CN114375312A

CN114375312A - Thermoplastic polyurethane resin and film

Info

Publication number: CN114375312A
Application number: CN202080064318.XA
Authority: CN
Inventors: 黑岩巧; 田子浩明; 高野辽; 金山宏
Original assignee: Mitsui Chemicals Inc
Current assignee: Mitsui Chemicals Inc
Priority date: 2019-09-30
Filing date: 2020-09-28
Publication date: 2022-04-19
Anticipated expiration: 2040-09-28
Also published as: WO2021065783A1; JPWO2021065783A1; TW202124494A; CN114375312B; JP7257541B2

Abstract

A thermoplastic polyurethane resin is obtained as a reaction product of a polyisocyanate component containing 1, 4-bis (isocyanatomethyl) cyclohexane containing trans-form in a proportion of 60 to 99.5 mol%, and a polyol component containing an amorphous polycarbonate diol which is liquid at 25 ℃ and a low-molecular-weight diol having 2 to 6 carbon atoms.

Description

Thermoplastic polyurethane resin and film

Technical Field

The present invention relates to a thermoplastic polyurethane resin and a film, and more particularly to a thermoplastic polyurethane resin and a film containing the thermoplastic polyurethane resin.

Background

Thermoplastic polyurethane resins (TPU) are generally rubber elastomers obtained by the reaction of polyisocyanates, high molecular weight polyols and low molecular weight polyols. The thermoplastic polyurethane resin is molded into a Film shape, for example, and is used as a protective Film (Paint Protection Film (PPF)) for protecting a painted surface of an automobile.

As the protective film, for example, a multilayer polyurethane protective film including a TPU layer obtained by reacting a polyol and a polyisocyanate is proposed, and further, a caprolactone polyol is proposed as the polyol, and dicyclohexylmethane diisocyanate is proposed as the polyisocyanate (for example, see patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese Kokai publication No. 2010-505663

Disclosure of Invention

Problems to be solved by the invention

On the other hand, the protective film is required to have a stretching property (restoring force) and heat resistance depending on the application. In this regard, the above-mentioned multilayer polyurethane protective film has a disadvantage of insufficient heat resistance.

The present invention relates to a thermoplastic polyurethane resin having both of stretch properties (restoring force) and heat resistance, and a film comprising the thermoplastic polyurethane resin.

Means for solving the problems

The invention [1] includes a thermoplastic polyurethane resin comprising the reaction product of: a reaction product of a polyisocyanate component comprising 1, 4-bis (isocyanatomethyl) cyclohexane containing trans-form in an amount of 60 to 99.5 mol%, and a polyol component comprising an amorphous polycarbonate diol which is liquid at 25 ℃ and a low-molecular-weight diol having 2 to 6 carbon atoms.

The invention [2] comprises the thermoplastic polyurethane resin according to [1], wherein the heat quantity of the melting peak of the thermoplastic polyurethane resin at 160 ℃ or higher as measured by differential scanning calorimetry (DSC method) is 15J/g or less.

The invention [3] comprises the thermoplastic polyurethane resin according to the above [1] or [2], wherein the heat quantity of the melting peak of the thermoplastic polyurethane resin at 160 ℃ or higher as measured by differential scanning calorimetry (DSC method) is 0.1J/g or higher.

The invention [4] includes a film comprising the thermoplastic polyurethane resin according to any one of the above [1] to [3 ].

Effects of the invention

The thermoplastic polyurethane resin and the film of the present invention contain, as raw material components: a polyisocyanate component containing 1, 4-bis (isocyanatomethyl) cyclohexane containing trans-form in a proportion of 60 to 99.5 mol%; and a polyol component containing an amorphous polycarbonate diol which is liquid at 25 ℃ and a low-molecular-weight diol having 2 to 6 carbon atoms.

That is, 1, 4-bis (isocyanatomethyl) cyclohexane, which has relatively high crystallinity, a low-molecular-weight diol, which has improved crystallinity due to a hard segment, and an amorphous polycarbonate diol, which has relatively low crystallinity, are used as raw material components.

Therefore, the thermoplastic polyurethane resin and the film of the present invention can adjust the cohesiveness of the polyurethane structure in a well-balanced manner, and can have both high heat resistance derived from the cohesiveness and low elasticity derived from the cohesiveness in a well-balanced manner.

Detailed Description

The thermoplastic polyurethane resin of the present invention is obtained by reacting a polyisocyanate component with a polyol component. In other words, the thermoplastic polyurethane resin is a reaction product obtained by the reaction of a polyisocyanate component and a polyol component as raw material components.

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

Among the 1, 4-bis (isocyanotomethyl) cyclohexane, there are 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, 1, 4-bis (isocyanatomethyl) cyclohexane contains trans 1, 4-isomer (trans isomer) in a predetermined ratio.

More specifically, the content ratio of trans 1, 4-isomer (trans isomer) is 60 mol% or more, preferably 70 mol% or more, more preferably 75 mol% or more, further preferably 80 mol% or more, and 99.5 mol% or less, preferably 99 mol% or less, more preferably 96 mol% or less, and further preferably 90 mol% or less, based on the total mole of 1, 4-bis (isocyanotomethyl) cyclohexane.

In other words, the total amount of trans-1, 4-isomer and cis-1, 4-isomer of 1, 4-bis (isocyanotomethyl) cyclohexane is 100 mol%, and therefore the content of cis-1, 4-isomer (cis-isomer) is 0.5 mol% or more, preferably 1 mol% or more, more preferably 4 mol% or more, further preferably 10 mol% or more, and 40 mol% or less, preferably 30 mol% or less, more preferably 25 mol% or less, and further preferably 20 mol% or less, based on the total mol of 1, 4-bis (isocyanotomethyl) cyclohexane.

When the content ratio of the trans 1, 4-mer is not less than the lower limit, the heat resistance can be improved.

The 1, 4-bis (isocyanatomethyl) cyclohexane can be produced by, for example, the methods described in international publication No. WO2009/051114, international publication No. WO2019/069802 and the like.

The 1, 4-bis (isocyanatomethyl) cyclohexane can be produced as a modified product within a range not impairing the excellent effects of the present invention.

Examples of the modified 1, 4-bis (isocyanotomethyl) cyclohexane include polymers of 1, 4-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 1, 4-bis (isocyanotomethyl) cyclohexane with water), allophanate modified products (e.g., allophanate modified products produced by the reaction of 1, 4-bis (isocyanotomethyl) cyclohexane with 1-or 2-membered alcohols), polyol modified products (e.g., polyol modified products (adducts) produced by the reaction of 1, 4-bis (isocyanotomethyl) cyclohexane with 3-membered alcohols), and the like), Examples of the modified carbodiimide include modified oxadiazinetrione (for example, oxadiazinetrione produced by a reaction of 1, 4-bis (isocyanotomethyl) cyclohexane with carbon dioxide), modified carbodiimide (for example, modified carbodiimide produced by a decarboxylation condensation reaction of 1, 4-bis (isocyanotomethyl) cyclohexane), and the like. These may be used alone or in combination of 2 or more.

