JP7257541B2 - Thermoplastic polyurethane resin and film - Google Patents

Description

The present invention relates to thermoplastic polyurethane resins and films, and more particularly to thermoplastic polyurethane resins and films comprising the thermoplastic polyurethane resins.

Thermoplastic polyurethane resins (TPUs) are generally rubber elastomers obtained by the reaction of polyisocyanates, high molecular weight polyols and low molecular weight polyols. Thermoplastic polyurethane resins, for example, are molded into films and used as protective films (Paint Protection Films (PPF)) for protecting painted surfaces of automobiles.

As a protective film, for example, a multi-layer polyurethane protective film containing a TPU layer obtained by reacting a polyol and a polyisocyanate has been proposed. Using is proposed (for example, refer to Patent Document 1.).

Special Table 2010-505663

On the other hand, the protective film is required to have stretchability (rebound force) and heat resistance depending on the application. In this respect, the multilayer polyurethane protective film described above has a problem of insufficient heat resistance.

The present invention is a thermoplastic polyurethane resin having both stretchability (return force) and heat resistance, and a film containing the thermoplastic polyurethane resin.

The present invention [1] provides a polyisocyanate component containing 1,4-bis(isocyanatomethyl)cyclohexane containing a trans isomer at a ratio of 60 mol% or more and 99.5 mol% or less, and a non-liquid at 25 ° C. It contains a thermoplastic polyurethane resin containing a reaction product with a polyol component containing a crystalline polycarbonate diol and a low molecular weight diol having 2 to 6 carbon atoms.

The present invention [2] is the above [1], wherein the thermoplastic polyurethane resin has a melting peak heat quantity of 15 J/g or less at 160°C or higher, measured by differential scanning calorimetry (DSC method). Contains thermoplastic polyurethane resin.

The present invention [3] is the above [1] or It contains the thermoplastic polyurethane resin described in [2].

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

The thermoplastic polyurethane resin and film of the present invention comprise, as a raw material component, a polyisocyanate component containing 1,4-bis(isocyanatomethyl)cyclohexane containing a trans isomer at a ratio of 60 mol% or more and 99.5 mol% or less. , an amorphous polycarbonate diol that is liquid at 25° C., and a polyol component containing a low-molecular-weight diol having 2 to 6 carbon atoms.

That is, as raw material components, 1,4-bis(isocyanatomethyl)cyclohexane with relatively high crystallinity, a low molecular weight diol that improves crystallinity with a hard segment, and an amorphous polycarbonate diol with relatively low crystallinity. is used.

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

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

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

1,4-bis(isocyanatomethyl)cyclohexane includes cis-1,4-bis(isocyanatomethyl)cyclohexane (hereinafter referred to as cis-1,4-isomer), and trans-1,4-bis ( There is a stereoisomer of isocyanatomethyl)cyclohexane (hereinafter referred to as trans 1,4 isomer).

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

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

In other words, 1,4-bis(isocyanatomethyl)cyclohexane has a total amount of trans-1,4- and cis-1,4-isomers of 100 mol%, so the total amount of 1,4-bis(isocyanatomethyl)cyclohexane The content of the cis-1,4-isomer (cis-isomer) is 0.5 mol% or more, preferably 1 mol% or more, more preferably 4 mol% or more, and still more preferably 10 mol%, relative to the mol. 40 mol % or less, preferably 30 mol % or less, more preferably 25 mol % or less, still more preferably 20 mol % or less.

If the content ratio of transformers 1 and 4 is equal to or higher than the above lower limit, heat resistance can be improved.

1,4-bis(isocyanatomethyl)cyclohexane can be produced, for example, by the methods described in International Publication WO2009/051114, International Publication WO2019/069802, and the like.

In addition, 1,4-bis(isocyanatomethyl)cyclohexane can also be prepared as a modified form as long as the excellent effects of the present invention are not impaired.

Modified forms of 1,4-bis(isocyanatomethyl)cyclohexane include, for example, 1,4-bis(isocyanatomethyl)cyclohexane polymers (dimers (e.g., uretdione modified forms), trimers (e.g., isocyanurate modified product, iminooxadiazinedione modified product, etc.), biuret modified product (e.g., biuret modified product produced by the reaction of 1,4-bis(isocyanatomethyl)cyclohexane and water), allophanate modified product ( For example, allophanate modified products produced by reaction of 1,4-bis(isocyanatomethyl)cyclohexane with monohydric alcohol or dihydric alcohol), polyol modified products (for example, 1,4-bis(isocyanatomethyl)cyclohexane polyol modified product (adduct) produced by reaction with trihydric alcohol), oxadiazinetrione modified product (for example, oxadiazinetrione modified product (for example, oxadiazine produced by reaction of 1,4-bis(isocyanatomethyl)cyclohexane and carbon dioxide) diazinetrione, etc.), modified carbodiimide (for example, modified carbodiimide produced by decarboxylation condensation reaction of 1,4-bis(isocyanatomethyl)cyclohexane), and the like. These can be used alone or in combination of two or more.

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

If the polyisocyanate component contains the above 1,4-bis(isocyanatomethyl)cyclohexane, the crystallinity derived from the symmetrical structure of 1,4-bis(isocyanatomethyl)cyclohexane makes the thermoplastic polyurethane resin It can improve heat resistance. That is, when the polyisocyanate component does not contain 1,4-bis(isocyanatomethyl)cyclohexane containing a trans isomer in a predetermined proportion, the crystallinity of the polyisocyanate component is not sufficient, and the thermoplastic polyurethane resin (described later) aggregates. The heat resistance may be deteriorated. On the other hand, if the polyisocyanate component contains the above 1,4-bis(isocyanatomethyl)cyclohexane, the polyisocyanate is derived from the symmetric structure of 1,4-bis(isocyanatomethyl)cyclohexane. Since the crystallinity of the component can be improved and the cohesiveness of the thermoplastic polyurethane resin can be improved, heat resistance can be improved.

