Polyurethane resin, polyurea resin

Abstract

To provide a polyurethane resin and a polyurea resin each of which is excellent in storage stability, and for example when used in coating material and a coating agent, little changes in color.SOLUTION: A polyurea resin or a polyurethane resin is provided, which a reaction product of a polyisocyanate compound (a), polycarbonate diol (b) and a chain extender (c), wherein the component (a) is an organic polyisocyanate compound having the average number of isocyanate groups in one molecule of 2.5 or less, the component (b) is a polycondensation product obtained by ester exchange reaction of a dihydroxy compound and a carbonate, a number average molecular amount of the component (b) is 250 or more and 3,000 or less, the component (b) contains 1 ppm or more and 25 ppm or less of specific metal (M1), and the component (b) has a Hazen color number of 50 or less.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polyurethane resin and a polyurea resin. [Background technology]

[0002] Conventionally, polyurethane resins and polyurea resins have been used in a wide range of fields, such as synthetic leather, artificial leather, adhesives, furniture paints, and automotive paints, and polyethers and polyesters are used as polyol components to react with isocyanates (see, for example, Patent Documents 1 and 2). However, in recent years, there has been an increasing demand for resin resistance, such as heat resistance, weather resistance, hydrolysis resistance, mold resistance, and oil resistance.

[0003] For example, Patent Document 3 proposes a polycarbonate diol copolymerized with 1,6-hexanediol and 1,4-butanediol as a soft segment having excellent resistance to hydrolysis, light resistance, resistance to oxidative deterioration, heat resistance, etc. Polyurea resins using these copolymerized polycarbonate diols have been attracting attention in recent years because of their excellent flexibility and low-temperature properties. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2000-95836 A [Patent Document 2] JP 2001-123112 A [Patent Document 3] Patent Publication No. 2021-88705 Summary of the Invention [Problem to be solved by the invention]

[0005] On the other hand, the polycarbonate diol disclosed in Patent Document 3 uses titanium tetrabutoxide as a polymerization catalyst, so the polyurea resin made of this polycarbonate diol may be discolored during storage due to the influence of the remaining titanium tetrabutoxide residue, and there is room for improvement. In addition, as in Patent Document 3, when such a polyurea resin is used in injection molded parts (gripping parts, steering wheels, airbag storage covers, watch straps, etc.), extrusion molded products (hoses, tubes, sheets, etc.), or dissolved in a solvent and used as a binder for synthetic leather, a skin material, a surface treatment agent, a coating agent for fibers, various surface treatment agents, and various adhesives, paints, coating agents, adhesives, pressure sensitive adhesives, etc., there is a risk of discoloration, and there is room for improvement.

[0006] An object of the present invention is to provide a polyurethane resin and a polyurea resin which have excellent storage stability and are less likely to discolor when used, for example, in paints, coating agents, and the like. [Means for solving the problem]

[0007] Means for Solving the Problems The present inventors have conducted extensive research and have found that use of a specific polycarbonate diol makes it possible to provide polyurethane resins and polyurea resins which are excellent in storage stability and which are less susceptible to discoloration when used in, for example, paints, coating agents, and the like, and have thus completed the present invention.

[0008] That is, the present invention includes the following aspects. [1] A reaction product of a polyisocyanate compound (a), a polycarbonate diol (b) and a chain extender (c), The polyisocyanate compound (a) is an organic polyisocyanate compound having an average number of isocyanate groups in one molecule of 2.5 or less, The (b) polycarbonate diol is a polycondensate obtained by an ester exchange reaction between a dihydroxy compound and a carbonate ester, 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 in groups 6, 7, 8, 9, 10, and 11 of the long periodic table in a total amount of 1 ppm or more and 25 ppm or less, The polycarbonate diol (b) has a Hazen color number of 50 or less as measured in accordance with JIS-K0071-1 (1998). [2] The polyurea resin according to [1], wherein the (b) polycarbonate diol contains at least one metal (M2) selected from the group consisting of metals in Group 1 of the long form periodic table in a total amount of 0.1 ppm or more and 12.5 ppm or less. [3] The polyurea resin according to [1] or [2], wherein the (a) organic polyisocyanate compound is an aliphatic organic diisocyanate compound and / or an alicyclic organic diisocyanate compound. [4] The polyurea resin according to any one of [1] to [3], wherein the chain extender (c) is an alicyclic diamine. [5] A reaction product of a polyisocyanate compound (a), a polycarbonate diol (b) and a chain extender (c), The polyisocyanate compound (a) is an organic polyisocyanate compound having an average number of isocyanate groups in one molecule of 2.5 or less, The (b) polycarbonate diol is a polycondensate obtained by an ester exchange reaction between a dihydroxy compound and a carbonate ester, 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 in groups 6, 7, 8, 9, 10, and 11 of the long periodic table in a total amount of 1 ppm or more and 25 ppm or less, The polyurethane resin (b) has a Hazen color number of 50 or less as measured in accordance with JIS-K0071-1 (1998). [6] The polyurethane resin according to [5], wherein the (b) polycarbonate diol contains at least one metal (M2) selected from the group consisting of metals in Group 1 of the long form periodic table in a total amount of 0.1 ppm or more and 12.5 ppm or less. [7] The polyurethane resin according to [5] or [6], wherein the (a) organic polyisocyanate compound is an aliphatic organic diisocyanate compound and / or an alicyclic organic diisocyanate compound. [8] The polyurethane resin according to any one of [5] to [7], wherein the chain extender (c) is an alicyclic diamine. [9] A film having a thickness of 10 μm to 500 μm, which is obtained by molding the polyurea resin according to any one of [1] to [4] and / or the polyurethane resin according to any one of [5] to [8] into a film shape.

[10] A synthetic leather using the polyurea resin according to any one of [1] to [4] and / or the polyurethane resin according to any one of [5] to [8]. Effect of the Invention

[0009] According to the present invention, it is possible to provide polyurethane resins and polyurea resins which are less discolored during storage, have excellent storage stability, and are less susceptible to discoloration when used, for example, in paints, coating agents, and the like. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, an embodiment for carrying out the present invention (hereinafter, abbreviated as "present embodiment") will be described in detail. Note that the present invention is not limited to the following embodiment, and can be carried out in various modifications within the scope of the gist of the present invention.

[0011] <Polyurethane resin and / or polyurea resin> The polyurethane resin and / or polyurea resin of the present embodiment is a reaction product of a polyisocyanate compound (a), a polycarbonate diol (b) and a chain extender (c), The polyisocyanate compound (a) is an organic polyisocyanate compound having an average number of isocyanate groups in one molecule of 2.5 or less, The (b) polycarbonate diol is a polycondensate obtained by an ester exchange reaction between a dihydroxy compound and a carbonate ester, 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 in groups 6, 7, 8, 9, 10, and 11 of the long periodic table in a total amount of 1 ppm or more and 25 ppm or less, The (b) polycarbonate diol is a polyurethane resin and / or a polyurea resin, the Hazen color number of which is 50 or less as measured in accordance with JIS-K0071-1 (1998).

[0012] <(a) Polyisocyanate compound> The component (a) used in the polyurethane resin and / or polyurea resin of this embodiment is an organic polyisocyanate compound having an average number of isocyanate groups in one molecule of 2.5 or less. Specific examples of such organic polyisocyanate compounds are not particularly limited, but include known aromatic diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and mixtures thereof (TDI), diphenylmethane-4,4'-diisocyanate (MDI), naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-biphenylene diisocyanate, crude TDI, polymethylene polyphenylisocyanate, and crude MDI; Examples of the polyisocyanate compound include known aromatic alicyclic diisocyanates such as silylene diisocyanate (XDI) and phenylene diisocyanate; known aliphatic diisocyanates such as 4,4'-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and cyclohexane diisocyanate (hydrogenated XDI), as well as isocyanurate-modified products, carbodiimide-modified products, and biuret-modified products of these isocyanates. Among these, the polyisocyanate compound (a) used in the present embodiment is preferably an alicyclic polyisocyanate. When an alicyclic polyisocyanate is used, the resulting polyurea resin tends to be excellent in strength, abrasion resistance, and chemical resistance. From the viewpoint of the strength and abrasion resistance of the resulting polyurea resin, diphenylmethane-4,4'-diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and 4,4'-methylenebiscyclohexyl diisocyanate (hydrogenated MDI) are particularly preferred, and among these, isophorone diisocyanate (IPDI) and 4,4'-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), which have excellent weather resistance, are particularly preferred.

[0013] In 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. In 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.

