TW202124494A - Thermoplastic polyurethane resin and film - Google Patents

Abstract

In the present invention, a thermoplastic polyurethane resin is obtained as a reaction product of: a polyisocyanate component which includes 1,4-bis(isocyanatomethyl)cyclohexane containing a trans-isomer in a proportion of 60-99.5 mol%; and a polyol component which includes amorphous polycarbonate diol that is liquid at 25 DEG C, and a low-molecular-weight diol having 2 to 6 carbon atoms.

Description

Thermoplastic polyurethane resin and film

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

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

As a protective film, for example, a multilayer polyurethane protective film containing a TPU layer obtained by reacting a polyol and a polyisocyanate has been proposed. In addition, it has been proposed to use a caprolactone polyol as a polyol and a bicyclic ring Hexylmethane diisocyanate is used as a polyisocyanate (for example, refer to Patent Document 1). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2010-505663

(The problem to be solved by the invention)

On the other hand, for protective films, stretch characteristics (resilience) and heat resistance are required depending on the application. In this regard, the above-mentioned multilayer polyurethane protective film has the disadvantage of insufficient heat resistance.

The present invention is a thermoplastic polyurethane resin having both stretch characteristics (recovery force) and heat resistance, and a film containing the thermoplastic polyurethane resin. (Technical means to solve the problem)

The present invention [1] comprises a thermoplastic polyurethane resin containing a reaction product of a polyisocyanate component and a polyol component; the polyisocyanate component contains 60 mol% or more and 99.5 mol% or less The proportion of 1,4-bis(isocyanatomethyl)cyclohexane containing the trans compound; the polyol component contains the amorphous polycarbonate diol which is liquid at 25°C and the carbon number is 2~6 The low molecular weight glycol.

The present invention [2] includes the thermoplastic polyurethane resin as described in [1] above, wherein the above-mentioned thermoplastic polyurethane resin is 160°C or higher as measured by differential scanning calorimetry (DSC method) The heat of melting peak of the resin is 15J/g or less.

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

The present invention [4] includes a film containing the thermoplastic polyurethane resin of any one of [1] to [3] above. (Compared to the effect of the previous technology)

The thermoplastic polyurethane resin and film of the present invention contain the following as raw material components: a polyisocyanate component containing 1, which contains a trans compound at a ratio of 60 mol% or more and 99.5 mol% or less, 4-bis(isocyanatomethyl)cyclohexane; and polyol component, it contains amorphous polycarbonate diol which is liquid at 25℃ and low molecular weight diol with carbon number 2-6.

That is, as raw material components, use: 1,4-bis(isocyanatomethyl)cyclohexane with higher crystallinity, low-molecular-weight diol with higher crystallinity through hard segment, and higher crystallinity Low amorphous polycarbonate diol.

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 can have both heat resistance from high cohesion and low heat resistance in a well-balanced manner. The elasticity of agglomeration.

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

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

The 1,4-bis(isocyanatomethyl)cyclohexane system includes cis-1,4-bis(isocyanatomethyl)cyclohexane (hereinafter referred to as cis 1,4) and trans-1 Stereoisomer of ,4-bis(isocyanatomethyl)cyclohexane (hereinafter referred to as trans 1,4 product).

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

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

In other words, since the total amount of 1,4-bis(isocyanatomethyl)cyclohexane series trans 1,4 and cis 1,4 is 100 mol%, it is relative to 1,4-bis(iso The total moles of cyanomethyl)cyclohexane and the content of cis 1,4 (cis) are 0.5 mol% or more, preferably 1 mol% or more, more preferably 4 mol% Above, 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.

Conversely, if the content ratio of the 1,4 substance is above the above lower limit, the heat resistance can be improved.

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

In addition, 1,4-bis(isocyanatomethyl)cyclohexane is within a range that does not hinder the advantageous effects of the present invention, and it can also be prepared as a modified product.

As a modification of 1,4-bis(isocyanatomethyl)cyclohexane, for example, a polymer (dimer ( For example, uretdione modified products, etc.), trimers (e.g., isocyanurate modified products, imino-diketone modified products, etc.), etc.), biuret modified products (e.g. from 1,4- Biuret modified products produced by the reaction of bis(isocyanatomethyl)cyclohexane and water, etc.), allophanate modified products (for example, using 1,4-bis(isocyanatomethyl) Cyclohexane, allophanate modified products produced by the reaction with monohydric alcohols or diols, etc.), polyol modified products (for example, from 1,4-bis(isocyanatomethyl)cyclohexane, Modified polyols (adducts) produced by the reaction with triols, etc.), modified triketones (such as 1,4-bis(isocyanatomethyl)cyclohexane and carbon dioxide) The bis(triketone, etc.) produced by the reaction), the carbodiimide modified product (for example, the carbodiamide produced by the decarbonation condensation reaction of 1,4-bis(isocyanatomethyl)cyclohexane) Imine-modified products, etc.) and so on. These can be used alone or in combination of two or more kinds.

As 1,4-bis(isocyanatomethyl)cyclohexane, for example, a monomer of 1,4-bis(isocyanatomethyl)cyclohexane is preferable.

If the polyisocyanate component contains the above-mentioned 1,4-bis(isocyanatomethyl)cyclohexane, the crystallinity derived from the symmetrical structure of 1,4-bis(isocyanatomethyl)cyclohexane, It can improve the heat resistance of thermoplastic polyurethane resin. That is, in the case where the polyisocyanate component does not contain 1,4-bis(isocyanatomethyl)cyclohexane containing trans in a specific ratio, the crystallinity of the polyisocyanate component is insufficient, and the thermoplastic polyamine group The cohesiveness of the formate resin (described later) is reduced, and the heat resistance may be poor. In contrast, if the polyisocyanate component contains the above-mentioned 1,4-bis(isocyanatomethyl)cyclohexane, it is derived from the symmetric structure of 1,4-bis(isocyanatomethyl)cyclohexane. The crystallinity of the polyisocyanate component can be improved, and the agglomeration of the thermoplastic polyurethane resin can be improved, so the heat resistance can be improved.