In addition, the polyisocyanate component can contain other polyisocyanates (polyisocyanates other than 1,4-bis(isocyanatomethyl)cyclohexane) as optional components within a range that does not impair the excellent effects of the present invention. .

Other polyisocyanates include, for example, aliphatic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates.

Examples of aliphatic polyisocyanates include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), octamethylene diisocyanate, nonamethylene diisocyanate, and 2,2'-dimethylpentane diisocyanate. , 2,2,4-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, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, bis( isocyanatoethyl) carbonate, bis(isocyanatoethyl) ether, 1,4-butylene glycol dipropyl ether-ω,ω'-diisocyanate, lysine isocyanatomethyl ester, lysine triisocyanate, 2-isocyanatoethyl-2,6 - chain aliphatic diisocyanates such as diisocyanatohexanoate, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, bis(4-isocyanato-n-butylidene)pentaerythritol, 2,6-diisocyanatomethylcaproate etc.

Aliphatic polyisocyanates also include alicyclic polyisocyanates (excluding 1,4-bis(isocyanatomethyl)cyclohexane).

Alicyclic polyisocyanates (excluding 1,4-bis(isocyanatomethyl)cyclohexane) include, for example, 1,3-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate (IPDI), trans, 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, 2,2'-dimethyldicyclohexylmethane diisocyanate, dimer acid diisocyanate, 2,5-diisocyanatomethylbicyclo[2,2,1]-heptane and its isomers 2,6-diisocyanatomethylbicyclo[2,2,1]-heptane (NBDI), 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-isocyanato propyl)-5-(2-isocyanatoethyl)-bicyclo-[2,2,1]-heptane, 2-isocyanatomethyl 3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)- bicyclo-[2,2,1]-heptane, 2-isocyanatomethyl 2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo-[2,2,1]-heptane, 2 -isocyanatomethyl 2-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo-[2,2,1]-heptane and other alicyclic diisocyanates.

Aromatic polyisocyanates include, for example, 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, and isomer mixtures of these tolylene diisocyanates (TDI), 4,4′-diphenylmethane diisocyanate, 2,4 '-diphenylmethane diisocyanate and 2,2'-diphenylmethane diisocyanate, and any isomer mixture (MDI) of these diphenylmethane diisocyanates, aromatic diisocyanates such as toluidine diisocyanate (TODI), paraphenylene diisocyanate, naphthalene diisocyanate (NDI), etc. mentioned.

Examples of araliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof (XDI), 1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof (TMXDI), etc. and araliphatic diisocyanates.

These and other polyisocyanates can be used alone or in combination of two or more.

In addition, other polyisocyanates can be prepared as modified products as long as they do not impair the excellent effects of the present invention. Modified products include, for example, multimers (uretdione modified products, isocyanurate modified products, iminooxadiazine dione modified products, etc.), biuret modified products, allophanate modified products, polyol modified products, oxadiazinetrione modified products, carbodiimide modified products. body, etc. These can be used alone or in combination of two or more.

The content ratio of other polyisocyanates is 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, relative to the total amount of the polyisocyanate component. is 5 mol % or less, particularly preferably 0 mol %.

In other words, the content of 1,4-bis(isocyanatomethyl)cyclohexane (including modified 1,4-bis(isocyanatomethyl)cyclohexane) relative to the total amount of polyisocyanate components is, for example, More than 50 mol%, preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and particularly preferably 100 mol%.

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

A polyol component is a compound containing two or more hydroxyl groups in the molecule.

The polyol component contains 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 as essential components.

In addition, when the polyol component has a molecular weight distribution, the number average molecular weight is adopted. Also, in such a case, the number average molecular weight can be determined by measurement by GPC method or by the hydroxyl value and formulation of each component of the polyol component (the same applies hereinafter).

A high molecular weight polyol is a compound having two or more hydroxyl groups in the molecule and exceeding 400.

The high molecular weight polyol contains, as an essential component, an amorphous polycarbonate diol that is liquid (liquid state) at 25°C. In other words, the polyol component contains 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. In the amorphous polycarbonate diol, “amorphous” means that it is liquid at 25° C. (viscosity at 25° C. measured by an E-type viscometer is 500000 mPa·s or less).

An amorphous polycarbonate diol can be obtained, for example, by modifying a ring-opening polymer of ethylene carbonate using a dihydric alcohol as an initiator with a dihydric alcohol as a modifier.

In the ring-opening polymer of ethylene carbonate, dihydric alcohols as initiators include, for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol (1,4-butylene glycol), 1,5- linear alkanediols having 2 to 8 carbon atoms such as pentanediol, 1,6-hexanediol and 1,8-octanediol; linear ether diols having 4 to 8 carbon atoms such as diethylene glycol and triethylene glycol; linear dihydric alcohols such as These dihydric alcohols can be used alone or in combination of two or more.

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

In the ring-opening polymer of ethylene carbonate, the dihydric alcohol as the modifier includes, for example, linear dihydric alcohols and branched dihydric alcohols. As the straight-chain dihydric alcohol, a straight-chain dihydric alcohol different from the dihydric alcohol used as the initiator is selected.

The straight-chain dihydric alcohol as the modifier may be of a different type from the dihydric alcohol as the initiator, but is preferably a straight-chain dihydric alcohol having more carbon atoms than the dihydric alcohol as the initiator. alcohol. More specifically, for example, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, etc. and straight-chain alkanediols having 4 to 10 carbon atoms. These linear dihydric alcohols can be used alone or in combination of two or more.

Branched dihydric alcohols as modifiers include, for example, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, and 2,2-dimethyl-1,3-propane. branched alkanediols having 4 to 10 carbon atoms such as diols; These branched dihydric alcohols can be used alone or in combination of two or more.

