阅读说明：本技术 热塑性聚氨酯树脂、其用途及制造方法 (Thermoplastic polyurethane resin, use thereof, and method for producing same ) 是由 筱原直树 景冈正和 山崎聪 于 2019-05-23 设计创作，主要内容包括：热塑性聚氨酯树脂包含相对于异氰酸酯基的总摩尔数而言以50摩尔％以上的比例含有1,4-双(异氰酸酯基甲基)环己烷的异氰酸酯基的多异氰酸酯成分、与包含大分子多元醇、异山梨醇、及碳原子数为3～8的脂肪族二醇的多元醇成分的反应产物。相对于异山梨醇及脂肪族二醇的总摩尔数而言,异山梨醇的含有比例为60摩尔％以上且95摩尔％以下。(The thermoplastic polyurethane resin comprises a reaction product of a polyisocyanate component containing isocyanate groups of 1, 4-bis (isocyanatomethyl) cyclohexane in a proportion of 50 mol% or more relative to the total number of moles of isocyanate groups, and a polyol component containing a macropolyol, isosorbide, and an aliphatic diol having 3 to 8 carbon atoms. The content ratio of isosorbide is 60 mol% or more and 95 mol% or less with respect to the total number of moles of isosorbide and aliphatic diol.)

1. A thermoplastic polyurethane resin comprising a reaction product of a polyisocyanate component containing isocyanate groups of 1, 4-bis (isocyanatomethyl) cyclohexane in a proportion of 50 mol% or more relative to the total number of moles of isocyanate groups and a polyol component comprising a macropolyol, isosorbide and an aliphatic diol having 3 to 8 carbon atoms,

the content ratio of isosorbide is 60 mol% or more and 95 mol% or less with respect to the total number of moles of isosorbide and aliphatic diol.

2. The thermoplastic polyurethane resin according to claim 1, wherein the 1, 4-bis (isocyanotomethyl) cyclohexane comprises trans-1, 4-bis (isocyanotomethyl) cyclohexane in a proportion of 70 to 95 mol%.

3. The thermoplastic polyurethane resin according to claim 1, wherein the aliphatic diol is a linear alkane diol having 3 to 5 carbon atoms and/or a cyclic alkane diol having 6 to 8 carbon atoms.

4. The thermoplastic polyurethane resin according to claim 1, wherein the macromolecular polyol comprises a polyoxy linear alkylene (having 2 to 4 carbon atoms) polyol having a number average molecular weight of 600 or more and 1300 or less.

5. The thermoplastic polyurethane resin according to claim 1, wherein the phosphorous acid-based antioxidant is contained in an amount of 0.1 to 0.8 parts by mass based on 100 parts by mass of the reaction product.

6. An optical polyurethane resin comprising the thermoplastic polyurethane resin according to claim 1.

7. A cover plate for a display panel, characterized in that it is a cover plate for a display panel of a smart device,

the cover plate for a display panel comprises the optical polyurethane resin according to claim 6.

8. An eyeglass material comprising the thermoplastic polyurethane resin according to claim 1.

9. An eyeglass lens comprising the eyeglass material according to claim 8.

10. An eyeglass lens as set forth in claim 9, comprising:

a lens body comprising said spectacle material, and

and a hard coat layer and/or an antireflection layer formed on at least one surface of the lens body.

11. An eyeglass frame comprising the eyeglass material of claim 8.

12. An automobile interior/exterior material part comprising the thermoplastic polyurethane resin according to claim 1.

13. A method for producing a thermoplastic polyurethane resin, comprising the steps of:

a prepolymer synthesis step of reacting a polyisocyanate component containing the isocyanate group of 1, 4-bis (isocyanatomethyl) cyclohexane in an amount of at least 50 mol% relative to the total number of moles of isocyanate groups with a macropolyol to obtain an isocyanate group-terminated prepolymer,

and a chain extension step of reacting and curing at least the isocyanate group-ended prepolymer with isosorbide and an aliphatic diol having 3 to 8 carbon atoms to obtain a thermoplastic polyurethane resin.

14. The method of producing a thermoplastic polyurethane resin according to claim 13, wherein the curing temperature in the chain extension step is 150 ℃ or higher and 240 ℃ or lower.

Technical Field

The present invention relates to a thermoplastic polyurethane resin, an optical polyurethane resin, a cover plate for a display panel, a spectacle material, a spectacle lens, a spectacle frame, a member for an interior or exterior material of an automobile, and a method for producing a thermoplastic polyurethane resin.

Background

The thermoplastic polyurethane resin (TPU) is generally a rubber elastomer obtained by the reaction of a polyisocyanate, a high molecular weight polyol and a low molecular weight polyol, and has a hard segment formed by the reaction of the polyisocyanate and the low molecular weight polyol and a soft segment formed by the reaction of the polyisocyanate and the high molecular weight polyol. By melt molding such a thermoplastic polyurethane resin, a molded article made of a polyurethane resin can be obtained.

More specifically, for example, a thermoplastic polyurethane obtained by reacting 4, 4' -methylenediphenyl diisocyanate, polytetramethylene ether glycol having a molecular weight of 1000, isosorbide, and butanediol has been proposed as a thermoplastic polyurethane resin (see, for example, patent document 2 (example 2A)).

In addition, as the thermoplastic polyurethane resin, for example, a rigid thermoplastic polyurethane obtained by reacting 1, 3-and 1, 4-bis (isocyanatomethyl) cyclohexane, cyclohexanedimethanol (CHDM-D), 1, 6-hexanediol, and polytetramethylene ether glycol has been proposed (for example, see patent document 1 (example 2)).

Documents of the prior art

Patent document

Patent document 1: japanese Kohyo publication No. 2017-519052

Patent document 2: japanese Kohyo publication No. 2010-528158

Disclosure of Invention

Problems to be solved by the invention

On the other hand, molded articles of thermoplastic polyurethane are required to have various physical properties depending on the application, and for example, in the field of covers of smart devices, they are required to have appearance, transparency, mechanical properties (such as hardness) and durability (such as impact resistance, heat resistance, chemical resistance and solvent resistance).

However, the thermoplastic polyurethanes described in patent documents 1 and 2 may have insufficient appearance, transparency, mechanical properties (hardness, etc.), and durability (impact resistance, heat resistance, chemical resistance, solvent resistance, etc.).

The present invention relates to a thermoplastic polyurethane resin, an optical polyurethane resin, a cover plate for a display panel, a spectacle material, a spectacle lens, a spectacle frame, a member for an interior or exterior material of an automobile, and a method for producing the thermoplastic polyurethane resin, which have appearance, transparency, mechanical properties, and durability.

Means for solving the problems

The present invention [1] comprises a thermoplastic polyurethane resin comprising a reaction product of a polyisocyanate component containing an isocyanate group of 1, 4-bis (isocyanatomethyl) cyclohexane in a proportion of 50 mol% or more relative to the total number of moles of isocyanate groups and a polyol component containing a macropolyol, isosorbide, and an aliphatic diol having 3 to 8 carbon atoms, wherein the proportion of isosorbide contained is 60 mol% or more and 95 mol% or less relative to the total number of moles of isosorbide and the aliphatic diol.

The invention [2] comprises the thermoplastic polyurethane resin according to [1], wherein the 1, 4-bis (isocyanotomethyl) cyclohexane contains trans-1, 4-bis (isocyanotomethyl) cyclohexane in a proportion of 70 to 95 mol%.

The invention [3] comprises the thermoplastic polyurethane resin according to the above [1] or [2], wherein the aliphatic diol is a linear alkane diol having 3 to 5 carbon atoms and/or a cyclic alkane diol having 6 to 8 carbon atoms.

The invention [4] comprises the thermoplastic polyurethane resin according to any one of the above [1] to [3], wherein the macromolecular polyol comprises a polyoxyalkylene linear alkylene (having 2 to 4 carbon atoms) polyol having a number average molecular weight of 600 or more and 1300 or less.

The invention [5] comprises the thermoplastic polyurethane resin according to any one of the above [1] to [4], wherein the phosphorous acid-based antioxidant is contained in a proportion of 0.1 to 0.8 parts by mass with respect to 100 parts by mass of the reaction product.

The invention [6] comprises an optical polyurethane resin comprising the thermoplastic polyurethane resin according to any one of the above [1] to [5 ].

The invention [7] is a cover plate for a display panel of a smart device, comprising the optical polyurethane resin according to [6 ].

The present invention [8] includes an eyeglass material comprising the thermoplastic polyurethane resin according to any one of the above [1] to [5 ].

The present invention [9] comprises a spectacle lens comprising the spectacle material according to [8] above.

The present invention [10] is the eyeglass lens according to [9], including: a lens body comprising the above-mentioned spectacle material, and a hard coat layer and/or an antireflection layer formed on at least one surface of the above-mentioned lens body.

The present invention [11] includes an eyeglass frame comprising the eyeglass material according to [8] above.

The invention [12] comprises an automobile interior/exterior material part comprising the thermoplastic polyurethane resin according to any one of the above [1] to [5 ].

The present invention [13] includes a method for producing a thermoplastic polyurethane resin, comprising the steps of: a prepolymer synthesis step of reacting a polyisocyanate component containing the isocyanate group of 1, 4-bis (isocyanatomethyl) cyclohexane in a proportion of at least 50 mol% relative to the total number of moles of isocyanate groups with a macropolyol to obtain an isocyanate group-terminated prepolymer; and a chain extension step of reacting and curing at least the isocyanate group-ended prepolymer with isosorbide and an aliphatic diol having 3 to 8 carbon atoms to obtain a thermoplastic polyurethane resin.

The invention [14] comprises the method for producing a thermoplastic polyurethane resin according to [13], wherein the curing temperature in the chain extension step is 150 ℃ to 240 ℃.

ADVANTAGEOUS EFFECTS OF INVENTION

The thermoplastic polyurethane resin, the optical polyurethane resin, the cover plate for a display panel, the eyewear material, the eyewear lens, the eyewear frame, and the member for an automotive interior or exterior material of the present invention contain, as raw material components, 1, 4-bis (isocyanatomethyl) cyclohexane, a macropolyol, and an aliphatic diol having 3 to 8 carbon atoms and isosorbide in a predetermined ratio, and therefore, have appearance, transparency, mechanical properties, and durability.

