JP7246910B2 - Thermoplastic polyurethane resin, molded article, and method for producing thermoplastic polyurethane resin - Google Patents

Description

TECHNICAL FIELD The present invention relates to thermoplastic polyurethane resins, molded articles, and methods for producing thermoplastic polyurethane resins.

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

As a thermoplastic polyurethane resin, for example, in a polyurethane elastomer obtained by reacting an isocyanate component containing 1,4-bis(isocyanatomethyl)cyclohexane with a polyol component, the polyol component contains a high-molecular-weight polyol and a low-molecular-weight polyol. It is proposed that the high molecular weight polyol contains amorphous polytetramethylene ether glycol. More specifically, 1,4-bis(isocyanatomethyl)cyclohexane and copolymerized polytetramethylene ether glycol (amorphous polytetramethylene ether glycol obtained by copolymerizing tetrahydrofuran and neopentyl glycol, number average molecular weight 1800) to synthesize a prepolymer, and reacting the prepolymer with 1,4-butanediol to produce a polyurethane elastomer (for example, Patent Document 1 (Synthesis See Example 9 and Example 9).).

JP 2013-023656 A

On the other hand, polyurethane elastomer molded articles are required to have various physical properties depending on the application.

However, the polyurethane elastomer described in Patent Document 1 may not have sufficient stretch properties (return stress, residual strain) and/or bloom resistance depending on the application.

The present invention provides a thermoplastic polyurethane resin having both stretchability (return stress, residual strain) and bloom resistance, a molded article obtained from the thermoplastic polyurethane resin, and a thermoplastic polyurethane capable of producing such a thermoplastic polyurethane resin. It is a manufacturing method of resin.

The present invention [1] comprises a polyisocyanate component containing bis(isocyanatomethyl)cyclohexane, a low molecular weight polyol having a molecular weight of 400 or less, and a polyol component containing an amorphous polyether polyol having a number average molecular weight of 2500 or more and 4000 or less. contains a thermoplastic polyurethane resin that is the reaction product of

The present invention [2] contains an unsaturated fatty acid amide, and the content of the unsaturated fatty acid amide is 0.01% by mass or more and 0.5% by mass or less with respect to the total amount of the thermoplastic polyurethane resin. , containing the thermoplastic polyurethane resin described in [1] above.

The present invention [3] contains the thermoplastic polyurethane resin according to the above [1] or [2], wherein the bis(isocyanatomethyl)cyclohexane contains 1,4-bis(isocyanatomethyl)cyclohexane. .

The present invention [4] is any one of the above [1] to [3], wherein the 1,4-bis(isocyanatomethyl)cyclohexane contains a trans isomer at a ratio of 70 mol% or more and 99 mol% or less. containing the thermoplastic polyurethane resin described in Section 1.

The present invention [5] includes a molded article containing the thermoplastic polyurethane resin according to any one of [1] to [4] above.

The present invention [6] includes the molded article according to [5] above, which is an elastic fiber obtained by melt spinning.

The present invention [7] is a step of reacting a polyisocyanate component containing bis(isocyanatomethyl)cyclohexane with an amorphous polyether polyol having a number average molecular weight of 2500 or more and 4000 or less to obtain an isocyanate group-terminated prepolymer. , and the step of reacting the isocyanate group-terminated prepolymer and a low-molecular-weight polyol having a molecular weight of 400 or less to obtain a thermoplastic polyurethane resin.

Amorphous polyether polyol having a number average molecular weight of 2500 or more and 4000 or less is used as a raw material (high molecular weight polyol) for the thermoplastic polyurethane resin and its molded article of the present invention.

When an amorphous polyether polyol is used as a raw material, the precipitation of hard segments can be suppressed due to its low crystallinity, and the bloom resistance can be improved.

On the other hand, if precipitation of hard segments is suppressed, cohesiveness between hard segments decreases, which may cause deterioration in stretchability. However, if the number average molecular weight of the amorphous polyether polyol is 2500 or more, it is possible to promote the precipitation of hard segments while suppressing the crystallization of the soft segment phase (domains composed of soft segments), thereby improving the stretch characteristics. can be improved.

In addition, if the number average molecular weight of the amorphous polyether polyol is 4000 or less, it is possible to suppress the decrease in cohesiveness due to the increase in the distance between the hard segments, and as a result, it is possible to maintain excellent stretchability. .

That is, by using an amorphous polyether polyol having a number average molecular weight of 2500 or more and 4000 or less as a raw material, it is possible to achieve both stretchability and bloom resistance in a well-balanced manner.

Moreover, according to the method for producing a thermoplastic polyurethane resin of the present invention, a thermoplastic polyurethane resin and a molded product having both stretchability and bloom resistance can be obtained.

The thermoplastic polyurethane resin of the present invention is obtained by reacting a polyisocyanate component and a polyol component, and then subjecting them to heat treatment (heat curing), as described later. In other words, the thermoplastic polyurethane resin is the reaction product of the polyisocyanate component and the polyol component.

The polyisocyanate component contains bis(isocyanatomethyl)cyclohexane as an essential component.

Bis(isocyanatomethyl)cyclohexane includes 1,3-bis(isocyanatomethyl)cyclohexane and 1,4-bis(isocyanatomethyl)cyclohexane, preferably the stretchability and bloom resistance of thermoplastic polyurethane resins. 1,4-bis(isocyanatomethyl)cyclohexane, which has a symmetrical structure, can be mentioned from the viewpoint of achieving both compatibility.

1,4-bis(isocyanatomethyl)cyclohexane includes cis-1,4-bis(isocyanatomethyl)cyclohexane (hereinafter referred to as cis-1,4-isomer), and trans-
,4-bis(isocyanatomethyl)cyclohexane (hereinafter referred to as trans-1,4-stereoisomer). For example, 60 mol% or more, preferably 70 mol% or more, more preferably 75 mol% or more, still more preferably 80 mol% or more, for example 99.8 mol% or less, preferably 99 mol% % or less, more preferably 96 mol % or less, more preferably 90 mol % or less. In other words, in 1,4-bis(isocyanatomethyl)cyclohexane, the total amount of trans-1,4-isomer and cis-1,4-isomer is 100 mol %, so the cis-1,4-isomer is, for example, 0.2 mol. % or more, preferably 1 mol % or more, more preferably 4 mol % or more, still more preferably 10 mol % or more, for example 40 mol % or less, preferably 30 mol % or less, more preferably 25 mol % % or less, more preferably 20 mol % or less.