These dihydric alcohols as modifiers can be used alone or in combination of two or more.

The dihydric alcohol as the modifier preferably includes a linear dihydric alcohol or a branched dihydric alcohol having more carbon atoms than the dihydric alcohol as the initiator, more preferably a branched chain dihydric alcohols, more preferably 3-methyl-1,5-pentanediol.

The method for modifying the ring-opening polymer of ethylene carbonate with a dihydric alcohol is not particularly limited, and a known method is employed. For example, ethylene carbonate is subjected to ring-opening polymerization by a known method using a dihydric alcohol as an initiator, and then the obtained ring-opening polymer is further copolymerized with a dihydric alcohol as a modifier.

These amorphous polycarbonate diols can be used alone or in combination of two or more. That is, a single type of amorphous polycarbonate diol may be used, or two or more types of amorphous polycarbonate diols having different number average molecular weights, dihydric alcohols as initiators, and dihydric alcohols as modifiers may be used. Polycarbonate diol may be used in combination.

The number average molecular weight of the amorphous polycarbonate diol (the average molecular weight of a mixture thereof when two or more kinds are used together) exceeds 400, preferably 500 or more, and more preferably, from the viewpoint of improving stretchability. 1000 or more, more preferably 1300 or more, 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, particularly preferably 2000 or less is.

The high-molecular-weight polyol can contain amorphous polycarbonate diol alone, but can also contain other high-molecular-weight polyols (high-molecular-weight polyols other than amorphous polycarbonate diols) as necessary.

That is, the high-molecular-weight polyol can contain other high-molecular-weight polyols (high-molecular-weight polyols other than amorphous polycarbonate diols) as optional components.

Other high-molecular-weight polyols include, for example, high-molecular-weight polyols (excluding amorphous polycarbonate diols) having a number average molecular weight of more than 400 and 10,000 or less. Amorphous polycarbonate polyols, polyether polyols, polyester polyols, polycaprolactone polyols, polyurethane polyols, etc., having 3 or more hydroxyl groups are included. These other high molecular weight polyols can be used alone or in combination of two or more.

Other high molecular weight polyols preferably include crystalline polycarbonate polyols.

A crystalline polycarbonate polyol is a polycarbonate polyol that is solid (solid state) at 25°C.

Examples of crystalline polycarbonate polyols include ring-opening polymers of ethylene carbonate using the above-mentioned dihydric alcohol as an initiator. These crystalline polycarbonate polyols can be used alone or in combination of two or more.

The ring-opening polymerization method of ethylene carbonate using a dihydric alcohol as an initiator is not particularly limited, and a known method is employed.

The number average molecular weight of the crystalline polycarbonate polyol exceeds 400, preferably 500 or more, more preferably 1000 or more, still more preferably 1300 or more, and particularly preferably 1300 or more, from the viewpoint of achieving both stretchability and heat resistance. , 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.

Further, the average number of hydroxyl groups per 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. be.

The blending ratio of other high molecular weight polyols is appropriately set within a range that does not impair the excellent effects of the present invention.

That is, if a high molecular weight polyol with relatively high crystallinity (crystalline polycarbonate polyol, polycaprolactone polyol, etc.) is used excessively as other high molecular weight polyols, the cohesiveness increases and the stretchability (rebound force) decreases. may provoke

Therefore, the ratio of other high-molecular-weight polyols (crystalline polycarbonate polyols, etc.) is adjusted within a range in which excellent stretchability can be maintained.

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

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

That is, the high-molecular-weight polyol particularly preferably contains only the amorphous polycarbonate diol without containing other high-molecular-weight polyols.

The molecular weight (number average molecular weight) of the high molecular weight polyol exceeds 400, preferably 500 or more, more preferably 1000 or more, still more preferably 1300 or more, especially from the viewpoint of achieving both stretchability and heat resistance. It is preferably 1,500 or more, for example, 10,000 or less, preferably 8,000 or less, more preferably 5,000 or less, still more preferably 3,000 or less, and particularly preferably 2,000 or less.

A low-molecular-weight polyol is a compound having two 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.

A low-molecular-weight diol having 2 to 6 carbon atoms is a compound having 2 to 6 carbon atoms in one molecule, two hydroxyl groups in one molecule, and a molecular weight of 400 or less.

Low molecular weight diols having 2 to 6 carbon atoms include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol (1,4-BD), 1,3-butanediol, 1, Carbon numbers such as 2-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol alkanediols having 2 to 6 carbon atoms (alkylene glycols having 2 to 6 carbon atoms), ether diols having 2 to 6 carbon atoms such as diethylene glycol, triethylene glycol and dipropylene glycol, such as 1,4-dihydroxy-2-butene alkene diols having 2 to 6 carbon atoms, such as 1,3- or 1,4-cyclohexanediol and mixtures thereof. These can be used alone or in combination of two 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, and 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, and 400 or less, preferably 300 or less.

From the viewpoint of improving heat resistance, the low-molecular-weight diol having 2 to 6 carbon atoms is preferably an alkanediol having 2 to 6 carbon atoms, more preferably 1,4-butanediol.

The low-molecular-weight polyol can contain a low-molecular-weight diol having 2 to 6 carbon atoms alone, but if necessary, other low-molecular-weight polyols (low-molecular-weight polyols excluding low-molecular-weight diols having 2 to 6 carbon atoms) can also contain

That is, the low-molecular-weight polyol can optionally contain other low-molecular-weight polyols (low-molecular-weight polyols excluding low-molecular-weight diols having 2 to 6 carbon atoms).

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

Other low-molecular-weight polyols include, for example, low-molecular-weight diols having 7 or more carbon atoms and low-molecular-weight polyols having a valence of 3 or more.