Preferred examples of the 1, 4-bis (isocyanatomethyl) cyclohexane include monomers (monomers) of 1, 4-bis (isocyanatomethyl) cyclohexane.

When the polyisocyanate component contains the above-mentioned 1, 4-bis (isocyanotomethyl) cyclohexane, the heat resistance of the thermoplastic polyurethane resin can be improved by the crystallinity derived from the symmetrical structure of 1, 4-bis (isocyanotomethyl) cyclohexane. That is, when the polyisocyanate component does not contain 1, 4-bis (isocyanatomethyl) cyclohexane containing trans-form in a predetermined ratio, the crystallinity of the polyisocyanate component is insufficient, and the thermoplastic polyurethane resin (described later) may be deteriorated in cohesiveness and heat resistance. On the other hand, when the polyisocyanate component contains the above-mentioned 1, 4-bis (isocyanotomethyl) cyclohexane, the crystallinity of the polyisocyanate component can be improved due to the symmetrical structure of the 1, 4-bis (isocyanotomethyl) cyclohexane, and the cohesiveness of the thermoplastic polyurethane resin can be improved, so that the heat resistance can be improved.

In addition, the polyisocyanate component may contain other polyisocyanate (polyisocyanate other than 1, 4-bis (isocyanotomethyl) cyclohexane) as an optional component within a range not to impair 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, trimethylene diisocyanate, tetramethylene diisocyanate, Pentamethylene Diisocyanate (PDI), Hexamethylene Diisocyanate (HDI), octamethylene diisocyanate, nonamethylene diisocyanate, 2' -dimethylpentane diisocyanate, 2, 4-trimethylhexane diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1, 3-butadiene-1, 4-diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, 1,6, 11-undecamethylene triisocyanate, 1,3, 6-hexamethylene triisocyanate, 1, 8-diisocyanato-4-isocyanatomethyloctane, 2, and chain aliphatic diisocyanates such as 5, 7-trimethyl-1, 8-diisocyanato-5-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1, 4-butanediol dipropyl ether- ω, ω' -diisocyanate, lysine isocyanatomethyl ester, lysine triisocyanate, 2-isocyanatoethyl-2, 6-diisocyanatohexanoate, 2-isocyanatopropyl-2, 6-diisocyanatohexanoate, bis (4-isocyanato-n-butylene) pentaerythritol, 2, 6-diisocyanatomethylhexanoate and the like.

The aliphatic polyisocyanate includes alicyclic polyisocyanate (excluding 1, 4-bis (isocyanatomethyl) cyclohexane).

Examples of the alicyclic polyisocyanate (except for 1, 4-bis (isocyanotomethyl) cyclohexane) include 1, 3-bis (isocyanotomethyl) cyclohexane, isophorone diisocyanate (IPDI), trans-, trans, cis-, and cis-polyisocyanatesOf the formula (II) cis-dicyclohexylmethane diisocyanate and mixtures thereof (hydrogenated MDI, H)₁₂MDI), 1, 3-or 1, 4-cyclohexane diisocyanate and mixtures thereof, 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, 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, alicyclic diisocyanates such as 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 aromatic diisocyanates such as arbitrary isomer Mixtures (MDI) of these diphenylmethane diisocyanates, toluidine diisocyanate (TODI), p-phenylene diisocyanate, and Naphthalene Diisocyanate (NDI).

Examples of the araliphatic polyisocyanate include araliphatic diisocyanates such as 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.

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 include a polymer (uretdione modified product, isocyanurate modified product, iminooxadiazinedione modified product, etc.), a biuret modified product, an allophanate modified product, a polyol modified product, an oxadiazinetrione modified product, a carbodiimide modified product, and the like. These may be used alone or in combination of 2 or more.

The content ratio of the other polyisocyanate may be appropriately selected within a range not impairing the excellent effects of the present invention.

More specifically, the content of the other polyisocyanate is, for example, less than 50 mol%, preferably 30 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol% or less, and particularly preferably 0 mol% based on the total amount of the polyisocyanate component.

In other words, the content of 1, 4-bis (isocyanotomethyl) cyclohexane (including a modified product of 1, 4-bis (isocyanotomethyl) cyclohexane) is, for example, higher than 50 mol%, preferably 70 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more, and particularly preferably 100 mol% based on the total amount of the polyisocyanate component.

That is, the polyisocyanate component preferably contains 1, 4-bis (isocyanatomethyl) cyclohexane alone.

The polyol component is a compound having 2 or more hydroxyl groups in the molecule.

The polyol component contains, as essential components, a high molecular weight polyol having a molecular weight of more than 400 and a low molecular weight polyol having a molecular weight of 400 or less.

When the polyol component has a molecular weight distribution, a number average molecular weight can be used. In this case, the number average molecular weight can be determined by measurement by GPC method, the hydroxyl value of each component of the polyol component, and the formulation (the same applies hereinafter).

The high molecular weight polyol is a compound having 2 or more hydroxyl groups in the molecule and higher than 400.

The high molecular weight polyol contains, as an essential component, an amorphous polycarbonate diol which is liquid (liquid state) at 25 ℃. In other words, the polyol component contains the amorphous polycarbonate diol as an essential component.

The amorphous polycarbonate diol is an amorphous polycarbonate polyol having an average number of hydroxyl groups of 2. The non-crystalline polycarbonate diol is a polycarbonate diol which is in a liquid state at 25 ℃ (viscosity at 25 ℃ measured with an E-type viscometer is 500000mPa · s or less).

The amorphous polycarbonate diol can be obtained by modifying a ring-opened polymer of ethylene carbonate using a 2-membered alcohol as an initiator with a 2-membered alcohol as a modifier.

In the ring-opened polymer of ethylene carbonate, examples of the 2-membered alcohol as an initiator include linear alkane diols having 2 to 8 carbon atoms such as ethylene glycol, 1, 3-propanediol, 1, 4-butanediol (butane diol), 1, 5-pentanediol, 1, 6-hexanediol, and 1, 8-octanediol, and linear 2-membered alcohols such as linear ether diols having 4 to 8 carbon atoms such as diethylene glycol and triethylene glycol. These 2-membered alcohols may be used alone or in combination of 2 or more.

The 2-membered alcohol as the initiator is preferably a linear 2-membered alcohol, and more preferably a linear alkanediol having 2 to 8 carbon atoms.

In the ring-opened polymer of ethylene carbonate, examples of the 2-membered alcohol as the modifier include a linear 2-membered alcohol and a branched 2-membered alcohol. As the linear 2-membered alcohol, a different kind of linear 2-membered alcohol from the above-mentioned 2-membered alcohol as the initiator can be selected.