If the content of transformers 1 and 4 is equal to or higher than the above lower limit, it is possible to improve stretchability and heat resistance. Further, when the content ratio of the transformers 1 and 4 is equal to or less than the above upper limit, the bloom resistance can be improved.

Bis(isocyanatomethyl)cyclohexane can be produced, for example, by the method described in International Publication WO2009/051114.

Moreover, bis(isocyanatomethyl)cyclohexane can also be prepared as a modified form within a range that does not impair the excellent effects of the present invention.

Modified forms of bis(isocyanatomethyl)cyclohexane include, for example, bis(isocyanatomethyl)cyclohexane oligomers (dimers (e.g., uretdione modified forms), trimers (e.g., isocyanurate modified forms, iminooxadiazinedione modified product, etc.), biuret modified product (e.g., biuret modified product produced by the reaction of bis (isocyanatomethyl) cyclohexane and water), allophanate modified product (e.g., bis (isocyanatomethyl) cyclohexane and monovalent Allophanate modified product produced by reaction with alcohol or dihydric alcohol, etc.), polyol modified product (for example, polyol modified product (adduct) produced by reaction of bis(isocyanatomethyl)cyclohexane and trihydric alcohol), Modified oxadiazinetrione (e.g., oxadiazinetrione produced by reaction of bis(isocyanatomethyl)cyclohexane and carbon dioxide), modified carbodiimide (e.g., decarboxylation condensation reaction of bis(isocyanatomethyl)cyclohexane) carbodiimide modified product produced by) and the like.

In addition, the polyisocyanate component may contain other polyisocyanates such as aliphatic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates as optional components within a range that does not impair the excellent effects of the present invention. can be done.

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 bis(isocyanatomethyl)cyclohexane).

Alicyclic polyisocyanates (excluding bis(isocyanatomethyl)cyclohexane) include, for example, isophorone diisocyanate (IPDI), trans, trans-, trans, cis- and cis, cis-dicyclohexylmethane diisocyanate and mixtures thereof (hydrogenated MDI), 1,3- or 1,4-cyclohexane diisocyanate and mixtures thereof, 1,3- or 1,4-bis(isocyanatoethyl) cyclohexane, methylcyclohexane diisocyanate, 2,2′-dimethyldicyclohexyl methane diisocyanate, dimer acid diisocyanate, 2,5-diisocyanatomethylbicyclo[2,2,1]-heptane, its isomer 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-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo-[2,2, 1]-heptane, 2-isocyanatomethyl 3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo-[2,2,1]-heptane, 2-isocyanatomethyl 2-( 3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo-[2,2,1]-heptane, 2-isocyanatomethyl 2-(3-isocyanatopropyl)-6-(2-isocyanate Natoethyl)-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.

Examples of other modified polyisocyanates include polymers of other polyisocyanates (dimers, trimers, etc.), biuret modified products, allophanate modified products, polyol modified products, oxadiazinetrione modified products, carbodiimide modified products, etc. mentioned.

When other polyisocyanate is contained, the content is, for example, 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, relative to the total amount of the polyisocyanate component.

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

In the present invention, the polyol component is a compound containing two or more hydroxyl groups in the molecule.

The polyol component comprises a low molecular weight polyol having a molecular weight of 400 or less and an amorphous polyether polyol having a number average molecular weight of 2500 or more and 4000 or less, preferably essentially consisting of a low molecular weight polyol having a molecular weight of 400 or less and a number average molecular weight of and an amorphous polyether polyol having a molecular weight of 2500 or more and 4000 or less.

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).

Examples of low-molecular-weight polyols include compounds (monomers) having two or more hydroxyl groups in the molecule and having a molecular weight of 50 or more and 400 or less. Specifically, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol (1,4-butanediol, 1,4-BD), 1,3-butylene glycol, 1, C2-4 alkanediols such as 2-butylene glycol, e.g. 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethyl pentanediol, 3,3-dimethylolheptane, alkane (C7-20) diols, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol and their mixture, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A and hydrogenated products thereof, diethylene glycol, triethylene glycol, dipropylene glycol, 1,2- dihydric alcohols such as benzenediol, 1,3-benzenediol and 1,4-benzenediol; trihydric alcohols such as glycerin, trimethylolpropane and triisopropanolamine; Tetrahydric alcohols such as glycerin, Pentahydric alcohols such as xylitol, Hexahydric alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, dipentaerythritol, Heptahydric alcohols such as perseitol , for example, polyhydric alcohols such as octahydric alcohols such as sucrose.

In addition, as the low-molecular-weight polyol, polyoxyalkylene polyol (polyoxyalkylene polyol ( including random and/or block copolymers).

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

Low-molecular-weight polyols preferably include dihydric alcohols (low-molecular-weight diols), more preferably C2-C4 alkanediols, and even more preferably 1,4-butanediol.

If the low-molecular-weight polyol is the one described above, it is possible to obtain a molded article (described later) having excellent mechanical properties.

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

When the molecular weight of the low-molecular-weight polyol is within the above range, a molded article (described later) having excellent mechanical properties can be obtained.

In the amorphous polyether polyol, “amorphous” means that the melting point obtained by differential scanning calorimetry (DSC measurement) described later is 23° C. or lower. The crystallinity means that the melting point obtained by differential scanning calorimetry (DSC measurement), which will be described later, exceeds 23°C.

That is, an amorphous polyether polyol is a polyether polyol having a melting point of 23° C. or lower as measured by DSC. A polyether polyol is a high molecular weight compound (preferably a polymer) having one or more ether bonds and two or more hydroxyl groups in the molecule.

As the amorphous polyether polyol, more specifically, amorphous polyoxyethylene polyol, amorphous polyoxypropylene polyol, amorphous polyoxyethylene-polyoxypropylene copolymer (random/block), non-crystalline Amorphous polyoxyalkylene polyols such as crystalline polytrimethylene ether polyols and amorphous polytetramethylene ether polyols are included, and amorphous polytrimethylene ether polyols and amorphous polytetramethylene ether polyols are preferred. and more preferably amorphous polytetramethylene ether polyol.

Amorphous polytrimethylene ether polyol is a polyether polyol having an oxy linear alkylene group having 3 carbon atoms as a main chain.