Further, according to the method for producing a thermoplastic polyurethane resin of the present invention, a thermoplastic polyurethane resin having appearance, transparency, mechanical properties and durability can be easily obtained.

Detailed Description

The thermoplastic polyurethane resin of the present invention can be obtained by reacting raw material components including a polyisocyanate component and a polyol component (described later).

In other words, the thermoplastic polyurethane resin contains a reaction product of a polyisocyanate component and a polyol component as a main component. The main component means: the content is, for example, 90 mass% or more, preferably 95 mass% or more, based on the total amount of the thermoplastic polyurethane resin (thermoplastic polyurethane resin composition).

The polyisocyanate component contains 1, 4-bis (isocyanatomethyl) cyclohexane (1, 4-H)₆XDI) as an essential component.

More specifically, the polyisocyanate component contains 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and particularly preferably 100 mol% of isocyanate groups of 1, 4-bis (isocyanatomethyl) cyclohexane relative to the total number of moles of isocyanate groups.

The 1, 4-bis (isocyanotomethyl) cyclohexane includes stereoisomers of cis-1, 4-bis (isocyanotomethyl) cyclohexane (hereinafter, referred to as cis-1, 4 isomer) and trans-1, 4-bis (isocyanotomethyl) cyclohexane (hereinafter, referred to as trans-1, 4 isomer).

In the present invention, the 1, 4-bis (isocyanatomethyl) cyclohexane contains trans 1, 4-isomer in a proportion of, for example, 60 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more, further preferably 85 mol% or more, for example, 99.8 mol% or less, preferably 99 mol% or less, more preferably 95 mol% or less, further preferably 90 mol% or less.

The total amount of trans-1, 4-isomer and cis-1, 4-isomer was 100 mol%.

That is, the 1, 4-bis (isocyanatomethyl) cyclohexane contains the cis-1, 4-isomer in a proportion of, for example, 0.2 mol% or more, preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, for example, 40 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less, further preferably 15 mol% or less.

When the content ratio of the trans-1, 4-mer is in the above range, the transparency, mechanical properties and durability can be improved.

1, 4-bis (isocyanatomethyl) cyclohexane can be produced by the method described in, for example, WO2009/051114 pamphlet.

In addition, 1, 4-bis (isocyanatomethyl) cyclohexane can also be produced as a modified product within a range that does not impair the excellent effects of the present invention.

Examples of the modified 1, 4-bis (isocyanotomethyl) cyclohexane include polymers of bis (isocyanotomethyl) cyclohexane (dimers (e.g., uretdione modified products), trimers (e.g., isocyanurate modified products, iminooxadiazinedione modified products), biuret modified products (e.g., biuret modified products produced by the reaction of bis (isocyanotomethyl) cyclohexane with water), allophanate modified products (e.g., allophanate modified products produced by the reaction of bis (isocyanotomethyl) cyclohexane with monohydric or dihydric alcohols), polyol modified products (e.g., polyol modified products (adduct) produced by the reaction of bis (isocyanotomethyl) cyclohexane with a trihydric alcohol), oxadiazinetrione modified products (e.g., oxadiazinetrione and the like generated by the reaction of bis (isocyanotomethyl) cyclohexane with carbon dioxide), carbodiimide-modified products (for example, carbodiimide-modified products generated by decarboxylation condensation reaction of bis (isocyanotomethyl) cyclohexane and the like), and the like.

In addition, the polyisocyanate component may contain other polyisocyanates as optional components within a range that does not hinder the excellent effects of the present invention.

Examples of the other polyisocyanate include aliphatic polyisocyanate, aromatic polyisocyanate, and araliphatic polyisocyanate.

Examples of the aliphatic polyisocyanate include ethylene diisocyanate, 1, 3-propane diisocyanate, 1, 4-butane diisocyanate, 1, 5-Pentane Diisocyanate (PDI), 1, 6-Hexane Diisocyanate (HDI), 1, 8-octane diisocyanate, 1, 9-nonane diisocyanate, 2' -dimethylpentane diisocyanate, 2, 4-trimethylhexane diisocyanate, 1, 10-decane diisocyanate, butene diisocyanate, 1, 3-butadiene-1, 4-diisocyanate, 2,4, 4-trimethyl-1, 6-hexane diisocyanate, 1,6, 11-undecamethylene triisocyanate, 1,3, 6-hexamethylene triisocyanate, 1, 8-diisocyanato-4-isocyanatomethyl octane, and the like, 2,5, 7-trimethyl-1, 8-diisocyanato-5-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1, 4-butanediol dipropyl ether-omega, omega' -diisocyanate, lysine methyl ester isocyanate, lysine triisocyanate, 2-isocyanatoethyl 2, 6-diisocyanatohexanoate, 2-isocyanatopropyl 2, 6-diisocyanatohexanoate, bis (4-isocyanaton-butylidene) pentaerythritol, 2, 6-diisocyanatohexanoate, and the like.

In addition, the aliphatic polyisocyanate includes cycloaliphatic polyisocyanate (excluding 1, 4-bis (isocyanatomethyl) cyclohexane).

Examples of the alicyclic polyisocyanate (excluding 1, 4-bis (isocyanatomethyl) cyclohexane.) include isophorone diisocyanate (IPDI), trans-, trans, cis-, and cis, cis-dicyclohexylmethane diisocyanate, and a mixture thereof (H)₁₂MDI), 1, 3-or 1, 4-cyclohexane diisocyanate and mixtures thereof, 1, 3-bis (isocyanatomethyl) cyclohexane (1, 3-H)₆XDI), 1, 3-or 1, 4-bis (isocyanatoethyl) cyclohexane, methylcyclohexane diisocyanate, 2' -dimethyldicyclohexylmethane diisocyanate, dimer acid diisocyanate, 2, 5-diisocyanatomethylbicyclo [2, 2, 1] -heptane, 2, 6-diisocyanatomethylbicyclo [2, 2, 1] -heptane (NBDI) as its isomer, 2-isocyanatomethyl 2- (3-isocyanatopropyl) -5-isocyanatomethylbicyclo [2, 2, 1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6-isocyanatomethylbicyclo [2, 2, 1] -heptane, 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-isocyanatomethyl) -6- (2-isocyanatoethyl) -bicyclo- [2, 2, 1] -heptane and the like.

Examples of the aromatic polyisocyanate include 2, 4-tolylene diisocyanate and 2, 6-tolylene diisocyanate, and isomer mixtures (TDI) of these tolylene diisocyanates, 4 ' -diphenylmethane diisocyanate, 2,4 ' -diphenylmethane diisocyanate and 2,2 ' -diphenylmethane diisocyanate, and arbitrary isomer Mixtures (MDI), toluidine diisocyanate (TODI), p-phenylene diisocyanate, Naphthalene Diisocyanate (NDI) of these diphenylmethane diisocyanates.

Examples of the araliphatic polyisocyanate include 1, 3-or 1, 4-xylylene diisocyanate or a mixture thereof (XDI), 1, 3-or 1, 4-tetramethylxylylene diisocyanate or a mixture Thereof (TMXDI), and the like.

These other polyisocyanates may be used alone or in combination of 2 or more.

In addition, other polyisocyanates may be prepared as modified products within a range not to impair the excellent effects of the present invention.

Examples of the modified product of another polyisocyanate include a polymer (dimer, trimer, etc.) of another polyisocyanate, a biuret modified product, an allophanate modified product, a polyol modified product, an oxadiazinetrione modified product, a carbodiimide modified product, and the like.

The other polyisocyanate (that is, the polyisocyanate that can be used in combination with 1, 4-bis (isocyanatomethyl) cyclohexane) is preferably an aliphatic polyisocyanate (including an alicyclic polyisocyanate), more preferably 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, diisocyanatomethylbicyclo [2, 2, 1] -heptane, still more preferably 1, 6-hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, diisocyanatomethylbicyclo [2, 2, 1] -heptane, and particularly preferably 1, 6-hexamethylene diisocyanate.

The content of the other polyisocyanate is, for example, 50% by mass or less, preferably 30% by mass or less, and more preferably 20% by mass or less, based on the total amount of the polyisocyanate component.

The proportion of the isocyanate group of the other polyisocyanate is, for example, 50 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less, and particularly preferably 0 mol% relative to the total number of moles of the isocyanate group in the polyisocyanate component.

As the polyisocyanate component, 1, 4-bis (isocyanatomethyl) cyclohexane is particularly preferably used alone.

In the present invention, the polyol component is a composition containing a compound having 2 or more hydroxyl groups in the molecule, and specifically, the polyol component contains a macropolyol, isosorbide, and an aliphatic diol having 3 to 8 carbon atoms, and preferably consists of a macropolyol, isosorbide, and an aliphatic diol having 3 to 8 carbon atoms.

The macropolyol is an organic compound (polymer) having 2 or more hydroxyl groups and a number average molecular weight of 400 or more, preferably 500 or more, and examples thereof include polyether polyol, polyester polyol, polycarbonate polyol, polyurethane polyol, epoxy polyol, vegetable oil polyol, polyolefin polyol, acrylic polyol, vinyl monomer-modified polyol, and the like, and preferable examples thereof include polyether polyol, polyester polyol, and polycarbonate polyol.

Examples of the polyether polyol include a polyoxy linear alkylene (having 2 to 4 carbon atoms) polyol, a polyoxy branched alkylene (having 3 to 4 carbon atoms) polyol, a polyoxy linear/branched alkylene (having 2 to 4 carbon atoms) polyol and the like.

The polyoxyalkylene linear alkylene (having 2 to 4 carbon atoms) polyol is a polyoxyalkylene polyol having a linear oxyalkylene unit, having no branched oxyalkylene unit, and having 2 to 4 carbon atoms in the oxyalkylene unit.

More specifically, examples of the polyoxyalkylene linear alkylene (having 2 to 4 carbon atoms) polyol include polyoxyethylene polyol, polytrimethylene ether glycol, polytetramethylene ether glycol, and the like.

Examples of the polyoxyethylene polyol include addition polymers of ethylene oxide using a low molecular weight polyol, a known low molecular weight polyamine, or the like as an initiator.