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

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

The aliphatic polyisocyanate includes, for example, ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), and hexamethylene diisocyanate (HDI). Methylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butylene diisocyanate Isocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecemethylene triisocyanate, 1,3 ,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyl octane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate Methyl octane, bis(isocyanatoethyl) carbonate, bis(isocyanatoethyl) ether, 1,4-butanediol dipropyl ether-ω,ω'-diisocyanate, lysine Acid isocyanate methyl ester, lysine triisocyanate, 2-isocyanatoethyl-2,6-diisocyanate caproate, 2-isocyanatopropyl-2,6-diisocyanate hexanoate Chain aliphatic diisocyanates such as acid esters, bis(4-isocyanate-n-butylene) pentaerythritol, 2,6-diisocyanate methyl hexanoate, etc.

In addition, the aliphatic polyisocyanate system contains alicyclic polyisocyanate (excluding 1,4-bis(isocyanatomethyl)cyclohexane).

As alicyclic polyisocyanates (except 1,4-bis(isocyanatomethyl)cyclohexane), for example, 1,3-bis(isocyanatomethyl)cyclohexane, isophor Ketone diisocyanate (IPDI), trans, trans, trans, cis, and cis, cis-dicyclohexylmethane diisocyanate and their mixtures (hydrogenated MDI, H ₁₂ MDI); 1,3- or 1,4 -Bis(isocyanatoethyl)cyclohexane, methylcyclohexane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, dimer acid diisocyanate, 2,5-diisocyanate Acid methylbicyclo[2,2,1]-heptane, 2,6-diisocyanatomethylbicyclo[2,2,1]-heptane (NBDI), 2- Isocyanatomethyl 2-(3-isocyanatopropyl)-5-isocyanatomethyl bicyclo-[2,2,1]-heptane, 2-isocyanatomethyl-2 -(3-isocyanatopropyl)-6-isocyanatomethyl bicyclo-[2,2,1]-heptane, 2-isocyanatomethyl 3-(3-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.

As the aromatic polyisocyanate, for example, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, and isomer mixtures (TDI) of these toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and 2,2'-diphenylmethane diisocyanate, and any isomers of these diphenylmethane diisocyanates Mixture (MDI), toluidine diisocyanate (TODI), p-phenylene diisocyanate, naphthalene diisocyanate (NDI) and other aromatic diisocyanates.

As the aromatic aliphatic polyisocyanate, for example, 1,3- or 1,4-xylylene diisocyanate or its mixture (XDI); 1,3- or 1,4-tetramethylxylylene Aromatic aliphatic diisocyanates such as diisocyanates or their mixtures (TMXDI).

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

In addition, other polyisocyanates can be prepared as modified products within the range that does not hinder the advantageous effects of the present invention. Examples of modified materials include polymers (uretdione modified materials, isocyanurate modified materials, imino diketone modified materials, etc.), biuret modified materials, allophanic acid Ester modified material, polyol modified material, bis-triketone modified material, carbodiimide modified material, etc. These can be used alone or in combination of two or more kinds.

The content ratio of other polyisocyanates is appropriately selected within a range that does not impair the superior effects of the present invention.

More specifically, the content ratio of other polyisocyanates relative to the total amount of polyisocyanate components is, for example, less than 50 mol%, preferably 30 mol% or less, more preferably 10 mol% or less, and more Preferably, it is 5 mol% or less, and particularly preferably, it is 0 mol%.

In other words, relative to the total amount of polyisocyanate components, 1,4-bis(isocyanatomethyl)cyclohexane (including 1,4-bis(isocyanatomethyl)cyclohexane modified products) The content ratio 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, particularly preferably 100 mol%.

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

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

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

Furthermore, when the polyol component has a molecular weight distribution, the number average molecular weight is used. In this case, the number average molecular weight can be measured by the GPC method, or determined by the hydroxyl value of each component of the polyol component and the formula (the same applies below).

High-molecular-weight polyols are compounds having two or more hydroxyl groups in the molecule and more than 400.

The high-molecular-weight polyol contains an amorphous polycarbonate diol that is liquid (liquid) at 25°C as an essential component. In other words, the polyol component system contains amorphous polycarbonate diol as an essential component.

The amorphous polycarbonate diol is an amorphous polycarbonate polyol with an average number of hydroxyl groups of 2. Among the amorphous polycarbonate diols, the so-called amorphous system means that it is liquid at 25°C (the viscosity at 25°C measured with an E-type viscometer is 500,000 mPa·s or less).

The amorphous polycarbonate diol system can be obtained, for example, by modifying a ring-opening polymer of ethylene carbonate with a diol as a starting agent, and modifying it with a diol as a modifier.

In the ring-opening polymer of ethylene carbonate, the diol as the starter can include, for example, ethylene glycol, 1,3-propanediol, and 1,4-butanediol (1,4-butanediol; 1,4-butanediol; 1,4-butanediol; 1,4-butanediol; Butylene glycol), 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol and other linear alkanediols with carbon number 2~8, such as diethylene glycol, triethylene glycol Alcohols and other straight-chain ether glycols with 4 to 8 carbon atoms and other straight-chain diols, etc. These diols can be used alone or in combination of two or more kinds.

As the diol as the starter, preferably, for example, a linear diol, and more preferably, for example, a linear alkanediol having 2 to 8 carbon atoms.

In the ring-opening polymer of ethylene carbonate, the diol as a modifier includes, for example, linear diols and branched diols. The linear diol is selected from a different kind of linear diol from the above-mentioned diol as the starter.

The straight-chain diol as the modifier may be of a different kind from the diol as the starter, preferably, for example, a straight-chain diol with more carbon numbers than the diol as the starter alcohol. More specifically, examples include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1, 10-decanediol and other linear alkanediols with 4 to 10 carbon atoms, etc. These linear diols can be used alone or in combination of two or more kinds.

In addition, branched chain diols as modifiers include, for example, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, and 2,2-dimethyl- 1,3-propanediol and other branched alkanediols with 4 to 10 carbon atoms, etc. These branched chain diols can be used alone or in combination of two or more kinds.

These glycols as modifiers can be used alone or in combination of two or more kinds.

The diol as the modifier preferably includes, for example, a linear diol having more carbon numbers than the diol as a starter, or a branched diol, and more preferably, for example, a branched diol. The chain diols are more preferably 3-methyl-1,5-pentanediol.

