CN114375312B

CN114375312B - Thermoplastic polyurethane resin and film

Info

Publication number: CN114375312B
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: 2024-04-09
Anticipated expiration: 2040-09-28
Also published as: JPWO2021065783A1; WO2021065783A1; TW202124494A; JP7257541B2; CN114375312A

Abstract

The thermoplastic polyurethane resin is obtained as a reaction product of a polyisocyanate component containing 1, 4-bis (isocyanatomethyl) cyclohexane containing a trans-form in a proportion of 60 mol% 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 typically rubber elastomers obtained by the reaction of a polyisocyanate, a high molecular weight polyol, and a low molecular weight polyol. 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 coated 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 has been proposed, and further, a caprolactone polyol has been proposed as a polyol and a dicyclohexylmethane diisocyanate has been proposed as a polyisocyanate (for example, see patent literature 1.).

Prior art literature

Patent literature

Patent document 1: japanese patent laying-open No. 2010-505563

Disclosure of Invention

Problems to be solved by the invention

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

The present invention relates to a thermoplastic polyurethane resin having both 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 containing 1, 4-bis (isocyanatomethyl) cyclohexane containing a 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 invention [2] includes the thermoplastic polyurethane resin described in [1] above, wherein the heat quantity of the melting peak of the thermoplastic polyurethane resin at 160℃or higher, as measured by a differential scanning calorimeter (DSC method), is 15J/g or less.

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

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

Effects of the invention

The thermoplastic polyurethane resin and film of the present invention contain, as raw material components: a polyisocyanate component containing 1, 4-bis (isocyanatomethyl) cyclohexane containing a trans-form in a proportion of 60 mol% 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.

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

Accordingly, the thermoplastic polyurethane resin and the film of the present invention can adjust the cohesiveness of the polyurethane structure with good balance, and can have both high heat resistance due to the cohesiveness and stretch properties due to the low cohesiveness with good balance.

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 reacting a polyisocyanate component and a polyol component as raw material components.

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

Stereoisomers of cis-1, 4-bis (isocyanatomethyl) cyclohexane (hereinafter, referred to as cis-1, 4-isomer) and trans-1, 4-bis (isocyanatomethyl) cyclohexane (hereinafter, referred to as trans-1, 4-isomer) exist in 1, 4-bis (isocyanatomethyl) cyclohexane.

In the present invention, 1, 4-bis (isocyanatomethyl) cyclohexane contains trans 1, 4-isomer (trans-isomer) in a predetermined ratio.

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

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

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

The 1, 4-bis (isocyanatomethyl) cyclohexane can be produced by, for example, a method described in International publication No. WO2009/051114 or International publication No. WO 2019/069802.

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

Examples of the modified product of 1, 4-bis (isocyanatomethyl) cyclohexane include a polymer of 1, 4-bis (isocyanatomethyl) cyclohexane (for example, a uretdione modified product, etc.), a trimer (for example, an isocyanurate modified product, an iminooxadiazinedione modified product, etc.), a biuret modified product (for example, a biuret modified product generated by a reaction of 1, 4-bis (isocyanatomethyl) cyclohexane with water, etc.), an allophanate modified product (for example, an allophanate modified product generated by a reaction of 1, 4-bis (isocyanatomethyl) cyclohexane with 1-or 2-membered alcohol, etc.), a polyol modified product (for example, a polyol modified product (adduct) generated by a reaction of 1, 4-bis (isocyanatomethyl) cyclohexane with 3-membered alcohol, etc.), an oxadiazinetrione modified product (for example, oxadiazinetrione generated by a reaction of 1, 4-bis (isocyanatomethyl) cyclohexane with carbon dioxide), a carbodiimide modified product (for example, a reaction of 1, 4-bis (isocyanatomethyl) cyclohexane with carbodiimide, etc.). They may be used singly or in combination of 2 or more.

The monomer (monomer) of 1, 4-bis (isocyanatomethyl) cyclohexane is preferably 1, 4-bis (isocyanatomethyl) cyclohexane.