Examples of low molecular weight diols 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- Dihydric alcohols having 7 or more carbon atoms such as octene-3,8-diol, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, hydrogenated bisphenol A and bisphenol A can be mentioned. These low-molecular-weight diols having 7 or more carbon atoms can be used alone or in combination of two or more.

A trivalent or higher low-molecular-weight polyol has a molecular weight of 400 or less and has 3 hydroxyl groups in one molecule.
compounds having one or more, such as glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, tri trihydric alcohols (low molecular weight triols) such as methylolpropane and 2,2-bis(hydroxymethyl)-3-butanol; tetramethylolmethane (pentaerythritol); tetrahydric alcohols such as diglycerin; Pentahydric alcohols such as hexahydric alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol and dipentaerythritol; heptahydric alcohols such as perseitol; octahydric alcohols such as sucrose; mentioned. These trivalent or higher low-molecular-weight polyols can be used alone or in combination of two or more.

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

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

The blending ratio of other low-molecular-weight polyols is appropriately set within a range that does not impair the excellent effects of the present invention.

More specifically, the content of other low-molecular-weight polyols (low-molecular-weight polyols excluding low-molecular-weight diols having 2 to 6 carbon atoms) is, for example, 50 parts by mass or less with respect to 100 parts by mass of the total amount of low-molecular-weight polyols. , preferably 20 parts by mass or less, more preferably 10 parts by mass or less, particularly preferably 0 parts by mass.

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, relative to 100 parts by mass of the total amount of the low-molecular-weight polyols. Part by mass or more, particularly preferably 100 parts by mass.

That is, the low-molecular-weight polyol preferably does not contain other low-molecular-weight polyols (low-molecular-weight polyols excluding low-molecular-weight diols having 2 to 6 carbon atoms), and contains low-molecular-weight diols having 2 to 6 carbon atoms alone. .

The polyol component contains, as essential components, 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. 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, with respect to the total amount thereof, the high 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, still more preferably less than 50 mol %, particularly preferably 40 mol % or less. In addition, 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 50 mol% or more, and particularly preferably 60 mol% or more. , for example, 80 mol % or less, preferably 70 mol % or less.

A thermoplastic polyurethane resin can be obtained by reacting a polyisocyanate component and a polyol component.

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

For reacting the components (the polyisocyanate component and the polyol component), known methods such as the one-shot method and the prepolymer method are employed. From the viewpoint of improving various physical properties, the prepolymer method is preferably adopted.

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 form an isocyanate group-terminated prepolymer. A polymer is synthesized (prepolymer synthesis step).

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

In bulk polymerization, for example, under a nitrogen stream, a polyisocyanate component and a high molecular weight polyol are reacted at a reaction temperature of, for example, 50° C. or higher, for example, 250° C. or lower, preferably 200° C. or lower, for example, 0.5 The reaction is allowed to proceed for an hour or more, for example, 15 hours or less.

In solution polymerization, a polyisocyanate component and a high molecular weight polyol are added to an organic solvent, and the reaction temperature is, for example, 50° C. or higher, for example, 120° C. or lower, preferably 100° C. or lower, for example, for 0.5 hours or longer. , for example, 15 hours or less.

Examples of organic solvents 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 hexane, n-heptane and octane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, aromatic hydrocarbons such as toluene, xylene and ethylbenzene, and 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, ethyl-3-ethoxypropionate and other glycol ether esters ethers such as diethyl ether, tetrahydrofuran, dioxane; halogenated aliphatic hydrocarbons such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, methylene iodide, dichloroethane; and polar aprotons such as N-methylpyrrolidone, dimethylformamide, N,N'-dimethylacetamide, dimethylsulfoxide, hexamethylphosphonylamide, and the like.

In addition, in the above polymerization reaction, for example, known urethanization catalysts such as amines and organometallic compounds can be added as necessary.

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

Examples of organometallic compounds include tin acetate, tin octoate (tin octylate), tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin organotin compounds such as tin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, dibutyltin dichloride; organolead compounds such as lead octanoate and lead naphthenate; organonickel compounds such as nickel naphthenate; Examples include organic cobalt compounds such as cobalt naphthenate, organic copper compounds such as copper octenoate, and organic bismuth compounds such as bismuth octanoate (bismuth octylate) and bismuth neodecanoate, preferably octyl. stannous acid and bismuth octylate.

Furthermore, examples of urethanization catalysts include potassium salts such as potassium carbonate, potassium acetate, and potassium octylate.

These urethanization catalysts can be used alone or in combination of two or more.

The addition ratio of the urethanization catalyst is, for example, 0.001 parts by mass or more, preferably 0.01 parts by mass or more, for example, 1 part by mass with respect to the total amount of 10000 parts by mass of the polyisocyanate component and the high molecular weight polyol. Below, it is preferably 0.5 parts by mass or less.

The urethanization catalyst can be added as a solution or dispersion diluted with a known catalyst diluent (solvent), if necessary.

Further, in the above polymerization reaction, the unreacted polyisocyanate component and, if an organic solvent is used, the organic solvent can be removed by known removal means such as distillation or extraction.

In the prepolymer synthesis step, the blending ratio of each component is such that the equivalent ratio of isocyanate groups in the polyisocyanate component to hydroxyl groups in the high-molecular-weight polyol (isocyanate groups/hydroxyl groups) is, for example, 1.3 or more, preferably 1. 0.5 or more, for example, 20 or less, preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

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 10 parts by mass or more of the polyisocyanate component with respect to 100 parts by mass of the high molecular weight polyol. is 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.

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

In this method, the isocyanate group content is, for example, 1.0% by mass or more, preferably 1.5% by mass or more, more preferably 3.0% by mass or more, and still more 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, and even more preferably 12.0% by mass or less. Let Thereby, an isocyanate group-terminated 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-terminated prepolymer obtained above 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 the polyisocyanate component and the polyol component. obtained (chain elongation step).