Furthermore, the method of modifying the ring-opening polymer of ethylene carbonate with glycol is not particularly limited, and a known method can be used. For example, a diol is used as a starting agent, and ethylene carbonate is ring-opened and polymerized according to a known method, and then the resulting ring-opening polymer is further copolymerized with a diol as a modifier.

These amorphous polycarbonate diols can be used alone or in combination of two or more kinds. That is, a single type of amorphous polycarbonate diol may be used, or two or more different from each other, such as number average molecular weight, diol as a starter, diol as a modifier, etc., can also be used in combination. Amorphous polycarbonate diol.

The number average molecular weight of the amorphous polycarbonate diol (when two or more types are used in combination, the average molecular weight of the mixture thereof) is more than 400, preferably more than 500, from the viewpoint of achieving improvement in stretch characteristics. It is more preferably 1000 or more, still more preferably 1300 or more, particularly preferably 1500 or more, and is, 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.

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

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

Examples of other high-molecular-weight polyols include high-molecular-weight polyols having a number average molecular weight exceeding 400 and 10,000 or less (excluding amorphous polycarbonate diols), and more specifically, crystalline polycarbonate polyols. , Amorphous polycarbonate polyols, polyether polyols, polyester polyols, polycaprolactone polyols, polyurethane polyols, etc. with an average hydroxyl number of 3 or more. These other high molecular weight polyols can be used alone or in combination of two or more.

As other high molecular weight polyols, for example, crystalline polycarbonate polyols are preferable.

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

As the crystalline polycarbonate polyol, for example, a ring-opening polymer of ethylene carbonate using the aforementioned diol as a starter, and the like can be mentioned. These crystalline polycarbonate polyols can be used singly or in combination of two or more kinds.

In addition, the ring-opening polymerization method of ethylene carbonate using a diol as a starting agent is not particularly limited, and a known method can be adopted.

The number average molecular weight of the crystalline polycarbonate polyol is more than 400, preferably more than 500, more preferably more than 1,000, still more preferably more than 1300, particularly preferably 1500 or more, and 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.

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

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

That is, as other high-molecular-weight polyols, if high-molecular-weight polyols (crystalline polycarbonate polyols, polycaprolactone polyols, etc.) with high crystallinity are used excessively, the cohesiveness becomes high, which may cause expansion and contraction. When the characteristic (restoring force) is reduced.

Therefore, the ratio of other high-molecular-weight polyols (crystalline polycarbonate polyols, etc.) is adjusted to a range in which superior stretch characteristics can be maintained.

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

In other words, relative to the total moles of high molecular weight polyols, the content ratio of amorphous polycarbonate polyols is, for example, 40 mole% or more, preferably 50 mole% or more, and usually 100 mole% or less, Especially preferred is 100 mol%.

That is, the high-molecular-weight polyols are particularly preferred to contain no other high-molecular-weight polyols, but to contain amorphous polycarbonate polyols alone.

The molecular weight (number average molecular weight) of the high molecular weight polyol is more than 400, preferably more than 500, more preferably more than 1,000, and even more preferably more than 1300, from the viewpoint of achieving both stretch characteristics and heat resistance. It is 1500 or more, and is, 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.

The 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.

Low-molecular-weight polyols contain low-molecular-weight diols with carbon numbers 2-6 as essential components. In other words, the polyol component contains a low-molecular-weight diol with 2-6 carbon atoms as an essential component.

Low-molecular-weight diols with 2 to 6 carbon atoms are compounds with a carbon number of 2 or more and 6 or less per molecule, two hydroxyl groups per molecule, and a molecular weight of 400 or less.

Examples of low-molecular-weight diols with 2 to 6 carbon atoms include ethylene glycol, propylene glycol, 1,3-propanediol, 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, 2,2-dimethyl- 1,3-propanediol and other C2-C6 alkylene glycols (alkylene glycols with C2-C6), such as diethylene glycol, triethylene glycol, dipropylene glycol and other C2-C6 ethers Diols, such as 1,4-dihydroxy-2-butene and other olefin diols with carbon numbers from 2 to 6, such as 1,3- or 1,4-cyclohexanediol and mixtures thereof. These can be used alone or in combination of two or more kinds.

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

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

As a low molecular weight diol having 2 to 6 carbon atoms, from the viewpoint of achieving improvement in heat resistance, preferably, for example, alkanediol having 2 to 6 carbon atoms, and more preferably, 1,4-butanediol.

Low-molecular-weight polyols may also contain low-molecular-weight diols with 2-6 carbons alone, and other low-molecular-weight polyols (except low-molecular-weight diols with 2-6 carbons) as needed.

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

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

Examples of other low-molecular-weight polyols include low-molecular-weight diols with 7 or more carbon atoms, and low-molecular-weight polyols with more than trivalent.

Examples of low-molecular-weight polyols having 7 or more carbons include 1,8-octanediol, 1,9-nonanediol, and other alkane-1,2-diols with 7 to 20 carbons, and 2,6-di Methyl-1-octene-3,8-diol, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, hydrogenated bisphenol A, bisphenol A, etc. Two of the carbon number 7 or more Alcohol. These low molecular weight diols having 7 or more carbon atoms can be used singly or in combination of two or more kinds.

Low-molecular-weight polyols with three valences or more are compounds having a molecular weight of 400 or less and having three or more hydroxyl groups in one molecule, such as glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2, Triols such as 4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, trimethylolpropane, 2,2-bis(hydroxymethyl)-3-butanol ( Low molecular weight triols), such as tetrahydric alcohols such as tetramethylolmethane (pentaerythritol) and diglycerol, such as pentahydric alcohols such as xylitol, such as sorbitol, mannitol, allitol, iditol , Galactitol, psicitol, inositol, dipentaerythritol and other hexahydric alcohols, such as heptahydric alcohols such as pentitol, such as octahydric alcohols such as sucrose and the like. These low-molecular-weight polyols with three or more valences 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 kinds.

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 superior effects of the present invention.

More specifically, the content ratio of other low-molecular-weight polyols (low-molecular-weight polyols other than low-molecular-weight diols with carbon numbers 2 to 6) is based on 100 parts by mass of the total amount of low-molecular-weight polyols, for example, 50 parts by mass Parts by mass or less, 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 ratio of the low molecular weight diol with carbon number 2 to 6 is relative to 100 parts by mass of the total amount of the low molecular weight polyol, and is, for example, 50 parts by mass or more, preferably 80 parts by mass or more, more preferably 90 parts by mass Above, 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 other than low-molecular-weight diols with 2-6 carbons), but contains low-molecular-weight diols with 2-6 carbons alone.