If the polyisocyanate component contains the above-mentioned 1, 4-bis (isocyanatomethyl) cyclohexane, the heat resistance of the thermoplastic polyurethane resin can be improved by the crystallinity derived from the symmetrical structure of the 1, 4-bis (isocyanatomethyl) cyclohexane. That is, when the polyisocyanate component does not contain 1, 4-bis (isocyanatomethyl) cyclohexane containing a trans-form in a predetermined ratio, crystallinity of the polyisocyanate component may be insufficient, and the thermoplastic polyurethane resin (described later) may be degraded in cohesiveness and poor in heat resistance. In contrast, when the polyisocyanate component contains the above-mentioned 1, 4-bis (isocyanatomethyl) cyclohexane, the crystallinity of the polyisocyanate component can be improved due to the symmetrical structure of the 1, 4-bis (isocyanatomethyl) cyclohexane, and the cohesiveness of the thermoplastic polyurethane resin can be improved, and therefore, the heat resistance can be improved.

In addition, as the polyisocyanate component, other polyisocyanates (polyisocyanates other than 1, 4-bis (isocyanatomethyl) cyclohexane) may be contained as an optional component within a range that does not hinder the excellent effects of the present invention.

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

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-trimethylhexamethylene diisocyanate, 1,6, 11-undecamethylene triisocyanate, 1,3, 6-hexamethylene triisocyanate, 1, 8-diisocyanato-4-isocyanatomethyl octane, 2,5, 7-trimethyl-1, 8-diisocyanato-5-isocyanatomethyl octane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1, 4-butanediol dipropyl ether-. Omega., omega' -diisocyanate, lysine isocyanatomethyl ester, lysine triisocyanate, 2-isocyanatoethyl-2, 6-diisocyanatohexanoate, 2-isocyanatopropyl-2, 6-diisocyanatohexanoate, bis (4-isocyanaton-butylene) pentaerythritol, 2, 6-diisocyanatomethylhexanoate, and the like.

In addition, alicyclic polyisocyanates (excluding 1, 4-bis (isocyanatomethyl) cyclohexane) are included in the aliphatic polyisocyanates.

Examples of alicyclic polyisocyanates (excluding 1, 4-bis (isocyanatomethyl) cyclohexane) include 1, 3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate (IPDI), trans-, trans, cis-, and cis, cis-dicyclohexylmethane diisocyanate, and mixtures thereof (hydrogenated MDI, H) ₁₂ MDI), 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-diisocyanatomethyl bicyclo [ 2,1 ] -heptane, 2, 6-diisocyanatomethyl bicyclo [ 2,1 ] -heptane (NBDI) as its isomer 2-isocyanatomethyl 2- (3-isocyanatopropyl) -5-isocyanatomethyl bicyclo- [ 2,1 ] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6-isocyanatomethyl bicyclo- [ 2,1 ] -heptane, 2-isocyanatomethyl 3- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo- [ 2,1 ] -heptane, Alicyclic diisocyanates such as 2-isocyanatomethyl 3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo- [ 2,1 ] -heptane, 2-isocyanatomethyl 2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo- [ 2,1 ] -heptane, 2-isocyanatomethyl 2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo- [ 2,1 ] -heptane, and the like.

Examples of the aromatic polyisocyanate include 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate, and isomer mixtures (TDI) of these toluene diisocyanates, 4' -diphenylmethane diisocyanate, 2,4' -diphenylmethane diisocyanate and 2,2' -diphenylmethane diisocyanate, and aromatic diisocyanates such as any isomer Mixtures (MDI) of these diphenylmethane diisocyanates, toluidine diisocyanate (TODI), p-phenylene diisocyanate, naphthalene Diisocyanate (NDI), and the like.

Examples of the aromatic aliphatic polyisocyanate include aromatic aliphatic 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.

In addition, other polyisocyanates may be prepared in the form of modified products within a range that does not hinder the excellent effects of the present invention. Examples of the modified product include polymers (such as uretdione modified product, isocyanurate modified product, and iminooxadiazinedione modified product), biuret modified product, allophanate modified product, polyol modified product, oxadiazinetrione modified product, and carbodiimide modified product. They may be used singly or in combination of 2 or more.

The content ratio of the other polyisocyanate may be appropriately selected within a range that does not impair 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 (isocyanatomethyl) cyclohexane (including modified products of 1, 4-bis (isocyanatomethyl) cyclohexane) is, for example, higher than 50 mol%, preferably 70 mol% or higher, more preferably 90 mol% or higher, still more preferably 95 mol% or higher, and particularly preferably 100 mol% with respect to 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 a high molecular weight polyol having a molecular weight higher than 400 and a low molecular weight polyol having a molecular weight of 400 or less as essential components.

