WO2011125540A1

WO2011125540A1 - Thermoplastic polyurethane resin and molded article

Info

Publication number: WO2011125540A1
Application number: PCT/JP2011/057325
Authority: WO
Inventors: 泰之添田; 長二郎樋口; 敏弘田中; イー李; 誠助川
Original assignee: 三井化学株式会社
Priority date: 2010-03-31
Filing date: 2011-03-25
Publication date: 2011-10-13
Also published as: JPWO2011125540A1

Abstract

Disclosed is a thermoplastic polyurethane resin which is obtained by at least having a polyisocyanate, a high molecular weight polyol and a chain extender react with each other. The chain extender contains an amide group-containing diol that is represented by general formula (1), and the content of a hard segment that is formed by the reaction between the polyisocyanate and the amide group-containing diol is 30-60% by mass relative to the total mass of the thermoplastic polyurethane resin. HO-R²-CO-NH-R¹-NH-CO-R³-OH (1) (In the formula, R¹ represents a divalent aliphatic hydrocarbon group having 2-8 carbon atoms, a divalent alicycle-containing hydrocarbon group having 3-8 carbon atoms or a divalent aromatic aliphatic hydrocarbon group having 7 or 8 carbon atoms; and R² and R³ may be the same or different and each represents a divalent aliphatic hydrocarbon group having 1-5 carbon atoms or a divalent alicycle-containing hydrocarbon group having 3-5 carbon atoms.)

Description

Thermoplastic polyurethane resins and molded products

The present invention relates to a thermoplastic polyurethane resin and a molded product.

The polyurethane resin is manufactured, for example, as a thermosetting polyurethane resin (cast polyurethane resin), a thermoplastic polyurethane resin, a kneaded polyurethane resin (millable polyurethane resin), etc., for example, an elastomer, an elastic molded product (spandex), Widely used as RIM molded products, foam molded products and the like.

Thermoplastic polyurethane resin (TPU) is a rubber elastic body obtained by reaction of polyisocyanate, high molecular weight polyol and chain extender (low molecular weight polyol), and is a hard segment formed by reaction of polyisocyanate and chain extender And a soft segment formed by the reaction of polyisocyanate and high molecular weight polyol.

In such a thermoplastic polyurethane resin, various physical properties such as elastic modulus can be adjusted by changing the types and blending ratios of polyisocyanate, high molecular weight polyol and chain extender. Excellent properties such as strength (such as tensile strength) can be ensured.

Therefore, thermoplastic polyurethane resins are used as molding materials in thermoplastic resin molding methods such as extrusion molding and injection molding, for example, shoe soles and insoles, ski shoes, automobile exterior parts and interior parts. It is often used in various industrial fields such as electrical parts, casters, rolls, hoses, tubes, sheets and fibers.

On the other hand, a kneaded polyurethane resin is a polyurethane resin that does not substantially contain a hard segment, and can be easily kneaded and molded by using, for example, a rubber kneader and can be cured by vulcanization. For example, it is often used in a transport belt, a drive belt, a transport roll, a drive roll, and the like.

As such a kneaded polyurethane resin, for example, 4,4′-diaminodiphenylmethane, 4,4′-diaminodicyclohexylmethane, hexamethylenediamine, ethylenediamine, butylenediamine, p- A polymerization initiator composed of an amine compound such as phenylenediamine is reacted with ε-caprolactone to produce an amide group-containing poly-ε-caprolactone diol having an average chain number of ε-caprolactone of about 6, and then obtained. A method of producing a millable urethane type polyamide ester urethane by reacting the obtained amide group-containing poly-ε-caprolactone diol with 4,4′-diphenylmethane diisocyanate has been proposed (for example, Patent Document 1 below) See Examples 1-12).)

JP 2000-302864 A

On the other hand, thermoplastic polyurethane resins are also required to be improved in heat resistance, thermal stability and mechanical strength.

However, since the thermoplastic polyurethane resin needs to be melted and molded again after synthesis, it is necessary to improve heat resistance, thermal stability and mechanical strength while maintaining thermoplasticity.