[0014] 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 calculated from the isocyanate group content (mass%) determined by 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 standard by gel permeation chromatography (GPC), according to the following formula (i). Average functionality=number average molecular weight of organic polyisocyanate×isocyanate group content (mass%) / 100% / 42 (i)

[0015] The specific analytical methods for the isocyanate group content and the number average molecular weight of the organic polyisocyanate are as follows.

[0016] (Physical property 1) Isocyanate group content The polyisocyanate composition is used as a sample, and the isocyanate group content is measured according to the method described in JIS K7301-1995 (Test method for tolylene diisocyanate prepolymer for thermosetting urethane elastomer). A more specific method for measuring the isocyanate group content is described below. (1) Place 1 g of sample in a 200 mL Erlenmeyer flask, add 20 mL of toluene to the flask, and dissolve the sample. (2) Then, add 20 mL of 2.0 N di-n-butylamine-toluene solution to the flask and let stand for 15 minutes. (3) 70 mL of 2-propanol is added to the flask and dissolved to obtain a solution. (4) The solution obtained in (3) above is titrated with 1 mol / L hydrochloric acid to determine the sample titer. (5) Even if no sample is added, measurements are carried out in the same manner as in (1) to (3) above to determine the blank titer.

[0017] The isocyanate group content is calculated from the sample titer and blank titer determined above according to the following formula (ii).

[0018] Isocyanate group content (mass%)=(blank titration amount-sample titration amount)×42 / [sample mass (g)×1,000]×100%. (ii)

[0019] (Property 2) Number average molecular weight of organic polyisocyanate Using a polyisocyanate composition as a sample, the number average molecular weight of the polyisocyanate including the modified polyisocyanate and the unreacted polyisocyanate in the polyisocyanate composition is measured by gel permeation chromatography (GPC) using the following apparatus and conditions, based on the number average molecular weight of polystyrene standard.

[0020] Equipment: Tosoh Corporation HLC-8120GPC (product name) Column: TSKgelSuperH1000 (product name) x 1, TSKgelSuperH2000 (product name) x 1, TSKgelSuperH3000 (product name) x 1, manufactured by Tosoh Corporation Carrier: Tetrahydrofuran Detection method: Differential refractometer

[0021] (Property 3) Average number of isocyanate functional groups Using a polyisocyanate composition as a sample, the average number of isocyanate functional groups is the number of isocyanate functional groups statistically contained in one molecule of polyisocyanate, and is calculated from the number average molecular weight of the organic polyisocyanate measured in (Physical Property 2) and the isocyanate group content measured in (Physical Property 1) according to the following formula (iii).

[0022] Average functionality = number average molecular weight of organic polyisocyanate × isocyanate group content (mass%) / 100% / 42 (iii)

[0023] <2.(b) Polycarbonate diol> The method for producing the polycarbonate diol (b) used in the polyurethane resin and / or polyurea resin of this embodiment is not particularly limited, but includes, for example, a step of obtaining a polycarbonate diol by polycondensation through transesterification in the presence of a transesterification catalyst using a dihydroxy compound and a carbonate ester as raw material monomers, and the transesterification catalyst preferably contains at least one metal (M1) selected from the group consisting of metals of Groups 6, 7, 8, 9, 10 and 11 of the long-form periodic table. The method for producing the polycarbonate diol (b) used in the polyurethane resin and / or polyurea resin of this embodiment is preferable because the polycarbonate diol can be efficiently produced by using such a transesterification catalyst containing a specific metal.

[0024] In addition, it is more efficient (specifically, for example, under milder reaction conditions and in a shorter time) and more preferable that the transesterification catalyst comprises a transesterification catalyst A1 containing at least one metal (M1) selected from the group consisting of metals in Groups 6, 7, 8, 9, 10 and 11 of the long-form periodic table, and a transesterification catalyst A2 containing at least one metal (M2) selected from the group consisting of metals in Group 1 of the long-form periodic table.

[0025] The method for producing the polycarbonate diol (b) used for the polyurethane resin and / or polyurea resin of the present embodiment can efficiently produce a polycarbonate diol by using at least two kinds of transesterification catalysts containing specific metals as described above, and is more preferable because it 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 that is less discolored when used for, for example, synthetic leather, paint, coating agent, adhesive, pressure sensitive adhesive, etc.

[0026] <2-1. Raw material monomer> The method for producing the polycarbonate diol (b) used in this embodiment uses a dihydroxy compound and a carbonate ester as raw material monomers.

[0027] <2-1-1. Dihydroxy compounds> In the method for producing polycarbonate diol (b) used in the present embodiment, the dihydroxy compound serving as the raw material monomer is not particularly limited, and examples thereof include linear terminal dihydroxy compounds such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, and 1,20-eicosanediol; dihydroxy compounds having an ether group such as diethylene glycol, triethylene glycol, tetraethylene glycol, polypropylene glycol, and polytetramethylene glycol; thioether diols such as bishydroxyethyl thioether; 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, and the like. 2,2-Dialkyl-substituted 1,3-propanediol, such as 2,2-dialkyl glycol, 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 abbreviated as neopentyl glycol), 2-ethyl-2-butyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol and 2-pentyl-2-propyl-1,3-propanediol. Propanediols (hereinafter sometimes referred to as 2,2-dialkyl-1,3-propanediols); tetraalkyl-substituted alkylenediols such as 2,2,4,4-tetramethyl-1,5-pentanediol and 2,2,9,9-tetramethyl-1,10-decanediol, and dihydroxy compounds containing a cyclic group such as 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane;Dihydroxy compounds having branched chains such as 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)thioether, and 2,2,4,4-tetramethyl-3-cyano-1,5-pentanediol; 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 4,4-dicyclohexyldimethylmethanediol, 2,2'-bis(4-hydroxycyclohexyl)propane, 1,4-di Dihydroxy compounds having a cyclic group in the molecule, such as hydroxyethylcyclohexane, isosorbide, spiroglycol, 2,5-bis(hydroxymethyl)tetrahydrofuran, 4,4'-isopropylidenedicyclohexanol, and 4,4'-isopropylidenebis(2,2'-hydroxyethoxycyclohexane); dihydroxy compounds having an aromatic ring, such as 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy-2-methyl)phenyl)fluorene, nitrogen-containing dihydroxy compounds, such as diethanolamine and N-methyl-diethanolamine; and sulfur-containing dihydroxy compounds, such as bis(hydroxyethyl)sulfide;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-bis(4-hydroxyphenyl)pentane, 2,4'-dihydroxy-diphenylmethane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane, 1,1-bis(4-hydroxyphenyl)pentane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane, bis(4-hydroxyphenyl)pentane ... aromatic bisphenols such as 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;

[0028] In particular, from the viewpoint of weather resistance of polyurethane resins and polyurea resins obtained by using the polycarbonate diol (b) 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). [ka] (In the formula, R1 represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 20 carbon atoms.)

[0029] Among these dihydroxy compounds, the aliphatic dihydroxy compounds are particularly preferably 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, and 2-methyl-1,8-octanediol, and the alicyclic dihydroxy compounds are particularly preferably 1,4-cyclohexanedimethanol and tricyclodecanedimethanol.Of these dihydroxy compounds, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are more preferred because the resulting aqueous polyurethane resin and polyurea resin have excellent flexibility.

[0030] These dihydroxy compounds may be used alone or in combination of two or more depending on the required performance of the resulting polycarbonate diol, but it is preferable to combine a plurality of them to form a copolymer polycarbonate diol. The copolymer polycarbonate diol is generally inhibited from crystallizing, has higher fluidity than homopolycarbonate diol, and is excellent in operability when processed into polyurethane resin and polyurea resin, and can impart flexibility and texture to the polyurethane resin and polyurea resin.

[0031] Regarding the composition ratio of copolymerization, for example, when two kinds of 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 even more preferably 30 mol% or more relative to the total dihydroxy compounds. When two or more kinds of dihydroxy compounds are used, it is more preferable to use at least two kinds of dihydroxy compounds selected from 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol, because the obtained aqueous polyurethane resin and polyurea resin have excellent flexibility.

[0032] <2-1-2. Carbonate ester> In the method for producing the polycarbonate diol (b) used in this embodiment, the carbonate ester usable as the raw material monomer is not limited as long as the effect of the present invention is not lost, and examples thereof include dialkyl carbonate, diaryl carbonate, and alkylene carbonate.

[0033] Among the carbonate esters that can be used in the method for producing the polycarbonate diol (b) used in this embodiment, specific examples of dialkyl carbonates are not particularly limited, but include, for example, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diisobutyl carbonate, ethyl-n-butyl carbonate, and ethyl isobutyl carbonate.

[0034] Examples of diaryl carbonates include, but are not limited to, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, di-m-cresyl carbonate, and the like.