In addition, the polyol component is as described above, with amorphous polycarbonate diol containing high-molecular-weight polyol and low-molecular-weight diol with carbon number 2 to 6 of low-molecular-weight polyol as essential components, preferably from non-crystalline polycarbonate It is composed of crystalline polycarbonate diol and low molecular weight diol with carbon number 2-6.

In the polyol component, the content ratio of the high-molecular-weight polyol and the low-molecular-weight polyol is relative to the total amount. The high-molecular-weight polyol is, for example, 20 mol% or more, preferably 30 mol% or more, and 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 more than 50 mol%, particularly preferably 60 mol% or more , And is, for example, 80 mol% or less, preferably 70 mol% or less.

Furthermore, the thermoplastic polyurethane resin can be obtained by reacting a polyisocyanate component and a polyol component.

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

When the above-mentioned components (polyisocyanate component, polyol component) are reacted, for example, a known method such as a single pass method or a prepolymer method is used. From the viewpoint of improving various physical properties, it is preferable to adopt the prepolymer method.

Specifically, the prepolymer method first reacts a polyisocyanate component containing 1,4-bis(isocyanatomethyl)cyclohexane with a high molecular weight polyol containing an amorphous polycarbonate polyol. Synthesis of isocyanate group terminal prepolymer (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 the case of bulk polymerization, for example, under a nitrogen stream, the polyisocyanate component and the 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 hours or longer, and for example 15 hours. Less than hours.

In solution polymerization, for example, a polyisocyanate component and a high molecular weight polyol are added to an organic solvent, and the reaction is carried out depending on the reaction temperature of, for example, 50°C or higher, such as 120°C or lower, preferably 100°C or lower, for example, 0.5 hours or longer, such as 15 Less than hours.

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, such as nitriles such as acetonitrile, methyl acetate, ethyl acetate, butyl acetate, and isoacetate. Alkyl esters such as butyl ester, such as aliphatic hydrocarbons such as n-hexane, n-heptane, and octane, such as cyclohexane, methylcyclohexane, and other alicyclic hydrocarbons, such as toluene, xylene, ethylbenzene Aromatic hydrocarbons, such as methyl serosol acetate, ethyl serosol acetate, methyl carbitol acetate, ethyl carbitol acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether ethyl Glycol ether esters such as esters, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, etc., such as diethyl ether, tetrahydrofuran, dioxane and other ethers Types, such as methyl chloride, dichloromethane, chloroform, carbon tetrachloride, methyl bromide, dibromomethane, dichloroethane and other halogenated aliphatic hydrocarbons, such as N-methylpyrrolidone, dimethylformamide, N , N-dimethyl acetamide, dimethyl sulfide, hexamethyl phosphinamide and other polar aprotic species.

Moreover, in the above-mentioned polymerization reaction, if necessary, for example, a well-known ethyl urethane catalyst such as an amine or an organometallic compound may be added.

啉等3級胺類，例如四乙基羥基銨等4級銨鹽，例如咪唑、2-乙基-4-甲基咪唑等咪唑類等。Examples of amines include triethylamine, triethylenediamine, bis-(2-dimethylaminoethyl) ether, and N-methyl

Tertiary amines such as morpholines, for example, quaternary ammonium salts such as tetraethylhydroxyammonium, and imidazoles such as imidazole and 2-ethyl-4-methylimidazole.

Examples of organic metal compounds include tin acetate, tin octoate, tin oleate, tin laurate, dibutyl tin diacetate, dimethyl tin dilaurate, dibutyl tin dilaurate, dibutyl tin dithiolate, and maleic acid. Organotin compounds such as dibutyltin diacid, dibutyltin dineodecanoate, dioctyltin dithiolate, dioctyltin dilaurate, and dibutyltin dichloride, such as lead octoate, lead naphthalate and other organic lead compounds, for example Organic nickel compounds such as nickel naphthalate, organic cobalt compounds such as cobalt naphthalate, organic copper compounds such as copper octylate, organic bismuth compounds such as bismuth octoate, bismuth neodecanoate, etc., preferably, for example, tin octoate, octanoic acid, etc. bismuth.

In addition, examples of the urethane-forming catalyst include potassium salts such as potassium carbonate, potassium acetate, and potassium octoate.

These urethane-forming catalysts can be used alone or in combination of two or more kinds.

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

Furthermore, the urethane catalyst can be added as a solution or dispersion diluted with a known catalyst diluent (solvent) as necessary.

In addition, in the above-mentioned polymerization reaction, the unreacted polyisocyanate component or the organic solvent when an organic solvent is used can be removed by known removal means such as distillation or extraction.

In the prepolymer synthesis step, the blending ratio of each component is based on the equivalent ratio of isocyanate groups in the polyisocyanate component (isocyanate group/hydroxyl group) relative to the hydroxyl groups in the high molecular weight polyol, and is, for example, 1.3 or more, preferably 1.5 or more, and for example 20 or less, preferably 15 or less, more preferably 10 or less, and still more preferably 8 or less.

More specifically, the mixing ratio of the components in the prepolymer synthesis step is based on 100 parts by mass of the high molecular weight polyol, and the polyisocyanate component is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, and more preferably 15 parts by mass. Parts by mass or more, and 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, the low-molecular-weight polyol and the like may be blended together with the high-molecular-weight polyol in an appropriate ratio.

Furthermore, in this method, the above-mentioned components are reacted until the isocyanate group content reaches, 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, And, for example, it is 30.0% by mass or less, preferably 19.0% by mass or less, more preferably 16.0% by mass or less, and still more preferably 12.0% by mass or less. In this way, an isocyanate group-terminated prepolymer can be obtained.

In addition, the isocyanate group content (isocyanate group content) can be obtained by a known method such as the titration method of 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 with a carbon number of 2-6 to obtain a reaction product of the polyisocyanate component and the polyol component物 (chain elongation step).

That is, in this method, a low-molecular-weight polyol containing a low-molecular-weight diol with a carbon number of 2-6 is a chain extender.