Examples of amorphous polytrimethylene ether polyols include addition polymers of trimethylene oxide using the above low-molecular-weight polyol as an initiator. The initiator preferably includes dihydric alcohol and trihydric alcohol, more preferably dihydric alcohol. The method for addition polymerization of trimethylene oxide to the dihydric alcohol is not particularly limited, and a known method is employed.

By addition polymerization of trimethylene oxide to dihydric alcohol, divalent amorphous polytrimethylene ether polyol (also known as amorphous poly (1,3-propanediol), amorphous poly (oxy-1, 3-propylene)diol, amorphous polytrimethylene ether glycol (amorphous PT(C3)MEG)) can be obtained.

Examples of divalent amorphous polytrimethylene ether polyols include glycols obtained by polycondensation reaction of 1,3-propanediol derived from plant components.

These amorphous polytrimethylene ether polyols can be used alone or in combination of two or more.

The amorphous polytrimethylene ether polyol preferably includes a divalent amorphous polytrimethylene ether polyol.

Examples of amorphous polytetramethylene ether polyols include amorphous polytetramethylene ether glycol (amorphous PT(C4)MEG) obtained by copolymerizing polymerized units such as tetrahydrofuran with the above dihydric alcohol.

More specifically, amorphous polytetramethylene ether glycol is, for example, a copolymer of tetrahydrofuran and alkyl-substituted tetrahydrofuran (eg, 3-methyltetrahydrofuran) (tetrahydrofuran/alkyl-substituted tetrahydrofuran (molar ratio) = 15 /85 to 85/15), and copolymers of tetrahydrofuran and branched glycol (e.g., neopentyl glycol, etc.) (tetrahydrofuran/branched glycol (molar ratio) = 15/85 to 85/15), etc. can be obtained as

In addition, as the amorphous polytetramethylene ether polyol, commercially available products can be used. Examples of such commercial products include "PTXG" series manufactured by Asahi Kasei Fibers Co., Ltd. ” series.

These amorphous polytetramethylene ether polyols can be used alone or in combination of two or more.

The amorphous polytetramethylene ether polyol preferably includes a divalent amorphous polytetramethylene ether polyol (amorphous polytetramethylene ether glycol).

Amorphous polyether polyols can be used alone or in combination of two or more.

The amorphous polyether polyol preferably includes a divalent amorphous polyether polyol (amorphous polyether diol).

In addition, the amorphous polyether polyol preferably includes amorphous polytrimethylene ether polyol and amorphous polytetramethylene ether polyol from the viewpoint of easy availability and resistance to moisture absorption. From the viewpoint of achieving both blooming properties, amorphous polytetramethylene ether polyol is more preferable, and amorphous polytetramethylene ether glycol is more preferable.

The number average molecular weight of the amorphous polyether polyol is 2500 or more, preferably 2700 or more, more preferably 2800 or more, still more preferably 3000 or more, and particularly preferably, from the viewpoint of achieving both stretchability and bloom resistance. is 3,200 or more, and is 4,000 or less, preferably 3,900 or less, more preferably 3,800 or less, still more preferably 3,700 or less, and particularly preferably 3,600 or less.

By using the amorphous polyether polyol having the above number average molecular weight, it is possible to achieve both stretchability and bloom resistance.

More specifically, if an amorphous polyether polyol is used as a raw material, the precipitation of hard segments can be suppressed due to its low crystallinity, and the bloom resistance can be improved.

On the other hand, if precipitation of hard segments is suppressed, cohesiveness between hard segments decreases, which may cause deterioration in stretchability. However, if the number average molecular weight of the amorphous polyether polyol is 2500 or more, precipitation of hard segments can be promoted while crystallization of the soft segment phase is suppressed, and stretchability can be improved.

In addition, if the number average molecular weight of the amorphous polyether polyol is 4000 or less, it is possible to suppress the decrease in cohesiveness due to the increase in the distance between the hard segments, and as a result, it is possible to maintain excellent stretchability. .

That is, by using an amorphous polyether polyol having a number average molecular weight of 2500 or more and 4000 or less as a raw material, it is possible to achieve both stretchability and bloom resistance in a well-balanced manner.

In the polyol component, the content of the low-molecular-weight polyol and the amorphous polyether polyol is, with respect to the total amount thereof, the amorphous polyether polyol is, for example, 5 mol% or more, preferably 7 mol% or more, or more. It is preferably 10 mol % or more, more preferably 15 mol % or more, for example, 75 mol % or less, preferably 65 mol % or less, more preferably 50 mol % or less. In addition, the low molecular weight polyol is, for example, 25 mol% or more, preferably 35 mol% or more, more preferably 50 mol% or more, and for example, 95 mol% or less, preferably 93 mol% or less, more preferably is 90 mol % or less, more preferably 85 mol % or less.

The polyol component can also contain other polyols (polyol compounds other than the low-molecular-weight polyols described above and the amorphous polyether polyols described above).

Other polyols include, for example, high-molecular-weight polyols (excluding amorphous polyether polyols) having a number average molecular weight of more than 400 and not more than 10,000. More specifically, crystalline polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, polybutadiene polyols, and the like.

Examples of other polyols include amorphous polyether polyols other than amorphous polyether polyols having a number average molecular weight of 2500 or more and 4000 or less. and less than 2,500, for example, amorphous polyether polyols with a number average molecular weight of more than 4,000 and 10,000 or less.

The content of other polyols is, for example, 20% by mass or less, preferably 10% by mass or less, more preferably 1% by mass or less, and particularly preferably 0% by mass, relative to the total amount of the polyol component. be.

That is, the polyol component particularly preferably contains only a low molecular weight polyol and an amorphous polyether polyol having a number average molecular weight of 2500 or more and 4000 or less.

Then, the thermoplastic polyurethane resin is obtained by the method for producing a thermoplastic polyurethane resin described below.

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 and an amorphous polyether polyol having a number average molecular weight of 2500 or more and 4000 or less (and, if necessary, other polyols described above (hereinafter the same)) They are reacted to synthesize an isocyanate group-terminated prepolymer (prepolymer synthesis step).

In the prepolymer synthesis step, the polyisocyanate component and the amorphous polyether polyol are reacted by a polymerization method such as bulk polymerization or solution polymerization.

In bulk polymerization, for example, under a nitrogen stream, the polyisocyanate component and the amorphous polyether 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. .5 hours or longer, for example, 15 hours or shorter.