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

A 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 an amorphous polycarbonate diol which is in a liquid state (liquid state) at 25 ℃ as an essential component. In other words, the polyol component contains an amorphous polycarbonate diol as an essential component.

The amorphous polycarbonate diol is an amorphous polycarbonate polyol having an average hydroxyl number of 2. The term "amorphous" means a state of liquid at 25℃and (a viscosity of 500000 mPas or less at 25℃as measured by an E-type viscometer).

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

Among the ring-opening polymers of ethylene carbonate, examples of the 2-polyol used 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, 1, 8-octanediol, and linear 2-polyols having 4 to 8 carbon atoms such as diethylene glycol, triethylene glycol, and the like. These 2-alcohols may be used alone or in combination of 2 or more.

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

Among the ring-opening polymers of ethylene carbonate, as the 2-polyol as a modifier, for example, a linear 2-polyol and a branched 2-polyol can be cited. As the linear 2-polyol, a different type of linear 2-polyol from the above-mentioned 2-polyol as an initiator can be selected.

The linear 2-polyol as the modifier may be of a different type from the 2-polyol as the initiator, but a linear 2-polyol having a carbon number greater than that of the 2-polyol as the initiator is preferable. More specifically, examples thereof include linear 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. These linear 2-alcohols may be used alone or in combination of 2 or more.

Further, examples of the branched 2-polyol as the modifier include branched alkane diols 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-alcohols may be used alone or in combination of 2 or more.

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

The 2-polyol as the modifier is preferably a linear 2-polyol having more carbon atoms than the 2-polyol as the initiator, or a branched 2-polyol, more preferably a branched 2-polyol, and still more preferably 3-methyl-1, 5-pentanediol.

The method for modifying the ring-opened polymer of ethylene carbonate with 2-diol is not particularly limited, and known methods can be used. For example, after ring-opening polymerization of ethylene carbonate by a known method using 2-polyol as an initiator, the obtained ring-opened polymer is further copolymerized with 2-polyol as a modifier.

These amorphous polycarbonate diols may be used alone or in combination of 2 or more. That is, a single type of amorphous polycarbonate diol may be used, or 2 or more types of amorphous polycarbonate diols different from each other, for example, a number average molecular weight, a 2-polyol as an initiator, a 2-polyol as a modifier, and the like may be used in combination.

From the viewpoint of improving the expansion and contraction 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, particularly preferably 2000 or less.

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

That is, the high molecular weight polyol may contain other high molecular weight polyols (high molecular weight polyols other than the 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 400 or more and 10000 or less (excluding amorphous polycarbonate diols), 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.

The other high molecular weight polyol is preferably crystalline polycarbonate polyol.

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

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

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

The number average molecular weight of the crystalline polycarbonate polyol is higher than 400, preferably 500 or more, more preferably 1000 or more, still more preferably 1300 or more, and particularly preferably 1500 or more, for example 10000 or less, preferably 8000 or less, more preferably 5000 or less, still more preferably 3000 or less, and particularly preferably 2000 or less, from the viewpoint of achieving both the expansion and contraction properties and the heat resistance.

The average hydroxyl number of the crystalline polycarbonate polyol per 1 molecule 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 can be appropriately set within a range that does not impair the excellent effects of the present invention.

That is, when a relatively high crystalline high molecular weight polyol (crystalline polycarbonate polyol, polycaprolactone polyol, or the like) is used in excess as another high molecular weight polyol, there is a case where aggregation becomes high, and the expansion and contraction characteristics (restoring force) are lowered.

Therefore, the ratio of the other high molecular weight polyol (crystalline polycarbonate polyol or the like) can be adjusted to a range in which excellent expansion and contraction characteristics 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 mole of the high molecular weight polyol.

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 mole of the high molecular weight polyol.

That is, the high molecular weight polyol is particularly preferably not containing other high molecular weight polyol but containing the amorphous polycarbonate diol alone.

From the viewpoint of achieving both the expansion and contraction properties 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, still more preferably 1300 or more, and particularly preferably 1500 or more, for example 10000 or less, preferably 8000 or less, more preferably 5000 or less, still more preferably 3000 or less, and particularly preferably 2000 or less.