The linear 2-membered alcohol as the modifier may be different from the 2-membered alcohol as the initiator, but preferably, a linear 2-membered alcohol having a larger number of carbon atoms than the 2-membered alcohol as the initiator is used. More specifically, for example, straight-chain alkane diols having 4 to 10 carbon atoms such as 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 9-nonanediol, and 1, 10-decanediol are mentioned. These linear 2-membered alcohols may be used alone or in combination of 2 or more.

Examples of the branched 2-membered alcohol as the modifier include branched alkanediols having 4 to 10 carbon atoms such as 3-methyl-1, 5-pentanediol, 2-methyl-1, 3-propanediol and 2, 2-dimethyl-1, 3-propanediol. These branched 2-membered alcohols may be used alone or in combination of 2 or more.

These 2-membered alcohols as modifiers may be used alone or in combination of 2 or more.

The 2-membered alcohol as the modifier preferably includes a linear 2-membered alcohol or a branched 2-membered alcohol having a larger number of carbon atoms than the 2-membered alcohol as the initiator, more preferably includes a branched 2-membered alcohol, and still more preferably includes 3-methyl-1, 5-pentanediol.

The method for modifying the ring-opened polymer of ethylene carbonate with 2-membered alcohol is not particularly limited, and a known method can be used. For example, ethylene carbonate is ring-opened by a known method using 2-membered alcohol as an initiator, and the resulting ring-opened polymer is further copolymerized with 2-membered alcohol as a modifier.

These amorphous polycarbonate diols may be used alone or in combination of 2 or more. That is, a single kind of amorphous polycarbonate diol may be used, and 2 or more kinds of amorphous polycarbonate diols different from each other, such as 2-membered alcohol as an initiator, 2-membered alcohol as a modifier, and the like, may be used in combination.

From the viewpoint of improving the stretching properties, the number average molecular weight of the amorphous polycarbonate diol (in the case of using 2 or more types in combination, the average molecular weight of a mixture thereof) is higher than 400, preferably 500 or more, more preferably 1000 or more, further preferably 1300 or more, particularly preferably 1500 or more, for example 10000 or less, preferably 8000 or less, more preferably 5000 or less, further preferably 3000 or less, and particularly preferably 2000 or less.

The high molecular weight polyol may contain the amorphous polycarbonate diol alone, but may contain other high molecular weight polyols (except for the amorphous polycarbonate diol) as required.

That is, the high molecular weight polyol may contain other high molecular weight polyol (high molecular weight polyol other than the non-crystalline polycarbonate diol) as an optional component.

Examples of the other high-molecular-weight polyol include high-molecular-weight polyols having a number average molecular weight of more than 400 and 10000 or less (except for amorphous polycarbonate diol), and more specifically, crystalline polycarbonate polyols, amorphous polycarbonate polyols having an average hydroxyl number of 3 or more, polyether polyols, polyester polyols, polycaprolactone polyols, polyurethane polyols, and the like. These other high molecular weight polyols may be used alone or in combination of 2 or more.

As other high molecular weight polyols, crystalline polycarbonate polyols are preferably used.

The crystalline polycarbonate polyol is a polycarbonate polyol which is in a solid state (solid state) at 25 ℃.

Examples of the crystalline polycarbonate polyol include the ring-opened polymer of ethylene carbonate using the above-mentioned 2-membered alcohol as an initiator. These crystalline polycarbonate polyols may be used alone or in combination of 2 or more.

The ring-opening polymerization method of ethylene carbonate using a 2-membered alcohol as an initiator is not particularly limited, and a known method can be used.

From the viewpoint of achieving both of the stretch property and the heat resistance, the number average molecular weight of the crystalline polycarbonate polyol is higher than 400, preferably 500 or more, more preferably 1000 or more, further preferably 1300 or more, particularly preferably 1500 or more, for example 10000 or less, preferably 8000 or less, more preferably 5000 or less, further preferably 3000 or less, and particularly preferably 2000 or less.

The average number of hydroxyl groups per 1 molecule of the crystalline polycarbonate polyol is, for example, 1.8 or more, preferably 2 or more, for example, 4 or less, preferably 3 or less, and particularly preferably 2.

The blending ratio of the other high molecular weight polyol may be appropriately set within a range not impairing the excellent effects of the present invention.

That is, when a high-molecular-weight polyol having relatively high crystallinity (crystalline polycarbonate polyol, polycaprolactone polyol, or the like) is used in excess as the other high-molecular-weight polyol, the cohesiveness may be high, and the stretching property (restoring force) may be reduced.

Therefore, the ratio of the other high molecular weight polyol (crystalline polycarbonate polyol, etc.) can be adjusted to a range in which excellent stretching properties can be maintained.

More specifically, the content of the other high-molecular-weight polyol (crystalline polycarbonate polyol, polycaprolactone polyol, etc.) is, for example, 60 mol% or less, preferably 50 mol% or less, usually 0 mol% or more, and particularly preferably 0 mol% based on the total moles of the high-molecular-weight polyols.

In other words, the content of the amorphous polycarbonate diol is, for example, 40 mol% or more, preferably 50 mol% or more, usually 100 mol% or less, and particularly preferably 100 mol% based on the total mol of the high molecular weight polyol.

That is, the high molecular weight polyol is particularly preferably free of other high molecular weight polyols and contains the amorphous polycarbonate diol alone.

From the viewpoint of achieving both of the stretching property and the heat resistance, the molecular weight (number average molecular weight) of the high molecular weight polyol is higher than 400, preferably 500 or more, more preferably 1000 or more, further preferably 1300 or more, particularly preferably 1500 or more, for example 10000 or less, preferably 8000 or less, more preferably 5000 or less, further preferably 3000 or less, particularly preferably 2000 or less.

The low-molecular-weight polyol is a compound having 2 or more hydroxyl groups in the molecule and having a molecular weight of 400 or less, for example, 50 or more.

The low-molecular-weight polyol contains a low-molecular-weight diol having 2 to 6 carbon atoms as an essential component. In other words, the polyol component contains a low molecular weight diol having 2 to 6 carbon atoms as an essential component.

The low molecular weight diol having 2 to 6 carbon atoms is a compound having 2 to 6 carbon atoms in 1 molecule and 2 hydroxyl groups in 1 molecule and having a molecular weight of 400 or less.

