JP2022071425A - Polycarbonate polyol and polyurethane resin - Google Patents

Abstract

To provide a polycarbonate polyol that can give a polyurethane resin having a good balance between strength and flexibility and having excellent hydrolysis resistance.SOLUTION: A polycarbonate polyol has a structure derived from an aliphatic diol, a structure derived from a polyhydric alcohol with three or more functional hydroxy groups, and a structure derived from a carbonate, and includes at least one inorganic metal compound or organic metal compound selected from the group consisting of metals of the groups 1 and 2 in the periodic table, and a resin stabilizer, the polycarbonate polyol having an average number of functional hydroxy groups of more than 2.SELECTED DRAWING: None

Description

The present invention relates to polycarbonate polyols and polyurethane resins.

Similar to polyester polyols and polyether polyols, polycarbonate polyols are useful as raw materials for producing polyurethane resins by reacting with polyisocyanate compounds, and as raw materials for adhesives, paints, and the like. Since the polyester polyol has an ester bond, the polyurethane resin obtained from them has a drawback of being inferior in hydrolysis resistance, and since the polyether polyol has an ether bond, it has a drawback of being inferior in weather resistance and heat resistance. On the other hand, the resin obtained from the polycarbonate polyol is expected to be excellent in durability such as heat resistance, weather resistance, hydrolysis resistance and chemical resistance.

Further, in recent years, in leather applications using the obtained polyurethane resin, good texture such as flexibility is required.

Therefore, it is disclosed that a polyurethane resin is obtained by using a copolycarbonate polyol that has various durability and can improve the texture such as flexibility. However, while the texture is good, the mechanical properties tend to decrease (Patent Document 1).

In order to improve this mechanical characteristic, it is disclosed that a polycarbonate polyol is polyfunctionalized using a highly active basic catalyst (Non-Patent Document 1). However, when the polyfunctionalized polycarbonate polyol is made into polyurethane, the mechanical properties are improved, but the durable physical properties tend to be lowered.

International release WO2002 / 070584

RSC Adv. , 2017, 7, 12550-12560

The present invention has been made in view of the above background techniques, and an object of the present invention is to provide a polycarbonate polyol capable of obtaining a polyurethane resin having an excellent balance between strength and flexibility and excellent hydrolysis resistance. ..

As a result of diligent research to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by adding a specific resin stabilizer to the polyfunctional polycarbonate polyol component, and complete the present invention. I came to do.

That is, the present invention includes the following embodiments.

[1] A metal of Group 1 of the periodic table, having a structure derived from an aliphatic diol (A), a structure derived from a polyhydric alcohol (B) having 3 or more hydroxyl group functional groups, and a structure derived from a carbonic acid ester (C). , And at least one inorganic metal compound or organic metal compound (D) selected from the group consisting of metals of Group 2 of the periodic table, and the average number of hydroxyl group functional groups containing the resin stabilizer (E) exceeds 2. Characteristic polycarbonate polyol.

[2] The polycarbonate polyol according to the above [1], wherein the aliphatic diol is a divalent aliphatic hydrocarbon having 2 to 8 carbon atoms.

[3] At least one inorganic metal compound or organometallic compound (D) selected from the group consisting of the metal of Group 1 of the Periodic Table and the metal of Group 2 of the Periodic Table is characterized by containing lithium. , The polycarbonate polyol according to the above [1] or [2].

[4] The polycarbonate polyol according to any one of the above [1] to [3], wherein the resin stabilizer (E) is an acidic phosphoric acid ester.

[5] A polyurethane resin composition which is a reaction product of a polyol component containing the polycarbonate polyol according to any one of the above [1] to [4] and an isocyanate component.

[6] An aqueous polyurethane resin dispersion which is a reaction product of a polyol component containing the polycarbonate polyol according to any one of the above [1] to [4] and an isocyanate component.

[7] Synthetic leather or artificial leather obtained by using the polyurethane resin composition according to the above [5].

[8] Synthetic leather or artificial leather obtained by using the aqueous polyurethane resin dispersion according to the above [6].

[9] A coating material obtained by using the polyurethane resin composition according to the above [5].