The low molecular weight polyol is a compound having 2 or more hydroxyl groups in the molecule and 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 a molecular weight of 400 or less, which has 2 hydroxyl groups in 1 molecule.

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

Among the low molecular weight diols 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 is preferably an alkane diol having 2 to 6 carbon atoms, more preferably 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 required.

That is, the low molecular weight polyol 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 an optional component.

Examples of the other low molecular weight polyol include compounds other than low molecular weight diols having 2 to 6 carbon atoms, which have 2 to 400 hydroxyl groups in the molecule and a molecular weight of 50 to 400.

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

Examples of the low molecular weight diol having 7 or more carbon atoms include alkane-1, 2-diol 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, a mixture thereof, and 2-diol 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 low molecular weight polyol having 3 or more is a compound having a molecular weight of 400 or less and 3 or more hydroxyl groups in 1 molecule, and examples thereof include glycerol, 6-membered alcohols such as 2-methyl-2-hydroxymethyl-1, 3-propanediol, 2, 4-dihydroxy-3-hydroxymethylpentane, 1,2, 6-hexanetriol, trimethylolpropane, 2-bis (hydroxymethyl) -3-butanol and the like (low molecular weight triol), 4-membered alcohols such as tetramethylolmethane (pentaerythritol), diglycerol and the like, 5-membered alcohols such as xylitol and the like, 6-membered alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altrose alcohol, inositol, dipentaerythritol and the like, 7-membered alcohols such as avocaditol and the like, and 8-membered alcohols such as sucrose and the like. These 3-membered or more low molecular weight polyols 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, preferably 300 or less.

The blending ratio of the other low molecular weight polyol may be appropriately set within a range that does not impair the excellent effects of the present invention.

More specifically, the content 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, based on 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 based on 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 (low molecular weight polyol other than the low molecular weight diol having 2 to 6 carbon atoms) but contains the 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.

The content of the high molecular weight polyol and the low molecular weight polyol in the polyol component 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, still more preferably less than 50 mol%, and particularly preferably 40 mol% or less, based on the total amount of these components. The low molecular weight polyol is, for example, 5 mol% or more, preferably 10 mol% or more, more preferably 30 mol% or more, still more preferably more than 50 mol%, particularly preferably 60 mol% or more, for example, 80 mol% or less, and preferably 70 mol% or less.

The thermoplastic polyurethane resin can be obtained by reacting a polyisocyanate component with a polyol component.

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

For the reaction of the above components (polyisocyanate component, 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 and a high molecular weight polyol containing an amorphous polycarbonate polyol are reacted 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 reaction of the polyisocyanate component and the high molecular weight polyol is carried out under a nitrogen flow at a reaction temperature of, for example, 50 ℃ or higher, for example, 250 ℃ or lower, preferably 200 ℃ or lower for, 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 an 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 higher, for example, 15 hours or lower.

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, polar non-aliphatic subclasses such as methyl cellosolve acetate, ethyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, and ethyl 3-ethoxypropionate, ethers such as diethyl ether, tetrahydrofuran, and dioxane, and halogenated aliphatic hydrocarbons such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, bromomethane, diiodomethane, and dichloroethane, and polar non-aliphatic subclasses such as N-methyl pyrrolidone, dimethylformamide, N' -dimethylacetamide, dimethyl sulfoxide, and hexamethylphosphoramide.

In the polymerization reaction, a known urethane catalyst such as an amine or an organometallic 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, imidazoles such as imidazole and 2-ethyl-4-methylimidazole, and the like.

Examples of the organometallic compound include organic tin compounds such as tin acetate, tin octoate (tin octoate), tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dithiooxide, dibutyltin maleate, dibutyltin dineodecanoate, dioctyltin dithiooxide, dioctyltin dilaurate, dibutyltin dichloride, organic lead compounds such as lead octoate and lead naphthenate, organic nickel compounds such as nickel naphthenate, organic cobalt compounds such as cobalt naphthenate, organic copper compounds such as copper octenoate, and organic bismuth compounds such as bismuth octoate (bismuth octoate) and bismuth neodecanoate, and preferably include tin octoate and bismuth octoate.

Examples of the urethanization catalyst include potassium salts such as potassium carbonate, potassium acetate and potassium octoate.

These urethanization catalysts may be used alone or in combination of 2 or more.