Examples of the low molecular weight diol having 2 to 6 carbon atoms include ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol (1,4-BD), 1, 3-butanediol, 1, 2-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, alkane diols having 2 to 6 carbon atoms (alkylene diols having 2 to 6 carbon atoms) such as neopentyl glycol, 3-methyl-1, 5-pentanediol and 2, 2-dimethyl-1, 3-propanediol, ether diols having 2 to 6 carbon atoms such as diethylene glycol, triethylene glycol and dipropylene glycol, alkene diols having 2 to 6 carbon atoms such as 1, 4-dihydroxy-2-butene, 1, 3-or 1, 4-cyclohexanediol, and mixtures thereof. These may be used alone or in combination of 2 or more.

In the low molecular weight diol having 2 to 6 carbon atoms, the number of carbon atoms is 2 or more, preferably 3 or more, 6 or less, preferably 5 or less, and particularly preferably 4.

The molecular weight of the low molecular weight diol having 2 to 6 carbon atoms is, for example, 50 or more, preferably 70 or more, 400 or less, preferably 300 or less.

The low molecular weight diol having 2 to 6 carbon atoms preferably includes alkane diols having 2 to 6 carbon atoms, and more preferably includes 1, 4-butanediol, from the viewpoint of improving heat resistance.

The low-molecular-weight polyol may contain a low-molecular-weight diol having 2 to 6 carbon atoms alone, but may contain other low-molecular-weight polyols (low-molecular-weight polyols other than the low-molecular-weight diol having 2 to 6 carbon atoms) as needed.

That is, the low-molecular-weight polyol may contain another low-molecular-weight polyol (a low-molecular-weight polyol other than the low-molecular-weight diol having 2 to 6 carbon atoms) as an optional component.

Examples of the other low-molecular-weight polyol include compounds other than a low-molecular-weight diol having 2 or more hydroxyl groups in the molecule, a molecular weight of 50 or more and 400 or less, and 2 to 6 carbon atoms.

Examples of the other low-molecular-weight polyol include a low-molecular-weight diol having 7 or more carbon atoms, a low-molecular-weight polyol having 3 or more members, and the like.

Examples of the low molecular weight diol having 7 or more carbon atoms include alkane-1, 2-diols having 7 to 20 carbon atoms such as 1, 8-octanediol and 1, 9-nonanediol, 2, 6-dimethyl-1-octene-3, 8-diol, 1, 3-or 1, 4-cyclohexanedimethanol and mixtures thereof, and 2-membered alcohols having 7 or more carbon atoms such as hydrogenated bisphenol a and bisphenol a. These low molecular weight diols having 7 or more carbon atoms may be used alone or in combination of 2 or more.

The 3-or higher-molecular-weight polyol has a molecular weight of 400 or less and has 3 or more hydroxyl groups in 1 molecule, and examples thereof include 3-or higher-molecular-weight alcohols (low-molecular-weight triols) such as glycerin, 2-methyl-2-hydroxymethyl-1, 3-propanediol, 2, 4-dihydroxy-3-hydroxymethylpentane, 1,2, 6-hexanetriol, trimethylolpropane, 2-bis (hydroxymethyl) -3-butanol, 4-or higher-molecular-weight triols such as tetramethylolmethane (pentaerythritol), diglycerin, 5-or higher-molecular-weight alcohols such as xylitol, 6-or higher-molecular-weight alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altol, inositol, dipentaerythritol, 7-or higher-molecular-weight alcohols such as avocado-sugar, and the like. These low molecular weight polyols having 3 or more members may be used alone or in combination of 2 or more.

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

The molecular weight of the other low-molecular-weight polyol is, for example, 50 or more, preferably 70 or more, 400 or less, and preferably 300 or less.

The blending ratio of the other low-molecular-weight polyols may be appropriately set within a range not impairing the excellent effects of the present invention.

More specifically, the content ratio of the other low-molecular-weight polyols (low-molecular-weight polyols other than the low-molecular-weight diol having 2 to 6 carbon atoms) is, for example, 50 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 0 part by mass, relative to 100 parts by mass of the total amount of the low-molecular-weight polyols.

In other words, the content of the low-molecular-weight diol having 2 to 6 carbon atoms is, for example, 50 parts by mass or more, preferably 80 parts by mass or more, more preferably 90 parts by mass or more, and particularly preferably 100 parts by mass, relative to 100 parts by mass of the total amount of the low-molecular-weight polyol.

That is, the low-molecular-weight polyol preferably contains no other low-molecular-weight polyol (a low-molecular-weight polyol other than the low-molecular-weight diol having 2 to 6 carbon atoms) and contains a low-molecular-weight diol having 2 to 6 carbon atoms alone.

The polyol component contains, as described above, an amorphous polycarbonate diol as a high-molecular-weight polyol and a low-molecular-weight diol having 2 to 6 carbon atoms as a low-molecular-weight polyol as essential components, and is preferably formed of an amorphous polycarbonate diol and a low-molecular-weight diol having 2 to 6 carbon atoms.

In the polyol component, the content ratio of the high molecular weight polyol and the low molecular weight polyol is, for example, 20 mol% or more, preferably 30 mol% or more, for example, 95 mol% or less, preferably 90 mol% or less, more preferably 70 mol% or less, further preferably less than 50 mol%, and particularly preferably 40 mol% or less, with respect to the total amount thereof. The low-molecular-weight polyol is, for example, 5 mol% or more, preferably 10 mol% or more, more preferably 30 mol% or more, further preferably more than 50 mol%, particularly preferably 60 mol% or more, for example, 80 mol% or less, preferably 70 mol% or less.

Further, the thermoplastic polyurethane resin can be obtained by reacting a polyisocyanate component with a polyol component.

More specifically, in this method, the polyisocyanate component and the polyol component are reacted (reaction step).

For the reaction of the above components (polyisocyanate component and polyol component), known methods such as a one-shot method and a prepolymer method can be used. From the viewpoint of improving various physical properties, the prepolymer method is preferably used.

Specifically, in the prepolymer method, first, a polyisocyanate component containing 1, 4-bis (isocyanatomethyl) cyclohexane is reacted with a high molecular weight polyol containing an amorphous polycarbonate polyol to synthesize an isocyanate group-terminated prepolymer (prepolymer synthesis step).

In the prepolymer synthesis step, the polyisocyanate component is reacted with the high molecular weight polyol by a polymerization method such as bulk polymerization or solution polymerization.

In the bulk polymerization, for example, the polyisocyanate component and the high molecular weight polyol are reacted under a nitrogen stream at a reaction temperature of, for example, 50 ℃ or higher, for example, 250 ℃ or lower, and preferably 200 ℃ or lower, for example, 0.5 hours or higher, for example, 15 hours or lower.