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

The reaction temperature is, for example, room temperature or higher, preferably 50°C or higher, and 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, and for example 72 hours or shorter , Preferably it is 48 hours or less.

In addition, the compounding ratio of each component is based on the equivalent ratio of isocyanate groups (isocyanate groups/hydroxy groups) in the isocyanate group-terminated prepolymer relative to the hydroxyl groups in the low molecular weight polyol, and is, for example, 0.75 or more, preferably 0.9 or more , And is, for example, 1.3 or less, preferably 1.1 or less.

More specifically, the blending ratio of each component in the chain extension step is based on 100 parts by mass of the isocyanate group-terminated prepolymer, and the low molecular weight polyol 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, more preferably 4.5 parts by mass or more, particularly preferably 5.5 parts by mass or more, and, 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.

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

Furthermore, in this reaction, the above-mentioned urethane formation catalyst may be added as needed. The urethane catalyst can be formulated in the isocyanate group-terminated prepolymer and/or low molecular weight polyol, and can also be separately formulated during the mixing of these.

In addition, as a method for obtaining the above-mentioned reaction product, when the single-pass method is used, the equivalent ratio of isocyanate groups in the polyisocyanate component (isocyanate group/hydroxyl group) to the hydroxyl group in the polyol component is, for example, 0.9 or more, Preferably it is 0.95 or more, more preferably 0.98 or more, and is, for example, 1.2 or less, preferably 1.1 or less, more preferably 1.08 or less in a ratio. The polyisocyanate component and the polyol component (containing high molecular weight polyol and low molecular weight polyol Alcohol) was prepared and stirred and mixed at the same time.

In addition, the stirring and mixing system is, for example, under an inert gas (such as nitrogen) environment, the reaction temperature is, for example, 40°C or higher, preferably 70°C or higher, and for example, 280°C or lower, preferably 260°C or lower, and the reaction time is, for example, It is carried out for 30 seconds or more and 1 hour or less.

In addition, during stirring and mixing, the above-mentioned urethane catalyst or organic solvent may be added in an appropriate ratio as necessary.

Thereby, a thermoplastic polyurethane resin can be obtained according to the type of the reaction product.

Furthermore, in this method, the obtained reaction product may be subjected to heat treatment (heat treatment step) as necessary.

The heat treatment step is a step of heat-treating the above-mentioned 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 allowed to stand at a predetermined heat treatment temperature for a predetermined heat treatment period, and after heat treatment is performed, it is dried as 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.

When the heat treatment temperature is in the above range, a thermoplastic polyurethane resin having particularly good stretch characteristics and heat resistance can be obtained.

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

If the heat treatment period is in the above range, a thermoplastic polyurethane resin having particularly good stretch characteristics and heat resistance can be obtained.

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

These additives can be added during the mixing, synthesis or after synthesis of the ingredients.

The timing of addition of the additives is not particularly limited. For example, it can be added to the polyisocyanate component, or can be added to the polyol component, can also be added at the same time when the polyisocyanate component and the polyol component are mixed, and can also be added to the polyisocyanate component. Add to this mixture after mixing with polyol components.

In addition, the amount of additives added is not particularly limited, and is appropriately set depending on the purpose and use.

Moreover, the thermoplastic polyurethane resin obtained in this way contains a polyisocyanate component and a polyol component as raw material components, and the polyisocyanate component is contained in a proportion of 60 mol% or more and 99.5 mol% or less. 1,4-bis(isocyanatomethyl)cyclohexane in trans form; this polyol component contains amorphous polycarbonate diol that is liquid at 25°C and carbon number 2~6 Low molecular weight glycol.

That is, as raw material components, 1,4-bis(isocyanatomethyl)cyclohexane, which has higher crystallinity, and low molecular weight diol, which enhances crystallinity by a hard segment, is used, which has better crystallinity. Low amorphous polycarbonate diol.

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 can have both heat resistance from high cohesiveness and low heat resistance in a well-balanced manner. The elasticity of agglomeration.

In addition, 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, still more preferably 15% by mass or more, and For example, 30% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less.

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

More specifically, the hard segment concentration can be calculated by the following formula from the formulation (filling amount) of each component when the prepolymer method is used, for example. [Chain extender (g) + (chain extender (g) / molecular weight of chain extender (g/mol)) × average molecular weight of polyisocyanate component (g/mol)] ÷ (polyisocyanate component (g) + multiple The total mass of alcohol components (g)) ×100 In addition, the heat (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 more, preferably 0.5 J/g or more, more preferably 1.0 J/g or more, more preferably 1.5 J/g or more, particularly preferably 2.0 J/g or more, and for example, 20 J/g or less, preferably 15 J/g or less, more preferably 10.5 J/g or less, and It is more preferably 7.0 J/g or less, still more preferably 5.0 J/g or less, still more preferably 4.0 J/g or less, and particularly preferably 3.0 J/g or less.

If the heat of the melting peak of the thermoplastic polyurethane resin above 160°C exceeds the above lower limit, since the agglomeration of the thermoplastic polyurethane resin is not too low, superior heat resistance can be obtained.

In addition, if the heat of melting peak of the thermoplastic polyurethane resin at 160°C or higher is less than the above upper limit, since the agglomeration of the thermoplastic polyurethane resin is not too high, superior stretch characteristics can be obtained.

That is, if the heat of the melting peak of the thermoplastic polyurethane resin above 160°C is within the above range, the agglomeration can be adjusted appropriately, and the heat resistance and expansion of the thermoplastic polyurethane resin can be achieved. characteristic.

In addition, the heat of the melting peak was measured by differential scanning calorimetry (DSC measurement) according to the examples described later.

In addition, the expansion and contraction characteristics are evaluated by, for example, the restoring force after stretching deformation (the shape recovery rate after expansion and contraction deformation).

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

In addition, the restoring force (shape recovery rate) after 60% tension for 15 seconds is measured by a tension tester or the like according to the examples described later.

In addition, the heat resistance is more specifically evaluated by the storage elastic coefficient (E').

Specifically, from the viewpoint of heat resistance, the storage elastic coefficient (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, and for example, 50×10 ⁶ MPa or less, preferably 40×10 ⁶ MPa or less, more preferably 30×10 ⁶ MPa or less.