The amount 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, based on 10000 parts by mass of the total amount of the polyisocyanate component and the high-molecular-weight polyol.

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

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 ratio of the components 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 even more preferably 8 or less, in terms of the equivalent ratio (isocyanate group/hydroxyl group) of the isocyanate groups in the polyisocyanate component to the hydroxyl groups in the high molecular weight polyol.

More specifically, the blending 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, based on 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 in an appropriate ratio in order to adjust the hard segment concentration (described later) of the obtained thermoplastic polyurethane resin.

In this method, the above components are reacted until the isocyanate group content is, for example, 1.0 mass% or more, preferably 1.5 mass% or more, more preferably 3.0 mass% or more, still more preferably 5.0 mass% or more, for example, 30.0 mass% or less, preferably 19.0 mass% or less, still more preferably 16.0 mass% or less, still more preferably 12.0 mass% or less. Thus, an isocyanate group-ended prepolymer can be obtained.

The isocyanate group content (isocyanate group content) can be determined by a known method such as titration with di-n-butylamine.

Next, 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 bulk polymerization or solution polymerization as described above.

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

More specifically, the mixing 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, still more 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, based on 100 parts by mass of the isocyanate group-ended prepolymer.

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

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

In the case of using the one-shot method as a method for obtaining the reaction product, the polyisocyanate component and the polyol component (including the high-molecular-weight polyol and the low-molecular-weight polyol) are mixed together with stirring at a ratio of, 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, and more preferably 1.08 or less, of the equivalent ratio of the isocyanate groups in the polyisocyanate component to the hydroxyl groups in the polyol component (isocyanate groups/hydroxyl groups).

The stirring and mixing are carried out under an inert gas (e.g., nitrogen) atmosphere at a reaction temperature of, for example, 40 ℃ or higher, preferably 70 ℃ or higher, for example, 280 ℃ or lower, preferably 260 ℃ or lower, and a reaction time of, for example, 30 seconds or higher and 1 hour or lower.

In addition, the urethane catalyst and the organic solvent may be added in 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 a heat treatment (heat treatment step), if necessary.

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 be heat-treated, and then dried as necessary.

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

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

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

When the heat treatment period falls within the above range, a thermoplastic polyurethane resin having both of the stretch properties and the heat resistance can be obtained particularly well.

In the production of the thermoplastic polyurethane resin, additives such as antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, water-blocking inhibitors (carbodiimide compounds, etc.), dyes (bluing agents, etc.), plasticizers, antiblocking agents, surface modifiers, lubricants, mold release agents, pigments, fillers, rust inhibitors, fillers, etc. may be added as necessary.

These additives may be added at the time of mixing, synthesis or post-synthesis of the components.

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

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 a raw material component: a polyisocyanate component containing 1, 4-bis (isocyanatomethyl) cyclohexane containing a trans-form in a proportion of 60 mol% 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 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, still more preferably 15 mass% or more, for example, 30 mass% or less, preferably 25 mass% or less, and still 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 blending ratio (charge) of the components by a known method, for example.

More specifically, for example, when the prepolymer method is used, 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) ]. Times. 100 (total mass of polyisocyanate component (g) +polyol component (g)). Times. 100

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

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

In addition, if the heat of the melting peak of the thermoplastic polyurethane resin at 160 ℃ or higher is lower than the upper limit, the thermoplastic polyurethane resin will not have excessively high cohesiveness, and thus excellent stretch characteristics can be obtained.

That is, if the heat quantity of the melting peak of the thermoplastic polyurethane resin at 160 ℃ or higher is within the above-mentioned range, the cohesiveness can be appropriately adjusted, and both the heat resistance and the expansion/contraction characteristics of the thermoplastic polyurethane resin can be achieved.

The heat quantity of the melting peak can be measured by differential scanning calorimetric measurement (DSC measurement) according to examples described later.

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

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

The recovery force (shape recovery rate) after 15 seconds and 60% stretching can be measured by a tensile tester or the like according to examples described later.

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

Specifically, from the viewpoint of heat resistance, the storage elastic modulus (E') at 80℃of the thermoplastic polyurethane resin is, for example, 10X 10 ⁶ MPa or more, preferably 15×10 ⁶ MPa or aboveMore preferably 20X 10 ⁶ MPa or more, for example, 50×10 ⁶ MPa or less, preferably 40×10 ⁶ MPa or less, more preferably 30X 10 ⁶ And MPa or below.