In the solution polymerization, a polyisocyanate component and an amorphous polyether 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. The reaction is allowed to proceed for 5 hours or more, 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, with respect to the total amount of 10000 parts by mass of the polyisocyanate component and the amorphous polyether polyol. , 1 part by mass or less, 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 preferably, for example, 1.3 or more as an equivalent ratio of isocyanate groups in the polyisocyanate component to hydroxyl groups in the amorphous polyether polyol (isocyanate groups/hydroxyl groups). is 1.5 or more, and is, for example, 20 or less, preferably 15 or less, more preferably 10 or less, still 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 of the polyisocyanate component with respect to 100 parts by mass of the amorphous polyether polyol. , more preferably 15 parts by mass or more, for example, 150 parts by mass or less, preferably 100 parts by mass or less, more preferably 90 parts by mass or less.

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 to obtain a reaction product of the polyisocyanate component and the polyol component (chain elongation step).

Thus, in this method, the low molecular weight polyol is the chain extender.

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 resulting thermoplastic polyurethane resin, together with the low molecular weight polyol, the above amorphous polyether polyol and other polyols are blended in an appropriate ratio. You can also

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 a one-shot method is employed as a method for obtaining the above reaction product, a polyisocyanate component and a polyol component (including amorphous polyether polyol and low-molecular-weight polyol) are added to the polyol component. The equivalent ratio of isocyanate groups in the polyisocyanate component to hydroxyl groups (isocyanate groups/hydroxyl groups) is, for example, 0.9 or more, preferably 0.95 or more, more preferably 0.98 or more, such as 1.2. Subsequently, these ingredients are blended at the same time and stirred and mixed at a ratio of preferably 1.1 or less, more preferably 1.08 or less.

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 that has both excellent stretchability and bloom resistance.

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.

When the heat treatment period is within the above range, it is possible to obtain a thermoplastic polyurethane resin having particularly good stretchability and bloom resistance.

Moreover, in the method for producing a thermoplastic polyurethane resin, preferably, a surface modifier (lubricant) is added. In other words, the thermoplastic polyurethane resin preferably contains a surface modifier (lubricant).

Examples of surface modifiers include fatty acid amides, and examples of fatty acid amides include saturated fatty acid amides and unsaturated fatty acid amides.

Saturated fatty acid amide is an amide compound of saturated fatty acid, and is not particularly limited. amides, saturated fatty acid bisamides such as ethylenebislaurylamide, ethylenebisoleylamide and ethylenebisstearylamide; and hydroxyl group-containing saturated fatty acid bisamides such as methylenebis12-hydroxystearylamide and ethylenebis12-hydroxystearylamide. These can be used alone or in combination of two or more.

The unsaturated fatty acid amide is an amide compound of an unsaturated fatty acid, and is not particularly limited. , unsaturated fatty acid bisamides such as ethylenebiserucamide, and hydroxyl group-containing unsaturated fatty acid bisamides such as methylenebishydroxyoleylamide and ethylenebishydroxyoleylamide. These can be used alone or in combination of two or more.

Surface modifiers can be used alone or in combination of two or more.

As the surface modifier, fatty acid amides are preferred, and unsaturated fatty acid amides are more preferred, from the viewpoint of improving bloom resistance. That is, the thermoplastic polyurethane resin preferably contains fatty acid amides, more preferably unsaturated fatty acid amides.

Moreover, the surface modifier preferably includes bisamides (saturated fatty acid bisamides and unsaturated fatty acid bisamides), and particularly preferably unsaturated fatty acid bisamides.

When the thermoplastic polyurethane resin contains a surface modifier (preferably unsaturated fatty acid amide), the content of the surface modifier (preferably unsaturated fatty acid amide) is , For example, 0.001% by mass or more, more preferably 0.005% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.05% by mass or more, for example, 1.0 % by mass or less, preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and even more preferably 0.2% by mass or less.

If the content of the surface modifier (preferably unsaturated fatty acid amide) is within the above range, the bloom resistance can be improved particularly favorably.

The surface modifier (lubricant) can be added at any timing (for example, during synthesis of each component, after synthesis, during mixing, during reaction, etc.).

In addition, in the method for producing a thermoplastic polyurethane resin, if necessary, additives other than the surface modifiers, such as antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, and Hydrolysis inhibitors (carbodiimide compounds, etc.), dyes (bluing agents, etc.), plasticizers, antiblocking agents, release agents, pigments, fillers, rust inhibitors, fillers and the like can be added. These additives can be added during mixing of each component, during synthesis, or after synthesis.

The antioxidant is not particularly limited, and includes known antioxidants (for example, listed in the BASF Japan catalog), more specifically, for example, phenolic antioxidants, hindered phenolic antioxidants agents and the like.

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

The ultraviolet absorber is not particularly limited, and includes known ultraviolet absorbers (for example, listed in the BASF Japan catalog), more specifically, for example, benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers. , benzophenone-based UV absorbers, and the like.

The light stabilizer is not particularly limited, and includes known light stabilizers (for example, listed in the ADEKA catalog), more specifically, for example, benzoate light stabilizers, hindered amine light stabilizers, and the like. mentioned.

These additives (excluding surface modifiers) are, for example, 0.001% by mass or more, preferably 0.01% by mass or more, and, for example, 3.0% by mass or less, relative to the thermoplastic polyurethane resin. , preferably at a rate of 2.0% by mass or less.

The thermoplastic polyurethane resin to which the surface modifier and other additives are added is also a resin composition containing the polyurethane resin and additives (surface modifier and other additives). collectively referred to as "thermoplastic polyurethane resin".

According to such a method for producing a thermoplastic polyurethane resin, it is possible to obtain a thermoplastic polyurethane resin that achieves both stretchability and bloom resistance in a well-balanced manner.

That is, in the above method for producing a thermoplastic polyurethane resin, a polyisocyanate component containing bis(isocyanatomethyl)cyclohexane, a low molecular weight polyol having a molecular weight of 400 or less, and an amorphous polyether having a number average molecular weight of 2500 or more and 4000 or less A polyol component containing a polyol is reacted.

Therefore, the thermoplastic polyurethane resin obtained by such a production method includes hard segments formed by the reaction of the polyisocyanate component and the low molecular weight polyol, the polyisocyanate component and the amorphous polyether polyol (number average molecular weight of 2500 to 4000 A soft segment formed by the reaction of an amorphous polyether polyol below).