[0035] Specific examples of alkylene carbonates include, but are not 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. These may be used alone or in combination of two or more.

[0036] Among these carbonate esters, dimethyl carbonate, diethyl carbonate, ethylene carbonate, and diphenyl carbonate are particularly preferred because they are available inexpensively as industrial raw materials, have good reactivity, and produce small amounts of alcohol as by-products.

[0037] <2-1-3. Usage ratio of raw material monomers> In the method for producing the polycarbonate diol (b) used in this embodiment, the amount of carbonate ester used must be appropriately changed depending on the target molecular weight of the polycarbonate diol, and is not particularly limited, but the lower limit is usually preferably 0.5, more preferably 0.7, and even more preferably 0.8 in terms of the molar ratio relative to 1 mole of the total of dihydroxy compounds, and the upper limit is usually 1.5, preferably 1.3, and more preferably 1.2. When the amount of carbonate diester used is less than the upper limit, the proportion of the polycarbonate diol whose terminal group is not a hydroxyl group can be suppressed, or the polycarbonate diol (b) used in this embodiment whose molecular weight is in a predetermined range tends to be produced, and when the amount is more than the lower limit, polymerization tends to proceed up to the predetermined molecular weight.

[0038] <2-2. Transesterification catalyst> The method for producing the polycarbonate diol (b) used in the present embodiment is not particularly limited, but it is preferable to use an ester exchange catalyst containing at least one metal (M1) selected from the group consisting of metals of Groups 6, 7, 8, 9, 10 and 11 of the long form periodic table.

[0039] One form of the transesterification catalyst containing at least one metal (M1) selected from the group consisting of metals of Groups 6, 7, 8, 9, 10 and 11 of the long form periodic table is preferably at least one metal complex and / or a hydrate thereof represented by the following formula (2): [ka] (In the formula, R2 and R4 each independently represent a monovalent hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group of R2 and R4 may be substituted with a halogen atom or may have an oxygen atom; R3 represents hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group of R3 may be substituted with a halogen atom or may have an oxygen atom; M1 represents at least one metal selected from the group consisting of metals of groups 6, 7, 8, 9, 10 and 11 of the long form periodic table; and n is 1, 2 or 3. The metal complex represented by formula (2) may be an association of a plurality of metals.)

[0040] The metal (M1) selected from the group consisting of groups 6, 7, 8, 9, 10 and 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 these, manganese is particularly preferred.

[0041] In addition, together with the transesterification catalyst represented by formula (2), it is also possible to use, as an auxiliary, a basic compound such as a transition metal compound, a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound.

[0042] In the present embodiment, the organometallic complexes with acetylacetone analogues used as transesterification catalysts can also be used as hydrates.

[0043] Another embodiment of the transesterification catalyst containing at least one metal (M1) selected from the group consisting of metals in groups 6, 7, 8, 9, 10, and 11 of the long periodic table is preferably a salt of at least one carboxylic acid and at least one metal (M1) selected from the group consisting of metals in groups 6, 7, 8, 9, 10, and 11 of the long periodic table and / or a hydrate thereof, as represented by the following formula (3): [ka] (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 or may have an oxygen atom.)

[0044] The carboxylic acid is not particularly limited, but examples thereof include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, palmitic acid, margaric acid, stearic acid, and the like. Of these, acetic acid, propionic acid, and butyric acid are preferred, and acetic acid is particularly preferred.

[0045] The metal (M1) selected from the group consisting of groups 6, 7, 8, 9, 10 and 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 these, manganese is particularly preferred.

[0046] In the present embodiment, the salts of these carboxylic acids used as the transesterification catalyst may also be used as hydrates.

[0047] The amount of the transesterification catalyst used in this embodiment, as the total amount of the metal (M1), is 0.5 ppm, preferably 1 ppm, more preferably 2 ppm, and the upper limit is 20 ppm, preferably 10 ppm, more preferably 7 ppm, based on the total amount of all dihydroxy compounds and carbonate esters. When the amount of the transesterification catalyst is 0.5 ppm or more in total amount as the metal (M1), the reaction rate of transesterification tends to be faster. In addition, when the amount of the transesterification catalyst is 20 ppm or less in 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 polyurethane resin and / or polyurea resin of this embodiment, the urethanization reaction tends to be stable, and when used in synthetic leather, paint, coating agent, adhesive, pressure sensitive adhesive, etc., the polyurethane resin and / or polyurea resin of this embodiment that is less discolored can be provided, which is more preferable.

[0048] 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, but it is more preferable to use the above-mentioned transesterification catalyst A1 in combination with the transesterification catalyst A2 containing at least one metal (M2) selected from the group consisting of metals in Group 1 of the long periodic table.

[0049] The metal of Group 1 of the long periodic table is not particularly limited, but examples thereof include lithium, sodium, potassium, rubidium, cesium, and francium. Among these, lithium, sodium, and potassium are preferred because of their high catalytic activity. Lithium is particularly preferred because it has high activity and produces a polycarbonate diol with a small amount of ether bonds.

[0050] The form of the transesterification catalyst A2 containing at least one metal (M2) selected from the group consisting of metals in Group 1 of the long form periodic table is not particularly limited, and examples thereof include salts with inorganic acids, salts with organic acids, alcoholates of various alcohols, and hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and titanium hydroxide.

[0051] Among these, an alcoholate of at least one alcohol and at least one metal (M2) selected from the group consisting of metals in Group 1 of the long form periodic table, as represented by the following formula (4), is preferred because it has high catalytic activity and little coloration. [ka] (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 or may have an oxygen atom.)

[0052] The alcoholate of at least one alcohol and a metal of Group 1 of the long periodic table represented by formula (4) is not particularly limited, and examples thereof include lithium methylate (lithium methoxide), lithium ethylate (lithium ethoxide), lithium propoxide, lithium butoxide, sodium methylate (sodium methoxide), sodium ethylate (sodium ethoxide), sodium propoxide, sodium butoxide, potassium methylate (potassium methoxide), potassium ethylate (potassium ethoxide), potassium propoxide, potassium butoxide, rubidium methoxide, rubidium ethoxide, cesium methoxide, cesium ethoxide, etc. Among these alcoholates, lithium methylate, lithium ethylate, sodium methylate, and sodium ethylate are preferred, as they have high catalytic activity and produce polycarbonate diol with a small amount of ether bonds and little coloring, and lithium methylate and lithium ethylate are particularly preferred.

[0053] In the method for producing the polycarbonate diol (b) used for the polyurethane resin and / or polyurea resin of the present embodiment, there is no particular limitation, but when at least two kinds of transesterification catalysts, namely, a transesterification catalyst A1 containing at least one metal (M1) selected from the group consisting of metals of Groups 6, 7, 8, 9, 10 and 11 of the long 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 periodic table, are used in combination, the amount of the transesterification catalyst A1 used, as the total amount of the metal (M1), is preferably 0.5 ppm, more preferably 1 ppm, even more preferably 2 ppm, and is preferably 20 ppm, more preferably 10 ppm, even more preferably 7 ppm, based on the total amount of all dihydroxy compounds and carbonate esters.

[0054] The amount of the transesterification catalyst A2, in terms of the total amount of the metal (M2), relative to the total amount of all dihydroxy compounds and carbonate esters, has a lower limit of preferably 0.05 ppm, more preferably 0.2 ppm, even more preferably 0.5 ppm, and particularly preferably 1 ppm, and an upper limit of preferably 10 ppm, more preferably 5 ppm, and even more preferably 3 ppm.

[0055] When the amount of transesterification catalyst A1 is 0.5 ppm or more in total as metal (M1), the reaction rate of transesterification tends to be faster. When the amount of transesterification catalyst is 20 ppm or less in total as metal (M1), the (b) polycarbonate diol used in polyurethane resin and / or polyurea resin is less colored during storage, and when used in, for example, synthetic leather, paint, coating agent, adhesive, pressure sensitive adhesive, etc., it is more preferable to provide polyurethane resin and / or polyurea resin that is less discolored.

[0056] In addition, when the amount of the transesterification catalyst A2 is 0.05 ppm or more in total as the metal (M2), the reaction rate of transesterification tends to be faster. In addition, when the amount of the transesterification catalyst is 10 ppm or less in total as 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 reaction tends to be stable, the color tone of the obtained urethane becomes good, and the heat resistance tends to be improved.

[0057] <2-3. Method for producing polycarbonate diol> In this embodiment, it is preferable to produce a polycarbonate diol by transesterifying one or more of the dihydroxy compounds described above with one or more of the carbonate esters described above in the presence of the transesterification catalyst described above.