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

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

Examples of the molding method in the one-shot molding include thermal compression molding, injection molding, extrusion molding, cutting molding, melt spinning molding, 3D printer molding, and the like. They may be used singly or in combination of 2 or more.

Examples of the shape of the primary molded article include pellet, plate, fiber, strand, film, sheet, tube, hollow, and box, and pellet is preferable.

For example, in the case of obtaining a pellet-shaped thermoplastic polyurethane resin as a primary molded article, it is preferable to obtain a secondary molded article of the thermoplastic polyurethane resin by subjecting the pellet-shaped thermoplastic polyurethane resin to secondary molding by a known molding method.

The molding method in the secondary molding is preferably extrusion molding.

Examples of the shape of the secondary molded article include pellet, plate, fiber, strand, film, sheet, tube, hollow, and box, and preferably include film.

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

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

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

Such a film contains the thermoplastic polyurethane resin, and therefore has excellent stretch properties and heat resistance.

Therefore, films containing thermoplastic polyurethane resins can be suitably used in fields requiring the above-mentioned various physical properties. For example, the film can be suitably used as a base film 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.

The protective film (PPF) is a laminated film for protecting the surfaces of various products (particularly, automobiles, motorcycles, etc.) by adhering a film containing a polyurethane resin to the coated surfaces of the various products. The protective film (PPF) includes, for example, a release layer including 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 characteristics and heat resistance can be obtained, and various products (automobiles, motorcycles, etc.) can be well protected.

The thermoplastic polyurethane resin is not limited to a film, and can be suitably used in various industrial fields where stretching characteristics and heat resistance are required.

More specifically, the thermoplastic polyurethane resin can be suitably used in the fields of, for example, yarns, fibers (yarns, composite fibers used in tubes, body suits, shoe covers, sportswear, sporting goods, protective clothing, swimwear, etc.), monofilaments, films (stretchable films for clothing, hot melt films, wound-covering films, etc.).

The thermoplastic polyurethane resin described above can be suitably used for, for example, transparent rigid plastic, coating material, adhesive, waterproof material, potting agent, ink, adhesive, sheet, tape (for example, tape such as a watchband, tape such as a transmission belt for an automobile, various industrial transmission belts (conveyor belts), etc.), tube (for example, tube such as an air tube, hydraulic tube, electric wire tube, etc. in addition to a medical tube, a catheter, etc., for example, hoses such as fire hoses), blades, speakers, sensors, LED packages for high brightness, organic EL members, solar power generation members, robot members, intelligent robot members, wearable members, clothing articles, sanitary articles, toiletry articles, food packaging members, sports articles, recreational articles, medical articles, nursing articles, housing members, acoustic members, lighting members, chandeliers, outdoor lamps, sealing materials, packaging materials, cork, fillers, vibration/shock/vibration-absorbing/vibration-insulating members, soundproof members, daily necessities, groceries, buffers, bedding, stress absorbing materials, stress relaxing materials, automobile interior and exterior decorative parts, railway members, aircraft members, optical members, OA equipment members, grocery surface protecting members, semiconductor packaging materials, self-repairing materials, health articles, eyeglass lenses, toys, cable jackets, wiring, electrical communication cables, automobile wiring, computer wiring, articles such as telescopic wires, sheets, membranes and other articles such as nursing articles, industrial articles, recreational articles, vibration/entertainment, various groceries, vibration/vibration-absorbing materials, impact absorbing materials, optical materials, light guide membranes and other articles, automobile surface protecting sheets, transfer sheets and the like, tape members such as semiconductor protective tapes, string members for golf ball, tennis racket, agricultural films, wallpaper, antifogging agents, nonwoven fabrics, furniture articles such as mattresses and sofas, clothing articles such as brassieres and shoulder pads, medical articles such as disposable diapers, cloth towels, cushioning materials for medical tapes, sanitary articles such as cosmetics, face-washing sponges and pads, shoe articles such as soles (outsoles), midsoles and casing materials, pressure-sensitive dispersing articles such as mats for vehicles, cushioning articles such as bumpers, hand-contacting members such as door trim, instrument panels and shift handles, impact absorbing materials such as refrigerators, heat insulating materials for buildings, shock absorbers, filling materials, steering wheels for vehicles, automobile interior decorative members, automobile exterior decorative members, and semiconductor manufacturing articles such as Chemical Mechanical Polishing (CMP) pads.