Examples of the low-molecular-weight polyol include organic compounds having 2 or more hydroxyl groups in the molecule and having a molecular weight of 50 or more and less than 400, preferably 300 or less.

Specific examples of the low-molecular-weight polyol include 1, 2-ethanediol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, 1, 2-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 2,2, 2-trimethylpentanediol, 3-dimethylolheptane, alkane (C7-20) diol, 1, 3-or 1, 4-cyclohexanedimethanol and a mixture thereof, 1, 3-or 1, 4-cyclohexanediol and a mixture thereof, hydrogenated bisphenol A, 1, 4-dihydroxy-2-butene, 2, 6-dimethyl-1-octene-3, dihydric alcohols such as 8-diol, bisphenol A, and ether glycols having 4 to 6 carbon atoms (e.g., diethylene glycol, triethylene glycol, and dipropylene glycol), trihydric alcohols such as glycerin, trimethylolpropane, and triisopropanolamine, tetrahydric alcohols such as tetramethylolmethane (pentaerythritol), and diglycerin, pentahydric alcohols such as xylitol, hexahydric alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, and dipentaerythritol, heptahydric alcohols such as avocado sugar, and octahydric alcohols such as sucrose.

These low-molecular-weight polyols may be used alone or in combination of 2 or more.

The low-molecular-weight polyol preferably includes a diol and a triol, and more preferably includes a diol.

Specific examples of such polyoxyethylene polyols include polyoxyethylene glycol and polyoxyethylene triol, and preferred examples thereof include polyoxyethylene glycol.

Examples of polytrimethylene ether glycol include a glycol obtained by polycondensation of 1, 3-propanediol derived from a plant component.

Examples of the polytetramethylene ether polyol include ring-opened polymers (polytetramethylene ether glycol (crystalline)) obtained by cationic polymerization of tetrahydrofuran, amorphous (noncrystalline) polytetramethylene ether glycols obtained by copolymerizing a polymerized unit such as tetrahydrofuran with an alkyl-substituted tetrahydrofuran or the above-mentioned diols, and the like.

The polyoxybranched alkylene (having 3 to 4 carbon atoms) polyol is a polyoxyalkylene polyol having a branched oxyalkylene unit, having no straight oxyalkylene unit, and having 3 to 4 carbon atoms in the oxyalkylene unit.

More specifically, examples of the polyoxybranched alkylene (having 3 to 4 carbon atoms) polyol include addition polymers of propylene oxide and butylene oxide using the above-mentioned low molecular weight polyol, a known low molecular weight polyamine, and the like as an initiator.

In other words, examples of the polyoxybranched alkylene (having 3 to 4 carbon atoms) polyol include polyoxypropylene polyol (polyoxy-1, 2-propylene polyol), polyoxybutylene polyol (polyoxy-1, 2-or-1, 3-butylene polyol), and the like. The polyoxybranched alkylene (having 3 to 4 carbon atoms) polyol is preferably a polyoxypropylene polyol.

The polyoxyalkylene polyol has both a linear oxyalkylene unit and a branched oxyalkylene unit, and the number of carbon atoms in the oxyalkylene unit is 2 to 4.

More specifically, examples of the polyoxy linear or branched alkylene (having 2 to 4 carbon atoms) polyol include the above-mentioned low molecular weight polyol, a known low molecular weight polyamine, and a random and/or block copolymer of propylene oxide and ethylene oxide as an initiator.

These polyether polyols may be used alone or in combination of 2 or more.

The polyether polyol preferably includes a polyoxy linear alkylene (having 2 to 4 carbon atoms) polyol, more preferably a polyoxy linear alkylene (having 2 to 4 carbon atoms) glycol, and still more preferably polytrimethylene ether glycol or polytetramethylene ether glycol, from the viewpoint of appearance, mechanical properties, and durability.

Examples of the polyester polyol include polycondensates obtained by reacting a low-molecular-weight polyol with a polybasic acid under known conditions.

Examples of the low-molecular-weight polyol include the above-mentioned low-molecular-weight polyols, preferably diols, and more preferably propylene glycol and neopentyl glycol.

Examples of the polybasic acid include saturated aliphatic dicarboxylic acids (C11-13) such as oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1-dimethyl-1, 3-dicarboxylpropane, 3-methyl-3-ethylglutaric acid, azelaic acid and sebacic acid, unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, toluic acid and naphthalenedicarboxylic acid, alicyclic dicarboxylic acids such as hexahydrophthalic acid, other carboxylic acids such as dimer acid, hydrogenated dimer acid and chlorendic acid, acid anhydrides derived from these carboxylic acids, such as oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl (C12-C18) succinic anhydride, tetrahydrophthalic anhydride and the like, Trimellitic anhydride, and acid halides derived from these carboxylic acids and the like, such as oxalyl dichloride, adipoyl dichloride, sebacoyl dichloride, and the like.

These polybasic acids may be used alone or in combination of 2 or more.

The polybasic acid preferably includes a saturated aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, and an acid anhydride, more preferably includes adipic acid, phthalic acid, and phthalic anhydride, and still more preferably includes adipic acid.

Examples of the polyester polyol include vegetable oil-based polyester polyols obtained by condensation reaction of a hydroxyl group-containing vegetable oil fatty acid (e.g., castor oil fatty acid containing ricinoleic acid, hydrogenated castor oil fatty acid containing 12-hydroxystearic acid, etc.) and other hydroxycarboxylic acids under known conditions using a vegetable-derived polyester polyol, specifically, the above-mentioned low molecular weight polyol as an initiator.

Examples of the polyester polyol include lactone-based polyester polyols such as polycaprolactone polyols and polypentanolide polyols obtained by ring-opening polymerization of lactones such as e-caprolactone and y-valerolactone, and of lactides such as L-lactide and D-lactide, and alcohol-modified lactone polyols obtained by copolymerization of these compounds with the above-mentioned diol, using the above-mentioned low-molecular-weight polyol (preferably diol) as an initiator.

These polyester polyols may be used alone or in combination of 2 or more.

The polyester polyol preferably includes a lactone-based polyester polyol, and more preferably includes a polycaprolactone polyol.

Examples of the polycarbonate polyol include a ring-opened polymer of ethylene carbonate (crystalline polycarbonate polyol) using the above-mentioned low-molecular-weight polyol (preferably the above-mentioned diol) as an initiator, and an amorphous polycarbonate polyol obtained by copolymerizing a diol having 4 to 6 carbon atoms and a ring-opened polymer.

These polycarbonate polyols may be used alone or in combination of 2 or more.

These macromolecular polyols may be used alone or in combination of 2 or more.

From the viewpoint of improving mechanical properties and durability, the macromolecular polyol preferably includes a polyether polyol, more preferably a polyoxy linear alkylene (having 2 to 4 carbon atoms) polyol, still more preferably a polyoxy linear alkylene (having 2 to 4 carbon atoms) glycol, and particularly preferably a polytrimethylene ether glycol or a polytetramethylene ether glycol.

The average hydroxyl value of the macromolecular polyol (according to JIS K1557-1 (2007)) is, for example, 10mgKOH/g or more, preferably 20mgKOH/g or more, more preferably 40mgKOH/g or more, for example, 500mgKOH/g or less, preferably 300mgKOH/g or less, more preferably 100mgKOH/g or less.

From the viewpoint of appearance, mechanical properties, and durability, the number average molecular weight (molecular weight in terms of polystyrene measured by GPC) of the macropolyol is 400 or more, preferably 500 or more, more preferably 600 or more, further preferably 800 or more, for example, 5000 or less, preferably 3000 or less, more preferably 1300 or less, and further preferably 1200 or less.

Isosorbide is a compound having 2 hydroxyl groups (diol compound), specifically, 1,4:3, 6-dianhydro-glucitol (alias 1,4:3, 6-dianhydro-sorbitol).

Isosorbide can be produced by a known method, and can be obtained as a commercially available product.

The aliphatic diol having 3 to 8 carbon atoms (hereinafter, sometimes referred to as C3 to 8 aliphatic diol) is a compound having a hydrocarbon group having 3 to 8 carbon atoms and 2 hydroxyl groups, and examples thereof include a chain alkane diol having 3 to 8 carbon atoms, a cyclic alkane diol having 3 to 8 carbon atoms, and the like.

Examples of the chain alkanediol having 3 to 8 carbon atoms include straight-chain alkanediols having 3 to 8 carbon atoms such as 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, and 1, 8-octanediol, and branched alkanediols having 3 to 8 carbon atoms such as 1, 2-propanediol, 1, 3-butanediol, 1, 2-butanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, and 2,2, 2-trimethylpentanediol.

These C3-8 chain alkane diols may be used alone or in combination of 2 or more.

The chain alkanediol having 3 to 8 carbon atoms is preferably a linear alkanediol having 3 to 8 carbon atoms, more preferably a linear alkanediol having 3 to 5 carbon atoms, from the viewpoint of durability.

Examples of the cyclic alkanediol having 3 to 8 carbon atoms include alicyclic diols having 6 to 8 carbon atoms in total, such as 1, 2-cyclopropanediol, 1, 2-or 1, 3-cyclobutanediol, 1, 2-or 1, 3-cyclopentanediol, 1,2-, 1, 3-or 1, 4-cyclohexanediol, 1,2-, 1, 3-or 1, 4-cycloheptanediol, 1,2-, 1,3-, 1, 4-or 1, 5-cyclooctanediol, and 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol, such as 1, 2-cyclopropanedimethanol, 1, 2-or 1, 3-cyclobutanedimethanol, 1, 2-or 1, 3-cyclopentanedimethanol, and 1, 2-cyclobutanediol, Alicyclic dimethanol having 6 to 8 total carbon atoms such as 1, 3-or 1, 4-cyclohexanedimethanol, for example, alicyclic diethanol having 6 to 8 total carbon atoms such as 1, 2-cyclopropanediethanol, 1, 2-or 1, 3-cyclobutanediethanol, and the like.

The cyclic alkanediol having 3 to 8 carbon atoms preferably includes a cyclic alkanediol having 6 to 8 carbon atoms, and more preferably includes an alicyclic dimethanol having 6 to 8 carbon atoms.