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, for example 30% by mass. Below, it is 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. can.

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
If the hard segment concentration of the thermoplastic polyurethane resin is within the above range, the resulting molded article (described later) can be improved in stretchability and bloom resistance.

That is, in the above-described method for producing a thermoplastic polyurethane resin, an amorphous polyether polyol having a number average molecular weight of 2500 or more and 4000 or less is used as a raw material (high molecular weight polyol), so that the stretching property and the bloom resistance are balanced. can be well matched.

For example, the melting peak temperature (melting point) of the hard segment phase (domain composed of hard segments) of the thermoplastic polyurethane resin is, for example, 200° C. or higher, preferably 205° C. or higher, and more preferably 210° C. or higher. , for example, 250° C. or lower, preferably 240° C. or lower, more preferably 230° C. or lower, still more preferably 220° C. or lower.

Further, the melting enthalpy of the soft segment phase (domain composed of soft segments) of the thermoplastic polyurethane resin is, for example, 5 mJ/mg or more, preferably 10 mJ/mg or more, more preferably 15 mJ/mg or more, For example, it is 30 mJ/mg or less, preferably 25 mJ/mg or less, more preferably 20 mJ/mg or less, still more preferably 18 mJ/mg or less.

When the melting peak of the hard segment phase is within the above range and the melting enthalpy of the soft segment phase is within the above range, the thermoplastic polyurethane resin retains the cohesive force of the hard segment phase and the crystals of the soft segment phase. degeneration is suppressed. Therefore, breakage of the thermoplastic polyurethane resin during expansion and contraction can be suppressed, and excellent expansion and contraction properties can be obtained.

The melting peak of the hard segment phase and the melting enthalpy of the soft segment phase are obtained by differential scanning calorimetry (DSC measurement) according to the examples described later.

More specifically, the elastic property is evaluated by return stress and residual strain after repeated elongation deformation.

The return stress of the thermoplastic polyurethane resin (based on Examples described later) is, for example, 1.8 MPa or more, preferably 2.0 or more, more preferably 2.2 MPa or more, and for example, 3.0 MPa or less. be.

Also, the residual strain of the thermoplastic polyurethane resin (according to Examples described later) is, for example, 25% or more, and for example, 60% or less, preferably 55% or less, more preferably 50% or less.

That is, the above thermoplastic polyurethane resin can obtain excellent return stress while maintaining relatively low residual strain, and is excellent in stretchability.

The residual strain and return stress are measured in accordance with Examples described later.

Further, the above thermoplastic polyurethane resin is also excellent in heat resistance.

For example, the temperature at which the storage modulus (E′) of the thermoplastic polyurethane resin exhibits 1×10 ⁶ Pa (hereinafter referred to as the heat resistant temperature) is, for example, 160° C. or higher, preferably 170° C. or higher, more preferably , 180° C. or higher, more preferably 190° C. or higher, and for example, 250° C. or lower.

The heat resistance temperature is determined by dynamic viscoelasticity measurement in accordance with the examples described later.

The present invention also includes a molded article containing the thermoplastic polyurethane resin described above. A molded article is molded from a thermoplastic polyurethane resin.

For example, the above thermoplastic polyurethane resin is molded by a known molding method, such as heat compression molding and injection molding using a specific mold, extrusion molding using a sheet winding device, such as melt spinning. Thermoforming processing methods such as molding, for example, by 3D printer processing, for example, molding into various shapes such as pellets, plates, fibers, strands, films, sheets, pipes, hollows, and boxes. can be obtained by

Preferably, the molded article is an elastic fiber obtained by melt spinning.

Since the obtained molded article is a molded article of the thermoplastic polyurethane resin, it can have both stretchability and bloom resistance.

Therefore, the molded article can be suitably used in fields where the above various physical properties are required, and in particular, yarns and fibers (tubes, tights, spats, sportswear, sports goods, supporters, swimwear, etc.) composite fibers), monofilaments, films (elastic films for clothing, hot-melt films, wound covering films, etc.).

In addition to the above applications, the molded article can be widely used industrially, and specifically, for example, transparent hard plastics, coating materials, adhesives, adhesives, waterproof materials, potting agents, inks , binders, films (e.g. paint protection films, films such as chipping films, films for impregnating substrates such as soft carbon sheets), sheets, bands (e.g. bands such as watch bands, e.g. automobile transmission belts, Belts such as 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, hoses such as fire hoses), Blades, speakers, sensors, high-brightness LED encapsulants, organic EL components, photovoltaic 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, chandeliers, outdoor lights, sealing materials, sealing materials, cork, packing, vibration/damping/seismic isolation materials, soundproofing 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, eyeglasses Industrial products such as lenses, toys, cable sheaths, wire harnesses, telecommunication cables, automotive wiring, computer wiring, curled cords, nursing care products such as sheets and films, sporting goods, leisure goods, miscellaneous goods, anti-vibration materials, anti-vibration materials, Shock absorbers, optical materials, films such as light guide films, automobile parts, surface protection sheets, decorative sheets, transfer sheets, tape members such as semiconductor protective tape, golf ball members, strings for tennis rackets, agricultural films, wallpaper, Anti-fogging 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, sanitary items such as face wash puffs and pillows, shoes Footwear such as soles (outsoles), midsoles, and cover materials; body pressure dispersion products such as vehicle pads and cushions; Thermal insulation materials for buildings, shock absorbing materials such as shock absorbers, filling materials, vehicles steering wheels, automobile interior members, automobile exterior members and other vehicle articles, semiconductor manufacturing articles such as chemical mechanical polishing (CMP) pads, and the like.

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 resilience and wear resistance due to repeated expansion, contraction, and compression deformation.