In the solution polymerization, the polyisocyanate component and the high molecular weight polyol 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, and 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, if 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 organic tin compounds such as tin acetate, tin octylate (tinoctylate), tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dithiolate, dibutyltin maleate, dibutyltin dineodecanoate, dioctyltin dithiolate, dioctyltin dilaurate and dibutyltin dichloride, organic lead compounds such as lead octylate and lead naphthenate, organic nickel compounds such as nickel naphthenate, organic cobalt compounds such as cobalt naphthenate, organic copper compounds such as copper octylate, organic bismuth compounds such as bismuth octylate (bismuth octylate) and bismuth neodecanoate, and tin octylate and bismuth octylate 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 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, relative to 10000 parts by mass of the total amount of the polyisocyanate component and the high-molecular-weight polyol.

The urethane-forming catalyst may be added in the form of a solution or dispersion diluted with a known catalyst diluent (solvent) as needed.

In the polymerization reaction, the unreacted polyisocyanate component and the organic solvent in the case of using the organic solvent can be removed by known removal means such as distillation and 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 high molecular weight polyol.

More specifically, the mixing ratio of each component in the prepolymer synthesis step is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, for example, 150 parts by mass or less, preferably 100 parts by mass or less, more preferably 90 parts by mass or less, relative to 100 parts by mass of the high molecular weight polyol.

In the prepolymer synthesis step, the low-molecular-weight polyol and the like may be blended together with the high-molecular-weight polyol at an appropriate ratio in order to adjust the hard segment concentration (described later) of the thermoplastic polyurethane resin obtained.

In this method, the above components are reacted until the content of the isocyanate group becomes, for example, 1.0% by mass or more, preferably 1.5% by mass or more, more preferably 3.0% by mass or more, further preferably 5.0% by mass or more, for example 30.0% by mass or less, preferably 19.0% by mass or less, more preferably 16.0% by mass or less, further preferably 12.0% by mass or less. Thus, an isocyanate group-ended 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.

In this method, the isocyanate group-ended prepolymer obtained in the above manner is reacted with a low-molecular-weight polyol containing a low-molecular-weight diol having 2 to 6 carbon atoms to obtain a reaction product of a polyisocyanate component and a polyol component (chain extension step).

That is, in this method, a low-molecular-weight polyol containing a low-molecular-weight diol having 2 to 6 carbon atoms is used as a chain extender.

In the chain extension step, the isocyanate group-ended prepolymer is reacted with the low molecular weight polyol by a polymerization method such as the above-mentioned bulk polymerization or the above-mentioned solution polymerization.

The reaction temperature is, for example, room temperature or higher, preferably 50 ℃ or higher, for example 200 ℃ or lower, preferably 150 ℃ or lower, and the reaction time is, for example, 5 minutes or higher, preferably 1 hour or higher, for example 72 hours or lower, preferably 48 hours or lower.

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-ended prepolymer to the hydroxyl group in the low molecular weight polyol.

More specifically, the blending ratio of each component in the chain extension step is, for example, 1.0 part by mass or more, preferably 2.5 parts by mass or more, more preferably 3.5 parts by mass or more, further preferably 4.5 parts by mass or more, particularly preferably 5.5 parts by mass or more, for example 15.0 parts by mass or less, preferably 10.0 parts by mass or less, more preferably 9.0 parts by mass or less, relative to 100 parts by mass of the isocyanate-terminated prepolymer.

In the chain extension step, the high-molecular-weight polyol and the like may be blended together with the low-molecular-weight polyol at an appropriate ratio in order to adjust the hard segment concentration (described later) of the thermoplastic polyurethane resin obtained.

In this reaction, the above-mentioned urethanization catalyst may be added, if necessary. The urethane-forming catalyst may be added to the isocyanate group-ended prepolymer and/or the low-molecular-weight polyol, or may be added separately when they are mixed.

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 high molecular weight polyol and the low molecular weight polyol) are mixed together at a ratio such that the equivalent ratio (isocyanate group/hydroxyl group) of the isocyanate group in the polyisocyanate component to the hydroxyl group in the polyol component becomes, 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, under conditions of a reaction temperature of, for example, 40 ℃ or more, preferably 70 ℃ or more, for example, 280 ℃ or less, preferably 260 ℃ or less, and a reaction time of, for example, 30 seconds or more and 1 hour or less.

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

Thus, as a reaction product, a thermoplastic polyurethane resin can be obtained.

In this method, the obtained reaction product may be subjected to heat treatment (heat treatment step) as needed.

The heat treatment step is a step of heat-treating the reaction product (the reaction product before heat treatment (primary product)) to obtain a secondary product (the reaction product after heat treatment).

In the heat treatment step, the primary product obtained in the reaction step is allowed to stand at a predetermined heat treatment temperature for a predetermined heat treatment period to perform heat treatment, and then dried as necessary.

The heat treatment temperature is, for example, 50 ℃ or higher, preferably 60 ℃ or higher, more preferably 70 ℃ or higher, and is, for example, 100 ℃ or lower, preferably 90 ℃ or lower.

When the heat treatment temperature is within the above range, a thermoplastic polyurethane resin having particularly good stretching properties and heat resistance can be obtained.

The heat treatment period is, for example, 3 days or more, preferably 4 days or more, more preferably 5 days or more, further preferably 6 days or more, for example 10 days or less, preferably 9 days or less, and more preferably 8 days or less.

When the heat treatment period is within the above range, a thermoplastic polyurethane resin having particularly good stretching properties and heat resistance can be obtained.

In addition, in the production of the above-mentioned thermoplastic polyurethane resin, additives such as an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a hydrolysis preventing agent (carbodiimide compound and the like), a dye (bluing agent and the like), a plasticizer, an antiblocking agent, a surface modifier, a lubricant, a mold release agent, a pigment, a filler, a rust preventive, a filler and the like may be added as necessary.

These additives may be added at the time of mixing, at the time of synthesis, or after synthesis of the respective components.

The timing of adding the additive is not particularly limited, and for example, the additive may be added to the polyisocyanate component, the polyol component, the polyisocyanate component and the polyol component may be added simultaneously during mixing, or the polyisocyanate component and the polyol component may be added to the mixture after mixing.

The amount of the additive to be added is not particularly limited, and may be appropriately set according to the purpose and use.

The thermoplastic polyurethane resin thus obtained contains, as raw material components: a polyisocyanate component containing 1, 4-bis (isocyanatomethyl) cyclohexane containing trans-form in a proportion of 60 to 99.5 mol%; and a polyol component containing an amorphous polycarbonate diol which is liquid at 25 ℃ and a low-molecular-weight diol having 2 to 6 carbon atoms.

The hard segment concentration of the thermoplastic polyurethane resin is, for example, 5 mass% or more, preferably 7 mass% or more, more preferably 10 mass% or more, and still more preferably 15 mass% or more, for example, 30 mass% or less, preferably 25 mass% or less, and more preferably 20 mass% or less.

The concentration of the hard segment (hard segment formed by the reaction of the polyisocyanate component and the low-molecular-weight polyol) of the thermoplastic polyurethane resin can be calculated from the mixing ratio (charge) of the components by a known method, for example.