These C3-8 aliphatic diols may be used alone or in combination of 2 or more.

When an aliphatic diol having 2 carbon atoms (e.g., ethylene glycol) is used as the aliphatic diol, the appearance and transparency are poor. In addition, when an aliphatic diol having 9 or more carbon atoms (such as decanediol) is used, mechanical properties and durability are poor. Therefore, as the aliphatic diol, an aliphatic diol having 3 to 8 carbon atoms can be used.

The C3-8 aliphatic diol preferably includes a linear alkane diol having 3-5 carbon atoms and/or a cyclic alkane diol having 6-8 carbon atoms, more preferably includes 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 4-cyclohexanedimethanol, and further preferably includes 1, 3-propanediol and 1, 4-butanediol, from the viewpoint of appearance, transparency, mechanical properties, and durability.

In the polyol component, the proportions of the high molecular weight polyol, isosorbide and C3-8 aliphatic diol can be adjusted within the range of the reaction equivalent ratio described later.

For example, the content of the high-molecular-weight polyol is, for example, 35 parts by mass or more, preferably 45 parts by mass or more, for example 75 parts by mass or less, preferably 65 parts by mass or less, the content of isosorbide is, for example, 20 parts by mass or more, preferably 30 parts by mass or more, for example 55 parts by mass or less, preferably 45 parts by mass or less, and the content of the C3 to 8 aliphatic diol is, for example, 2 parts by mass or more, preferably 5 parts by mass or more, for example 30 parts by mass or less, preferably 20 parts by mass or less, based on 100 parts by mass of the total amount of the polyol components.

The content of isosorbide is, for example, 40 parts by mass or more, preferably 50 parts by mass or more, for example, 100 parts by mass or less, preferably 90 parts by mass or less, per 100 parts by mass of the high molecular weight polyol.

The content of the C3-8 aliphatic diol is, for example, 3 parts by mass or more, preferably 5 parts by mass or more, for example, 30 parts by mass or less, preferably 20 parts by mass or less, per 100 parts by mass of the high molecular weight polyol.

The content of isosorbide is, for example, 200 moles or more, preferably 250 moles or more, for example 800 moles or less, preferably 700 moles or less, based on 100 moles of the high molecular weight polyol. The content of the C3-8 aliphatic diol is, for example, 30 moles or more, preferably 50 moles or more, for example, 350 moles or less, preferably 250 moles or less.

The total ratio of isosorbide and C3-8 aliphatic diol is, for example, 230 moles or more, preferably 300 moles or more, for example 1150 moles or less, preferably 950 moles or less, based on 100 moles of the high molecular weight polyol.

From the viewpoint of achieving both appearance, transparency, mechanical properties, and durability, the content of isosorbide is 60 mol% or more, preferably 65 mol% or more, more preferably 70 mol% or more, further preferably 75 mol% or more, particularly preferably 78 mol% or more, and 95 mol% or less, preferably 90 mol% or less, more preferably 88 mol% or less, further preferably 85 mol% or less, and particularly preferably 83 mol% or less, based on the total number of moles of isosorbide and C3 to 8 aliphatic diol. The content of the C3 to 8 aliphatic diol is, for example, 5 mol% or more, preferably 10 mol% or more, more preferably 12 mol% or more, further preferably 15 mol% or more, particularly preferably 17 mol% or more, for example 40 mol% or less, preferably 35 mol% or less, more preferably 30 mol% or less, further preferably 25 mol% or less, and particularly preferably 22 mol% or less.

The content of isosorbide is, for example, 70% by mass or more, preferably 75% by mass or more, more preferably 78% by mass or more, further preferably 80% by mass or more, for example, 98% by mass or less, preferably 93% by mass or less, more preferably 90% by mass or less, further preferably 88% by mass or less, based on the total mass of isosorbide and C3 to 8 aliphatic diol. The content of the C3-8 aliphatic diol is, for example, 2 mass% or more, preferably 5 mass% or more, more preferably 8 mass% or more, further preferably 10 mass% or more, for example, 30 mass% or less, preferably 25 mass% or less, more preferably 23 mass% or less, and further preferably 20 mass% or less.

When the ratio of isosorbide to the C3-8 aliphatic diol is in the above range, a thermoplastic polyurethane resin having appearance, transparency, mechanical properties and durability can be obtained.

The thermoplastic polyurethane resin can be produced by reacting the above-mentioned raw material components. For the reaction of the raw material components, known methods such as a one-shot method and a prepolymer method can be used. The prepolymer method is preferably used from the viewpoint of improving appearance, transparency, mechanical properties and durability.

In the prepolymer method, first, an isocyanate-terminated prepolymer is synthesized by reacting a polyisocyanate component with a macromolecular polyol (prepolymer synthesis step).

More specifically, in the prepolymer synthesis step, the polyisocyanate component and the macropolyol are reacted by a polymerization method such as bulk polymerization or solution polymerization.

In the bulk polymerization, for example, the polyisocyanate component and the macropolyol are reacted at a reaction temperature of, for example, 50 ℃ or higher, for example, 250 ℃ or lower, preferably 200 ℃ or lower, for example, 0.5 hours or longer, for example, 15 hours or shorter, under a nitrogen gas flow.

In the solution polymerization, the polyisocyanate component and the macropolyol are added to the organic solvent, and the reaction is carried out at a reaction temperature of, for example, 50 ℃ or higher, for example, 120 ℃ or lower, preferably 100 ℃ or lower, for example, 0.5 hours or longer, for example, 15 hours or shorter.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, nitriles such as acetonitrile, alkyl esters such as methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate, aliphatic hydrocarbons such as n-hexane, n-heptane and octane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, aromatic hydrocarbons such as toluene, xylene and ethylbenzene, glycol ether esters such as methylcellosolve acetate, ethylcellosolve acetate, methylcarbitol acetate, ethylcarbitol acetate, ethyleneglycolethylether acetate, propyleneglycolmethyletheracetate, 3-methyl-3-methoxybutyl acetate and ethyl 3-ethoxypropionate, ethers such as diethyl ether, tetrahydrofuran and dioxane, methyl chloride, dichloromethane, chloroform, carbon tetrachloride, Halogenated aliphatic hydrocarbons such as methyl bromide, diiodomethane and dichloroethane, and polar non-protic hydrocarbons such as N-methylpyrrolidone, dimethylformamide, N' -dimethylacetamide, dimethyl sulfoxide and hexamethylphosphoramide.

In the above polymerization reaction, a known urethanization catalyst such as an amine or an organic metal compound may be added as necessary.

Examples of the amines include tertiary amines such as triethylamine, triethylenediamine, bis- (2-dimethylaminoethyl) ether, and N-methylmorpholine, quaternary ammonium salts such as tetraethylammonium hydroxide, and imidazoles such as imidazole and 2-ethyl-4-methylimidazole.

Examples of the organic metal compound include tin acetate, tin octoate (stannous octoate), tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dithiolate, dibutyltin maleate, dibutyltin dineodecanoate, dioctyltin dithiolate, dioctyltin dilaurate, dibutyltin dichloride and other organic tin compounds, for example, lead octoate, lead naphthenate and other organic lead compounds, for example, nickel naphthenate and other organic nickel compounds, for example, cobalt naphthenate and other organic cobalt compounds, for example, copper octenate and other organic copper compounds, for example, bismuth octoate (bismuth octoate), bismuth neodecanoate and other organic bismuth compounds, and tin octoate and bismuth octoate are preferably used.

Examples of the carbamation catalyst include potassium salts such as potassium carbonate, potassium acetate, and potassium octylate.

These urethane-forming catalysts may be used alone or in combination of 2 or more.

The proportion of the urethane-forming catalyst to be added is, for example, 0.001 parts by mass or more, preferably 0.01 parts by mass or more, for example, 1 part by mass or less, preferably 0.5 parts by mass or less, per 10000 parts by mass of the total amount of the polyisocyanate component and the macropolyol.

In the polymerization reaction, for example, unreacted polyisocyanate component and an organic solvent in the case of using an organic solvent can be removed by a known removal method such as distillation or extraction.

In the prepolymer synthesis step, the blending ratio of each component is, for example, 1.3 or more, preferably 1.5 or more, for example, 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 8 or less in terms of the equivalent ratio (isocyanate group/hydroxyl group) of the isocyanate group in the polyisocyanate component to the hydroxyl group in the macropolyol.

More specifically, the mixing ratio of each component in the prepolymer synthesis step is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, for example, 200 parts by mass or less, and preferably 150 parts by mass or less, relative to 100 parts by mass of the macropolyol.

In this method, the above components are reacted until the isocyanate group content reaches, for example, 5.0 mass% or more, more preferably 10.0 mass% or more, for example, 30.0 mass% or less, preferably 25.0 mass% or less. Thus, an isocyanate group-terminated prepolymer can be obtained.

The content of isocyanate groups (content of isocyanate groups) can be determined by a known method such as titration with di-n-butylamine and FT-IR analysis.

Next, in this method, the isocyanate group-terminated prepolymer obtained in the above manner is subjected to a chain extension reaction (curing reaction) with isosorbide and a C3 to 8 aliphatic diol to obtain a reaction product of a polyisocyanate component and a polyol component (chain extension step).

That is, in this method, isosorbide and a C3-8 aliphatic diol are used as chain extenders.

In the chain extension step, the isocyanate group-terminated prepolymer is reacted with isosorbide and a C3-8 aliphatic diol by a polymerization method such as the above-mentioned bulk polymerization or the above-mentioned solution polymerization.

In the chain extension step, the blending ratio of each component is, for example, 0.75 or more, preferably 0.9 or more, for example, 1.3 or less, preferably 1.1 or less, in terms of the equivalent ratio (isocyanate group/hydroxyl group) of the isocyanate group in the isocyanate group-terminated prepolymer to the total amount of the hydroxyl group in the isosorbide and the hydroxyl group in the C3 to 8 aliphatic diol.

More specifically, the blending ratio of each component in the chain extension step is, for example, 1.0 part by mass or more, preferably 2.0 parts by mass or more, more preferably 3.0 parts by mass or more, for example 50 parts by mass or less, preferably 40 parts by mass or less, and more preferably 30 parts by mass or less, relative to 100 parts by mass of the isocyanate-terminated prepolymer.