Next, the present invention will be described based on Production Examples, Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to 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-BIC: 1,4-bis(isocyanatomethyl)cyclohexane synthesized by the method described in Production Examples 1 to 5 below <Amorphous polyether polyol (b)>
b-1) PTG-L (number average molecular weight (Mn) 2000): amorphous polyether glycol obtained by copolymerizing tetrahydrofuran and methyltetrahydrofuran; trade name; PTG-L2000; hydroxyl value = 56.2 mgKOH/g; b-2) PTG-L (number average molecular weight (Mn) 3000) manufactured by Tsuchiya Kagaku Kogyo Co., Ltd.: Amorphous polyether glycol obtained by copolymerizing tetrahydrofuran and methyltetrahydrofuran, trade name; PTG-L3000, hydroxyl value = 37. 3 mgKOH/g, manufactured by Hodogaya Chemical Industry Co., Ltd. b-3) PTG-L (number average molecular weight (Mn) 3500): Amorphous polyether glycol obtained by copolymerizing tetrahydrofuran and methyltetrahydrofuran; trade name: PTG-L3500; Hydroxyl value = 32.0 mgKOH/g, Hodogaya Chemical Co., Ltd. b-4) Velvetol (number average molecular weight (Mn) 2700): amorphous polytrimethylene ether glycol, trade name; Velvetol H2700, hydroxyl value = 41.9 mgKOH /g, manufactured by ALLESSA b-5) PTXG (number average molecular weight (Mn) 1800): amorphous polyether glycol obtained by copolymerizing tetrahydrofuran and neopentyl glycol, trade name; PTXG1800, hydroxyl value = 62.5 mgKOH/ g, manufactured by Asahi Kasei <Crystalline polyether polyol (b')>
b-6) PTMEG (number average molecular weight (Mn) 2000): polytetramethylene ether glycol, trade name; PTG2000SN, hydroxyl value = 56.3 mgKOH / g, manufactured by Hodogaya Chemical Co., Ltd. b-7) PTMEG (number average molecular weight (Mn) 3000): Polytetramethylene ether glycol, trade name: PTG3000SN, hydroxyl value = 37.2 mgKOH/g, b-8 manufactured by Hodogaya Chemical Industry Co., Ltd.) PTMEG (number average molecular weight (Mn) 3500): polytetramethylene Ether glycol, trade name; PTG3500SN, hydroxyl value = 32.6 mgKOH/g, b-9 manufactured by Hodogaya Chemical Industry Co., Ltd.) PTMEG (number average molecular weight (Mn) 4000): polytetramethylene ether glycol, trade name; PTMG4000, hydroxyl group Value = 29.1 mgKOH/g, manufactured by Mitsubishi Chemical Corporation <Low molecular weight polyol (c)>
1,4-BD: 1,4-butanediol, manufactured by Mitsubishi Chemical Corporation <Urethane catalyst>
Bismuth-based catalyst: Bismuth octylate, trade name: Neostan U-600, manufactured by Nitto Kasei <Catalyst diluent>
Diisononyl adipate: Product name: DINA, manufactured by Daihachi Chemical Industry Co., Ltd. <Surface modifier (lubricant)>
Ethylenebisoleylamide: unsaturated fatty acid amide, trade name Slipax O, manufactured by Mitsubishi Chemical Corporation Ethylenebisstearylamide: saturated fatty acid amide, trade name Kaowax EB-P, manufactured by Kao Chemical <Other additives>
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)>
・Production of 1,4-bis(isocyanatomethyl)cyclohexane (1,4-H ₆ XDI) Production Example 1 (1,4-bis(isocyanatomethyl)cyclohexane (1) (hereinafter referred to as 1,4-BIC ( 1) Manufacturing method)
While purging with nitrogen, 1,4-BIC (2) described in Production Example 2 described later was filled in a petroleum can and allowed to stand in an incubator at 1° C. for 2 weeks. The resulting coagulum was quickly filtered under reduced pressure using a 4 μm mesh membrane filter to remove the liquid phase and obtain the solid phase. 1,4-BIC(1) was obtained by repeating the above-described operations on the solid phase portion. 1,4-BIC(1) had a purity of 99.9% by gas chromatography, a hue of 5 by APHA, and a trans/cis ratio of 99.5/0.5 by ¹³ C-NMR. The hydrolyzable chlorine concentration (hereinafter referred to as HC concentration) was 18 ppm.

Production Example 2 (Method for producing 1,4-bis(isocyanatomethyl)cyclohexane (2) (hereinafter referred to as 1,4-BIC(2)))
According to the description of Production Example 6 of JP-A-2014-55229, 1,4-bis(aminomethyl)cyclohexane with a purity of 99.5% or more and a trans/cis ratio of 98/2 was obtained with a yield of 92%. Got at a rate.

Thereafter, in accordance with the description of Production Example 1 of JP-A-2014-55229, using this 1,4-bis(aminomethyl)cyclohexane as a raw material, a two-stage cold/heat phosgenation process was carried out under pressure to obtain 1 , 4-BIC(2).

The obtained 1,4-BIC (2) had a purity of 99.9% by gas chromatography, a hue of 5 by APHA measurement, and a trans/cis ratio of 98/2 by ¹³ C-NMR measurement. . HC concentration was 18 ppm.

Production Example 3 (Method for producing 1,4-bis(isocyanatomethyl)cyclohexane (3) (hereinafter referred to as 1,4-BIC(3)))
789 parts by mass of 1,4-BIC (2) of Production Example 2 and 1,4-BIC of Production Example 6 described later were placed in a four-necked flask equipped with a stirrer, thermometer, reflux tube, and nitrogen inlet tube. 211 parts by mass of (6) was charged and stirred at room temperature for 1 hour under nitrogen atmosphere. The obtained 1,4-BIC (3) had a purity of 99.9% by gas chromatography, a hue of 5 by APHA measurement, and a trans/cis ratio of 86/14 by ¹³ C-NMR measurement. HC concentration was 19 ppm.

Production Example 4 (Method for producing 1,4-bis(isocyanatomethyl)cyclohexane (4) (hereinafter referred to as 1,4-BIC(4)))
561 parts by mass of 1,4-BIC (2) of Production Example 2 and 1,4-BIC of Production Example 6 described later were added to a four-necked flask equipped with a stirrer, thermometer, reflux tube, and nitrogen inlet tube. 439 parts by mass of (6) was charged and stirred at room temperature for 1 hour under a nitrogen atmosphere. The obtained 1,4-BIC (4) had a purity of 99.9% by gas chromatography, a hue of 5 by APHA measurement, and a trans/cis ratio of 73/27 by ¹³ C-NMR measurement. HC concentration was 20 ppm.

Production Example 5 (Method for producing 1,4-bis(isocyanatomethyl)cyclohexane (5) (hereinafter referred to as 1,4-BIC(5)))
474 parts by mass of 1,4-BIC (2) of Production Example 2 and 1,4-BIC of Production Example 6 described later were added to a four-necked flask equipped with a stirrer, thermometer, reflux tube, and nitrogen inlet tube. 526 parts by mass of (6) was charged and stirred at room temperature for 1 hour under a nitrogen atmosphere. The obtained 1,4-BIC (5) had a purity of 99.9% by gas chromatography, a hue of 5 by APHA measurement, and a trans/cis ratio of 68/32 by ¹³ C-NMR measurement. HC concentration was 21 ppm.