[10] A coating material obtained by using the aqueous polyurethane resin dispersion according to the above [6].

[11] A coating film obtained from the coating material according to the above [9] or [10].

According to the polycarbonate polyol of the present invention, when used as a constituent material of polyurethane, a polyurethane resin composition having good tensile strength, elongation, texture and durability, a molded body using the resin composition, and a coating material. Can be provided.

Hereinafter, the polycarbonate polyol of the present invention will be described in detail.

The polycarbonate polyol of the present invention has a structure derived from an aliphatic diol (A), a structure derived from a polyhydric alcohol having 3 or more hydroxyl group functional groups (hereinafter, also referred to as a polyhydric alcohol) (B), and a carbonate ester (C). At least one inorganic metal compound or organic metal compound (hereinafter, also referred to as a metal compound) having a structure of origin and selected from the group consisting of a metal of Group 1 of the periodic table and a metal of Group 2 of the periodic table. It contains D) and a resin stabilizer (E), and is characterized by having an average number of hydroxyl group functional groups exceeding 2.

<Alphatic diol (A)>
Examples of the aliphatic diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentane. Diol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptan, diethylene glycol, dipropylene glycol, neopentyl Glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, ethylene oxide and propylene oxide adduct of bisphenol A, bis (β-hydroxyethyl) benzene, xylylene glycol and the like can be mentioned. .. These may be used alone or in combination of two or more.

<Multivalent alcohol (B) with 3 or more hydroxyl group functional groups>
Examples of the polyhydric alcohol include compounds having three or more hydroxyl groups in one molecule such as trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, dipentaerythritol, and sorbitol. These may be used alone or in combination of two or more.

<Mole ratio of aliphatic diol to polyhydric alcohol>
The molar ratio of the aliphatic diol to the polyhydric alcohol is preferably in the range of 1 to 25 as "the number of moles of the aliphatic diol / the number of moles of the polyhydric alcohol", and more preferably in the range of 3 to 20. By setting the molar ratio of the aliphatic diol to the polyhydric alcohol in the above range, it is possible to obtain a polyurethane resin having high strength and high elongation mechanical properties by balancing the cohesive force of the polycarbonate polyol, the urethane group concentration and the crosslink density. can.

<Carbonate ester (C)>
Examples of the carbonic acid ester include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate and dibutyl carbonate; dialkyl carbonates such as diphenyl carbonate; alkylenes such as ethylene carbonate, trimethylene carbonate and 1,2-propylene carbonate. Examples include carbonic acid. From the viewpoint of easy availability and easy setting of conditions for the polymerization reaction, it is preferable to use dimethyl carbonate, diethyl carbonate, diphenyl carbonate, dibutyl carbonate, or ethylene carbonate. These may be used alone or in combination of two or more.

<Metallic compound (D)>
In obtaining the polycarbonate polyol of the present invention, at least one inorganic metal compound or organic metal compound selected from the group consisting of the metal of Group 1 of the Periodic Table and the metal of Group 2 of the Periodic Table is used. Examples of such metal compounds include metal alkoxides such as lithium methoxyd, sodium methoxyd, sodium ethoxydo, potassium methoxyd, and potassium ethoxydo, lithium acetylacetonate, aluminum acetylacetonate, zirconium acetylacetonate, and the like. Metal enolates, metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, metal carboxylic acids such as lithium acetate, sodium acetate, potassium acetate. Examples include salt. These may be used alone or in combination of two or more as appropriate. Among them, a compound containing lithium is preferable, and lithium acetylacetonate is particularly preferable, because the yield is good.