In the chain extension step, in order to adjust the hard segment concentration of the thermoplastic polyurethane resin obtained, a macropolyol may be blended in an appropriate ratio in addition to isosorbide and the C3 to 8 aliphatic diol.

In this reaction, the above-mentioned urethanization catalyst may be added, if necessary. The urethane-forming catalyst may be added to the isocyanate group-terminated prepolymer, isosorbide and/or C3-8 aliphatic diol, or may be added separately when they are mixed.

The curing temperature (reaction temperature) in the chain extension step is, for example, room temperature (23 ℃) or higher, preferably 100 ℃ or higher, more preferably 150 ℃ or higher, for example 300 ℃ or lower, preferably 260 ℃ or lower, and more preferably 240 ℃ or lower.

The curing time (reaction time) is, for example, 30 minutes or more, preferably 1 hour or more, for example, 48 hours or less, preferably 24 hours or less.

When the curing temperature and the curing time are within the above ranges, a thermoplastic polyurethane resin having appearance, transparency, mechanical properties and durability can be obtained.

In the chain extension step, the curing reaction (primary heating) may be followed by secondary heating to complete the reaction, if necessary.

The secondary heating temperature is, for example, room temperature (23 ℃) or higher, preferably 50 ℃ or higher, more preferably 80 ℃ or higher, for example 200 ℃ or lower, preferably 160 ℃ or lower, and more preferably 140 ℃ or lower.

The secondary heating time is, for example, 3 hours or more, preferably 5 hours or more, for example 72 hours or less, preferably 48 hours or less.

By such secondary heating, the chain extension reaction is completed, and a reaction product of the polyisocyanate component and the polyol component can be obtained, and a thermoplastic polyurethane resin can be obtained.

The obtained thermoplastic polyurethane resin may be cured, for example, for 1 to 7 days at room temperature (23 ℃) to 40 ℃ as required.

Further, such a thermoplastic polyurethane resin has appearance, transparency, mechanical properties, and durability because it contains 1, 4-bis (isocyanatomethyl) cyclohexane, a macropolyol, and an aliphatic diol having 3 to 8 carbon atoms and isosorbide in a predetermined ratio as raw material components.

Further, by the above-mentioned method for producing a thermoplastic polyurethane resin, a thermoplastic polyurethane resin having appearance, transparency, mechanical properties and durability can be easily obtained.

In addition, in the case of using the one-shot method as a method for obtaining the above-mentioned reaction product, the polyisocyanate component and the polyol component (including the macropolyol, the isosorbide and the C3 to 8 aliphatic diol) are blended together in such a ratio that the equivalent ratio of the isocyanate group in the polyisocyanate component to the hydroxyl group in the polyol component (isocyanate group/hydroxyl group) is, for example, 0.9 or more, preferably 0.95 or more, more preferably 0.98 or more, for example, 1.2 or less, preferably 1.1 or less, more preferably 1.08 or less, and stirred and mixed.

The stirring and mixing are carried out, for example, under an inert gas (e.g., nitrogen) atmosphere at a reaction temperature of, for example, 40 ℃ or higher, preferably 100 ℃ or higher, for example, 280 ℃ or lower, preferably 260 ℃ or lower, for a reaction time of, for example, 30 seconds or longer and 1 hour or shorter.

In addition, the urethane-forming catalyst and the organic solvent may be added at an appropriate ratio as required during stirring and mixing.

By this method, a reaction product of the polyisocyanate component and the polyol component can be obtained, and a thermoplastic polyurethane resin can be obtained.

The thermoplastic polyurethane resin may contain a phosphorous acid antioxidant as needed in addition to the reaction product of the polyisocyanate component and the polyol component.

Examples of the phosphite-based antioxidant include triphenyl phosphite, trisnonylphenyl phosphite, tricresyl phosphite, triethyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tris (tridecyl) phosphite, trioleyl phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl mono (tridecyl) phosphite, trilauryl trithiophosphite, diethyl phosphite, tetraphenylpropylene glycol diphosphite, tetraphenyl (tetra (tridecyl)) pentaerythritol tetraphosphite, bis (2-ethylhexyl) phthalate, tetrakis (C12-C15 alkyl) -4, 4' -isopropylidene (isopropylidene) diphenyl diphosphite, and mixtures thereof, Phosphites such as bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (decyl) pentaerythritol diphosphite, bis (tridecyl) pentaerythritol diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, tris (2, 4-di-t-butylphenyl) phosphite, hydrogenated bisphenol a pentaerythritol phosphite polymers, and hydrogenated bisphenol a phosphite polymers.

These phosphorous acid antioxidants may be used alone or in combination of 2 or more.

The phosphite antioxidant is preferably a phosphite ester, and more preferably bis (decyl) pentaerythritol diphosphite.

The phosphorous acid-based antioxidant may be added to the polyisocyanate component and/or the polyol component, for example, simultaneously with the mixing of the polyisocyanate component and the polyol component, or may be added after the mixing of the polyisocyanate component and the polyol component.

The content ratio of the phosphorous acid-based antioxidant is, for example, 0.05 parts by mass or more, preferably 0.10 parts by mass or more, more preferably 0.30 parts by mass or more, for example 2.0 parts by mass or less, preferably 1.0 parts by mass or less, more preferably 0.8 parts by mass or less, relative to 100 parts by mass of the reaction product of the polyisocyanate component and the polyol component.

When the content ratio of the phosphorous acid-based antioxidant is within the above range, a thermoplastic polyurethane resin having excellent appearance, transparency, mechanical properties and durability can be obtained.

In addition, the raw material components may contain other known additives as needed. Examples of such additives include a heat stabilizer, an ultraviolet absorber, a light stabilizer, an antioxidant (excluding a phosphorous antioxidant), a hydrolysis inhibitor, a plasticizer, an antiblocking agent, a mold release agent, a pigment, a dye, a lubricant, a filler, a rust inhibitor, and a filler. These additives may be added at the time of mixing, at the time of synthesis, or after synthesis of the respective components.

The heat stabilizer is not particularly limited, and known heat stabilizers (for example, described in the catalog of BASF Japan) can be mentioned, and more specifically, phosphorus-based processing heat stabilizers, lactone-based processing heat stabilizers, sulfur-based processing heat stabilizers and the like can be mentioned.

The ultraviolet absorber is not particularly limited, and known ultraviolet absorbers (for example, those described in the catalogues of BASF Japan), and more specifically, benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and the like are mentioned.

The light stabilizer is not particularly limited, and known light stabilizers (for example, those described in the product catalog of ADEKA) can be mentioned, and more specifically, a benzoate-based light stabilizer, a hindered amine-based light stabilizer, and the like can be mentioned.

The addition amount of these additives can be appropriately set according to the purpose and use.

The additive may be added to the polyisocyanate component and/or the polyol component, simultaneously with the mixing of the polyisocyanate component and the polyol component, or after the mixing of the polyisocyanate component and the polyol component.

Such a thermoplastic polyurethane resin can be used as various molded articles by molding it by a known molding method.

More specifically, the molded article of the thermoplastic polyurethane resin can be obtained by molding the thermoplastic polyurethane resin into various shapes such as a pellet shape, a plate shape, a fiber shape, a strand shape, a film shape, a sheet shape, a tube shape, a hollow shape, a box shape, and the like, for example, by a known molding method such as hot compression molding and injection molding using a specific mold, extrusion molding using a sheet winding device, or thermoforming processing such as melt spinning molding.

The resulting molded article can have appearance, transparency, mechanical properties, and durability. Therefore, the molded article can be suitably used in fields where the above-mentioned various physical properties are required.

More specifically, the above thermoplastic polyurethane resin can be suitably used for the polyurethane resin for optical use.

The optical polyurethane resin containing the thermoplastic polyurethane resin has appearance, transparency, mechanical properties and durability, and thus satisfies desired optical properties and is excellent in practical use.

Therefore, the optical urethane resin can be suitably used as a cover plate for a display panel, for example.

Examples of the display panel include display panels of various information processing terminals such as smart devices (smart phones, tablet computers (tablet PCs), and the like), desktop computers, and notebook computers. These display panels generally include an image display panel such as a liquid crystal panel, and a light-transmitting cover sheet (cover sheet for display panel) is laminated on the surface of the image display panel to protect the image display panel.

Such a cover plate for a display panel is required to have excellent appearance, transparency, mechanical properties, and durability. Therefore, the molded article of the optical urethane resin is suitable as a cover plate for a display panel.

In other words, the display cover plate obtained using the above-described optical polyurethane resin has excellent appearance, transparency, mechanical properties, and durability.

The thermoplastic polyurethane resin can be suitably used as a material for spectacles, for example.

The spectacle material is used for molding spectacle lenses, spectacle frames, and the like in spectacles such as corrective spectacles, protective spectacles, sunglasses, and goggles.

That is, the spectacle lens and the spectacle frame are sometimes required to have excellent appearance, transparency, mechanical properties, and durability.

Therefore, the thermoplastic polyurethane resin can be suitably used as a spectacle material, and a molded article of the thermoplastic polyurethane can be suitably used as a spectacle lens, a spectacle frame, or the like.

Specifically, in the production of a spectacle lens, a spectacle material containing the thermoplastic polyurethane resin is molded into a lens shape by a known method to form a lens body. Then, a hard coat layer and/or an antireflection layer is preferably laminated on at least one surface of the lens body. Thereby, a spectacle lens was obtained.

The hard coat layer may have a known structure, and examples thereof include a Si coat layer containing silicon oxide, trimethoxymethylsilane, a hydrolysate thereof, and the like. The antireflection layer may have a known structure, and examples thereof include a metal deposition layer of a metal oxide (e.g., silicon oxide or zirconium oxide). The hard coat layer and the antireflection layer may be a single layer or a plurality of layers.

In addition, in the production of the eyeglass frame, the eyeglass material containing the thermoplastic polyurethane resin is molded into the shape of each member of the eyeglass frame by a known method.

Examples of the members of the eyeglass frame include lenses, nose pads (nose pad portions), temples (ear pad portions), temples (hanging portions), rims (lens peripheral portions), rim beams (rim connecting portions), stubs (both front end portions), hinges (connecting portions between the stubs and the temples), and the like.