Production Example 6 (Method for producing 1,4-bis(isocyanatomethyl)cyclohexane (6) (hereinafter referred to as 1,4-BIC(6)))
Using 1,4-bis(aminomethyl)cyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd.) with a trans/cis ratio of 41/59 as measured by ¹³ C-NMR, the production example 1 of JP-A-2014-55229 is used as a raw material. 1,4-BIC (6) was obtained according to the description.

The obtained 1,4-BIC (6) had a purity of 99.9% by gas chromatography, a hue of 5 by APHA measurement, and a trans/cis ratio of 41/59 by ¹³ C-NMR measurement. . HC concentration was 22 ppm.

2) Production of thermoplastic polyurethane resin Synthesis Examples 1-16, Reference Example 1 , Examples 2-3, Reference Examples 4-5, Examples 6-7, Reference Example 8, Examples 9-16 and Comparative Examples 1- 6
According to the formulations shown in Tables 1 and 2, the polyisocyanate component (a) and the amorphous polyether polyol (b) or crystalline polyether polyol (b') were mixed with a stirrer, a thermometer, a reflux tube and A four-necked flask equipped with a nitrogen inlet tube was charged, and the mixture was stirred at 80° C. for 1 hour under a nitrogen atmosphere.

After that, bismuth octylate (trade name: Neostan U-600, manufactured by Nitto Kasei Co., Ltd.) diluted in advance with DINA (manufactured by Daihachi Chemical Co., Ltd.) to 4% by mass was added to the polyisocyanate component (a) and the amorphous polyether. It was added so that the catalyst amount (solid content) was 2 ppm with respect to the total amount of polyol (b) or crystalline polyether polyol (b').

Then, under temperature control of 80° C., while stirring and mixing under a nitrogen stream, the reaction is advanced until the isocyanate group content shown in Tables 1 and 2 is reached, and the isocyanate group-terminated prepolymers (a) to (p) are obtained. Obtained.

After that, the isocyanate group concentration of the isocyanate group-terminated prepolymer was measured at 80°C.

Then, 1,4-butanediol (1,4-BD) as a low-molecular-weight polyol has an equivalent ratio (NCO index) of isocyanate groups in the isocyanate-terminated prepolymer to hydroxyl groups in the low-molecular-weight polyol of 1.01. The temperature was adjusted to 80° C. in a stainless steel cup.

The isocyanate group-terminated prepolymer was then weighed into another stainless steel cup. Then, with respect to the total amount of 100 parts by mass of the isocyanate group-terminated prepolymer and 1,4-BD, Irganox 245 (BASF Corporation heat stabilizer) 2 parts by mass, Tinuvin 234 (BASF Corporation UV absorber) 0.3 Each additive was added to the isocyanate group-terminated prepolymer at a rate of 0.3 parts by mass of ADEKA STAB LA-72 (HALS manufactured by ADEKA).

Furthermore, in addition to Example 4, ethylene bisoleylamide (non Saturated fatty acid amide, trade name Slipax O, manufactured by Mitsubishi Chemical Corporation) or ethylene bisstearylamide (saturated fatty acid amide, trade name Kaowax EB-P, manufactured by Kao Chemical Co., Ltd.) was added to the isocyanate group-terminated prepolymer.

Thereafter, the isocyanate group-terminated prepolymer was stirred and mixed for 3 minutes in an oil bath at 80° C. under stirring at 1000 to 3000 rpm using a high-speed stirring disper.

Then, 1,4-BD preliminarily weighed and adjusted to 80° C. was added to the isocyanate group-terminated prepolymer, and stirred and mixed for 3 to 10 minutes under stirring at 1000 to 3000 rpm using a high-speed stirring disper. .

Next, the mixed liquid was poured into a Teflon (registered trademark) vat whose temperature was adjusted to 150° C. in advance, 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 a thermoplastic polyurethane. Resin primary products (A) to (V) were obtained.

Next, the primary products (A) to (V) of the thermoplastic polyurethane resin were removed from the vat, cut into dice with a bale cutter, and the dice-shaped resin was pulverized with a pulverizer to obtain pulverized pellets.

Next, the pulverized pellets were heat-treated (cured and aged) under conditions of a heat treatment temperature of 80° C. and a heat treatment period of 5 days, and dried at 80° C. for 12 hours under vacuum and reduced pressure.

After that, using the obtained pulverized pellets, a single screw extruder (model: SZW40-28MG, manufactured by Technobel) is used to extrude and cut strands at a screw rotation speed of 30 rpm and a cylinder temperature of 200 to 270 ° C. to obtain pellets of thermoplastic polyurethane resins (A) to (V).

Example 17 (fiber (molded article))
Pellets of the thermoplastic polyurethane resin (B) of Example 2 were dried in advance at 80° C. for 12 hours under vacuum and reduced pressure.

Next, using a capillary rheometer (model: Capilograph 1C, manufactured by Toyo Seiki Co., Ltd.), a thermoplastic polyurethane resin is extruded from a die (L/D = 30 mm/1 mm) at a piston speed of 100 mm/min and a cylinder temperature of 230°C, A fiber with a diameter of 70 μm was obtained by taking it up with a take-up device.

Thereafter, the obtained fibers were cured for 7 days under constant temperature and humidity conditions of room temperature 23° C. and relative humidity 55% to obtain polyurethane fibers.

As a result of measuring the return stress and residual strain after repeated elongation deformation described later using this, the return stress was 2.3 MPa and the residual strain was 43%.

3) Molding of sample for evaluation <Method of molding polyurethane film>
Pellets of thermoplastic polyurethane resins (A) to (V) are dried in advance at 80° C. for 12 hours under vacuum and reduced pressure, and are extruded by screw rotation using a single screw extruder (model: SZW40-28MG, manufactured by Technobell). At several 20 rpm and a cylinder temperature of 200 to 270° C., the resin was extruded from a T-die and taken up by a belt conveyor. This gave films with a thickness of 100 μm and 10 μm.

The resulting film was cured for 7 days under constant temperature and humidity conditions of room temperature of 23° C. and relative humidity of 55% to obtain a polyurethane film.