In addition, in the case of the optical fiber, the molded article described above can be suitably used for coating materials (coating materials for films, sheets, belts, wires, metal rotating equipment, wheels, drills, etc.), extrusion molding applications (extrusion molding applications for strings of tennis balls, shuttlecocks, etc. and bundling materials thereof, etc.), hollow molded articles in powder form based on micropellets, etc., artificial leather, skins, sheets, coating rolls (coating rolls of steel, etc.), sealants, rolls, gears, shells or core materials for balls, bats (shells or core materials for golf balls, basketball, volleyball, softball, baseball, etc.), mats, ski wear products, boots, tennis products, grips (grips for golf clubs, two-wheeled vehicles, etc.), rack covers, wipers, seat cushion members, films for nursing products, 3D printing molded articles, fiber reinforced materials (reinforcing materials for carbon fibers, lignin, kenaf, nanocellulose fibers, etc.), safety goggles, sunglasses, polishing frames, spectacles, gas-contact lenses, foam-assisted skiing, vibration-damping devices, vibration-damping devices, etc., vibration-damping devices, etc. (they may be in the form of foaming and molding devices for foaming and forming polyurethane resins), and vibration-damping devices, etc.

Examples

The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" and "%" are based on mass. Specific numerical values such as the blending ratio (containing ratio), physical property value, and parameter used in the following description may be replaced with the upper limit value (numerical value defined in the form of "below", "lower", or "numerical value defined in the form of" above "," higher ") or the lower limit value (numerical value defined in the form of" lower ", or" numerical value defined in the form of "higher", which are described in the above "specific embodiment", and which correspond to the blending ratio (containing ratio), physical property value, and parameter.

1) Raw materials

< polyisocyanate component (a) >)

1,4-H ₆ XDI: 1, 4-bis (isocyanatomethyl) cyclohexane synthesized by the method described in production example 1, 86 mol% of the trans form per 14 mol% of the cis form

H ₁₂ MDI:4,4' -dicyclohexylmethane diisocyanate

< high molecular weight polyol (b) >)

b-1) UH100W: a crystalline polycarbonate diol having a number average molecular weight (Mn) of 1000, a trade name of ETERNACOLL UH-100W, an average hydroxyl number of 2, manufactured by Yucheng

b-2) UH200W: number average molecular weight (Mn) of 2000, crystalline polycarbonate diol, trade name ETERNACOLL UH-200W, average hydroxyl number of 2, manufactured by Yucheng

b-3) UP100: a number average molecular weight (Mn) of 1000, an amorphous polycarbonate diol, trade name ETERNACOLL UP-100, an average hydroxyl number of 2, manufactured by Yucheng

b-4) UP200: number average molecular weight (Mn) of 2000, amorphous polycarbonate diol, trade name ETERNACOLL UP-200, average hydroxyl number of 2, manufactured by Yucheng

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

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

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

< Low molecular weight polyol (c) >)

1,4-BD:1, 4-butanediol, low molecular weight diol having 2 to 6 carbon atoms (C) manufactured by Mitsubishi chemical Co., ltd

< catalyst for urethanization >)

Stanoc: tin octoate, trade name; STANOCT, API CORPORATION

Catalyst diluent

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

< additive >)

Antioxidant: a hindered phenol compound, trade name; IRGANOX 245,BASF Japan Ltd System

Ultraviolet absorber: benzotriazole compounds, trade names; TINUVIN 234,BASF Japan Ltd System

Light-resistant stabilizer: a hindered amine compound, trade name; ADK STAB LA-72 manufactured by ADEKA

Production of polyisocyanate component (a)

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

According to the description of production example 3 of International publication WO2019/069802, 1, 4-bis (isocyanatomethyl) cyclohexane (1, 4-H) ₆ XDI)。

The obtained 1,4-H ₆ XDI has a purity of 99.9% as measured by gas chromatography, a hue of 5 as measured by APHA, and a molecular weight of ¹³ The trans-form/cis-form ratio obtained by C-NMR measurement was 86 mol% of the trans-form and 14 mol% of the cis-form.