More specifically, for example, in the case of the prepolymer method, the hard segment concentration can be calculated from the following formula according to the formulation (charge) of each component.

[ chain extender (g) + (chain extender (g)/molecular weight of chain extender (g/mol)). times.average molecular weight of polyisocyanate component (g/mol) ]/(polyisocyanate component (g) + total mass of polyol component (g)). times.100

The heat quantity (change in enthalpy) of the melting peak (endothermic peak) of the thermoplastic polyurethane resin at 160 ℃ or higher is, for example, 0.1J/g or more, preferably 0.5J/g or more, more preferably 1.0J/g or more, further preferably 1.5J/g or more, particularly preferably 2.0J/g or more, for example, 20J/g or less, preferably 15J/g or less, more preferably 10.5J/g or less, further preferably 7.0J/g, further preferably 5.0J/g or less, further preferably 4.0J/g, particularly preferably 3.0J/g or less.

When the heat quantity of the melting peak of the thermoplastic polyurethane resin at 160 ℃ or higher exceeds the lower limit, the thermoplastic polyurethane resin does not have too low cohesiveness, and therefore excellent heat resistance can be obtained.

When the heat quantity of the melting peak of the thermoplastic polyurethane resin at 160 ℃ or higher is less than the upper limit, the thermoplastic polyurethane resin does not have too high an aggregation property, and therefore, excellent stretch properties can be obtained.

That is, when the heat quantity of the melting peak of the thermoplastic polyurethane resin at 160 ℃ or higher is within the above range, the coagulability can be appropriately adjusted, and the heat resistance and the stretch property of the thermoplastic polyurethane resin can be achieved at the same time.

The heat quantity of the melting peak can be measured by differential scanning calorimetry (DSC measurement) in accordance with the examples described later.

The expansion and contraction characteristics can be evaluated by, for example, the restoring force after the expansion and contraction deformation (the shape restoring rate after the expansion and contraction deformation).

Specifically, from the viewpoint of the stretch property, the recovery force (shape recovery rate) of the thermoplastic polyurethane resin after 60% stretching in 15 seconds is, for example, 97.0% or more, preferably 97.5% or more, more preferably 98.0% or more, further preferably 98.2% or more, and usually 100.0% or less.

The recovery force (shape recovery rate) after 60% elongation at 15 seconds can be measured by a tensile tester or the like in accordance with the examples described later.

In addition, more specifically, the heat resistance can be evaluated by the storage elastic modulus (E').

Specifically, the storage elastic modulus (E') at 80 ℃ of the thermoplastic polyurethane resin is, for example, 10X 10 from the viewpoint of heat resistance⁶MPa or more, preferably 15X 10⁶MPa or more, more preferably 20X 10⁶MPa or more, e.g. 50X 10⁶MPa or less, preferably 40X 10⁶MPa or less, more preferably 30X 10⁶MPa or less.

The storage elastic modulus (E') at 80 ℃ can be measured by dynamic viscoelasticity measurement in accordance with examples described later.

The thermoplastic polyurethane resin can be molded into an arbitrary shape by, for example, molding (primary molding) the thermoplastic polyurethane resin by a known molding method, and a molded article (primary molded article) containing the thermoplastic polyurethane resin can be obtained.

Examples of the molding method in the primary molding include thermal compression molding, injection molding, extrusion molding, cutting molding, melt spinning molding, and 3D printer molding. These may be used alone or in combination of 2 or more.

Examples of the shape of the primary molded article include 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, and preferably a pellet shape.

For example, when the thermoplastic polyurethane resin in pellet form is obtained as a primary molded article, it is preferable that the thermoplastic polyurethane resin in pellet form is subjected to secondary molding by a known molding method to obtain a secondary molded article of the thermoplastic polyurethane resin.

The molding method in the secondary molding may be the above-mentioned molding method, and preferably extrusion molding.

Examples of the shape of the secondary molded article include 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, and a preferable example is a film shape.

That is, as a molded article of the thermoplastic polyurethane resin, a film is preferably used.

Further, the present invention includes a film comprising the above thermoplastic polyurethane resin.

That is, the film of the present invention is molded from the above thermoplastic polyurethane resin. That is, the film of the present invention is a molded article of the above thermoplastic polyurethane resin.

Such a film is excellent in stretch properties and heat resistance because it contains the thermoplastic polyurethane resin described above.

Therefore, a film containing a thermoplastic polyurethane resin can be suitably used in a field where the above-described various physical properties are required. For example, the Film can be suitably used as a base Film or the like of a protective Film (Paint Protection Film (PPF)) for protecting a coated surface of various products in various industrial fields such as the automobile industry.

A protective film (PPF) is a laminated film for protecting the surface of various products (in particular, automobiles, motorcycles, and the like) by adhering a film containing a polyurethane resin to the coated surface of the products. The protective film (PPF) includes, for example, a release layer containing a polyester resin, an acrylic adhesive layer disposed on the release layer, and a base film layer disposed on the acrylic adhesive layer. The protective film may further include a surface protective layer disposed on the base film layer.

By using a film containing the thermoplastic polyurethane resin as a base film layer in such a protective film (PPF), excellent stretch properties and heat resistance can be obtained, and various products (automobiles, motorcycles, and the like) can be protected satisfactorily.

The thermoplastic polyurethane resin is not limited to films, and can be suitably used in various industrial fields where stretch properties and heat resistance are required.

More specifically, the thermoplastic polyurethane resin can be suitably used in the fields of, for example, yarn, fiber (yarn and composite fiber used for tubes, body suits, shoe covers, sportswear, sporting goods, protective clothing, swimwear, and the like), monofilament, and film (stretch film for clothing, hot-melt film, wound dressing film, and the like).