In addition, the storage elastic coefficient (E') at 80°C was measured by dynamic viscoelasticity measurement according to the examples described later.

Furthermore, by molding the above-mentioned thermoplastic polyurethane resin by, for example, a known molding method (one-shot molding), the thermoplastic polyurethane resin can be molded into any shape, and a thermoplastic polyurethane resin can be obtained. A molded product of urethane resin (primary molded product).

As a molding method of one-shot molding, for example, thermocompression molding, injection molding, extrusion molding, cutting molding, melt spinning molding, 3D printing molding, and the like can be mentioned. These can be used alone or in combination of two or more kinds.

As the shape of the primary molded product, for example, a pellet shape, a plate shape, a fiber shape, a strand shape, a film shape, a sheet shape, a tube shape, a hollow shape, a box shape, etc. may be mentioned, and a pellet shape is preferred.

For example, when obtaining a pelletized thermoplastic polyurethane resin as a primary molded product, it is preferable to perform secondary molding of the pelletized thermoplastic polyurethane resin according to a known molding method to obtain A secondary molded product of thermoplastic polyurethane resin.

Examples of the secondary molding method include the above-mentioned molding methods, and preferably, extrusion molding is used.

The shape of the secondary molded product includes, for example, a pellet shape, a plate shape, a fiber shape, a strand shape, a film shape, a sheet shape, a tube shape, a hollow shape, a box shape, etc., and a film shape is preferred.

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

Furthermore, the present invention includes a film containing the above-mentioned thermoplastic polyurethane resin.

That is, the film of the present invention is formed of the above-mentioned thermoplastic polyurethane resin. That is, the film of the present invention is a molded product of the above-mentioned thermoplastic polyurethane resin.

Since such a film contains the above-mentioned thermoplastic polyurethane resin, it has excellent stretch characteristics and heat resistance.

Therefore, a film containing a thermoplastic polyurethane resin can be suitably used in fields requiring various physical properties as described above. For example, the above-mentioned film is suitable as a base film of Paint Protection Film (PPF) for protecting the painted surface of various products in various industrial fields such as the automobile industry.

Protective film (PPF) is a laminated film used to stick a film containing polyurethane resin on the coating surface of various products (especially automobiles, motorcycles, etc.) to protect the surface of various products. The protective film (PPF) is provided with, for example, a release layer containing polyester resin, an acrylic adhesive layer arranged on the release layer, and a base film layer arranged on the acrylic adhesive layer. In addition, the protective film may further include a surface protective layer disposed on the base layer.

In this kind of protective film (PPF), by using the above-mentioned thermoplastic polyurethane resin-containing film as the base film layer, superior stretch characteristics and heat resistance can be obtained, and various products (automobiles, motorcycles) can be protected well. Wait).

Furthermore, the above-mentioned thermoplastic polyurethane resin is not limited to a film, and can be suitably used in various industrial fields requiring stretch characteristics and heat resistance.

More specifically, the above-mentioned thermoplastic polyurethane resin can be applied to, for example, yarns, fibers (for tubes, elastic tights, elastic pants (spats), sportswear, sports goods, support protectors). , Swimwear and other yarns, composite fibers), monofilament, film (stretchable film for clothing, hot melt film, wound covering film, etc.).

In addition, the above-mentioned thermoplastic polyurethane resin is suitable for use in, for example, transparent rigid plastics, coating materials, adhesives, adhesives, waterproofing materials, sealing agents, inks, adhesives, sheets, tapes (such as table Belts and other belts, such as automotive transmission belts, various industrial conveyor belts (conveyor belts, etc.), pipes (such as parts for medical pipes, catheters, etc., air pipes, hydraulic pipes, electric wires, etc., such as fire fighting Water pipes, etc.), vanes, loudspeakers, sensors, high-brightness LED sealants, organic EL components, solar power generation components, robot components, Android components, wearable components, clothing products, sanitary products, cosmetics Supplies, food packaging components, sports goods, leisure goods, medical supplies, nursing supplies, residential components, audio components, lighting components, crystal lamps, street lamps, sealing materials, sealing materials, soft plugs, cushion materials, shockproof and vibration control ‧Isolation components, soundproof components, daily necessities, miscellaneous goods, cushioning materials, bedding, stress absorbing materials, stress relief materials, automotive interior and exterior parts, railway components, aerospace components, optical components, OA equipment components, and sundries surface protection Components, semiconductor sealing materials, self-repair materials, health appliances, glasses lenses, toys, cable sheaths, wiring harnesses, telecommunication cables, automotive wiring, computer wiring, crimped wires and other industrial supplies, sheets, films and other nursing supplies , Sports goods, leisure goods, various miscellaneous goods, anti-vibration, anti-vibration materials, shock-absorbing materials, optical materials, light guide films, etc. films, automotive parts, surface protection sheets, cosmetic sheets, transfer sheets, semiconductor protection tapes, etc. Components, golf components, tennis racket strings, agricultural films, wallpapers, anti-fogging agents, non-woven fabrics, mattresses or sofas and other furniture products, bras or shoulder pads and other clothing products, paper diapers, sanitary napkins, cushioning materials for medical tapes, etc. Medical products, cosmetics, sanitary products such as face wash pads or pillows, footwear products such as soles (outsoles), midsoles, covering materials, and body pressure dispersion products such as cushions or cushioning materials for vehicles, door trims, Components that are touched by hands such as instrument panels and shift levers, shock-absorbing materials such as thermal insulation materials, shock absorbers, etc. of electric refrigerators or buildings, filling materials, handles of vehicles, interior components of automobiles, exterior components of automobiles, etc. Vehicle supplies, chemical mechanical polishing (CMP) pads and other semiconductor manufacturing supplies, etc.