[0058] <2-3-1. Reaction conditions, etc.> The method for charging the reaction raw materials is not particularly limited, and the method can be freely selected from the following methods: one or more dihydroxy compounds, a carbonate ester, and a catalyst are all charged at the same time and subjected to a reaction; when the carbonate ester is a solid, the carbonate ester is first charged and heated to melt, and then the dihydroxy compound and the catalyst are added; and conversely, when the dihydroxy compound is a solid, the dihydroxy compound is first charged and melted, and then the carbonate ester and the catalyst are added.

[0059] The reaction temperature during the transesterification reaction can be arbitrarily selected as long as it is a temperature at which a practical reaction rate can be obtained. The temperature is not particularly limited, but the lower limit is preferably 80°C, more preferably 110°C, and even more preferably 130°C. The upper limit of the reaction temperature is preferably 220°C, more preferably 200°C, even more preferably 180°C, and particularly preferably 170°C. When the reaction temperature is equal to or higher than the lower limit, the transesterification reaction tends to proceed at a practical rate. When the reaction temperature is equal to or lower than the upper limit, the coloring of the resulting polycarbonate diol can be suppressed, the formation of ether bonds can be suppressed, and the quality tends to be improved, such as the turbidity being improved.

[0060] In particular, the method for producing the polycarbonate diol (b) used for the polyurethane resin and / or polyurea resin of the present embodiment uses a transesterification catalyst containing a specific metal (M1) and having higher activity than conventional methods, and thereby can efficiently produce a polycarbonate diol in a short time under mild reaction conditions, for example, even at a low temperature of 160° C. or lower (preferably 150° C. or lower).

[0061] The reaction can be carried out at normal pressure, but the transesterification reaction is an equilibrium reaction, and the reaction can be biased toward the product system by distilling off the monohydroxy compound or dihydroxy compound produced outside the system. Therefore, it is usually preferable to adopt reduced pressure conditions in the latter half of the reaction to carry out the reaction while distilling off the monohydroxy compound or dihydroxy compound produced. Alternatively, it is also possible to carry out the reaction while distilling off the monohydroxy compound or dihydroxy compound produced by gradually lowering the pressure from the middle of the reaction. If the pressure is gradually lowered from the middle of the reaction, the volatilization of the low-boiling unreacted monomer can be suppressed, the yield is improved, and a polycarbonate diol with a predetermined molecular weight is obtained, or in the case of copolymerization, a polycarbonate diol with a predetermined copolymerization composition ratio is obtained.

[0062] The pressure during the reaction is appropriately selected depending on the type of alcohol derived from the carbonate ester to be distilled, and for example, when the alcohol to be distilled has a relatively low boiling point such as methanol, the pressure of the reactor is preferably 5 kPa to normal pressure, more preferably 7 kPa to 15 kPa. When the alcohol to be distilled has a relatively high boiling point such as ethylene glycol, the pressure of the reactor is preferably 1 to 10 kPa, more preferably 3 kPa to 7 kPa.

[0063] Furthermore, in order to prevent the distillation of the raw materials in the early stage of the reaction, the reactor may be equipped with a rectification column having a theoretical number of 10 or more, preferably 15 or more, and more preferably 20 or more, so that the monohydroxy compound or dihydroxy compound produced by the reaction from the carbonate ester can be efficiently separated and distilled off while refluxing and separating the raw material carbonate ester and dihydroxy compound, by azeotropy. In this case, the raw material monomers charged are not lost and the quantitative ratio of the reagents can be accurately adjusted, which is preferable.

[0064] In addition, at the final stage of the reaction, it is usually preferable to switch to simple distillation and increase the degree of vacuum to carry out the reaction, since this makes it possible to efficiently distill off by-produced alcohols, diols, phenols, and other monohydroxy compounds or dihydroxy compounds, residual monomers such as carbonate esters, and further cyclic carbonates (cyclic oligomers) which may cause turbidity.

[0065] In this case, the reaction pressure at the end of the reaction is not particularly limited, but 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 off these low-boiling components, the reaction can also be carried out while passing a small amount of an inert gas such as nitrogen, argon, or helium into the reaction system.

[0066] When a carbonate ester or a dihydroxy compound having a low boiling point is used in the transesterification reaction, the reaction may be carried out at a temperature close to the boiling point of the carbonate diester or dihydroxy compound in the early stage of the reaction, and the temperature may be gradually increased as the reaction proceeds to further proceed. This is preferable because it is possible to prevent the distillation of the unreacted carbonate diester or dihydroxy compound in the early stage of the reaction.

[0067] <2-3-2. Polymerization reactor> The polymerization reaction (polycondensation reaction) can be carried out either batchwise or continuously. The apparatus used may be any of tank, tube, and tower types, and known polymerization tanks equipped with various stirring blades can be used. There are no particular limitations on the atmosphere during the temperature rise of the apparatus, but from the viewpoint of product quality, it is preferable to carry out the reaction in an inert gas such as nitrogen gas under normal pressure or reduced pressure.

[0068] <2-3-3. Reaction time> In the method for producing the polycarbonate diol (b) used in the polyurethane resin and / or polyurea resin of the present embodiment, the time required for the ester exchange reaction (polymerization reaction or polycondensation reaction) varies greatly depending on the types and amounts of the dihydroxy compound, carbonic acid diester, and ester exchange catalyst used, and therefore cannot be generally specified, but the reaction time required to reach a predetermined molecular weight is preferably 30 hours or less, more preferably 20 hours or less, and even more preferably 10 hours or less.

[0069] <2-3-4. Catalyst deactivation> As described above, when a transesterification catalyst is used in the transesterification reaction, the transesterification catalyst or its residue remains in the polycarbonate diol obtained, which may cause discoloration because the reaction cannot be controlled during the polyurethane reaction. In order to suppress the influence of the remaining catalyst, a catalyst deactivator, such as an acidic compound or a phosphorus-based or sulfur-based compound that decomposes to an acidic compound, may be added in an amount approximately equal to the molar amount of the transesterification catalyst used. Furthermore, if the catalyst is heated after the addition as described below, the transesterification catalyst can be efficiently deactivated. In addition, the color development derived from the transesterification catalyst can be reduced by deactivating the catalyst, and a polycarbonate diol can be obtained in which the Hazen color number measured in accordance with JIS-K0071-1 (1998) is preferably 50 or less, more preferably 30 or less, and even more preferably 20 or less.

[0070] In addition, the addition of a catalyst deactivator can suppress coloration and changes in physical properties that occur due to changes in the terminal structure and skeleton of the polycarbonate diol and the remaining catalyst when the obtained polycarbonate diol composition is stored or handled at high temperature for a long period of time.

[0071] The compound used for inactivating the transesterification catalyst (hereinafter sometimes referred to as a catalyst deactivator) is not particularly limited, but 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, sulfonate esters, etc. These may be used alone or in combination of two or more.

[0072] The amount of the catalyst deactivator used is not particularly limited, but as described above, it is sufficient that the amount is approximately equimolar to the amount of the transesterification catalyst used. Specifically, the upper limit is preferably 5 mol, more preferably 2 mol, and the lower limit is preferably 0.8 mol, more preferably 1.0 mol, relative to 1 mol of the transesterification catalyst used.

[0073] Inactivation of the transesterification catalyst by adding a catalyst deactivator can be carried out at room temperature, but is more efficient when heated. The temperature of this heat treatment is not particularly limited, but the upper limit is preferably 140°C, more preferably 130°C, and even more preferably 120°C, and the lower limit is preferably 80°C, more preferably 100°C, and even more preferably 110°C. At temperatures above the lower limit, the time required for deactivation of the transesterification catalyst is short and efficient, and the degree of deactivation is sufficient. On the other hand, at temperatures below 140°C, when a phosphorus-based compound is used as a deactivator, decomposition of the phosphorus-based compound can be suppressed, and deactivation tends to be stable. Therefore, coloration of the resulting polycarbonate diol can be suppressed, and when used as a urethane raw material, the urethane reaction tends to be stable.

[0074] The time for the reaction with the catalyst deactivator is not particularly limited, but is, for example, 1 to 5 hours.

[0075] <2-4.(b) Physical properties of polycarbonate diol> Preferred physical properties of the (b) polycarbonate diol used in the polyurethane resin and / or polyurea resin of this embodiment will be described below.