That is, in this method, low molecular weight polyols, including low molecular weight diols having 2 to 6 carbon atoms, are chain extenders.

Then, in the chain elongation step, the isocyanate group-terminated prepolymer and the low-molecular-weight polyol are reacted by a polymerization method such as the above-described bulk polymerization or the above-described solution polymerization.

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

In addition, the blending ratio of each component is, for example, 0.75 or more, preferably 0.9, as an 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. For example, it is 1.3 or less, preferably 1.1 or less.

More specifically, the blending ratio of each component in the chain elongation step is, for example, 1.0 parts by mass or more, preferably 2.5 parts by mass of the low molecular weight polyol per 100 parts by mass of the isocyanate group-terminated prepolymer. parts or more, more preferably 3.5 parts by mass or more, 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 It is 10.0 parts by mass or less, more preferably 9.0 parts by mass or less.

In addition, in the chain elongation step, in order to adjust the hard segment concentration (described later) of the thermoplastic polyurethane resin to be obtained, together with the low molecular weight polyol, the above high molecular weight polyol etc. can be blended in an appropriate ratio.

Furthermore, in this reaction, the above-described urethanization catalyst can be added, if necessary. The urethanization catalyst can be blended with the isocyanate group-terminated prepolymer and/or the low-molecular-weight polyol, or can be blended separately when they are mixed.

Further, when the one-shot method is adopted as a method for obtaining the above reaction product, a polyisocyanate component and a polyol component (including high-molecular-weight polyol and low-molecular-weight polyol) are added to the hydroxyl groups in the polyol component, The isocyanate group equivalent ratio (isocyanate group/hydroxyl group) in the polyisocyanate component is, for example, 0.9 or more, preferably 0.95 or more, more preferably 0.98 or more, for example, 1.2 or less, preferably is 1.1 or less, more preferably 1.08 or less, and mixed at the same time with stirring.

Further, this stirring and mixing is performed, for example, under an inert gas (e.g., nitrogen) atmosphere at a reaction temperature of, for example, 40° C. or higher, preferably 70° C. or higher, for example, 280° C. or lower, preferably 260° C. or lower. , the reaction time is, for example, 30 seconds or more and 1 hour or less.

Moreover, at the time of stirring and mixing, if necessary, the above-described urethanization catalyst and organic solvent can be added in an appropriate proportion.

Thereby, a thermoplastic polyurethane resin is obtained as a reaction product.

Moreover, in this method, the obtained reaction product can be heat-treated as needed (heat treatment step).

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

In the heat treatment step, the primary product obtained in the above reaction step is heat treated by allowing it to stand at a predetermined heat treatment temperature for a predetermined heat treatment period, and then dried if necessary.

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

If the heat treatment temperature is within the above range, it is possible to obtain a thermoplastic polyurethane resin having both stretchability and heat resistance 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, and for example, 10 days or less, preferably 9 days or less, or more. Preferably, it is 8 days or less.

If the heat treatment period is within the above range, it is possible to obtain a thermoplastic polyurethane resin having both stretchability and heat resistance particularly well.

In addition, in the production of the above thermoplastic polyurethane resin, if necessary, for example, antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, hydrolysis inhibitors (carbodiimide compounds, etc.), dyes ( bluing agents, etc.), plasticizers, anti-blocking agents, surface modifiers, lubricants, release agents, pigments, fillers, rust inhibitors, fillers, and other additives can be added.

These additives can be added during mixing of each component, during synthesis, or after synthesis.

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

Moreover, the amount of the additive added is not particularly limited, and is appropriately set according to the purpose and application.

The thermoplastic polyurethane resin thus obtained is a poly containing 1,4-bis(isocyanatomethyl)cyclohexane containing a trans isomer at a ratio of 60 mol% or more and 99.5 mol% or less as a raw material component. It contains an isocyanate component, an amorphous polycarbonate diol that is liquid at 25° C., and a polyol component containing a low molecular weight diol having 2 to 6 carbon atoms.

That is, as raw material components, 1,4-bis(isocyanatomethyl)cyclohexane with relatively high crystallinity, a low molecular weight diol that improves crystallinity with a hard segment, and an amorphous polycarbonate diol with relatively low crystallinity. is used.

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

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

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

More specifically, the hard segment concentration can be calculated from the formulation (preparation) of each component by the following equation, for example, when the prepolymer method is employed.
[chain extender (g) + (chain extender (g) / molecular weight of chain extender (g / mol)) × average molecular weight of polyisocyanate component (g / mol)] ÷ (polyisocyanate component (g) + polyol Total mass of components (g)) x 100
The heat quantity (enthalpy change) of the melting peak (endothermic peak) of the thermoplastic polyurethane resin at 160° C. or higher is, for example, 0.1 J/g or higher, preferably 0.5 J/g or higher, more preferably 1.5 J/g or higher. 0 J/g or more, more preferably 1.5 J/g or more, particularly preferably 2.0 J/g or more, for example, 20 J/g or less, preferably 15 J/g or less, more preferably 10. It is 5 J/g or less, more preferably 7.0 J/g, more preferably 5.0 J/g or less, still more preferably 4.0 J/g, particularly preferably 3.0 J/g or less.

If the heat quantity at the melting peak of the thermoplastic polyurethane resin at 160° C. or higher is above the above lower limit, the cohesiveness of the thermoplastic polyurethane resin is not too low, and excellent heat resistance can be obtained.

Also, if the heat quantity at the melting peak of the thermoplastic polyurethane resin at 160° C. or higher is below the above upper limit, the thermoplastic polyurethane resin does not have too high agglomeration properties, and excellent stretchability can be obtained.

That is, if the heat quantity at the melting peak of the thermoplastic polyurethane resin at 160° C. or higher is within the above range, the cohesiveness can be appropriately adjusted, and both heat resistance and stretchability of the thermoplastic polyurethane resin can be achieved. .