Furthermore, the above-mentioned molded product can be suitable for coating materials (films, sheets, tapes, metal wires, wires, metal coating materials for rotating machines, wheels, drills, etc.) and extrusion molding applications (nets for tennis, badminton, etc.) Extrusion molding applications such as wire and its binding materials), powdered hollow molded products such as micro-particles, artificial leather, skins, sheets, covered rolls (covered rolls for steel, etc.), sealants, rolls The sheath or core material of, gears, balls, and sticks (the sheath or core material of golf, basketball, tennis, volleyball, softball, sticks, etc.) (these can also be foamed polyurethane resin Form)), mats, ski supplies, boots, tennis supplies, grips (golf clubs or two-wheeled vehicle grips), rack boots, wipers, seat cushioning members, film for nursing products, 3D printing Machine molded products, fiber reinforced materials (carbon fiber, lignin, kenaf, nanocellulose fiber, glass fiber and other fiber reinforced materials), safety goggles, sunglasses, spectacle frames, ski goggles, swimming goggles, contact lenses Glasses, gas-assisted injection molded foam products, shock absorbers, CMP polishing pads, dampers, bearings, dust caps, shut-off valves, cutting rollers, high-speed rotating rollers, tires, clocks, wearable belts, etc. require expansion and contraction characteristics and Use of heat resistance.

[Examples] Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited to these. In addition, unless otherwise mentioned, "parts" and "%" refer to quality standards. In addition, specific numerical values such as the blending ratio (content ratio), physical property values, and parameters used in the following description can be replaced with the blending ratio (content ratio), physical property values, etc. corresponding to these described in the above-mentioned "embodiment of the invention". The upper limit (defined as the value of "below" or "less than full") or the lower limit (defined as the value of "above" or "exceeding") of the parameter, etc. 1) Raw material <Polyisocyanate component (a)> 1,4-H ₆ XDI: 1,4-bis(isocyanatomethyl)cyclohexane synthesized according to the method described in Production Example 1, trans form 86 Mole%/cis compound 14 Mole% H ₁₂ MDI: 4,4'-dicyclohexylmethane diisocyanate <High molecular weight polyol (b)> b-1) UH100W: Number average molecular weight (Mn) 1000, crystal Polycarbonate diol, trade name ETERNACOLL UH-100W, average hydroxyl number 2, manufactured by Ube Industries b-2) UH200W: number average molecular weight (Mn) 2000, crystalline 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, manufactured by Ube Industries b-4) UP200: number average molecular weight (Mn) 2000, amorphous polycarbonate diol, trade name ETERNACOLL UP-200, average hydroxyl number 2, manufactured by 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 hydroxyl number 2, KURARAY ISOPRENE CHEMICAL b-6) 210N: number average molecular weight (Mn) 1000, polycaprolactone diol, trade name Placcel 210N, average hydroxyl number 2, DAICEL b-7) 220N: number average molecular weight (Mn) 2000, polycaprolactone diol, Trade name Placcel 220N, average hydroxyl number 2, DAICEL product <low molecular weight polyol (c)> 1,4-BD: 1,4-butanediol, manufactured by Mitsubishi Chemical Corporation, carbon number (C) 2~6 low molecular weight Diol <Ethyl carbamate catalyst> STANOCT: tin octoate, trade name: STANOCT, manufactured by API Corporation <catalyst diluent> Diisononyl adipate: trade name DINA, Dahachi Chemical Industry Co., Ltd. <Additive> Antioxidant: hindered phenol compound, trade name: IRGANOX245, BASF Japan UV absorber: benzotriazole compound, trade name: Tinuvin 234, BASF Japan light stabilizer: hindered amine compound, trade name : ADK STAB LA-72, manufactured by ADEKA Corporation <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 in International Patent Publication WO2019/069802, 1,4-bis(isocyanatomethyl)cyclohexane (1, 4-H ₆ XDI).

The purity of the obtained 1,4-H ₆ XDI measured by gas chromatography is 99.9%, the hue measured by APHA is 5, and the trans compound/cis compound measured ^{by 13 C-NMR} The ratio is 86 mol% for trans and 14 mol% for cis.

2) Thermoplastic polyurethane resin [Examples 1 to 5 and Comparative Examples 1 to 6] According to the formula described in Table 1, a thermoplastic polyurethane resin and sheet were prepared.

More specifically, first, measure the high-molecular-weight polyol (b) whose temperature has been adjusted to 80°C in advance, and use a high-speed stirring disperser in an oil bath at 80°C under a nitrogen environment to stir at 700±50 rpm for 1 hour. Next, to the high molecular weight polyol (b), IRGANOX245 (manufactured by BASF Japan, heat-resistant stabilizer), Tinuvin 571 (manufactured by BASF, ultraviolet absorber), and ADK STAB LA-72 (manufactured by ADEKA, HALS) are added as Additives, in a nitrogen environment, in an oil bath at 80°C, using a high-speed stirring disperser, stirring at 700 ± 50 rpm for 30 minutes. The amount of additives added is based on the final polyisocyanate component, high-molecular-weight polyol and low-molecular-weight polyol of 100 parts by mass, and is set to 0.3 parts by mass of IRGANOX245 (manufactured by BASF Japan, heat-resistant stabilizer), Tinuvin 571 (BASF) Company make, ultraviolet absorber) 0.4 part by mass, ADK STAB LA-72 (made by ADEKA company, HALS) 0.1 part by mass.

Next, the polyisocyanate component (a) is added to the resulting mixture, and then diisononyl adipate (DINA, manufactured by Daihachi Chemical Co., Ltd.) is diluted to 4% by mass of tin octoate (trade name: STanoct, API Corporation). Made by the company) is added so that the amount of catalyst (solid content) becomes 5 ppm.

Next, put the resulting mixture in an oil bath at 80° C., using a high-speed stirring disperser, and stirring and mixing at 700 ± 50 rpm for 5 minutes. In this way, an isocyanate group-terminated prepolymer is obtained (prepolymer synthesis step).

Next, add 1,4-butanediol (low-molecular-weight polyol (c)) measured in advance and adjusted to a temperature of 80°C to the obtained isocyanate group-terminated prepolymer, and use a high-speed stirring disperser to stir at 700±50 rpm. Stir and mix for 3-20 minutes (chain elongation step).

The addition amount of low molecular weight polyol (c) is carried out in such a way that the equivalent ratio of isocyanate groups in the isocyanate group-terminated prepolymer (isocyanate group/hydroxyl group) relative to the hydroxyl groups in the low molecular weight polyol (c) becomes 1.00 adjust.

Also, while paying attention to the heat generation rate, add the above-mentioned catalyst (DINA diluted tin octoate) appropriately.