The metal compounds include tertiary alkylamines such as trimethylamine, triethylamine, diisopropylethylamine and tributylamine, cyclic azines such as pyridine, pyrazine and quinoline, N-methylpyrrolidin, N-methylpiperidin and N, N'-dimethyl. Tertiary cyclic amines such as piperazine, N-methylmorpholin, diazabicycloundecene, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] undecene, t- Butyl iminotris (dimethylamino) phosphorane (P1-t-Bu), t-butyliminotri (pyrrolidino) phosphorane, t-octyliminotris (dimethylamino) phosphorane (P1-t-Oct), 1-t-butyl- 2,2,4,4,4-pentakis (dimethylamino) -2λ ^{5,4λ 5} -catenadi (phosphazen) (P2-t-Bu), 1-ethyl-2,2,4,4,4-pentakis ( Dimethylamino) -2λ ⁵ , 4λ ⁵ -Catenadi (phosphazene), 1-t-butyl-4,4,4-tris (dimethylamino) -2,2-bis [tris (dimethylamino) phosphoranilideneamino]- 2λ ⁵ , 4λ ⁵ -Catenadi (phosphazene) (P4-t-Bu), 1-tert-octyl-4,4,4-tris (dimethylamino) -2,2-bis [tris (dimethylamino) phosphoranilidene Amino] -2λ ⁵ , 4λ ⁵ -Catenadi (phosphazene) (P4-t-Oct) and other phosphazenes may be used in combination as necessary.

<Resin stabilizer (E)>
The polycarbonate polyol of the present invention contains a resin stabilizer (E). Examples of the resin stabilizer (E) include phosphate triesters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, di-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, and cresyl / diphenyl phosphate; methyl acid. Phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate. , Tetracosyl acid phosphate, ethylene glucol acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, dibutyl phosphate, monobutyl phosphate, monoisodecyl phosphate, bis (2-ethylhexyl) phosphate and other acidic phosphate esters; triphenylphos Fight, Trisnonylphenyl Phosphite, Tricresylphosphite, Triethylphosphite, Tris (2-ethylhexyl) Phosphite, Tridecylphosphite, Trilaurylphosphite, Tris (Tridecyl) Phosphite, Trioleylphosphite, Diphenyl Mono (2-ethylhexyl) phosphite, diphenylmonodecyl phosphite, diphenyl (monodecyl) phosphite, trilauryl phosphite, diethylhydrogen phosphite, bis (2-ethylhexyl) hydrogen phosphite, dilaurylhydrogen phosphite, diorail Hydrogen phosphite, diphenylhydrogen phosphite, tetraphenyldipropylene glycol diphosphite, bis (decyl) pentaerythritol diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di) -Tert-Butylphenyl) Subphosphate esters such as phosphite; Further, phosphoric acid, phosphite, hypophosphite and the like can be mentioned.

Of these, acidic phosphoric acid esters are preferable, and butyl acid phosphate, 2-ethylhexyl acid phosphate, and isodecyl acid phosphate are more preferable. By including the resin stabilizer (E), the durability of the obtained urethane resin can be improved.

<Polyisocyanate>
Examples of the polyisocyanate that can be used in the present invention include aromatic polyisocyanates, aromatic aliphatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. In addition, these isocyanurate-modified polyisocyanates, allophanate-modified polyisocyanates, uretdione-modified polyisocyanates, urethane-modified polyisocyanates, biuret-modified polyisocyanates, uretoimine-modified polyisocyanates, acylurea-modified polyisocyanates, etc. may be used alone or in combination of two or more as appropriate. can do.

Examples of the aromatic polyisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate mixture, 4,4'-diphenylmethane diisocyanate, 2 , 4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate / 4,4'-diphenylmethane diisocyanate mixture, m-xylylene diisocyanate, p-xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4 , 4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylenediisocyanate, Examples thereof include p-phenylenediisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate and the like.

Examples of the aromatic aliphatic polyisocyanate include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, or a mixture thereof; 1,3-bis (1-isocyanato-1-methylethyl) benzene, 1,4. -Bis (1-isocyanato-1-methylethyl) benzene or a mixture thereof; ω, ω'-diisocyanato-1,4-diethylbenzene and the like can be mentioned.

Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate, ethylene diisocyanate, and triisocyanate. Methylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexanediisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2 , 4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecantriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanato-4- (isocyanatomethyl) octane, 2,5, 7-trimethyl-1,8-diisocyanato-5- (isocyanatomethyl) octane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butylene glycol dipropyl ether-α, α'- Examples thereof include diisocyanate, lysine diisocyanatomethyl ester, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2-isocyanatopropyl-2,6-diisocyanatohexanoate and the like.