Such eyeglass frames and eyeglass lenses include the thermoplastic polyurethane resin, and thus have appearance, transparency, mechanical properties, and durability.

The thermoplastic polyurethane resin can be suitably used as a member for automobile interior and exterior materials.

Examples of the interior and exterior materials for automobiles include known interior and exterior materials for automobiles such as bumpers, headlamps, tail lamps, instrument panels, shift levers, and steering wheels.

Various members constituting such automotive interior and exterior materials (for example, a head lamp cover, a tail lamp cover, an instrument panel cover, a grip of a shift lever, a grip of a steering wheel, and the like) are sometimes required to have excellent appearance, transparency, mechanical properties, and durability.

Therefore, the molded article of the thermoplastic polyurethane resin can be suitably used as a member for automobile interior and exterior materials.

Specifically, in the production of the parts for automobile interior and exterior materials, the thermoplastic polyurethane resin is molded into various shapes of the parts for automobile interior and exterior materials by a known method. Thus, an automobile interior/exterior material part was obtained.

Such an automotive interior/exterior material member includes the thermoplastic polyurethane resin described above, and thus has appearance, transparency, mechanical properties, and durability.

In addition to the above-mentioned applications, the molded article of the thermoplastic polyurethane resin can be widely used industrially, and specifically, can be suitably used for, for example, a transparent rigid plastic, a coating material, an adhesive, a waterproof material, a potting agent, an ink, an adhesive, a film, a sheet, a tape (for example, a tape such as a watch band, a tape such as a power transmission belt for an automobile, various industrial transmission belts (a conveyor belt), a tube (for example, a tube such as an air tube, a hydraulic tube, and a wire tube, a hose such as a fire hose, in addition to a medical tube and a catheter), a blade, a speaker, a sensor, a high-brightness LED sealing agent, an organic EL member, a photovoltaic power generation member, a robot member, an intelligent robot member, a wearable member, clothing, a sanitary product, a cosmetic product, a food packaging member, a sporting product, a recreational product, a portable product, medical supplies, nursing materials, members for housing, acoustic members, illumination members, chandeliers, outdoor lamps, sealing materials, corks, fillers, vibration-proof, vibration-damping, and shock-proof members, sound-proof members, daily necessities, miscellaneous goods, bumpers, bedding, stress absorbing materials, stress relaxing materials, interior and exterior parts for automobiles, railway members, aircraft members, optical members, members for OA equipment, surface protecting members for miscellaneous goods, semiconductor packaging materials, self-repairing materials, health appliances, eyeglass lenses, toys, cable coverings, wiring, electrical communication cables, automobile wiring, industrial products such as computer wiring and extension lines, nursing materials such as sheets and films, sporting goods, entertainment goods, miscellaneous goods, vibration-proof, and shock-absorbing materials, optical materials, films such as light guide films, automobile parts, surface protecting sheets, and the like, A belt member such as a cosmetic sheet, a transfer sheet, a semiconductor protective tape, a golf ball member, a string for a tennis racket, an agricultural film, a wallpaper, an anti-fogging agent, a nonwoven fabric, a mattress, a sofa or the like furniture article, a brassiere, a shoulder pad or the like clothing article, a paper diaper, a cloth towel, a medical article such as a cushion material for a medical tape, a cosmetic, a sanitary article such as a washing sponge, a pad or the like, a shoe article such as a sole (outsole), a midsole, a casing material or the like, a vehicle pad, a body pressure-distributing article such as a cushion or the like, a door trim, an instrument panel, a shift knob or the like which is brought into contact with a hand, a refrigerator, a heat insulating material for a building, an impact-absorbing material such as a damper or the like, a filler.

Further, the molded article can be suitably used for a coating material (a coating material for a film, a sheet, a tape, a wire, an electric wire, a metal rotary machine, a wheel, a drill, etc.), a wire, a fiber (a wire or a composite fiber used for a tube, a panty brief, a sportswear, a swimsuit, etc.), an extrusion molding use (an extrusion molding use for strings of tennis balls, badminton balls, etc., and a bundling material thereof), a hollow molded article in a powder form based on micro-granulation, etc., an artificial leather, a skin, a sheet, a coating roller (a coating roller of steel, etc.), a sealant, a roller, a gear, a ball, a shell or core material of a bat (a shell or core material of a golf ball, a basketball, a tennis ball, a volleyball, a softball, a baseball, etc. (these may be in a form of a grip formed by foam molding of a thermoplastic polyurethane resin), a mat, a ski wear, a boot, a tennis wear, a golf, Handles of two-wheeled vehicles and the like), rack covers, wipers, seat cushion members, films for care products, 3D print moldings, fiber-reinforced materials (reinforcing materials of fibers such as carbon fiber, lignin, kenaf, nanofiber, and glass fiber), safety goggles, sunglasses, eyeglass frames, ski goggles, swimming goggles, contact lenses, gas-assisted foam moldings, shock absorbers, CMP pads, dampers (dampers), bearings, dust covers, cutting valves, cutting rollers, high-speed rotating rollers, tires, clocks, wearable belts, and the like.

Examples

The present invention will be described based on production examples, synthesis examples, and comparative examples, but the present invention is not limited to these. Unless otherwise specified, "part(s)" and "%" are based on mass. Specific numerical values such as the blending ratio (content ratio), the physical property value, and the parameter used in the following description may be replaced with upper limit values (numerical values defined as "below" and "insufficient") or lower limit values (numerical values defined as "above" and "exceeding") described in the above-described "embodiment" in accordance with the blending ratio (content ratio), the physical property value, and the parameter described therein.

< 1, 4-bis (isocyanatomethyl) cyclohexane (1, 4-H)₆XDI) production

Production example 11, 4-bis (isocyanatomethyl) cyclohexane (1) (hereinafter, referred to as 1,4-BIC (1).)

According to the description of production example 6 of Japanese patent application laid-open No. 2014-55229, 1, 4-bis (aminomethyl) cyclohexane having a trans-isomer/cis-isomer ratio of 98/2 and having a purity of 99.5% or more is obtained in a yield of 92%.

Then, 382 parts by mass of 1,4-BIC (1) was obtained by a two-step cold and hot phosgenation method under pressure using the 1, 4-bis (aminomethyl) cyclohexane as a raw material as described in production example 1 of Japanese patent application laid-open No. 2014-55229.

The purity of the obtained 1,4-BIC (1) was 99.9% as determined by gas chromatography¹³The trans/cis ratio was 98/2 as determined by C-NMR.

Production example 21, 4-bis (isocyanatomethyl) cyclohexane (2) (hereinafter, referred to as 1,4-BIC (2))

A four-necked flask equipped with a stirrer, a thermometer, a reflux tube and a nitrogen gas inlet was charged with 789 parts by mass of 1,4-BIC (1) of production example 1 and 211 parts by mass of 1,4-BIC (4) of production example 4 described later, and stirred at room temperature for 1 hour under a nitrogen atmosphere. The purity of the obtained 1,4-BIC (2) was 99.9% as determined by gas chromatography¹³The trans/cis ratio obtained by C-NMR measurement was 86/14.

Production example 31, 4-bis (isocyanatomethyl) cyclohexane (3) (hereinafter, 1,4-BIC (3).)

A four-necked flask equipped with a stirrer, a thermometer, a reflux tube and a nitrogen gas inlet was charged with 474 parts by mass of 1,4-BIC (1) of production example 1 and 526 parts by mass of 1,4-BIC (4) of production example 4 described later, and stirred at room temperature for 1 hour under a nitrogen atmosphere. The purity of the obtained 1,4-BIC (3) was 99.9% as determined by gas chromatography¹³The trans/cis ratio obtained by C-NMR measurement was 68/32.

Production example 41, 4-bis (isocyanatomethyl) cyclohexane (4) (hereinafter, 1,4-BIC (4).)

Will utilize¹³1, 4-bis (aminomethyl) cyclohexane (manufactured by Tokyo chemical industry Co., Ltd.) having a trans/cis ratio of 41/59 as a raw material in accordance with the description of production example 1 of Japanese patent application laid-open No. 2014-55229 was subjected to C-NMR measurement to obtain 388 parts by mass of 1,4-BIC (4).

The purity of the obtained 1,4-BIC (4) was 99.9% as determined by gas chromatography¹³The trans/cis ratio was 41/59 as determined by C-NMR.

< production and Molding of thermoplastic polyurethane resin >

Example 1

To a four-necked flask equipped with a stirrer, a thermometer, a reflux tube and a nitrogen introduction tube, 33.51 parts by mass of PTG1000SN (P) (polytetramethylene ether glycol using a biomass raw material, number average molecular weight: 1000, manufactured by baotu chemical industries co., ltd.), and 41.89 parts by mass of 1,4-BIC (2) having a trans/cis ratio of 86/14 was charged so that the equivalent ratio (NCO/OH) became 6.50. Then, the reaction was carried out until the isocyanate group content became 20.32 mass%, to obtain an isocyanate group-terminated prepolymer (hereinafter, may be simply referred to as a prepolymer).

75.71 parts by mass of a prepolymer previously adjusted to 80 ℃, 0.30 part by mass of IRGANOX 245 (manufactured by BASF Japan, heat-resistant stabilizer), 0.25 part by mass of TINUVIN 234 (manufactured by BASF Japan, ultraviolet absorber), 0.09 part by mass of ADK STAB LA-72 (manufactured by ADEKA, light stabilizer), JPE-10 (manufactured by North City chemical industry Co., Ltd., phosphorous acid-based antioxidant), and 0.013 part by mass of a catalyst liquid obtained by diluting Stanoct (manufactured by API Corporation, stannous octoate) to 4% by mass with DINA (J-PLUS Co., Ltd., diisononyl adipate) were put into a stainless steel container and stirred and mixed with a disperser at 800rpm for about 2 minutes by using a high speed.

Next, a mixture of isosorbide (POLYSORB P, manufactured by ROQUETTE) and 1, 4-butanediol (1,4-BD, manufactured by mitsubishi chemical corporation) as chain extenders (isosorbide: 1, 4-BD: 80:20 (molar ratio)) was adjusted to 80 ℃, and this mixture was added to the prepolymer so that the equivalent ratio (NCO/OH) became 1.00.