The thermoplastic polyurethane resin can be suitably used for, for example, transparent rigid plastics, coating materials, adhesives, waterproofing materials, potting agents, inks, adhesives, sheets, tapes (for example, tapes such as watch bands, tapes such as transmission belts for automobiles and various industrial conveyor belts), tubes (for example, tubes such as air tubes, hydraulic tubes, and electric wires, in addition to components such as medical tubes and catheters, tubes such as hoses such as fire hoses), blades, speakers, sensors, high-brightness LED sealing agents, organic EL members, photovoltaic power generation members, robot members, smart robot members, wearable members, clothing articles, hygiene articles, cosmetics, food packaging members, sporting goods, entertainment articles, medical articles, care articles, housing members, acoustic members, lighting members, optical members, and the like, Chandelier, outdoor lamp, sealing material, cork, filler, vibration-proof, vibration-damping, vibration-isolating member, soundproof member, daily necessities, sundry goods, bumper, bedding, stress absorbing material, stress relaxing material, interior and exterior parts for automobile, railway member, aircraft member, optical member, member for OA equipment, surface protecting member for sundry goods, semiconductor sealing material, self-repairing material, health equipment, eyeglass lens, toy, cable cover, wiring, electric communication cable, automobile wiring, computer wiring, industrial goods such as extension cord, sheet, film, care goods, sports goods, entertainment goods, miscellaneous goods, vibration-proof, vibration-isolating material, impact absorbing material, optical material, film such as light guide film, automobile part, surface protecting sheet, cosmetic sheet, transfer sheet, tape member such as semiconductor, and the like, Golf ball members, strings for tennis rackets, agricultural films, wallpaper, antifogging agents, nonwoven fabrics, furniture products such as mattresses and sofas, clothing products such as bras and shoulder pads, medical products such as disposable diapers, cloth towels and cushioning materials for medical tapes, sanitary products such as cosmetics, face washing sponges and pads, footwear products such as shoe soles (outsoles), midsoles and casing materials, body pressure-dispersing products such as pads and bumpers for vehicles, members for hand contact such as door trims, instrument panels and shift handles, vehicle products such as refrigerators, heat insulating materials for buildings and shock absorbers, impact-absorbing materials such as fillers, steering wheels for vehicles, interior automotive trim members and exterior automotive trim members, and semiconductor manufacturing products such as Chemical Mechanical Polishing (CMP) pads.

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 device, a wheel, a drill, etc.), an extrusion molding use (an extrusion molding use for strings of tennis balls, badminton balls, etc., a bundling material thereof, etc.), a powder-shaped hollow molded article based on granulation, etc., an artificial leather, a skin, a sheet, a coating roller (a coating roller of steel, etc.), a sealing agent, 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 obtained by foam molding a polyurethane resin), a mat, an article, a boot, a tennis article, a grip (a grip of a golf club, a two-wheel vehicle, etc.), a rack cover, a wiper, a seat member, a film of a care product, a 3D print molded article, Fiber-reinforced materials (reinforcing materials of fibers such as carbon fiber, lignin, kenaf, nanocellulose fiber, and glass fiber), safety goggles, sunglasses, eyeglass frames, ski goggles, swimming goggles, contact lenses, gas-assisted foam moldings, shock absorbers, CMP polishing pads, dampers (damper), bearings, dust covers, cutting valves, cutting rolls, high-speed rotating rolls, tires, clocks, wearable belts, and the like.

Examples

The present invention will be described below based on examples and comparative examples, but the present invention is not limited to these examples. Unless otherwise specified, "part" 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 "lower" and "lower") or lower limit values (numerical values defined as "upper" and "higher") described in the above-described "embodiment" in accordance with the blending ratio (content ratio), the physical property value, and the parameter described therein.

1) Raw materials

< polyisocyanate component (a) >)

1,4-H₆XDI: 1, 4-bis (isocyanatomethyl) cyclohexane synthesized by the method described in preparation example 1 had a trans isomer ratio of 86 mol%/cis isomer ratio of 14 mol%

H₁₂MDI: 4, 4' -dicyclohexylmethane diisocyanate

< high molecular weight polyol (b) >)

b-1) UH 100W: a number average molecular weight (Mn) of 1000, a crystalline polycarbonate diol having a trade name of ETERNACOLL UH-100W and an average hydroxyl number of 2, and was produced by Udo

b-2) UH 200W: a number average molecular weight (Mn) of 2000, a crystalline polycarbonate diol having a trade name of ETERNACOLL UH-200W and an average hydroxyl number of 2, and was produced by Udo

b-3) UP 100: amorphous polycarbonate diol having a number average molecular weight (Mn) of 1000, having a trade name of ETERNACOLL UP-100 and an average number of hydroxyl groups of 2, and was produced by Udo

b-4) UP 200: amorphous polycarbonate diol having a number average molecular weight (Mn) of 2000, having a trade name of ETERNACOLL UP-200 and an average number of hydroxyl groups of 2, was produced by Udo

b-5) C2090R: number average molecular weight (Mn) 2000, amorphous polycarbonate diol, trade name KURARAY POLYOL C-2090R, modifier: 3-methyl-1, 5-pentanediol, having an average hydroxyl number of 2, manufactured by Kuraray Isoprene Chemical

b-6) 210N: number average molecular weight (Mn) of 1000, polycaprolactone diol, Placcel 210N, average hydroxyl number of 2, manufactured by Daicel

b-7) 220N: number average molecular weight (Mn) 2000, polycaprolactone diol, Placcel 220N, average hydroxyl number 2, manufactured by Daicel

< Low molecular weight polyol (c) >)

1, 4-BD: 1, 4-butanediol, a C2-6 low molecular weight diol manufactured by Mitsubishi chemical corporation

< catalyst for urethane formation >

STATOCT: tin octoate, trade name; STATOC, API CORPORATION system

< catalyst Diluent >

Diisononyl adipate: trade name: DINA, manufactured by Daba chemical industries Ltd

< additive >

Antioxidant: hindered phenol compounds, trade name; IRGANOX 245 manufactured by BASF Japan Ltd

Ultraviolet absorber: benzotriazole compounds, trade name; TINUVIN 234 manufactured by BASF Japan Ltd

Light stabilizer resistance: hindered amine compounds, trade name; ADK STAB LA-72, manufactured by ADEKA

< production of polyisocyanate component (a) >

Synthesis example 11, 4-bis (isocyanatomethyl) cyclohexane (1, 4-H)₆XDI) Synthesis

1, 4-bis (isocyanatomethyl) cyclohexane (1, 4-H) was obtained according to the description of production example 3 of International publication WO2019/069802₆XDI)。

The 1,4-H obtained₆XDI had a purity of 99.9% as determined by gas chromatography, a hue of 5 as determined by APHA, and a hue of¹³The trans/cis ratio was 86 mol% for trans and 14 mol% for cis as measured by C-NMR.

2) Thermoplastic polyurethane resin

Examples 1 to 5 and comparative examples 1 to 6

Thermoplastic polyurethane resins and sheets were obtained according to the formulations shown in Table 1.

More specifically, first, the measurement was performed on the high molecular weight polyol (b) whose temperature had been adjusted to 80 ℃ in advance, and stirring was performed at 700. + -. 50rpm for 1 hour in an oil bath at 80 ℃ under a nitrogen atmosphere using a high-speed stirring disperser. Next, IRGANOX 245 (heat-resistant stabilizer manufactured by BASF), TINUVIN571 (ultraviolet absorber manufactured by BASF) and ADK STAB LA-72 (HALS manufactured by ADEKA) were added as additives to the high molecular weight polyol (b), and the mixture was stirred at 700. + -. 50rpm for 30 minutes in an oil bath at 80 ℃ under a nitrogen atmosphere using a high-speed stirrer. The additives were added in an amount of 0.3 parts by mass of IRGANOX 245 (heat stabilizer, BASF), 0.4 parts by mass of TINUVIN571 (ultraviolet absorber, BASF) and 0.1 parts by mass of ADK STAB LA-72 (HALS, ADEKA) based on 100 parts by mass of the total amount of the final polyisocyanate component, high molecular weight polyol and low molecular weight polyol.