The calorie of the melting peak is measured by differential scanning calorimetry (DSC measurement) in accordance with the examples described later.

In addition, the stretching property is evaluated by, for example, the restoring force after stretching deformation (shape recovery rate after stretching deformation).

Specifically, from the viewpoint of stretchability, the return force (shape recovery rate) of the thermoplastic polyurethane resin after being stretched 60% for 15 seconds is, for example, 97.0% or more, preferably 97.5% or more, or more. It is preferably 98.0% or more, more preferably 98.2% or more, and usually 100.0% or less.

The return force (shape recovery rate) after 60% tension for 15 seconds is measured by a tensile tester or the like according to the examples described later.

Moreover, the heat resistance is more specifically evaluated by the storage modulus (E').

Specifically, from the viewpoint of heat resistance, the storage modulus (E′) of the thermoplastic polyurethane resin at 80° C. is, for example, 10×10 ⁶ MPa or more, preferably 15×10 ⁶ MPa or more, more preferably , 20×10 ⁶ MPa or more, for example, 50×10 ⁶ MPa or less, preferably 40×10 ⁶ MPa or less, more preferably 30×10 ⁶ MPa or less.

The storage modulus (E′) at 80° C. is measured by dynamic viscoelasticity measurement in accordance with Examples described later.

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

Molding methods in primary molding include, for example, heat compression molding, injection molding, extrusion molding, cutting molding, melt spinning molding, and 3D printer molding. These can be used alone or in combination of two or more.

Examples of the shape of the primary molded product include pellets, plates, fibers, strands, films, sheets, pipes, hollows, and boxes, preferably pellets.

For example, when a pellet-shaped thermoplastic polyurethane resin is obtained as a primary molded product, preferably, the pellet-shaped thermoplastic polyurethane resin is secondary molded by a known molding method, and the thermoplastic polyurethane resin is secondary molded. you can get the goods.

The molding method in the secondary molding includes the molding methods described above, preferably extrusion molding.

Examples of the shape of the secondary molded product include pellet-like, plate-like, fiber-like, strand-like, film-like, sheet-like, pipe-like, hollow, and box-like shapes, preferably film-like. .

That is, films are preferably used as molded products of thermoplastic polyurethane resins.

And the present invention includes a film containing 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 product of the above thermoplastic polyurethane resin.

Since such a film contains the thermoplastic polyurethane resin, it is excellent in stretchability and heat resistance.

Therefore, a film containing a thermoplastic polyurethane resin can be suitably used in fields where the various physical properties described above are required. For example, the above film is suitably used as a base film for a protective film (Paint Protection Film (PPF)) for protecting the painted 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, etc.) by adhering a film containing a polyurethane resin to the painted surface of the various products. The protective film (PPF) includes, for example, a release layer containing a polyester resin, an acrylic adhesive layer placed on the release layer, and a base film layer placed on the acrylic adhesive layer. Also, the protective film can further comprise a surface protective layer disposed on the base film layer.

In such a protective film (PPF), by using a film containing the thermoplastic polyurethane resin as the base film layer, excellent stretchability and heat resistance can be obtained, and various products (automobiles, motorcycles, etc.) can be well protected.

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

More specifically, the above thermoplastic polyurethane resins are, for example, yarns, fibers (tubes, tights, spats, sportswear, sports goods, supporters, yarns used for swimwear, composite fibers), monofilaments, films (clothes elastic films, hot-melt films, wound covering films, etc.).

In addition, the above thermoplastic polyurethane resins include, for example, transparent hard plastics, coating materials, pressure-sensitive adhesives, adhesives, waterproof materials, potting agents, inks, binders, sheets, bands (e.g., watch bands and other bands, e.g., Belts such as automotive transmission belts, various industrial conveyor belts (conveyor belts), tubes (for example, parts such as medical tubes and catheters, tubes such as air tubes, hydraulic tubes, electric wire tubes, fire hoses, etc.) hoses, etc.), blades, speakers, sensors, high-brightness LED sealants, organic EL components, photovoltaic power generation components, robot components, android components, wearable components, clothing products, sanitary products, cosmetics, food packaging components , Sporting Goods, Leisure Goods, Medical Supplies, Nursing Care Products, Housing Materials, Acoustic Materials, Lighting Materials, Chandelier, Outdoor Lights, Sealing Materials, Sealing Materials, Cork, Packing, Anti-Vibration/Vibration Control/Seismic Isolation Materials, Sound Insulation Materials , daily necessities, miscellaneous goods, cushions, bedding, stress absorbing materials, stress relieving materials, automobile interior and exterior parts, railway materials, aircraft materials, optical materials, OA equipment materials, sundry surface protection materials, semiconductor sealing materials, self-healing materials , health equipment, eyeglass lenses, toys, cable sheaths, wire harnesses, telecommunication cables, automotive wiring, computer wiring, industrial products such as curl cords, nursing care products such as sheets and films, sporting goods, leisure products, miscellaneous goods, anti-vibration・Vibration-isolating materials, shock-absorbing materials, optical materials, films such as light guide films, automobile parts, surface protection sheets, decorative sheets, transfer sheets, tape members such as semiconductor protection tapes, golf ball members, strings for tennis rackets, agriculture films, wallpaper, anti-fog agents, non-woven fabrics, furniture items such as mattresses and sofas, clothing items such as brassieres and shoulder pads, disposable diapers, napkins, medical supplies such as cushioning materials for medical tape, cosmetics, facial cleansing puffs, pillows, etc. sanitary products, shoe products such as shoe soles (outsoles), midsoles, and cover materials, body pressure dispersion products such as vehicle pads and cushions, door trims, instrument panels, gear knobs, etc. Components, insulation materials for electric refrigerators and buildings, shock absorbers such as shock absorbers, fillers, vehicle handles, automotive interior materials, automotive exterior materials, semiconductor manufacturing supplies such as chemical mechanical polishing (CMP) pads etc., it is preferably used.