Examples of the alicyclic polyisocyanate include isophorone diisocyanate, cyclohexyldiisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, methylcyclohexyldiisocyanate, dicyclohexyldimethylmethanediisocyanate, 2,2'-dimethyldicyclohexylmethanediisocyanate, and bis (4-). Isocyanato-n-butylidene) pentaerythritol, diisocyanate hydride dimerate, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5- (isocyanatomethyl) bicyclo [2.2.1] heptane, 2- (Isocyanatomethyl) 3- (3-isocyanatopropyl) -6- (isocyanatomethyl) -bicyclo [2.2.1] heptane, 2- (isocyanatomethyl) -2- (3-isocyanatopropyl) -5- (Isocyanatomethyl) bicyclo [2.2.1] heptane, 2- (isocyanatomethyl) -2- (3-isocyanatopropyl) -6- (isocyanatomethyl) bicyclo [2.2.1] ] Heptane, 2- (isocyanatomethyl) -3- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) bicyclo [2.2.1] heptane, 2- (isocyanatomethyl) -3- (3-Isocyanatopropyl) -6- (2-isocyanatoethyl) bicyclo [2.2.1] heptane, 2- (isocyanatomethyl) -2- (3-isocyanatopropyl) -5- (2-) Isocyanatoethyl) bicyclo [2.2.1] heptane, 2- (isocyanatomethyl) -2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) bicyclo [2.2.1] heptane , 2,5-bis (isocyanatomethyl) bicyclo [2.2.1] heptane, diphenylmethane diisocyanate hydride, norbornan diisocyanate, tolylene diisocyanate hydride, xylene diisocyanate hydride, tetramethylxylene diisocyanate hydride and the like. ..

<Urethane compounding ratio>
The compounding ratio of the polycarbonate polyol and the polyisocyanate in the production of the polyurethane resin composition of the present invention is such that the molar ratio of the active hydrogen of the polycarbonate polyol to the isocyanate group in the polyisocyanate is 9: 1 to 1: 9. It is preferable, and it is more preferably 6: 4 to 4: 6. Within this range, a polyurethane resin having better performance can be obtained.

<Chain extender>
A chain extender can be used in the urethanization reaction. The chain extender can be appropriately selected depending on the purpose and application, and for example, water; ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1, 6-Hexanediol, Neopentylglycol, 1,10-Decandiol, 1,1-Cyclohexanedimethanol, 1,4-Cyclohexanedimethanol, Tricyclodecanedimethanol, Xylyleneglycol, Bis (p-hydroxy) diphenyl, Bis (p-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxyethoxy) phenyl] sulfone, 1,1-bis [4- ( 2-Hydroxyethoxy) phenyl] low molecular weight polyols such as cyclohexane; high molecular weight polyols such as polyester polyols, polyesteramide polyols, polyether polyols, polyether ester polyols, polycarbonate polyols, polyolefin polyols; ethylene diamine, isophorone diamine, 2- Polyamines such as methyl-1,5-pentanediol, aminoethylethanolamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine can be used.

<Urethane catalyst>
During the urethanization reaction, a catalyst can be added for the purpose of shortening the curing step and improving the reaction rate. Examples of the catalyst include tertiary amine catalysts such as triethylamine, triethylenediamine, tetramethylethylenediamine, tetramethylpropylenediamine and tetramethylhexamethylenediamine, or tins such as stanas octoate, stanas oleate and dibutyltin dilaurate. Examples thereof include metal catalysts typified by system catalysts, and these can be used alone or in combination of two or more.

<Solvent>
The urethanization reaction can also be carried out in the presence of a solvent, for example esters such as ethyl acetate, butyl acetate, propyl acetate, γ-butyrolactone, δ-valerolactone, ε-caprolactone; dimethylformamide, diethylformamide, dimethylacetamide. Amides such as; Sulfoxides such as dimethylsulfoxide; Esters such as tetrahydrofuran, dioxane, 2-ethoxyethanol; Ketones such as methylethylketone, methylisobutylketone, cyclohexanone; Fragrant hydrocarbons such as benzene and toluene Kinds can be used.