Subsequently, the polyisocyanate component (a) was added to the obtained mixture, and further, tin octylate (trade name: STATOC, API CORPORATION) which had been diluted to 4 mass% with diisononyl adipate (DINA, manufactured by DABAI CHEMICAL CO., LTD.) was added so that the amount of the catalyst (solid content) became 5 ppm.

Next, the resulting mixture was stirred and mixed at 700. + -. 50rpm for 5 minutes in an oil bath at 80 ℃ using a high-speed stirring disperser. Thus, an isocyanate group-ended prepolymer was obtained (prepolymer synthesis step).

Subsequently, 1, 4-butanediol (low molecular weight polyol (c)) which was measured in advance and adjusted to a temperature of 80 ℃ was added to the obtained isocyanate group-ended prepolymer, and the mixture was stirred at 700 ± 50rpm using a high-speed stirring disperser for 3 to 20 minutes (chain extension step).

The amount of the low-molecular-weight polyol (c) added was adjusted so that the equivalent ratio of isocyanate groups in the isocyanate group-terminated prepolymer to hydroxyl groups in the low-molecular-weight polyol (c) (isocyanate groups/hydroxyl groups) was 1.00.

The catalyst (tin octylate diluted with DINA) was appropriately added while observing the heat release rate.

Then, the obtained mixed solution was poured into a Teflon (registered trademark) barrel adjusted to 150 ℃ in advance, reacted at 150 ℃ for 2 hours, then further cooled to 100 ℃ and reacted for 20 hours to obtain a thermoplastic polyurethane resin (reaction product before heat treatment (primary product)) as a reaction product.

Next, the obtained thermoplastic polyurethane resin was taken out from the barrel, cut into a dice shape by a cutter, and the dice-shaped resin was pulverized by a pulverizer to obtain pulverized pellets. Subsequently, the pulverized pellets were heat-treated (cured and aged) for 7 days in an oven at 80 ℃ and dried under reduced pressure in vacuum at 23 ℃ for 12 hours. Thereby, a secondary product (reaction product after heat treatment) of the thermoplastic polyurethane resin was obtained.

Then, the obtained pulverized pellets (secondary product) were cut by extruding the strand with a single screw extruder (model: SZW40-28MG, manufactured by TECHNOLOGEL) at a screw rotation speed of 30rpm and a barrel temperature of 150 to 250 ℃.

Thus, pellets were obtained as a molded article (primary molded article) of the thermoplastic polyurethane resin.

Thereafter, the pellets were dried under reduced vacuum at 80 ℃ for 12 hours, and extrusion-molded using a single-screw extruder (model: SZW40-28MG, manufactured by TECHNOLOGEL) at a rotational speed of 20rpm and a cylinder temperature of 150 to 250 ℃ to obtain a molded article (secondary molded article) of a thermoplastic polyurethane resin having a thickness of 150 μm.

4) Evaluation of

< stretch Property: restoring force (shape restoring rate) >

A film having a thickness of 150 μm (10mm width. times.10 cm length) was set in a universal tester Model205N (manufactured by INTESCO, gauge line distance 80mm, stretching speed 500ml/min) to be elongated by 60% (48mm) of the gauge line distance, and then released.

After 15 seconds from the release, the distance between the marked lines was measured, and the restoring force of the film was measured.

The restoring force of the film is expressed as a ratio (%) of the length of the film before the elongation to the length of the film after the elongation, and a higher value (close to 100%) indicates a higher restoring force (shape restoring rate).

< Heat resistance: storage elastic modulus (E') >)

The dynamic viscoelasticity spectrum of a 150 μm film of a thermoplastic polyurethane resin was measured using a dynamic viscoelasticity measuring apparatus (IT Keisoku Seigyo Co., Ltd., model No.: DVA-220) under conditions of a measuring temperature of-100 to 250 ℃, a temperature rising rate of 5 ℃/min, a stretching mode, a length between gauge lines of 20mm, a static/dynamic stress ratio of 1.8, and a measuring frequency of 10 Hz.

Then, the storage elastic modulus E' at 80 ℃ was measured.

The higher E' indicates the more excellent heat resistance.

< enthalpy of fusion (unit: J/g) >

Measured using a differential scanning calorimeter (DSC7000X, manufactured by Hitachi High-Tech Science) as described below.

That is, about 10mg of the thermoplastic polyurethane resin was collected into an aluminum dish. The aluminum dish was covered with a lid and then bent to obtain a product as a measurement sample (sample). The alumina sample obtained in the same manner was used as a reference sample.

After the sample and the reference were set at a predetermined position in a chamber (cell), the sample was cooled from 20 ℃ to-100 ℃ at a rate of 10 ℃/min under a nitrogen flow of 30NmL/min, and after the temperature was maintained for 5 minutes, the temperature was raised to 270 ℃ at a rate of 10 ℃/min, and thereafter, the sample was cooled to-70 ℃ at a rate of 10 ℃/min.

Then, among the peaks appearing at a temperature rise from-100 ℃ to 270 ℃, the peak temperature of the endothermic peak (melting peak) at 160 ℃ or higher and the heat quantity (enthalpy change) of the peak (J/g) were measured.

[ Table 1]

TABLE 1

The present invention is provided as an exemplary embodiment of the present invention, but this is merely an example and is not to be construed as limiting. Variations of the invention that are obvious to those skilled in the art are intended to be encompassed by the following claims.

Industrial applicability

The thermoplastic polyurethane resin and the film of the present invention can be suitably used in various industrial fields such as the automobile industry.

Claims

1. A thermoplastic polyurethane resin characterized by comprising the reaction product of:

a polyisocyanate component comprising a trans-isomer-containing 1, 4-bis (isocyanatomethyl) cyclohexane in an amount of 60 to 99.5 mol%, and

a reaction product of a polyol component comprising an amorphous polycarbonate diol which is liquid at 25 ℃ and a low-molecular-weight diol having 2 to 6 carbon atoms.

2. The thermoplastic polyurethane resin according to claim 1, wherein the amount of heat of a melting peak of the thermoplastic polyurethane resin at 160 ℃ or higher as measured by differential scanning calorimetry (DSC method) is 15J/g or lower.

3. The thermoplastic polyurethane resin according to claim 1, wherein the amount of heat of the melting peak of the thermoplastic polyurethane resin at 160 ℃ or higher as measured by differential scanning calorimetry (DSC method) is 0.1J/g or higher.

4. A film comprising the thermoplastic polyurethane resin according to claim 1.