[0076] <2-4-1.Molecular weight / molecular weight distribution> The lower limit of the number average molecular weight (Mn) of the (b) polycarbonate diol used in the polyurethane resin and / or polyurea resin of this embodiment is 250, preferably 500, more preferably 750, and even more preferably 1000. On the other hand, the upper limit of the number average molecular weight (Mn) of the (b) polycarbonate diol used in the polyurethane resin and / or polyurea resin of this embodiment is 3000, preferably 2500, more preferably 2100, and particularly preferably 2000. When the number average molecular weight of the polycarbonate diol is equal to or higher than the above lower limit, the flexibility and the like tend to be good when the polycarbonate diol is made into a polyurethane resin and / or a polyurea resin. On the other hand, when the number average molecular weight of the (b) polycarbonate diol is equal to or lower than the above upper limit, the viscosity of the polycarbonate diol tends to decrease, and handling during polyurethane formation tends to be easier. The number average molecular weight (Mn) of the polycarbonate diol (b) used in this embodiment is preferably in the range of 250 to 3,000, more preferably 500 to 2,500, further preferably 750 to 2,100, and particularly preferably 1,000 to 2,000.

[0077] Here, the number average molecular weight of the polycarbonate diol is determined from the hydroxyl value (average hydroxyl value) of the polycarbonate diol, as shown in the examples given later.

[0078] The method for controlling the number average molecular weight (Mn) of the polycarbonate diol within the above range is not particularly limited, but 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 and adjusting the amount of the dihydroxy compound, which is a raw material monomer, to be extracted.

[0079] <2-4-2.APHA value> The color of the (b) polycarbonate diol used in the polyurethane resin and / or polyurea resin of this embodiment is preferably 50 or less, more preferably 40 or less, even more preferably 30 or less, and particularly preferably 20 or less, in terms of 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, but 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 from the polycarbonate diol as a raw material tends to be good, the commercial value is improved, and the thermal stability is good. The preferred range of the APHA value of the (b) polycarbonate diol is 10 to 50, preferably 10 to 40, and more preferably 10 to 30.

[0080] (b) The method for controlling the APHA value of the polycarbonate diol within the above range is not particularly limited, but examples thereof include a method in which the reaction temperature during the ester exchange reaction is within the above preferred temperature range, and a method in which the time required for the ester exchange reaction (polymerization reaction or polycondensation reaction) is within the above preferred range.

[0081] In this embodiment, the APHA value of the polycarbonate diol can be measured by the method described in the Examples below.

[0082] <2-4-3. Metals contained in polycarbonate diol> The (b) polycarbonate diol used in 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 in groups 6, 7, 8, 9, 10 and 11 of the long form periodic table.

[0083] In the (b) polycarbonate diol used in the polyurethane resin and / or polyurea resin of this embodiment, the lower limit of the total amount of at least one metal (M1) selected from the group consisting of metals in groups 6, 7, 8, 9, 10 and 11 of the long form periodic table is 1 ppm, preferably 2 ppm, more preferably 5 ppm, and the upper limit is 25 ppm, preferably 20 ppm, more preferably 15 ppm, and even more preferably 10 ppm.

[0084] The (b) polycarbonate diol used for the polyurethane resin and / or polyurea resin of this embodiment has a metal (M1) content of 1 ppm or more in total, and the APHA value is low, and when used as a raw material for polyurethane resin and / or polyurea resin, the reaction rate of urethanization tends to improve. In addition, the (b) polycarbonate diol used for the polyurethane resin and / or polyurea resin of this embodiment has a metal (M1) content of 25 ppm or less in total, and can suppress the coloring of the (b) polycarbonate diol due to heating, and can provide a polyurethane resin and / or polyurea resin that is less colored during storage and less discolored when used, for example, in synthetic leather, paint, coating agent, adhesive, pressure sensitive adhesive, etc., and is more preferable.

[0085] The polycarbonate diol (b) used in the polyurethane resin and / or polyurea resin of the present embodiment preferably contains at least one metal (M1) selected from molybdenum, manganese, iron, cobalt, nickel, and copper. Among these, the metal is more preferably manganese.

[0086] The metals contained in these polycarbonate diols may be present as residues of the polymerization catalyst, but may also be intentionally added in a predetermined amount after production.

[0087] In the (b) polycarbonate diol used in the polyurethane resin and / or polyurea resin of this embodiment, when at least one metal (M2) selected from the group consisting of metals in Group 1 of the long periodic table is contained, the lower limit of the total amount of the metal is preferably 0.1 ppm, more preferably 0.5 ppm, even more preferably 0.7 ppm, and particularly preferably 1 ppm, and the upper limit is preferably 12.5 ppm, more preferably 10 ppm, even more preferably 5 ppm, and particularly preferably 3 ppm.

[0088] The (b) polycarbonate diol used in the polyurethane resin and / or polyurea resin of this embodiment has a total content of metal (M2) of 0.1 ppm or more, and when used as a raw material for urethane, the APHA value is low, and the reaction rate of urethane formation tends to improve. In addition, the (b) polycarbonate diol used in the polyurethane resin and / or polyurea resin of this embodiment has a total content of metal (M2) of 12.5 ppm or less, and can suppress the coloring of the (b) polycarbonate diol due to heating, and can provide a polyurethane resin and / or polyurea resin that is less colored during storage and less discolored when used in, for example, synthetic leather, paint, coating agent, adhesive, pressure sensitive adhesive, etc., and is more preferable.

[0089] The metal (M2) contained in the polycarbonate diol (b) used in the polyurethane resin and / or polyurea resin of this embodiment is preferably at least one metal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and francium. Among these, at least one metal selected from the group consisting of lithium, sodium, and potassium is more preferable, and lithium is particularly preferable.

[0090] The metals contained in these polycarbonate diols may be present as residues of the polymerization catalyst, but may also be intentionally added in a predetermined amount after production.

[0091] In this embodiment, the type and amount of metal contained in the polycarbonate diol can be measured by the method described in the Examples below.

[0092] <3.(c) Chain extender> As the (c) chain extender used in the polyurethane resin and / or polyurea resin of the present embodiment, for example, a dihydroxy compound and a diamine compound are preferably used.

[0093] As the dihydroxy compound, aliphatic dihydroxy compounds and alicyclic dihydroxy compounds are preferred. The dihydroxy compound is not particularly limited, but examples thereof include linear terminal dihydroxy compounds such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, and 1,20-eicosanediol; dihydroxy compounds having an ether group such as diethylene glycol, triethylene glycol, tetraethylene glycol, polypropylene glycol, and polytetramethylene glycol; bishydroxyethylene glycol; thioether diols 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 abbreviated 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 alkylenediols 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)thioether, and 2,2,4,4-tetramethyl-1,5-pentanediol. dihydroxy compounds having a branched chain, such as ethyl-3-cyano-1,5-pentanediol; and 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, spiroglycol, 2,5-bis(hydroxymethyl)tetrahydrofuran, 4,4'-isopropylidenedicyclohexanol, and 4,4'-isopropylidenebis(2,2'-hydroxyethoxycyclohexane), 4,4'-biscyclohexanediol.

[0094] From the viewpoint of obtaining a polyurethane resin having excellent tensile strength at break, abrasion resistance, chemical resistance, and weather resistance, the chain extender (c) is more preferably a short-chain linear aliphatic diol such as ethylene glycol, 1,3-propanediol, or 1,4-butanediol, or an alicyclic diol such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, or 4,4'-biscyclohexanediol.

[0095] Specific examples of the diamine compound include, but are not limited to, diamines such as ethylenediamine, propylenediamine, hexamethylenediamine, tolylenediamine, xylylenediamine, diphenyldiamine, diaminodiphenylmethane, 4,4'-methylenebis(cyclohexylamine), piperazine, isophoronediamine (IPDA), and 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA).

[0096] From the viewpoint of obtaining a polyurea resin having excellent tensile breaking strength, abrasion resistance, chemical resistance, and weather resistance, the chain extender (c) is more preferably an alicyclic diamine, and specifically, 4,4'-methylenebis(cyclohexylamine), isophoronediamine (IPDA), or 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA) is preferred.

[0097] <4. Method for synthesizing polyurethane resin and polyurea resin> The polyurethane resin and / or polyurea resin of the present embodiment can be synthesized by simultaneously reacting three types of compounds, namely, a polyisocyanate compound (a), a polycarbonate diol (b), and a chain extender (c), or by reacting a polyisocyanate compound (a) with a polycarbonate diol (b) in advance to form a prepolymer, and then adding a chain extender (c) to extend the chain.

[0098] As synthetic raw materials for the polyurethane resin and / or polyurea resin of the present embodiment, in addition to the above-mentioned components (a) to (c), other components, such as the later-described (d) carboxyl group- and / or sulfone group-containing polyol or a salt thereof, and known polyols, may be used in combination within a range that does not impair the effects of the present invention.