Then, the obtained mixture was poured into a Teflon (registered trademark) cylinder whose temperature was previously adjusted to 150°C, and after reacting at 150°C for 2 hours, the temperature was lowered to 100°C and the reaction was continued for 20 hours to obtain the heat of the reaction product. Plastic polyurethane resin (reaction product before heat treatment (primary product)).

Next, the resulting thermoplastic polyurethane resin is taken out of the tank, and cut into dice shapes by a rubber cutter, and the dice-shaped resin is pulverized by a pulverizer to obtain pulverized particles. Next, the crushed particles were heat-treated (aged, matured) in an oven at 80°C for 7 days, and dried at 23°C for 12 hours under vacuum and reduced pressure. Thereby, the secondary product of the thermoplastic polyurethane resin (the reaction product after the heat treatment) is obtained.

After that, the obtained pulverized particles (secondary products) were subjected to a single-screw extruder (model: SZW40-28MG, manufactured by Technovel), with a screw rotation speed of 30 rpm and a cylinder temperature of 150 to 250°C. Extrusion of the thread and cutting.

Thereby, pellets of a molded product (primary molded product) of a thermoplastic polyurethane resin are obtained.

Thereafter, the pellets were dried in advance at 80°C under vacuum and reduced pressure for 12 hours, using a single-screw extruder (model: SZW40-28MG, manufactured by Technovel), with a rotation speed of 20 rpm and a cylinder temperature ranging from 150 to 250°C Extrusion molding was performed to obtain a 150 μm thick film of a molded product (secondary molded product) of a thermoplastic polyurethane resin.

4) Evaluation ＜Stretch characteristics: Resilience (shape recovery rate)＞ Install a film with a thickness of 150μm (10mm wide×10cm long) on a universal testing machine Mode 1205N (made by INTESCO, the distance between the markings is 80mm, and the stretching speed is 500ml/min) to extend the distance between the markings by 60% ( 48mm) before releasing.

After 15 seconds of release, measure the distance between the marking lines and measure the recovery force of the film.

In addition, the recovery force of the film is expressed in terms of the ratio (%) of the film length before stretching to the film length after stretching. The higher the value (closer to 100%), the higher the recovery force (shape recovery rate).

＜Heat resistance: Storage elasticity coefficient (E’)＞ Use a dynamic viscoelasticity measuring device (IT measuring control system, type: DVA-220), depending on the measuring temperature -100℃~250℃, heating rate 5℃/min, tension mode, length between markings 20mm, static/dynamic stress The ratio is 1.8, the measuring frequency is 10Hz, and the dynamic viscoelastic wave spectrum of a 150μm film of thermoplastic polyurethane resin is measured.

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

In addition, the higher the E', the better the heat resistance.

＜Melting heat (unit: J/g＞ Using a differential scanning calorimeter (DSC7000X, manufactured by Hitachi High-Tech Science), the measurement was performed as follows.

That is, about 10 mg of thermoplastic polyurethane resin was collected in an aluminum pan. The aluminum plate is covered with a protective material and held by the holder, and used as a measurement sample (sample). The same sample of alumina was used as a reference sample.

After installing the sample and reference at the predetermined position in the tank, cool the sample from 20°C to -100°C at a rate of 10°C/min under a nitrogen flow of 30NmL/min, and keep it at the same temperature for 5 minutes. The temperature is increased to 270°C at a rate of 10°C/min, and thereafter, it is cooled to -70°C at a rate of 10°C/min.

Then, measure the peak temperature of the endothermic peak (melting peak) above 160°C and the heat quantity (enthalpy change) (J/g) of the peak within the peak that appears during the temperature rise from -100°C to 270°C.

[Table 1] No. Comparative example 1 Comparative example 2 Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Blending formula (mole ratio) Polyisocyanate component (a) 1,4-H ₆ XDI 240 231 250 151 196 241 329 292 318 — — H ₁₂ MDI — — — — — — — — — 528 303 High molecular weight polyol (b) Crystalline polycarbonate diol UH100W 100 50 50 — — — — — — — — UH200W — 50 — — — — — — — — — Amorphous polycarbonate diol UP100 — — — 100 75 50 — — — — UP200 — — 50 — 25 50 — — — — — C2090R — — — — — 100 — — — — Polycaprolactone diol 210N — — — — — — — 100 — — 100 220N — — — — — — — — 100 100 — Low molecular weight polyol (c) C2-6 low molecular weight diol 1,4-BD 140 131 150 51 96 141 229 192 218 428 207 Equivalent ratio (NCO/OH) Prepolymer synthesis steps 2.40 2.31 2.50 1.51 1.96 2.41 3.29 2.92 3.18 5.28 3.03 Chain elongation step 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Evaluation Resilience % 95.0 96.7 97.9 97.4 98.2 97.6 98.4 94.5 Unrecovered 98.8 99.1 E'[80℃] ×10 ⁶ MPa 41 31 20 16 twenty three twenty one 25 52 — 5 5 Endothermic peak temperature °C 185 173 — — 165 192 214 188 — — — Calories J/g 17 13 5 0 2 3 2 20 0 0 0

Furthermore, the above-mentioned invention is provided in accordance with the exemplified embodiment of the present invention, but this is only a mere exemplification and is not a restrictive interpretation. Modifications of the present invention known to those with ordinary knowledge in this technical field are also included in the scope of the following patent applications. (Industrial availability)

The thermoplastic polyurethane resin and film of the present invention are suitable for various industrial fields such as the automobile industry.

Claims (4)

A thermoplastic polyurethane resin containing a reaction product of a polyisocyanate component and a polyol component; the polyisocyanate component contains a trans compound in a proportion of 60 mol% or more and 99.5 mol% or less 1,4-bis(isocyanatomethyl)cyclohexane; this polyol component contains amorphous polycarbonate diol which is liquid at 25°C and low molecular weight diol with carbon number 2-6. The thermoplastic polyurethane resin of claim 1, wherein the heat of the melting peak of the above-mentioned thermoplastic polyurethane resin at 160°C or higher as measured by differential scanning calorimetry (DSC method) is Below 15J/g. The thermoplastic polyurethane resin of claim 1, wherein the heat of the melting peak of the above-mentioned thermoplastic polyurethane resin at 160°C or higher as measured by differential scanning calorimetry (DSC method) is Above 0.1J/g. A film containing the thermoplastic polyurethane resin of claim 1.