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 high molecular weight polyol (b) having been previously temperature-adjusted to 80℃was measured, and stirred 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 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 stirring was performed at 700.+ -. 50rpm for 30 minutes in an oil bath at 80℃under a nitrogen atmosphere using a high-speed stirring disperser. The amount of the additive to be added was 0.3 part by mass of IRGANOX 245 (heat stabilizer manufactured by BASF), 0.4 part by mass of TINUVIN571 (ultraviolet absorber manufactured by BASF) and 0.1 part by mass of ADK STAB LA-72 (HALS manufactured by ADEKA) based on 100 parts by mass of the total amount of the final polyisocyanate component, the high molecular weight polyol and the low molecular weight polyol.

Then, the polyisocyanate component (a) was added to the obtained mixture, and tin octoate (trade name: STANOCT, manufactured by API CORPORATION) diluted to 4% by mass with diisononyl adipate (DINA, manufactured by Daba Okaki Co., ltd.) was further added so that the catalyst amount (solid component amount) became 5 ppm.

Next, the obtained 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).

Next, 1, 4-butanediol (low molecular weight polyol (c)) which has been 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 and stirred for 3 to 20 minutes (chain extension step).

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

The catalyst (tinoctanoate diluted with DINA) was added as appropriate while observing the heat release rate.

Then, the obtained mixed solution was poured into a Teflon (registered trademark) bucket which had been previously temperature-adjusted to 150℃and reacted at 150℃for 2 hours, and then cooled to 100℃and further reacted for 20 hours, whereby a thermoplastic polyurethane resin (a reaction product (primary product) before heat treatment) was obtained as a reaction product.

Then, the obtained thermoplastic polyurethane resin was taken out of the barrel, cut into dice-like pieces by a rubber cutter, and the dice-like pieces were pulverized by a pulverizer to obtain pulverized pellets. Next, the crushed pellets were subjected to heat treatment (curing, aging) in an oven at 80℃for 7 days, and dried at 23℃for 12 hours under reduced vacuum. Thereby, a secondary product (reaction product after heat treatment) of the thermoplastic polyurethane resin is obtained.

Thereafter, the obtained crushed pellets (secondary product) were extruded with a single screw extruder (model: SZW40-28MG, manufactured by TECHNOVEL Co.) at a screw speed of 30rpm and a barrel temperature of 150 to 250℃to cut the strands.

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

Thereafter, the pellets were dried at 80℃for 12 hours under reduced vacuum in advance, and extrusion molding was performed using a single screw extruder (model: SZW40-28MG, manufactured by TECHNOVEL Co.) 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. Mu.m.

4) Evaluation

< telescoping property: restoring force (shape recovery rate) >)

A film having a thickness of 150 μm (10 mm wide. Times.10 cm long) was set in a universal tester Model205N (manufactured by INTESCO), the distance between the gauge lines was 80mm, and the stretching speed was 500ml/min, and the film was stretched by 60% (48 mm) of the distance between the gauge lines and then released.

After 15 seconds from release, the distance between the reticles 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 elongation to the length of the film after elongation, and the higher the value (nearly 100%), the higher the restoring force (shape recovery ratio) is expressed.

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

A 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: DVA-220) under conditions of a measuring temperature of-100℃to 250 ℃, a heating rate of 5 ℃/min, a stretching mode, a length between graticules 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' means the more excellent the heat resistance.

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

The measurement was performed as described below using a differential scanning calorimeter (DSC 7000X, manufactured by Hitachi High-Tech Science).

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

After the sample and the reference were placed at predetermined positions in the chamber (cell), the sample was cooled from 20℃to-100℃at a rate of 10℃per minute under a nitrogen flow of 30NmL/min, kept at that temperature for 5 minutes, and then heated to 270℃at a rate of 10℃per minute, and thereafter cooled to-70℃at a rate of 10℃per minute.

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

TABLE 1

The invention described above is provided as an example embodiment of the invention, but this is merely an example and is not to be construed in a limiting sense. Variations of the present invention that are obvious to those skilled in the art are encompassed by the appended 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. Thermoplastic polyurethane resin characterized by comprising the reaction product of:

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

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

wherein the heat quantity of the melting peak of the thermoplastic polyurethane resin at 160 ℃ or higher is 2J/g or more and 10.5J/g or less as measured by differential scanning calorimetric measurement (DSC method).

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