[0099] When three kinds of agents, ie, (a) a polyisocyanate compound, (b) a polycarbonate diol, and (c) a chain extender, are reacted simultaneously, the compounding ratio is preferably such that the total equivalent of the hydroxyl groups of the (b) polycarbonate diol and the hydroxyl groups and / or amino groups of the (c) chain extender is the NCO equivalent of the (a) polyisocyanate compound, that is, (total equivalent of the hydroxyl groups and amino groups) / NCO equivalent=1 / 0.5 to 1 / 1.5, and more preferably (total equivalent of the hydroxyl groups and amino groups) / NCO equivalent=1 / 0.8 to 1 / 1.2. In the case where the (a) polyisocyanate compound, the (b) polycarbonate diol, and the (c) chain extender are reacted simultaneously, the amount of the (c) chain extender is preferably 3 to 40 mass %, more preferably 5 to 25 mass %, based on the total mass of the (a) polyisocyanate and the (b) polycarbonate diol (a).

[0100] In the case of using a method in which (a) a polyisocyanate compound and (b) a polycarbonate diol are reacted in advance to form a prepolymer, and then a chain extender (c) is added to extend the chain, a prepolymer is synthesized from (b) polycarbonate diol and (a) polyisocyanate compound preferably at a compounding ratio OH / NCO (equivalent ratio) of 1 / 1.5 to 2.5, more preferably at a compounding ratio OH / NCO (equivalent ratio) of 1 / 1.8 to 2.2, and then the chain extender (c) is added in an amount of preferably 0.5 to 1.5, more preferably 0.8 to 1.2, hydroxyl and / or amino group equivalent per NCO equivalent of the obtained prepolymer to carry out chain extension.

[0101] Furthermore, together with the polycarbonate diol (b) used in the present embodiment, a known polyol may be used in combination within a range that does not impair the effects of the present invention. Examples of known polyols include known polyester and polyether polyols described in Yoshio Imai, Polyurethane Foam Polymer Publishing Society, 1987, pp. 12-23.

[0102] The method for producing the polyurethane resin and / or polyurea resin of the present embodiment is not particularly limited, and a conventionally known technique for urethane reaction or urea reaction 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 (c) chain extender at room temperature to 200°C.

[0103] In the production of these, it is possible to use known polymerization catalysts such as tertiary amines and organic metal salts of tin, titanium, etc. (for example, those described in Yoshida Keiji (Polyurethane Resin), Nihon Kogyo Shimbun, p. 23-32 (1969)). These reactions may be carried out using a solvent, and preferred solvents include dimethylformamide, diethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, methyl isobutyl ketone, dioxane, cyclohexanone, benzene, toluene, ethyl cellosolve, etc.

[0104] In addition, in producing the polyurethane resin and / or polyurea resin of this embodiment, a compound containing only one active hydrogen that reacts with an isocyanate group, for example, a monohydric alcohol such as ethyl alcohol or propyl alcohol, a primary amine such as n-propylamine, n-butylamine, n-pentylamine or n-hexylamine, or a secondary amine such as diethylamine or di-n-propylamine, can be used as an end terminator.

[0105] The additives used in the present embodiment are preferably stabilizers such as heat stabilizers and light stabilizers. The heat stabilizers are not particularly limited, but may be, for example, phosphoric acid, phosphorous acid, aliphatic, aromatic or alkyl group-substituted aromatic esters, hypophosphorous acid derivatives, phosphorus compounds such as phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonates, dialkyl pentaerythritol diphosphite, and dialkyl bisphenol A diphosphite; phenol derivatives, particularly hindered phenol compounds, sulfur-containing compounds such as thioethers, dithioacid salts, mercaptobenzimidazoles, thiocarbanilides, and thiodipropionates; and tin compounds such as tin maleates and dibutyltin monoxide.

[0106] Preferred hindered phenol compounds include Irganox 1010 (trade name: manufactured by Ciba-Geigy) and Irganox 1520 (trade name: manufactured by Ciba-Geigy). Preferred phosphorus compounds as secondary antiaging agents include PEP-36, PEP-24G, HP-10 (all trade names: manufactured by Asahi Denka Co., Ltd.) and Irgafos 168 (trade name: manufactured by Ciba-Geigy). Preferred sulfur compounds include thioether compounds such as dilauryl thiopropionate (DLTP) and distearyl thiopropionate (DSTP).

[0107] The light stabilizer is not particularly limited, but examples thereof include benzotriazole-based and benzophenone-based compounds, etc. Radical scavenging light stabilizers such as hindered amine compounds are also preferably used.

[0108] These stabilizers may be used alone or in combination of two or more kinds. 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 further preferably 0.2 to 2 parts by mass, based on 100 parts by mass of the polyurethane resin and / or the polyurea resin.

[0109] Furthermore, a plasticizer may be added to the polyurethane resin and / or polyurea resin of the present embodiment as necessary. Examples of such plasticizers are not particularly limited, but include phthalates such as dioctyl phthalate, dibutyl phthalate, diethyl phthalate, butyl benzyl phthalate, di-2-ethylhexyl phthalate, diisodecyl phthalate, diundecyl phthalate, and diisononyl phthalate; phosphates such as tricresyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, trimethylhexyl phosphate, tris-chloroethyl phosphate, and tris-dichloropropyl phosphate; and octyl trimellitate. fatty acid esters such as dioctyl ester, trimellitic acid isodecyl ester, trimellitic acid esters, dipentaerythritol esters, dioctyl adipate, dimethyl adipate, di-2-ethylhexyl azelate, dioctyl azelate, dioctyl sebacate, di-2-ethylhexyl sebacate, and methyl acetyl lysinocate; pyromellitic acid esters such as pyromellitic acid octyl ester; epoxy-based plasticizers such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized fatty acid alkyl esters; polyether-based plasticizers such as adipic acid ether ester and polyether; liquid rubbers such as liquid NBR, liquid acrylic rubber, and liquid polybutadiene; and non-aromatic paraffin oil.

[0110] These plasticizers can be used alone or in combination of two or more kinds. The amount of the plasticizer to be added is appropriately selected depending on the required hardness and physical properties, but is preferably 0 to 50 parts by mass per 100 parts by mass of the polyurethane resin and / or polyurea resin of the present embodiment.

[0111] The polyurethane resin and / or polyurea resin of the present embodiment may contain inorganic fillers, lubricants, colorants, silicone oil, foaming agents, flame retardants, etc. Examples of inorganic fillers include, but are not limited to, calcium carbonate, talc, magnesium hydroxide, mica, barium sulfate, silicic acid (white carbon), titanium oxide, carbon black, etc.

[0112] <Application> The polyurethane resin and / or polyurea resin of this embodiment has excellent physical properties, and therefore can be used for injection molded parts (grip parts, steering wheels, airbag storage covers, watch straps, etc.), extrusion molded products (hoses, tubes, sheets, etc.), or dissolved in a solvent for use as binders for synthetic leather, skin materials, surface treatment agents, fiber coating agents, various surface treatment agents, various adhesives, etc. In particular, the polyurethane resin and / or polyurea resin of this embodiment is preferably used for synthetic leather.

[0113] <Film> The film of the present embodiment is a film having a thickness of 10 μm to 500 μm, which is produced by molding the above-mentioned polyurethane resin and / or polyurea resin into a film shape.

[0114] Specific examples of the film of the present embodiment include, but are not limited to, extrusion-molded films of the above-mentioned polyurethane resin and / or polyurea resin, and cast films prepared by dissolving the above-mentioned polyurethane resin and / or polyurea resin in a solvent, coating and drying. The film of the present embodiment is excellent in flexibility, strength, abrasion resistance, chemical resistance, and low-temperature properties, and is less susceptible to discoloration, and is therefore suitable for use as a skin material or surface treatment agent for synthetic leather, which requires good appearance. EXAMPLES

[0115] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. Analytical methods and evaluations of physical properties in the following examples and comparative examples were performed according to the following test methods.

