese.

33. The polyurethane resin according to claim 30, in, The (b) polycarbonate diol contains at least one metal (M2) selected from the group consisting of metals of Group 1 of the long-form periodic table in a total amount of 0.1 ppm to 12.5 ppm.

34. The polyurethane resin according to claim 33, in, The metal (M2) is lithium.

35. The polyurethane resin according to claim 30, in, The organic polyisocyanate compound as the (a) curing agent is an aliphatic organic diisocyanate compound and / or an alicyclic organic diisocyanate compound.

36. The polyurethane resin according to claim 30, in, The (b) polycarbonate diol has a Hazen color number of 50 or less as measured in accordance with JIS-K0071-1 (1998).

37. A film having a thickness of 10 to 500 μm, wherein the polyurea resin according to any one of claims 22 to 29 and / or the polyurethane resin according to any one of claims 30 to 36 is molded into a film shape.

38. A synthetic leather comprising the polyurea resin according to any one of claims 22 to 29 and / or the polyurethane resin according to any one of claims 30 to 36.

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