An object of the present invention is to provide a thermoplastic polyurethane resin having excellent mechanical strength, excellent heat resistance and thermal stability, and a molded product obtained by molding the thermoplastic polyurethane resin.

The thermoplastic polyurethane resin of the present invention is a thermoplastic polyurethane resin obtained by reacting at least a polyisocyanate, a high molecular weight polyol, and a chain extender, and the chain extender is represented by the following general formula (1 The hard segment content formed by the reaction of the polyisocyanate and the amide group-containing diol is 30 to 60 with respect to the total amount of the thermoplastic polyurethane resin. It is characterized by mass%.

HO—R ² —CO—NH—R ¹ —NH—CO—R ³ —OH (1)
(In the formula, R ¹ is a divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms, or a divalent aliphatic group having 7 to 8 carbon atoms. Each represents an araliphatic hydrocarbon group, and R ² and R ³ are the same or different from each other and represent a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms or a divalent fatty acid having 3 to 5 carbon atoms. Indicates a ring-containing hydrocarbon group.)
In the thermoplastic polyurethane resin of the present invention, it is preferable that the amide group-containing diol is represented by the following general formula (2).

HO— (CH ₂ ) ₅ —CO—NH—R ¹ —NH—CO— (CH ₂ ) ₅ —OH (2)
(Wherein, ^{R 1} represents the same meaning as ^{R 1} in the formula (1).)
In the thermoplastic polyurethane resin of the present invention, it is preferable that the amide group-containing diol is obtained by a reaction between an aliphatic diamine and hydroxycarboxylic acid or a derivative thereof.

In the thermoplastic polyurethane resin of the present invention, the high-molecular-weight polyol contains an oxyethylene group, and the content of the oxyethylene group is 20% by mass or more, based on the total amount of the thermoplastic polyurethane resin. It is suitable that it is below mass%.

Moreover, in the thermoplastic polyurethane resin of this invention, it is suitable that the water vapor transmission rate when it is set as a 20-micrometer-thick film is 10,000 g / m < ² > * 24h or more.

In the thermoplastic polyurethane resin of the present invention, it is preferable that the softening temperature is 160 ° C. or higher.

The molded article of the present invention is characterized by being obtained by molding the thermoplastic polyurethane resin.

Further, the molded article of the present invention is preferably obtained by molding the thermoplastic polyurethane resin into a film.

Further, it is preferable that the molded article of the present invention is obtained by extrusion molding of the thermoplastic polyurethane resin.

The molded product of the present invention is prepared by dissolving the thermoplastic polyurethane resin in an aprotic polar solvent to prepare a thermoplastic polyurethane resin solution, and then removing the aprotic polar organic solvent from the solution. It is suitable to form as a film by removing.

In the thermoplastic polyurethane resin of the present invention, the chain extender as a raw material contains the amide group-containing diol represented by the general formula (1), and a hard segment obtained by reaction of the chain extender and polyisocyanate. Is adjusted to 30 to 60% by mass with respect to the total amount of the thermoplastic polyurethane resin, so that excellent mechanical strength can be ensured and excellent heat resistance and thermal stability can be provided.

The heat resistance refers to the resistance to heat deformation of the resin accompanying heat rise (heat deformation resistance), the resistance to deterioration of physical properties after heating, and the resistance to decomposition of the primary structure of the resin due to heating (heat decomposition resistance). It is distinguished from The thermal stability corresponds to the above-mentioned thermal decomposition resistance.

Moreover, since the molded article of the present invention can be obtained by molding the thermoplastic polyurethane resin of the present invention, it can be produced efficiently.

The thermoplastic polyurethane resin of the present invention is a polyurethane resin that can be heated and melted again after synthesis, and is distinguished from a thermosetting polyurethane resin (cast polyurethane resin) that cannot be heated and melted after synthesis.

Therefore, the thermoplastic polyurethane resin can be once molded as a molding material such as pellets, and then molded into an arbitrary shape by, for example, extrusion molding or injection molding.