[0116] <Test Method> [(b) Measurement of hydroxyl (OH) value of polycarbonate diol] Acetic anhydride (12.5 g) was diluted with pyridine (50 mL) to prepare an acetylation reagent. 2.5 to 5.0 g of sample was precisely weighed into a 100 mL eggplant flask. 5 mL of acetylation reagent and 10 mL of toluene were added to the eggplant flask using a volumetric pipette, and then a cooling tube was attached and the solution in the eggplant flask was stirred and heated at 100°C for 1 hour. 2.5 mL of distilled water was added to the eggplant flask using a volumetric pipette, and the solution in the eggplant flask was heated and stirred for an additional 10 minutes. The solution in the eggplant flask was cooled for 2 to 3 minutes, and then 12.5 mL of ethanol was added. 2 to 3 drops of phenolphthalein were added to the eggplant flask as an indicator, and then the solution in the eggplant flask was titrated with 0.5 mol / L ethanolic potassium hydroxide. As a blank test, 5 mL of acetylation reagent, 10 mL of toluene, and 2.5 mL of distilled water were placed in a 100 mL eggplant flask, heated and stirred for 10 minutes, and titrated in the same manner as above. Based on this result, the hydroxyl (OH) value of the polycarbonate diol was calculated using the following formula (I). OH value (mg-KOH / g) = {(ba) x 28.05 x f} / e (I) a: titer of sample (mL) b: Titration volume of blank test (mL) e: Sample mass (g) f: factor of titrant

[0117] [Number average molecular weight (Mn)] The number average molecular weight of the polycarbonate diol was calculated by the following formula (II). Number average molecular weight = 2 / (OH value × 10 -3 / 56.11) (II)

[0118] [Measurement of APHA value] According to JIS K0071-1, the Hazen color number (APHA value) was measured by comparing with a standard solution placed in a colorimetric tube. For polycarbonate diol that is solid at room temperature, it was heated to 70°C, dissolved, and the APHA value was measured. The smaller the APHA value, the less coloring is evaluated.

[0119] [Residual amount of catalyst in polycarbonate diol] Approximately 0.1 g of polycarbonate diol was weighed out and dissolved in 4 mL of acetonitrile to obtain a solution. Then, 20 mL of pure water was added to the obtained solution to precipitate polycarbonate diol, and the precipitated polycarbonate diol was removed by filtration. The filtered solution was diluted with pure water to a predetermined concentration. The metal ion concentration in the diluted solution was analyzed by ion chromatography. The metal ion concentration of acetonitrile used as a solvent was measured as a blank value, and the metal ion concentration of this solvent was subtracted from the metal ion concentration in the diluted solution to obtain the metal ion concentration of the polycarbonate diol product. The measurement conditions were as shown below. The concentrations of various metals remaining in the polycarbonate diol were determined using the calibration curves of various metals prepared in advance. High-performance liquid chromatography (HPLC) measurement conditions Equipment: Waters 2690 Column: IonPac CS12A Flow rate: 1.0ml / min Injection amount: 1.5ml Pressure: 950~980psi Column temperature: 35℃ Detector sensitivity: RANGE 200μS Suppressor: CSRS 60mA Eluent: 20mmol / l methanesulfonic acid aqueous solution

[0120] <Evaluation method for polyurethane and / or polyurea resin film> [Tensile strength and elongation at break] A solution of 20% solid content polyurea resin in N,N-dimethylformamide (DMF) was applied onto a glass plate and heated at 80°C for 2 hours to prepare a film with a thickness of 40 μm. After leaving the film 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 to prepare a sample film. In a thermostatic chamber at 23°C, the tensile breaking strength (MPa), elongation at break (%), and stress at 100% elongation (100% modulus: MPa) of the sample film were measured at a chuck distance of 20 mm and a pulling speed of 10 mm / min using a Universal Testing Machine (Zwick Corp.). The lower the stress at 100% elongation, the softer and more flexible the film is evaluated to be.

[0121] [Chemical resistance] The film prepared in the same manner as in the above [Tensile breaking strength and breaking elongation] was immersed in oleic acid at 23°C for one week, after which the swelling ratio was measured. The swelling ratio was calculated using the following formula (III). The lower the swelling ratio (%), the better the chemical resistance is evaluated to be. Swelling ratio (%) = [(mass after test - mass before test) / mass before test] x 100 (III)

[0122] [Abrasion resistance] The abrasion resistance of the film prepared in the same manner as in [Tensile strength at break and elongation at break] above was measured using a Taber abrasion tester according to the method of JIS K5600-5-8. The change in mass (mg) between the mass of the coated plate before the abrasion test and the mass of the coated plate after the abrasion test (500 rotations) was measured and expressed. The smaller the mass change (mg), the better the abrasion resistance was evaluated.

[0123] [Coloring evaluation] A film was prepared in the same manner as in the above [Tensile strength at break and elongation at break]. The film was placed in a thermostatic chamber at 60°C for one month. The color difference of the film surface was measured using a spectrophotometer (CM-3700A) manufactured by Konica Minolta. * The smaller the value, the better the storage stability and the less discoloration.

[0124] [Compound abbreviation] The abbreviations for compounds in the following Examples and Comparative Examples are as follows. Mn(OAc)2·4H2O: Manganese(II) acetate tetrahydrate Mn(acac)2·2H2O: Manganese(II) acetylacetonate dihydrate Mn(acac)3: Manganese(III) acetylacetonate Mn(tBuCOCH2COtBu)2·2H2O: 2,2,6,6-tetramethyl-3,5-heptanedionate manganese(II) dihydrate Mn(CF3COCH2COCF3)2·2H2O: Manganese hexafluoroacetylacetonate dihydrate [Mo(acac)]2: Molybdenum(II) acetylacetonate dimer Fe(acac)3: Iron(III) acetylacetonate Co(acac)2·2H2O: Cobalt(II) acetylacetonate dihydrate Ni(acac)2·2H2O: Nickel(II) acetylacetonate dihydrate Cu(acac)2: Copper(II) acetylacetonate Ti(OBu)4: Tetra-n-butyl titanate Ti(acac)2(OiPr)2: Titanium(IV) bis(acetylacetonate) diisopropoxide Mg(acac)2·2H2O: Magnesium(II) acetylacetonate dihydrate Li-OMe: Lithium methoxide Na-OMe: Sodium methoxide K-OMe: Potassium methoxide Li-t-OBu: Lithium-t-butoxide EC: Ethylene carbonate DEC: Diethyl carbonate 14BDO: 1,4-butanediol 15PDO: 1,5-Pentanediol 16HDO: 1,6-Hexanediol

[0125] [Synthesis Example 1 of Polycarbonate Diol] In a 1L separable flask equipped with a stirrer, a thermometer, and a vacuum jacketed Oldershaw (15 theoretical plates) with a reflux head on top, 355g (3.00mol) of 1,6-hexanediol and 264g (3.00mol) of ethylene carbonate were charged as raw material monomers, and 13.8mg of manganese acetate (II) tetrahydrate was added as a catalyst (5ppm as metal amount relative to the total amount of all dihydroxy compounds and carbonate esters). The raw material in the flask was heated in an oil bath set at 160°C, and the raw material monomers were polycondensed by transesterification for 5 hours at an internal temperature of 140°C and a vacuum degree of 3kPa while removing a part of the distillate from the reflux head, to obtain a polycarbonate diol. Then, the distillation was switched to simple distillation, and the pressure was gradually reduced to 0.1 kPa. The temperature of the oil bath was set to 175°C, and the reaction was carried out for 3 hours at an internal temperature of 160°C in the flask, and the monomer was distilled to obtain a polycarbonate diol. After introducing nitrogen gas into the flask to normal pressure, the temperature of the oil bath was set to 125°C, and the internal temperature of the flask was set to 110 to 120°C. As a catalyst deactivator, monobutyl phosphate was added in an amount equivalent to the amount of the catalyst charged, and the mixture was stirred at a temperature of 110 to 120°C for 3 hours. The results of analyzing the obtained polycarbonate diol are shown in Table 1. The polycarbonate polyol is called PC1.

[0126] [Polycarbonate diol synthesis examples 2-10] A polycarbonate diol was obtained by polycondensing the raw material monomers through an ester exchange reaction in the same manner as in Synthesis Example 1, except that the type and amount of the catalyst added were the type and amount shown in Table 1. The analytical results are shown in Table 1. The obtained polycarbonate diols are called PC2 to PC10.

[0127] [Polycarbonate diol synthesis examples 11-13] A polycarbonate diol was obtained by polycondensing the raw material monomers by transesterification in the same manner as in Synthesis Example 1, except that the time for removing a part of the fraction from the reflux head was set to 12 hours at a vacuum degree of 3 kPa and the type and amount of the catalyst added were set to the types and amounts shown in Table 1. The analytical results are shown in Table 1. The obtained polycarbonate diols are called PC11 to PC13.

[0128] [Table 1]

[0129] [Synthesis Example 14] 355g (3.00mol) of 1,6-hexanediol and 264g (3.00mol) of ethylene carbonate were charged into a 1L separable flask equipped with a stirrer, a thermometer, and a vacuum jacketed Oldershaw type (15 theoretical plates) with a reflux head on top, and 13.8mg of manganese(II) acetate tetrahydrate and 6.7mg 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 for 4 hours at an internal temperature of 135°C and a vacuum degree of 3kPa while removing a part of the distillate from the reflux head, to obtain a polycarbonate diol. After that, the reaction was switched to simple distillation, and the pressure was gradually reduced to 0.1 kPa. The temperature of the oil bath was set to 165°C, and the reaction was carried out for 2 hours at an internal temperature of 150°C in the flask, and the monomer was distilled to obtain a polycarbonate diol. After introducing nitrogen gas to normal pressure, the temperature of the oil bath was set to 125°C, and the internal temperature of the flask was set to 110 to 120°C. As a catalyst deactivator, monobutyl phosphate was added in an amount equivalent to the amount of the catalyst charged, and the mixture was stirred at a temperature of 110 to 120°C for 3 hours. The results of analyzing the obtained polycarbonate diol are shown in Table 2. The polycarbonate diol is called PC14.