<Aqueous polyurethane resin dispersion>
The polycarbonate polyol of the present invention can also be used for an aqueous polyurethane resin dispersion. Specifically, the aqueous polyurethane resin dispersion is obtained by reacting, for example, the polycarbonate polyol, polyisocyanate, and acidic group-containing polyol of the present invention in the presence or absence of a solvent to form a urethane prepolymer. A step of neutralizing the acidic group in the prepolymer with a neutralizing agent, a step of dispersing the neutralized prepolymer in an aqueous medium, and a step of reacting the prepolymer dispersed in the aqueous medium with a chain extender are sequentially performed. It can be manufactured by doing. In each step, a catalyst can be used as needed to promote the reaction and control the amount of by-products. Since the aqueous polyurethane resin dispersion derived from the polycarbonate polyol of the present invention provides a film having excellent adhesion, flexibility and tactile sensation, it can be particularly applied to artificial leather and synthetic leather. As the polycarbonate polyol, polyisocyanate, solvent, and chain extender, those described above can be used.

<Polyol containing acidic groups>
Examples of the acidic group-containing polyol include a hydrophilic group-containing monomer having two terminal hydroxyl groups and capable of imparting hydrophilicity to the isocyanate group-terminal prepolymer obtained by reaction with isocyanate.

Examples of such an acidic group-containing polyol include dimethylol propionic acid, dimethylol butanoic acid, dimethylol pentanoic acid, dimethylol alkanoic acid such as dimethylol nonanoic acid, and the like.

<Neutralizer>
Specific examples of the neutralizing agent include ammonia, ethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, dimethylethanolamine and diethylethanolamine. , Morpholine, N-methylmorpholine, 2-amino-2-ethyl-1-propanol, organic amines such as higher alkyl-modified morpholine, alkali metals such as lithium, potassium and sodium, and inorganic alkalis of sodium hydroxide and potassium hydroxide. Kind and the like. Further, from the viewpoint of improving the durability and smoothness of the coating film, a highly volatile neutralizing agent that easily dissociates by heating such as ammonia, trimethylamine, and triethylamine is preferable. These neutralizers can be used alone or in combination of two or more.

<Anionic polar group-containing compound>
In producing the aqueous polyurethane resin dispersion, an anionic polar group-containing compound can be used. Specific examples of the anionic polar group-containing compound include those composed of an organic acid having one or more active hydrogens and a neutralizing agent. Examples of the organic acid include carboxylate, sulfonate, phosphate, phosphonate, phosphinate, thiosulfonate and the like, and these groups may be introduced independently or chelated. It may be associated with.

<Cationic polar group-containing compound>
In producing the aqueous polyurethane resin dispersion, a cationic polar group-containing compound can be used. Specific examples of the cationic polar group-containing compound include those selected from, for example, a tertiary amine having one or more active hydrogens, a neutralizing agent for an inorganic acid or an organic acid, and a quaternizing agent. be able to. Specific examples of tertiary amines having one or more active hydrogens include N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dipropylethanolamine, N, N-diphenylethanolamine, and N. -Methyl-N-ethylethanolamine, N-methyl-N-phenylethanolamine, N, N-dimethylpropanolamine, N-methyl-N-ethylpropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-methyl Dipropanolamine, N-phenyldiethanolamine, N-phenyldipropanolamine, N-hydroxyethyl-N-hydroxypropyl-methylamine, N, N'-dihydroxyethylpiperazine, triethanolamine, trisisopropanolamine, N-methyl- Examples thereof include bis- (3-aminopropyl) -amine, N-methyl-bis- (2-aminopropyl) -amine and the like. Further, those obtained by adding an alkylene oxide to a primary amine such as ammonia or methylamine and a secondary amine such as dimethylamine can also be used.