Then, the mixture was sufficiently stirred for about 10 minutes until the whole was uniform, and after the stirring was stopped, the uniformity of the reaction mixture was immediately confirmed, and then the reaction mixture was poured into a Teflon (registered trademark) layer on a SUS (stainless steel) barrel (vat) previously adjusted to 180 ℃ to perform a reaction at 180 ℃ for 2 hours, and then a reaction was performed at 100 ℃ for 20 hours to obtain a thermoplastic polyurethane resin.

The thermoplastic polyurethane resin was taken out from the barrel and aged for 3 days under constant temperature and humidity conditions at a room temperature of 23 ℃ and a relative humidity of 50%.

Then, the thermoplastic polyurethane is cut into dice by a cutter, and the dice-shaped resin is pulverized by a pulverizer. The pulverized particles were dried at 80 ℃ for a whole day and night under a nitrogen gas stream. Pellets of thermoplastic polyurethane were obtained by extruding a strand at a cylinder temperature of 185 to 250 ℃ using a single-screw extruder (model: SZW40-28MG, manufactured by TECHNOLOGEL Co., Ltd.) and cutting the strand. The resulting granules were further dried at 80 ℃ for a whole day and night under a nitrogen gas flow.

Next, the pellets were injection molded using an injection molding machine (model: SE-180DU, manufactured by Sumitomo heavy machinery industries, Ltd.) at a cylinder temperature of 185 to 250 ℃ and a nozzle temperature in the range of 185 to 245 ℃ to obtain a sheet (thickness: 2.0mm), a lens body (thickness: 2.0mm, diameter: 75mm, plane lens (plano), 4curve) and a slab (thickness: 10 cm. times.10 cm. times.12 mm) of the thermoplastic polyurethane resin.

Further, a hard coat layer and an antireflection layer are laminated on the lens body by the following processes.

That is, the lens body was annealed at 120 ℃ for 3 hours, then washed with a 10% aqueous solution of sodium hydroxide at 50 ℃ for 10 minutes in an ultrasonic washing tank, then washed with isopropyl alcohol, and the surface was dried at 50 ℃.

Next, the lens body was immersed in a hard coating composition containing silicon oxide, trimethoxymethylsilane, and a hydrolysate thereof, and then lifted up at a rate of 150 mm/min. Then, the hard coat composition was preheated at 80 ℃ for 10 minutes and then heated at 120 ℃ for 6 hours to cure it. Thereby, a hard coat layer is formed on the surface of the lens body.

Next, on the lens body on which the hard coat layer was formed, a 5-layer multi-layer antireflection layer made of silicon oxide and zirconium oxide was formed on the hard coat layer using a vacuum deposition apparatus.

Thus, a spectacle lens provided with a lens body, a hard coat layer and an antireflection layer was obtained.

Example 2

A thermoplastic polyurethane resin was produced and molded into a sheet, a slab and a spectacle lens in the same manner as in example 1 except that PTG1000SN (P) in example 1 was changed to 33.51 parts by mass, 1,4-BIC (2) was changed to 42.20 parts by mass, and the molar ratio of isosorbide to 1, 4-butanediol (isosorbide: 1,4-BD) was changed to 75: 25.

Comparative example 1

A thermoplastic polyurethane resin was produced and molded into a sheet, a slab and a spectacle lens in the same manner as in example 1 except that PTG1000SN (P) in example 1 was changed to 33.51 parts by mass, 1,4-BIC (2) was changed to 43.27 parts by mass, and the molar ratio of isosorbide to 1, 4-butanediol (isosorbide: 1,4-BD) was changed to 58: 42.

Comparative example 2

A thermoplastic polyurethane resin was produced and molded into a sheet, a slab and a spectacle lens in the same manner as in example 1 except that PTG1000SN (P) in example 1 was changed to 33.51 parts by mass, 1,4-BIC (2) was changed to 40.90 parts by mass, and the molar ratio of isosorbide to 1, 4-butanediol (isosorbide: 1,4-BD) was changed to 97: 3.

Comparative example 3

A thermoplastic polyurethane resin was produced in the same manner as in example 1 except that PTG1000SN (P) in example 1 was changed to 32.21 parts by mass, and 16.66 parts by mass of 1,4-BIC (2) and 26.53 parts by mass of diisocyanatomethylbicyclo [2, 2, 1] -heptane (NBDI, manufactured by mitsui chemical corporation) were used in place of 1,4-BIC (2) (1,4-BIC: NBDI: 40:60 (molar ratio)), and sheets, slabs, and spectacle lenses were molded.

Comparative example 4

A thermoplastic polyurethane resin was produced in the same manner as in example 1 except that PTG1000SN (P) in example 1 was changed to 33.51 parts by mass and 1,4-BIC (2) was changed to 42.06 parts by mass, and a mixture of 1, 4-cyclohexanedimethanol (manufactured by chanko industries, inc., CHDM-D) and 1, 4-butanediol (CHDM-D:1, 4-BD: 80:20 (molar ratio)) was used instead of the mixture of isosorbide and 1, 4-butanediol, and sheets, slabs, and spectacle lenses were molded.

Comparative example 5

A thermoplastic polyurethane resin was produced in the same manner as in example 1 except that PTG1000SN (P) in example 1 was changed to 33.51 parts by mass and 1,4-BIC (2) was changed to 40.73 parts by mass and 25.76 parts by mass of isosorbide was used instead of the mixture of isosorbide and 1, 4-butanediol, and sheets, slabs and spectacle lenses were molded.

Example 3

A thermoplastic polyurethane resin was produced in the same manner as in example 1 except that PTG1000SN (P) in example 1 was changed to 33.51 parts by mass and 41.89 parts by mass of 1,4-BIC (1) having a trans/cis ratio of 98/2 was used instead of 1,4-BIC (2), and sheets, slabs and spectacle lenses were molded.

Example 4

A thermoplastic polyurethane resin was produced in the same manner as in example 1 except that PTG1000SN (P) in example 1 was changed to 33.51 parts by mass and 41.89 parts by mass of 1,4-BIC (3) having a trans/cis ratio of 68/32 was used instead of 1,4-BIC (2), and sheets, slabs and spectacle lenses were molded.

Example 5

A thermoplastic polyurethane resin was produced in the same manner as in example 1 except that PTG1000SN (P) in example 1 was changed to 33.51 parts by mass, 1,4-BIC (2) was changed to 41.59 parts by mass, and a mixture of isosorbide and 1, 5-pentanediol (1, 5-petd yokoku co., ltd) was changed instead of the mixture of isosorbide and 1, 4-butanediol (isosorbide: 1, 5-petd: 80:20 (molar ratio)), and sheets, slabs, and spectacle lenses were molded.

Example 6

A thermoplastic polyurethane resin was produced in the same manner as in example 1 except that PTG1000SN (P) in example 1 was changed to 33.51 parts by mass, 1,4-BIC (2) was changed to 41.89 parts by mass, and a mixture of isosorbide and 1, 3-butanediol (1,3-BD and Wako pure chemical industries, Ltd.) was changed instead of the mixture of isosorbide and 1, 4-butanediol (isosorbide: 1,3-BD is 80:20 (molar ratio)), and sheets, slabs and spectacle lenses were molded.

Example 7

A thermoplastic polyurethane resin was produced in the same manner as in example 1 except that PTG1000SN (P) in example 1 was changed to 33.51 parts by mass and 1,4-BIC (2) was changed to 42.20 parts by mass and a mixture of isosorbide and 1, 3-propanediol (1,3-PrD, manufactured by DuPont, suserra, registered trademark, 1, 3-propanediol using biomass material) (isosorbide: 1, 3-PrD: 80:20 (molar ratio)) was used instead of the mixture of isosorbide and 1, 4-butanediol, and a sheet, a slab and a spectacle lens were molded.

Example 8

A thermoplastic polyurethane resin was produced in the same manner as in example 1 except that PTG1000SN (P) in example 1 was changed to 33.51 parts by mass, and 1,4-BIC (2) was changed to 40.77 parts by mass, instead of the mixture of isosorbide and 1, 4-butanediol, a mixture of isosorbide and 1, 4-cyclohexanedimethanol (changi corporation, CHDM-D: 80:20 (molar ratio)), and sheets, slabs, and spectacle lenses were molded.

Example 9

A thermoplastic polyurethane resin was produced and molded into a sheet, a slab and a spectacle lens in the same manner as in example 1 except that PTG1000SN (P) in example 1 was changed to 33.51 parts by mass, 1,4-BIC (2) was changed to 41.30 parts by mass, and the molar ratio of isosorbide to 1, 4-butanediol (isosorbide: 1,4-BD) was changed to 90: 10.

Example 10

A thermoplastic polyurethane resin was produced in the same manner as in example 1 except that PTG1000SN (P) in example 1 was changed to 33.51 parts by mass, 1,4-BIC (2) was changed to 43.14 parts by mass, and the molar ratio of isosorbide to 1, 4-butanediol (isosorbide: 1,4-BD) was changed to 60:40, and the resulting product was molded into a sheet, a slab and a spectacle lens.

Example 11

A thermoplastic polyurethane resin was produced in the same manner as in example 1 except that PTG1000SN (P) in example 1 was changed to 33.51 parts by mass, 1,4-BIC (2) was changed to 41.30 parts by mass, and a mixture of isosorbide and 1, 6-hexanediol (1,6-HD, manufactured by wako pure chemical industries, inc.) was changed instead of the mixture of isosorbide and 1, 4-butanediol (isosorbide: 1,6-HD is 80:20 (molar ratio)), and sheets, slabs, and spectacle lenses were molded.

Comparative example 6

A thermoplastic polyurethane resin was produced in the same manner as in example 1 except that PTG1000SN (P) in example 1 was changed to 33.51 parts by mass, 1,4-BIC (2) was changed to 42.51 parts by mass, and a mixture of isosorbide and 1, 2-ethanediol (1,2-ED, manufactured by wako pure chemical industries, inc.) was changed instead of the mixture of isosorbide and 1, 4-butanediol (isosorbide: 1,2-ED is 80:20 (molar ratio)), and sheets, slabs, and spectacle lenses were molded.