[0130] [Polycarbonate diol synthesis examples 15-26] Polycarbonate diols were obtained by polycondensing raw material monomers through transesterification in the same manner as in Synthesis Example 14, except that the type and amount of the catalyst added were the type and amount shown in Table 2. The analytical results are shown in Table 2. The obtained polycarbonate diols are called PC15 to PC26.

[0131] [Polycarbonate diol synthesis examples 27-29] A polycarbonate diol was obtained by polycondensing the raw material monomers by transesterification in the same manner as in Synthesis Example 14, except that the time for removing a part of the fraction from the reflux head was set to 12 hours at a vacuum degree of 3 kPa and the type and amount of the catalyst added were set to the types and amounts shown in Table 2. The analytical results are shown in Table 2. The obtained polycarbonate diols are called PC27 to PC29.

[0132] [Table 2]

[0133] [Synthesis Examples 30-33] A polycarbonate diol was obtained by polycondensing the raw material monomers by transesterification in the same manner as in Synthesis Example 14, except that the dihydroxy compound and carbonate ester used were of the types and amounts shown in Table 3. The properties of the obtained polycarbonate diol are shown in Table 3. The obtained polycarbonate diols are called PC30 to PC33, respectively.

[0134] [Synthesis Example 34] A polycarbonate diol was obtained by polycondensing the raw material monomers by transesterification in the same manner as in Synthesis Example 14, except that the dihydroxy compound and carbonate ester used were of the types and amounts shown in Table 3, and the reaction time after switching to simple distillation was 0.5 hours. The properties of the obtained polycarbonate diol are shown in Table 3. The obtained polycarbonate diol is called PC34.

[0135] [Synthesis Example 35] A polycarbonate diol was obtained by polycondensing the raw material monomers by transesterification in the same manner as in Synthesis Example 14, except that the dihydroxy compound and carbonate ester used were of the types and amounts shown in Table 3, and the reaction time after switching to simple distillation was 3 hours. The properties of the obtained polycarbonate diol are shown in Table 3. The obtained polycarbonate diol is called PC35.

[0136] [Synthesis Examples 36-39] A polycarbonate diol was obtained by polycondensing the raw material monomers by transesterification in the same manner as in Synthesis Example 14, except that the dihydroxy compound and carbonate ester used were of the types and amounts shown in Table 3. The properties of the obtained polycarbonate diol are shown in Table 3. The obtained polycarbonate diols are called PC36 to PC39, respectively.

[0137] [Table 3]

[0138] [Example 1] In a 500 mL separable flask equipped with a stirrer sealed with nitrogen gas, 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 charged and heated to 40 ° C to obtain a solution. In the flask, 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 was added as a catalyst were dropped over 30 minutes while stirring the solution. The reaction was carried out at 50 ° C for 2 hours while stirring to obtain a prepolymer with terminal isocyanate. After the temperature of the solution in the flask was lowered to room temperature, 6.8 g (0.04 mol) of isophoronediamine was added as a chain extender, and the reaction was carried out at room temperature for 1 hour. Then, 0.5 g of ethanol was added as a reaction terminator to obtain a DMF solution of polyurea resin (solid content approximately 20% by mass). The obtained N,N-dimethylformamide (DMF) solution of polyurea resin with a solid content of 20% by mass was applied to a glass plate and heated at 80°C for 2 hours to prepare a polyurea resin film with a thickness of 40 μm. After leaving it at room temperature for 24 hours, various physical properties were evaluated. The evaluation results are shown in Table 4.

[0139] [Examples 2 to 10] As shown in Table 4, polyurea resin films were obtained in the same manner as in Example 1, except that PC2 to PC10 were used as the polycarbonate diols, and the films were subjected to evaluation of various physical properties. The evaluation results are summarized in Table 4.

[0140] [Comparative Examples 1 to 3] As shown in Table 4, polyurea resin films were obtained in the same manner as in Example 1, except that PC11 to PC13 were used as the polycarbonate diols, and the films were subjected to evaluation of various physical properties. The evaluation results are summarized in Table 4.

[0141] [Table 4]

[0142] [Examples 11 to 23, Comparative Examples 4 to 6] As shown in Table 5, except that PC14, PC15, PC16, PC17, PC18, PC19, PC20, PC21, PC22, PC23, PC24, PC25, PC26, PC27, PC28, and PC29 were used instead of polycarbonate diol PC1, reactions were carried out in the same manner as in Example 1 to obtain polyurea resin films, which were then subjected to evaluation of various physical properties. The physical properties of the obtained polyurea resins are summarized in Table 5.

[0143] [Table 5]

[0144] [Examples 24 to 33] As shown in Table 6, except that PC30, PC31, PC32, PC33, PC34, PC35, PC36, PC37, PC38, and PC39 were used instead of polycarbonate diol PC1, the reaction was carried out in the same manner as in Example 1 to obtain polyurea resin films, which were then subjected to evaluation of various physical properties. The physical properties of the obtained polyurea resins are summarized in Table 6.

[0145] [Table 6]

[0146] [Examples 34 to 39] Except for using PC32 as the polycarbonate diol, and using the isocyanate and chain extender shown in Table 7, polyurethane resin and polyurea resin films were obtained in the same manner as in Example 1, and subjected to evaluation of various physical properties. The evaluation results are shown in Table 7. Note that polyurethane resins were synthesized in Examples 36 and 37, in which a diol was used as the chain extender. Also, polyurea resins were synthesized in Examples 34, 35, 38, and 39, in which a diamine was used as the chain extender.

[0147] [Table 7] [Industrial Applicability]

[0148] The polyurea resin and polyurethane resin of the present invention have excellent various physical properties and excellent coloring stability, and therefore can be used, for example, in injection molded parts (grip parts, steering holes, airbag storage covers, watch straps, etc.), extrusion molded products (hoses, tubes, sheets, etc.), or by dissolving them in a solvent, can be used as binders for synthetic leather, skin materials, surface treatment agents, fiber coating agents, various surface treatment agents, various adhesives, etc.

Claims

1. A reaction product of a polyisocyanate compound (a), a polycarbonate diol (b) and a chain extender (c), The polyisocyanate compound (a) is an organic polyisocyanate compound having an average number of isocyanate groups in one molecule of 2.5 or less, The (b) polycarbonate diol is a polycondensate obtained by an ester exchange reaction between a dihydroxy compound and a carbonate ester, 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 in Groups 6, 7, 8, 9, 10, and 11 of the long form periodic table in a total amount of 1 ppm to 25 ppm, The polycarbonate diol (b) has a Hazen color number of 50 or less as measured in accordance with JIS-K0071-1 (1998).

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

3. The polyurea resin according to claim 1 , wherein the (a) organic polyisocyanate compound is an aliphatic organic diisocyanate compound and / or an alicyclic organic diisocyanate compound.

4. The polyurea resin of claim 1 , wherein the chain extender (c) is a cycloaliphatic diamine.

5. A reaction product of a polyisocyanate compound (a), a polycarbonate diol (b) and a chain extender (c), The polyisocyanate compound (a) is an organic polyisocyanate compound having an average number of isocyanate groups in one molecule of 2.5 or less, The (b) polycarbonate diol is a polycondensate obtained by an ester exchange reaction between a dihydroxy compound and a carbonate ester, 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 in Groups 6, 7, 8, 9, 10, and 11 of the long form periodic table in a total amount of 1 ppm to 25 ppm, The polyurethane resin (b) has a Hazen color number of 50 or less as measured in accordance with JIS-K0071-1 (1998).

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

7. The polyurethane resin according to claim 5 , wherein the (a) organic polyisocyanate compound is an aliphatic organic diisocyanate compound and / or an alicyclic organic diisocyanate compound.

8. The polyurethane resin according to claim 5 , wherein the chain extender (c) is a cycloaliphatic diamine.

9. A film having a thickness of 10 μm to 500 μm, obtained by molding the polyurea resin according to any one of claims 1 to 4 and / or the polyurethane resin according to any one of claims 5 to 8 into a film.

10. A synthetic leather using the polyurea resin according to any one of claims 1 to 4 and / or the polyurethane resin according to any one of claims 5 to 8.

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