Furthermore, the above-mentioned moldings are used for coating materials (films, sheets, belts, wires, electric wires, coating materials for metal rotating equipment, wheels, drills, etc.), extrusion molding applications (guts for tennis, badminton, etc. and their convergence). extrusion molding of materials, etc.), slush molded products in powder form by micro-pelletization, artificial leather, skins, sheets, covering rolls (covering rolls of steel, etc.), sealants, rollers, gears, balls, bat covers or Core materials (covers or core materials for golf balls, basketballs, tennis balls, volleyballs, softballs, bats, etc. (these may be in the form of polyurethane resin foam molding)), mats, ski equipment, boots, tennis Goods, grips (grip for golf clubs, motorcycles, etc.), rack boots, wipers, seat cushions, films for nursing care products, 3D printer molded products, fiber reinforced materials (carbon fiber, lignin, kenaf, nanocellulose fiber, glass fiber, etc.) fiber reinforced materials), safety goggles, sunglasses, spectacle frames, ski goggles, swimming goggles, contact lenses, gas-assisted foam moldings, shock absorbers, CMP polishing pads, dampers, bearings, dust covers, cutting valves, chipping rolls , high-speed rotating rollers, tires, watches, wearable bands, and other applications that require stretchability and heat resistance.

Next, the present invention will be described based on Examples and Comparative Examples, but the present invention is not limited by these. "Parts" and "%" are based on mass unless otherwise specified. In addition, specific numerical values such as the mixing ratio (content ratio), physical property values, and parameters used in the following description are the corresponding mixing ratios ( Content ratio), physical properties, parameters, etc. be able to.
1) Raw material <Polyisocyanate component (a)>
1,4-H ₆ XDI: 1,4-bis(isocyanatomethyl)cyclohexane synthesized by the method described in Production Example 1, 86 mol% trans isomer/14 mol% cis isomer
H ₁₂ MDI: 4,4′-dicyclohexylmethane diisocyanate <High molecular weight polyol (b)>
b-1) UH100W: number average molecular weight (Mn) 1000, crystalline polycarbonate diol, trade name ETERNACOLL UH-100W, average number of hydroxyl groups 2, manufactured by Ube Industries b-2) UH200W: number average molecular weight (Mn) 2000, crystallinity Polycarbonate diol, trade name ETERNACOLL UH-200W, average number of hydroxyl groups: 2, manufactured by Ube Industries b-3) UP100: number average molecular weight (Mn) 1000, amorphous polycarbonate diol, trade name: ETERNACOLL UP-100, average number of hydroxyl groups: 2, Ube Industries b-4) UP200: number average molecular weight (Mn) 2000, amorphous polycarbonate diol, trade name ETERNACOLL UP-200, average number of hydroxyl groups 2, Ube Industries b-5) C2090R: number average molecular weight (Mn) 2000, amorphous polycarbonate diol, trade name Kuraray Polyol C-2090R, modifier: 3-methyl-1,5-pentanediol, average number of hydroxyl groups 2, Kuraray Isoprene Chemical b-6) 210N: number average molecular weight ( Mn) 1000, polycaprolactone diol, trade name PLAXEL 210N, average number of hydroxyl groups 2, manufactured by Daicel b-7) 220N: number average molecular weight (Mn) 2000, polycaprolactone diol, trade name PLAXEL 220N, average number of hydroxyl groups 2, Daicel <Low molecular weight polyol (c)>
1,4-BD: 1,4-butanediol, manufactured by Mitsubishi Chemical Corporation, a low-molecular-weight diol with a carbon number of (C) 2 to 6 <urethanization catalyst>
Stanoct: Tin octylate, trade name: Stanoct, manufactured by API Corporation <Catalyst diluent>
Diisononyl adipate: Product name: DINA, manufactured by Daihachi Chemical Industry <Additive>
Antioxidant: hindered phenol compound, trade name; Irganox 245, manufactured by BASF Japan UV absorber: benzotriazole compound, trade name; Tinuvin 234, manufactured by BASF Japan Light stabilizer: hindered amine compound, trade name: Adekastab LA -72, manufactured by ADEKA <Production of polyisocyanate component (a)>
Synthesis Example 1 Synthesis of 1,4-bis(isocyanatomethyl)cyclohexane (1,4-H ₆ XDI) According to the description of Production Example 3 of International Publication WO2019/069802, 1,4-bis(isocyanatomethyl) Natomethyl)cyclohexane (1,4-H ₆ XDI) was obtained.

The obtained 1,4-H ₆ XDI had a purity of 99.9% by gas chromatography, a hue of 5 by APHA measurement, and a trans/cis ratio of 86 mol % by ¹³ C-NMR measurement. It was 14 mol % of the cis isomer.

2) Thermoplastic polyurethane resin Examples 1-5 and Comparative Examples 1-6
A thermoplastic polyurethane resin and a sheet were obtained according to the formulations shown in Table 1.

More specifically, first, the high-molecular-weight polyol (b) previously heated to 80° C. is weighed and stirred at 700±50 rpm in an oil bath at 80° C. under a nitrogen atmosphere using a high-speed stirring disper. Stirred for an hour. Then, Irganox 245 (BASF heat stabilizer), Tinuvin 571 (BASF UV absorber) and ADEKA STAB LA-72 (ADEKA HALS) were added as additives to the high molecular weight polyol (b). under a nitrogen atmosphere in an oil bath at 80° C. using a high-speed stirring disper at 700±50 rpm for 30 min. The amount of additives added is 0.3 parts by mass of Irganox 245 (a heat stabilizer manufactured by BASF) and Tinuvin 571 ( BASF UV absorber) 0.4 parts by mass, ADEKA STAB LA-72 (ADEKA HALS) 0.1 parts by mass.