Specific examples of the inorganic acid and the organic acid include hydrochloric acid, acetic acid, lactic acid, cyanoacetic acid, phosphoric acid, sulfuric acid and the like. Specific examples of the quaternizing agent include dimethyl sulfate, benzyl chloride, bromoacetamide, chloroacetamide, and alkyl halides such as ethyl bromide, propyl bromide, and butyl bromide. In addition, examples of other cationic polar group-containing compounds include cationic compounds such as primary amine salts, secondary amine salts, tertiary amine salts, and pyridinium salts.

By using the polyurethane resin composition using the polycarbonate polyol of the present invention and the aqueous polyurethane resin dispersion shown above, synthetic leather, artificial leather, coating material, and coating material having excellent strength, flexibility, and texture are used. Etc. can be preferably obtained.

Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples. In addition,% and part notation in an Example are based on mass unless otherwise specified.

[Synthesis of Polycarbonate Polyol 1]
Trimethylolpropane 39.1g, 1,4-butanediol 393.6g, diethyl carbonate 567.4g, and lithium acetylacetonate in a 1L double-ended glass reactor with a stirrer, thermometer, heating device, and cooler. 0.05 g was mixed and reacted at 100 to 150 ° C. for 8 hours under normal pressure while removing low boiling point components. Further, the reaction temperature was set to 150 ° C., the pressure in the flask was reduced to 10 kPa, and the reaction was further carried out for 8 hours. Then, 0.1 g of JP-508 was added and heated at 120 ° C. for 1 hour to obtain a polycarbonate polyol (Polyol-1).

[Synthesis of Polycarbonate Polyol 2]
Trimethylolpropane 34.8g, 1,6-hexanediol 459.8g, diethyl carbonate 505.4g, and lithium acetylacetonate in a 1L double-ended glass reactor with a stirrer, thermometer, heating device, and cooler. 0.05 g was mixed and reacted at 100 to 150 ° C. for 8 hours under normal pressure while removing low boiling point components. Further, the reaction temperature was set to 150 ° C., the pressure in the flask was reduced to 10 kPa, and the reaction was further carried out for 8 hours. Then, 0.1 g of JP-508 was added and heated at 120 ° C. for 1 hour to obtain a polycarbonate polyol (Polyol-2).

[Synthesis of Polycarbonate Polyol 3]
Trimethylolpropane 36.8g, 1,4-butanediol 185.4g, 1,6-hexanediol 243.2g, carbonic acid in a 1L double-ended glass reactor with a stirrer, thermometer, heating device, and cooler. 534.7 g of diethyl and 0.05 g of lithium acetylacetonate were mixed and reacted at 100 to 150 ° C. for 8 hours under normal pressure while removing low boiling point components. Further, the reaction temperature was set to 150 ° C., the pressure in the flask was reduced to 10 kPa, and the reaction was further carried out for 8 hours. Then, 0.1 g of JP-508 was added and heated at 120 ° C. for 1 hour to obtain a polycarbonate polyol (Polyol-3).

[Synthesis of Polycarbonate Polyol 4]
A 1L double-ended glass reactor with a stirrer, thermometer, heating device, and cooler, 34.8 g of trimethylolpropane, 459.8 g of 3-methyl1.5pentanediol, 505.4 g of diethyl carbonate, and lithium acetyl. 0.05 g of acetonate was mixed and reacted at 100 to 150 ° C. for 8 hours under normal pressure while removing low boiling point components. Further, the reaction temperature was set to 150 ° C., the pressure in the flask was reduced to 10 kPa, and the reaction was further carried out for 8 hours. Then, 0.1 g of JP-508 was added and heated at 120 ° C. for 1 hour to obtain a polycarbonate polyol (Polyol-4).

[Synthesis of Polycarbonate Polyol 5]
Trimethylolpropane 39.1g, 1,4-butanediol 393.6g, diethyl carbonate 567.4g, and lithium acetylacetonate in a 1L double-ended glass reactor with a stirrer, thermometer, heating device, and cooler. 0.05 g was mixed and reacted at 100 to 150 ° C. for 8 hours under normal pressure while removing low boiling point components. Further, the reaction temperature was set to 150 ° C., the pressure in the flask was reduced to 10 kPa, and the reaction was further carried out for 8 hours to obtain a polycarbonate polyol (Polyol-5).