Example 12

A thermoplastic polyurethane resin was produced in the same manner as in example 1 except that a mixture (1: 1 in terms of molar ratio) of 12.04 parts by mass of PTG1000SN (P) and 23.30 parts by mass of PTG2000SN (P) (manufactured by baotou chemical industries, ltd., number average molecular weight 2000) using polytetramethylene ether glycol as a biomass raw material was used instead of PTG1000SN (P) in example 1, and 1,4-BIC (2) was changed to 40.06 parts by mass, and the resulting mixture was molded into a sheet, a slab and a spectacle lens.

Example 13

A thermoplastic polyurethane resin was produced in the same manner as in example 1 except that PTG1000SN (P) in example 1 was changed to PO3G H1000 (poly (trimethylene) ether glycol, manufactured by ALLESSA, having a number average molecular weight of 1000)33.51 parts by mass and 1,4-BIC (2) was changed to 41.89 parts by mass, and sheets, slabs and spectacle lenses were molded.

Example 14

A thermoplastic polyurethane resin was produced and molded into a sheet, a slab or a spectacle lens in the same manner as in example 1 except that PTG1000SN (P) in example 1 was changed to PLACCEL 210N (polycaprolactone diol, number average molecular weight: 1000, manufactured by Daicel) 33.47 parts by mass and 1,4-BIC (2) was changed to 41.94 parts by mass.

Example 15

A thermoplastic polyurethane resin was produced in the same manner as in example 1 except that PTG1000SN (P) in example 1 was changed to UH-100 (polycarbonate diol, having a number average molecular weight of 1000, manufactured by Utsu corporation) 33.52 parts by mass and 1,4-BIC (2) was changed to 41.88 parts by mass, and the resulting product was molded into a sheet, a slab and a spectacle lens.

Example 16

A thermoplastic polyurethane resin was produced and molded into a sheet, a slab and a spectacle lens in the same manner as in example 1 except that JPE-10 in example 1 was changed to 0.08 parts by mass.

Example 17

A thermoplastic polyurethane resin was produced and molded into a sheet, a slab and a spectacle lens in the same manner as in example 1 except that JPE-10 in example 1 was changed to 1.50 parts by mass.

Example 18

A thermoplastic polyurethane resin was produced in the same manner as in example 1 except that PTG1000SN (P) in example 1 was changed to 35.41 parts by mass and 1,4-BIC (2) was changed to 25.36 parts by mass in place of 1,4-BIC (2) and 14.64 parts by mass of 1, 6-hexamethylene diisocyanate (HDI, product name TAKENATE700, manufactured by mitsui chemical corporation) (1,4-BIC: HDI: 60:40 (molar ratio)), and sheets, slabs, and spectacle lenses were molded.

Example 19

A thermoplastic polyurethane resin was produced in the same manner as in example 1 except that the raw material components of the formulation of example 1 were reacted by a one-shot method, which is a known method, and molded into a sheet, a slab and a spectacle lens.

Example 20

A thermoplastic polyurethane resin was produced and molded into a sheet, a slab and a spectacle lens in the same manner as in example 1, except that the reaction mixture was poured into the Teflon (registered trademark) layer in the method of example 1, and then the reaction was carried out at 100 ℃ for 2 hours and then at 100 ℃ for 20 hours.

Example 21

A thermoplastic polyurethane resin was produced and molded into a sheet, a slab and a spectacle lens in the same manner as in example 1, except that the reaction mixture was poured into the Teflon (registered trademark) layer and then reacted at 280 ℃ for 2 hours and then at 100 ℃ for 20 hours in the method of example 1.

< evaluation >

The sheets, slabs and spectacle lenses of the thermoplastic polyurethane resins obtained in the examples and comparative examples were evaluated as follows. The results are shown in tables 1 to 3.

Table 1 to table 3 show the compounding recipes (based on moles) in each example and each comparative example.

1) Appearance of the product

The sheets obtained in the examples and comparative examples were visually checked for the presence or absence of clouding, coloring, blooming (fogging), and bleeding (sheeting). The case where these appearance defects were not present was denoted as "3", the case where there were slight defects was denoted as "2", and the case where there were significant defects was denoted as "1".

2) Transmittance and haze

As a measuring device, HAZE METER NDH-5000 manufactured by Nippon Denshoku industries Co., Ltd., was used to measure the transmittance and HAZE of the sheets obtained in each example and each comparative example.

3) Hardness of

The slab obtained in each example and each comparative example was horizontally pressed by an ASKER D durometer in accordance with JIS K7311(1995), and the stabilized value of the pin after 15 seconds was read.

4) Impact resistance (Izod impact)

The sheets obtained in examples and comparative examples were punched out using a notched (method A) dumbbell suitable for JIS K7110(1999), and subjected to Izod test at 23 ℃.

5) Heat resistance

From the sheets obtained in each example and each comparative example, a long test piece having a width of 10mm was cut, and a dynamic viscoelasticity spectrum was measured using a dynamic viscoelasticity measuring apparatus (model number: DVA-220, manufactured by IT measurement control Co., Ltd.) under conditions of a measurement start temperature of-100 ℃, a temperature rise rate of 5 ℃/min, a tensile mode, an inter-reticle length of 20mm, a static/dynamic stress ratio of 1.8, and a measurement frequency of 10 Hz. Then, the storage modulus E' at 70 ℃ was measured.

6) Chemical resistance

Each 74.4 mm. times.66.5 mm sheet was punched out from the sheets obtained in each example and each comparative example using a dumbbell, 0.5g of Nivea cream (Nivea cream) (trade name, manufactured by Nivea Kao corporation) was applied to one surface, and then the sheet was heated to 80 ℃ in an oven and heat-preserved for 24 hours.

After the heat preservation, the frost (frost) on the surface was washed away with water, and the change in appearance was confirmed. The appearance of each plate was confirmed.

The case where no change in appearance was observed was designated as "3", the case where surface roughness was observed was designated as "2", and the case where significant surface roughness, dimensional change, and warpage of each plate were observed was designated as "1".

7) Solvent resistance

Disks having a diameter of 30mm were punched out of the sheets obtained in each example and each comparative example using a dumbbell, and immersed in isopropanol at room temperature for 5 days. After removal from the isopropyl alcohol, the surface of the disc was wiped with a cotton yarn head (waste cloth) or the like to confirm the change in appearance.

The case where no change in the appearance of the disk occurred was denoted as "3", the case where surface roughness was observed was denoted as "2", and the case where significant surface roughness, dimensional change, and warpage of the disk were observed was denoted as "1".

8) Refractive index (nd) and Abbe number (. nu.d)

The refractive index and abbe number of the lens bodies obtained in each example and each comparative example were measured at 20 ℃.

9) Lens appearance

The lens bodies obtained in the examples and comparative examples were visually checked for the presence or absence of clouding, coloring, blooming, and bleeding.

The case where these appearance defects were not present was denoted as "3", the case where there were slight defects was denoted as "2", and the case where there were significant defects was denoted as "1".

10) Coating adhesion

The spectacle lenses obtained in the examples and comparative examples were evaluated for adhesion among the lens body, the hard coat layer, and the antireflection layer as follows.

That is, a checkerboard of 100 1mm × 1mm squares is formed in a 1cm × 1cm area of the spectacle lens.

In this area, an operation of attaching Nichiban tape (CT-408 AP-18 made by Nichiban) to the checkerboard and peeling it off was repeated 5 times.

In this case, the presence or absence of peeling of the hard coat layer and the antireflection layer from the lens body was confirmed.

The case of 10 or less peels is referred to as "3", the case of 11 to 20 peels is referred to as "2", and the case of 21 or more peels is referred to as "1".

11) Lens destruction energy

The high-speed impact resistance of the spectacle lens was evaluated by using an automatic drop weight impact tester "HYDROSHOT" (model HITS-P10, manufactured by Shimadzu corporation).

Specifically, the spectacle lenses obtained in examples and comparative examples were fixed to a holder having a diameter of 40mm in accordance with JIS K7211-2(2006), and a punch (striker) having a diameter of 20mm was passed through the holder by being impacted at a speed of 4.4 m/sec, and the energy of fracture (J) generated at the time of impact was measured. The above test was repeated 3 times, and the destruction energy was calculated as an average value thereof.

The abbreviations in the tables are as follows.

1,4-BIC (1): production example 1, 4-bis (isocyanatomethyl) cyclohexane (trans/cis ratio 98/2)

1,4-BIC (2): production example 2 of 1, 4-bis (isocyanatomethyl) cyclohexane (trans/cis ratio 86/14)

1,4-BIC (3): production example 3 of 1, 4-bis (isocyanatomethyl) cyclohexane (trans/cis ratio 68/32)

HDI: 1, 6-hexamethylene diisocyanate, manufactured by Mitsui chemical company, under the trade name TAKENATE700

NBDI: diisocyanate-based methylbicyclo [2, 2, 1] -heptane, manufactured by Mitsui chemical Co., Ltd

PTG1000SN (P): polytetramethylene ether glycol (PTMEG) having a number average molecular weight of 1000 and produced by Bao Gegu chemical industries, Ltd

PTG2000SN (P): polytetramethylene ether glycol (PTMEG) having a number average molecular weight of 2000 and produced by Baogu chemical industries, Ltd

PO3G H1000: poly (trimethylene) ether glycol having a number average molecular weight of 1000 manufactured by ALLESSA

PLACCEL 210N: polycaprolactone diol (PCL) having a number average molecular weight of 1000 manufactured by Daicel

UH-100: polycarbonate diol (PCD) having a number average molecular weight of 1000 manufactured by Yu Jong Co., Ltd

CHDM: cyclohexane dimethanol

1, 4-BD: 1, 4-butanediol

1, 5-PeD: 1, 5-pentanediol

1, 6-HD: 1, 6-hexanediol

1, 3-BD: 1, 3-butanediol

1, 3-PrD: 1, 3-propanediol

1, 2-EG: 1, 2-ethanediol

Industrial applicability

The thermoplastic polyurethane resin and the optical polyurethane resin of the present invention can be suitably used for cover plates for display panels, eyeglass materials, eyeglass lenses, eyeglass frames, parts for interior and exterior automotive materials, and the like.