Next, polyisocyanate component (a) is added to the resulting mixture, and tin octoate (trade names: Stanoct, API Corporation) was added so that the catalyst amount (solid content) was 5 ppm.

The resulting mixture was then stirred and mixed in an 80° C. oil bath using a high speed stirring disper at 700±50 rpm for 5 minutes. As a result, an isocyanate group-terminated prepolymer was obtained (prepolymer synthesis step).

Next, 1,4-butanediol (low molecular weight polyol (c)) weighed in advance and temperature-controlled to 80° C. was added to the obtained isocyanate group-terminated prepolymer, and the temperature was adjusted to 700±0 using a high-speed stirring disper. Stirred at 50 rpm and mixed for 3 to 20 minutes (chain elongation step).

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

Also, the above catalyst (DINA-diluted tin octoate) was appropriately added while observing the exotherm rate.

Next, the resulting mixed solution was poured into a Teflon (registered trademark) vat that had been temperature-controlled to 150°C in advance, and reacted at 150°C for 2 hours. The reaction was allowed to continue, and a thermoplastic polyurethane resin (reaction product before heat treatment (primary product)) was obtained as a reaction product.

Next, the obtained thermoplastic polyurethane resin was taken out from the vat, cut into dice with a bale cutter, and the dice-shaped resin was pulverized with a pulverizer to obtain pulverized pellets. The crushed pellets were then heat treated (cured, aged) in an oven at 80° C. for 7 days and dried at 23° C. for 12 hours under vacuum. As a result, a secondary product (reactive product after heat treatment) of thermoplastic polyurethane resin was obtained.

After that, the resulting pulverized pellets (secondary product) are extruded into strands by a single screw extruder (model: SZW40-28MG, manufactured by Technobel) at a screw rotation speed of 30 rpm and a cylinder temperature of 150 to 250 ° C. and cut.

As a result, pellets were obtained as moldings (primary moldings) of the thermoplastic polyurethane resin.

After that, the pellets are dried in advance at 80° C. for 12 hours under vacuum and reduced pressure, and a single-screw extruder (model: SZW40-28MG, manufactured by Technobel) is used at a rotation speed of 20 rpm and a cylinder temperature of 150 to 250° C. to obtain a film having a thickness of 150 μm as a thermoplastic polyurethane resin molding (secondary molding).

4) Evaluation <Stretchability: Returning force (shape recovery rate)>
A film with a thickness of 150 μm (10 mm width × 10 cm length) is set in a universal testing machine Model 205N (manufactured by Intesco, distance between gauge lines 80 mm, tensile speed 500 ml / min), and stretched by 60% (48 mm) of the distance between gauge lines. then released.

Fifteen seconds after release, the distance between the gauge lines was measured and the return force of the film was measured.

The restoring force of the film is shown as the ratio (%) of the length of the film before stretching to the length of the film after stretching. ) is high.

<Heat resistance: Storage modulus (E')>
The dynamic viscoelasticity spectrum of a 150 μm film of thermoplastic polyurethane resin is measured using a dynamic viscoelasticity measuring device (manufactured by IT Keisoku Co., Ltd., model: DVA-220), and the temperature is increased from -100 ° C. to 250 ° C. Measurement was performed under the conditions of a speed of 5° C./min, a tension mode, a gauge length of 20 mm, a static/dynamic stress ratio of 1.8, and a measurement frequency of 10 Hz.

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

It should be noted that the higher the E', the more excellent the heat resistance.

<Heat of fusion (unit: J/g)>
Using a differential scanning calorimeter (DSC7000X, manufactured by Hitachi High-Tech Science), measurements were made as follows.

That is, about 10 mg of thermoplastic polyurethane resin was collected in an aluminum pan. This aluminum pan was covered with a cover and crimped to obtain a sample for measurement. Alumina was similarly sampled and used as a reference sample.

After setting the sample and reference at a predetermined position in the cell, the sample is cooled from 20° C. to -100° C. at a rate of 10° C./min under a nitrogen stream with a flow rate of 30 NmL/min, and held at the same temperature for 5 minutes. , was heated to 270° C. at a rate of 10° C./min, and then cooled to −70° C. at a rate of 10° C./min.

Then, among the peaks that appear during the temperature rise from -100°C to 270°C, the peak temperature of the endothermic peak (melting peak) at 160°C or higher and the heat quantity (enthalpy change) (J/g) of that peak are measured. bottom.

It should be noted that although the above invention has been provided as an exemplary embodiment of the present invention, this is merely an illustration and should not be construed as limiting. Variations of the invention that are obvious to those skilled in the art are intended to be included in the following claims.

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

Claims (4)

A polyisocyanate component containing 1,4-bis(isocyanatomethyl)cyclohexane containing a trans isomer at a ratio of 60 mol% or more and 99.5 mol% or less;
Amorphous polycarbonate diols that are liquid at 25° C. (provided that liquid polyether polycarbonate diols and polycarbonate diols containing structural units derived from diaryl carbonate and structural units derived from 2,2-dialkyl-1,3-propanediol are ) and a reaction product with a polyol component containing a low molecular weight diol having 2 to 6 carbon atoms. 2. The thermoplastic polyurethane according to claim 1, wherein the thermoplastic polyurethane resin has a melting peak heat quantity of 15 J/g or less at 160° C. or higher as measured by differential scanning calorimetry (DSC method). resin. The heat according to claim 1, characterized in that the heat quantity of the melting peak of the thermoplastic polyurethane resin at 160 ° C. or higher measured by differential scanning calorimetry (DSC method) is 0.1 J / g or more. Plastic polyurethane resin. A film comprising the thermoplastic polyurethane resin of claim 1 .