[Synthesis of Polycarbonate Polyol 6]
Trimethylolpropane 34.8g, 1,6-hexanediol 459.8g, diethyl carbonate 505.4g, and lithium acetylacetonate in a 1L double-ended glass reactor with a stirrer, thermometer, heating device, and cooler. 0.05 g was mixed and reacted at 100 to 150 ° C. for 8 hours under normal pressure while removing low boiling point components. Further, the reaction temperature was set to 150 ° C., the pressure in the flask was reduced to 10 kPa, and the reaction was further carried out for 8 hours to obtain a polycarbonate polyol (Polyol-6).

[Synthesis of Polycarbonate Polyol 7]
Trimethylolpropane 36.8g, 1,4-butanediol 185.4g, 1,6-hexanediol 243.2g, carbonic acid in a 1L double-ended glass reactor with a stirrer, thermometer, heating device, and cooler. 534.7 g of diethyl and 0.05 g of lithium acetylacetonate were mixed and reacted at 100 to 150 ° C. for 8 hours under normal pressure while removing low boiling point components. Further, the reaction temperature was set to 150 ° C., the pressure in the flask was reduced to 10 kPa, and the reaction was further carried out for 8 hours to obtain a polycarbonate polyol (Polyol-7).

[Synthesis of Polycarbonate Polyol 8]
A 1L double-ended glass reactor with a stirrer, thermometer, heating device, and cooler, 1,4-butanediol 214.9 g, 1,6-hexanediol 281.9 g, diethyl carbonate 503.3 g, and tetra. 0.05 g of butyl titanate was mixed and reacted at 100 to 190 ° C. for 8 hours under normal pressure while removing low boiling point components. Further, the reaction temperature was set to 190 ° C., the pressure in the flask was reduced to 1.3 kPa, and the reaction was further carried out for 8 hours to obtain a polycarbonate polyol (Polyol-8).

[Synthesis of Polycarbonate Polyol 9]
A 1L double-ended glass reactor with a stirrer, thermometer, heating device, and cooler was mixed with 518.8 g of 1,6-hexanediol, 481.2 g of diethyl carbonate, and 0.05 g of tetrabutyl titanate. Under pressure, the reaction was carried out at 100 to 190 ° C. for 8 hours while removing low boiling point components. Further, the reaction temperature was set to 190 ° C., the pressure in the flask was reduced to 1.3 kPa, and the reaction was further carried out for 8 hours. Then, 0.1 g of JP-508 was added and heated at 120 ° C. for 1 hour to obtain a polycarbonate polyol (Polyol-9).

The raw materials used in Table 1 are as follows.
・ 1,4-Butanediol: manufactured by Fuji Film Wako Junyaku Co., Ltd. ・ 1,6-Hexanediol: manufactured by BASF-JAPAN manufactured by Sigma-Aldrich Co., Ltd. ・ 3-Methyl-1,5-pentanediol: manufactured by Fuji Film Wako Junyaku Co., Ltd. Trimethylol Propane: Sigma-Aldrich ・ diethyl carbonate: Sigma-Aldrich ・ Lithium acetylacetonate: Sigma-Aldrich ・ Tetrabutyl titanate: Sigma-Aldrich ・ JP-508: 2-ethylhexyl Acid phosphate, manufactured by Johoku Chemical Industry Co., Ltd. (trade name).

[Preparation of polyurethane cured film]
The polyol component (A), polyisocyanate component (B), curing catalyst and diluting solvent are mixed in a 200 mL glass bottle as shown in Table 2, and the liquid immediately after mixing is poured onto a release paper and placed on a bar coater. The film was cast to a thickness of 500 μm and cured at 25 ° C. for 30 minutes, 50 ° C. for 30 minutes, 80 ° C. for 30 minutes, 120 ° C. for 1 hour, and 50 ° C. for 18 hours to obtain a cured film. rice field. Using this film as a sample, the following items were evaluated. The compounding unit in the table is grams.