4) Evaluation <Melting enthalpy of soft segment phase (unit: mJ/mg)/Melting peak temperature of hard segment phase (unit: °C)>
A differential scanning calorimeter (trade name: EXSTAR6000 PC Station and DSC220C, manufactured by SII Nanotechnology Co., Ltd.) was used to measure as follows.

That is, about 8 mg of the polyurethane film was thinly cut into a shape that can be adhered to the aluminum pan as much as possible. 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 was cooled to -100 ° C. at a rate of 10 ° C./min under a nitrogen stream with a flow rate of 40 NmL / min. The temperature was raised to 270°C at a speed of min.

Among the endothermic peaks that appear during this temperature rise, the heat of fusion of the endothermic peak that appears below the melting point of the amorphous polyether polyol (b) (or crystalline polyether polyol (b′)) used is the soft segment phase. was defined as the melting enthalpy of (unit: mJ/mg).

In addition, among the endothermic peaks appearing on the higher temperature side than the melting point of the amorphous polyether polyol (b) (or crystalline polyether polyol (b′)) used, the endothermic peak temperature showing the highest temperature is defined as the hard segment phase was defined as the melting peak temperature (unit: ° C.).

The melting point and melting enthalpy of the amorphous polyether polyol (b) (or crystalline polyether polyol (b')), which are used as reference points in the above measurements, are measured using a differential scanning calorimeter (SII Nanotechnology Measured as follows using EXSTAR6000 PC Station and DSC220C (manufactured by the same company).

That is, about 8 mg of amorphous polyether polyol (b) (or crystalline polyether polyol (b')) was collected in a sealed aluminum pan. A sample for measurement was obtained by covering and crimping the closed pan made of aluminum with a cover. 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 was heated to 100 ° C. at a rate of 10 ° C./min under a nitrogen stream with a flow rate of 40 NmL / min. The temperature was lowered to -100°C at a speed of min.

Regarding the exothermic peak that appears during this temperature decrease, the peak temperature is the melting point (unit: ° C.) of the amorphous polyether polyol (b) (or the crystalline polyether polyol (b')), and the heat of fusion of the same peak is , melting enthalpy (unit: mJ/mg).

<Return stress (unit: MPa)>
A strip-shaped test piece with a width of 10 mm was cut out from a polyurethane film with a thickness of 100 μm, stretched to an elongation of 300% under conditions of a distance between chucks of 60 mm and a stretching speed of 500 mm/min, and then returned to the origin, and the operation was repeated three times.

When returning to the origin from 300% elongation in the third cycle, the stress at which the elongation showed 200% was measured as the return stress after repeated elongation deformation.

<Residual strain (unit: %)>
A strip-shaped test piece with a width of 10 mm was cut from a polyurethane film with a thickness of 10 μm, stretched to an elongation of 300% under conditions of a distance between chucks of 60 mm and an expansion and contraction rate of 500 mm/min, and the operation of returning to the origin was repeated three times. The elongation when the stress showed 0 MPa when returning to the origin from the elongation of 300% in the third cycle was measured as the residual strain after repeated elongation deformation.

<Heat resistant temperature>
A strip-shaped test piece with a width of 10 mm was cut out from a polyurethane film with a thickness of 100 μm, and a dynamic viscoelasticity measuring device (manufactured by IT Keisoku Co., Ltd., model: DVA-220) was used to measure the starting temperature of -100 ° C. A dynamic viscoelastic spectrum was measured under the conditions of a heating rate of 5° C./min, a tensile mode, a gauge length of 20 mm, a static/dynamic stress ratio of 1.8, and a measurement frequency of 10 Hz.

Then, in the dynamic viscoelastic spectrum in the temperature region (rubber-like region) at which the storage elastic modulus E′ is 1×10 ⁶ Pa (that is, the temperature region (rubber-like region) higher than the glass transition temperature (Tg), the storage elastic modulus E′ is 1 ×10 ⁶ Pa) was defined as the heat resistant temperature.

<Bloom resistance>
A 10 cm square piece was cut out from a polyurethane film having a thickness of 100 μm, and was allowed to stand under constant temperature and humidity conditions at a room temperature of 23° C. and a relative humidity of 55%. It was evaluated on a scale of 5 out of 5.
Evaluation 5: No dusting phenomenon occurred within 7 days of the test.
Evaluation 4: Powder blowing occurs within 7 days of the test.
Evaluation 3: Powder blowing occurs within 5 days of the test.
Evaluation 2: Powder blowing occurs within 3 days of the test.
Evaluation 1: Powder blowing occurs within 1 day of the test.

Claims (6)

a polyisocyanate component comprising bis(isocyanatomethyl)cyclohexane;
A thermoplastic polyurethane resin which is a reaction product with a polyol component containing a low molecular weight polyol having a molecular weight of 400 or less and an amorphous polyether polyol having a number average molecular weight of 2500 or more and 4000 or less,
containing unsaturated fatty acid amides,
A thermoplastic polyurethane resin, wherein the content of the unsaturated fatty acid amide is 0.01% by mass or more and 0.5% by mass or less with respect to the total amount of the thermoplastic polyurethane resin. The thermoplastic polyurethane resin of claim 1, wherein said bis(isocyanatomethyl)cyclohexane comprises 1,4-bis(isocyanatomethyl)cyclohexane. 3. The thermoplastic polyurethane resin according to claim 2 , wherein the 1,4-bis(isocyanatomethyl)cyclohexane contains a trans isomer at a ratio of 70 mol % or more and 99 mol % or less. A molded article comprising the thermoplastic polyurethane resin according to any one of claims 1 to 3. 5. The molded article according to claim 4, which is an elastic fiber obtained by melt spinning. A step of reacting a polyisocyanate component containing bis(isocyanatomethyl)cyclohexane and an amorphous polyether polyol having a number average molecular weight of 2500 or more and 4000 or less to obtain an isocyanate group-terminated prepolymer;
a step of reacting the isocyanate group-terminated prepolymer and a low molecular weight polyol having a molecular weight of 400 or less to obtain a thermoplastic polyurethane resin;
Furthermore, comprising a step of adding an unsaturated fatty acid amide to the thermoplastic polyurethane resin,
A method for producing a thermoplastic polyurethane resin, wherein the content of the unsaturated fatty acid amide is 0.01% by mass or more and 0.5% by mass or less with respect to the total amount of the thermoplastic polyurethane resin.