[Tension characteristics]
The tensile properties of the obtained film were measured according to JIS K6251. The results are shown in Table 2. In the evaluation of the heat-resistant heat-resistant property and the heat-resistant water property, the measurement was performed under the same conditions.
・ Test equipment: Autocom universal testing machine AC-10KN
-Measurement conditions: 25 ° C x 50% RH
-Head speed: 200 mm / min-Dumbbell No. 4 The tensile properties of the film before the durability test can be said to be good if the tensile strength at break is 10 MPa or more and the elongation at break is 300% or more.

[Moisture and heat resistance]
The moist heat resistance characteristics of the obtained film were evaluated by the retention rate of tensile strength. The results are shown in Table 2.
The moisture resistance heat resistance test was conducted under the following conditions.
・ Test equipment: ESPEC CORP (manufactured by Espec)
-Measurement conditions: 80 ° C. x 95% RH x 2 weeks and 4 weeks The tensile strength retention rate was determined by the following formula (2) and used as an index of moisture and heat resistance characteristics.
Tensile strength retention rate (%) = E / D × 100 (2)
E: Tensile strength (MPa) after moisture resistance test
D: Tensile strength (MPa) before moist heat resistance test
It can be said that it is good if the tensile strength retention rate is 80% or more.

[Heat-resistant water characteristics]
The heat-resistant water properties of the films obtained using Polyol-1,2,5,6,8,9 were evaluated by the retention rate of tensile strength. The results are shown in Table 2.
The heat-resistant water property test was conducted under the following conditions.
-Test equipment: Constant temperature water tank-Measurement conditions: 80 ° C. Hot water x 2 weeks and 4 weeks The tensile strength retention rate was calculated by the following formula (3) and used as an index of heat-resistant water characteristics.
Tensile strength retention rate (%) = G / F × 100 (3)
G: Tensile strength (MPa) after heat-resistant water test
F: Tensile strength (MPa) before heat resistant water test
It can be said that it is good if the tensile strength retention rate is 80% or more and 130% or less.
[Texture characteristic evaluation criteria]
It can be said that the texture characteristics are good when the 100% modulus in the tensile strength measurement is 3 MPa or less. This evaluation standard is the same before and after the durability test.

The raw materials used in Table 2 are as follows.
C-2612: Product name: Coronate 2612 (hexamethylene diisocyanate adduct-modified polyisocyanate, isocyanate content = 17.5%, manufactured by Toso Co., Ltd.)
・ DOTDL: Dioctyl tin dilaurate, manufactured by Kishida Chemical Industry Co., Ltd.

Claims (11)

It has a structure derived from an aliphatic diol (A), a structure derived from a polyhydric alcohol (B) having 3 or more hydroxyl group functional groups, and a structure derived from a carbonic acid ester (C). It is characterized in that the average number of hydroxyl group functional groups containing at least one inorganic metal compound or organic metal compound (D) selected from the group consisting of the metals of Group 2 in Table 2 and the resin stabilizer (E) exceeds 2. Polycarbonate polyol. The polycarbonate polyol according to claim 1, wherein the aliphatic diol is a divalent aliphatic hydrocarbon having 2 to 8 carbon atoms. Claimed, wherein at least one inorganic metal compound or organometallic compound (D) selected from the group consisting of a metal of Group 1 of the Periodic Table and a metal of Group 2 of the Periodic Table contains lithium. The polycarbonate polyol according to 1 or 2. The polycarbonate polyol according to any one of claims 1 to 3, wherein the resin stabilizer (E) is an acidic phosphoric acid ester. A polyurethane resin composition which is a reaction product of a polyol component containing the polycarbonate polyol according to any one of claims 1 to 4 and an isocyanate component. An aqueous polyurethane resin dispersion which is a reaction product of a polyol component containing the polycarbonate polyol according to any one of claims 1 to 4 and an isocyanate component. Synthetic leather or artificial leather obtained by using the polyurethane resin composition according to claim 5. Synthetic leather or artificial leather obtained by using the aqueous polyurethane resin dispersion according to claim 6. A coating material obtained by using the polyurethane resin composition according to claim 5. A coating material obtained by using the aqueous polyurethane resin dispersion according to claim 6. A coating film obtained from the coating material according to claim 9.