Such a thermoplastic polyurethane resin can be obtained by reacting at least a polyisocyanate, a high molecular weight polyol, and a chain extender.

Such a thermoplastic polyurethane resin, which will be described in detail later, is a hard segment formed by at least the reaction of the polyisocyanate and the chain extender with the soft segment formed by the reaction of the polyisocyanate and the high molecular weight polyol. With segments.

Polyisocyanate is an organic compound having two or more isocyanate groups, and examples thereof include diisocyanates such as aromatic diisocyanates, araliphatic diisocyanates, alicyclic diisocyanates, and aliphatic diisocyanates.

Examples of the aromatic diisocyanate include m- or p-phenylene diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof (TDI), 4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or mixtures thereof (MDI), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI) Etc.

Examples of the araliphatic diisocyanate 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), ω , Ω′-diisocyanate-1,4-diethylbenzene, and the like.

Examples of the alicyclic diisocyanate include 1,3-cyclopentene diisocyanate, 1,3- or 1,4-cyclohexane diisocyanate or a mixture thereof (CHDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate ( Isophorone diisocyanate (IPDI), 4,4'-, 2,4'- or 2,2'-dicyclohexylmethane diisocyanate or mixtures thereof (hydrogenated MDI, H ₁₂ MDI), methyl-2,4-cyclohexane diisocyanate, methyl- 2,6-cyclohexane diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or mixtures thereof (hydrogenated XDI, H ₆ XDI), bis (isocyanatomethyl) norbornane (NBDI), etc. Can be mentioned.

Examples of the aliphatic diisocyanate include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,2-, 2,3- or 1,3. -Butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate and the like.

Further, examples of the polyisocyanate include derivatives of the above-mentioned diisocyanates (aromatic diisocyanates, araliphatic diisocyanates, alicyclic diisocyanates, aliphatic diisocyanates, etc.).

Examples of the diisocyanate derivatives include the above-described diisocyanate multimers (eg, dimers, trimers (eg, isocyanurate-modified products, iminooxadiazine dione-modified products), pentamers, and 7-mers). , Allophanate-modified products (for example, allophanate-modified products generated from the reaction of the above-mentioned diisocyanates with alcohols), polyol-modified products (for example, polyol-modified products generated from the reaction of diisocyanate and low molecular weight polyols (described later) ( Polyol adducts, urethane modified products, etc.), biuret modified products (for example, biuret modified products produced by reaction of the above-mentioned diisocyanates with water and amines), urea modified products (for example, the above-mentioned diisocyanates and diamines) Modified urea produced by the reaction of , Oxadiazine trione-modified products (for example, oxadiazine trione produced by the reaction of the above-mentioned diisocyanate and carbon dioxide gas), carbodiimide-modified products (carbodiimide-modified product produced by the above-mentioned decarboxylation condensation reaction of diisocyanate), Examples include modified uretdione and modified uretonimine.

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

The polyisocyanate is preferably m- or p-phenylene diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof (TDI), 4,4'-, 2,4'- or 2 , 2'-Diphenylmethane diisocyanate or its mixture (MDI), 1,5-naphthalene diisocyanate (NDI)
1,3- or 1,4-xylylene diisocyanate or a mixture thereof (XDI), 1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof (TMXDI), 1,4- or 1,3- Cyclohexane diisocyanate or mixtures thereof (CHDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate; IPDI), 4,4'-, 2,4'- or 2,2'-dicyclohexylmethane Diisocyanate or a mixture thereof (hydrogenated MDI, H ₁₂ MDI), 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or a mixture thereof (hydrogenated XDI, H ₆ XDI), bis (isocyanatomethyl) norbornane (NBDI), penta Examples include methylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), and derivatives thereof. More preferably, m- or p-phenylene diisocyanate or a mixture thereof, 4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or a mixture thereof (MDI), 1,5-naphthalene diisocyanate (NDI) 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate; IPDI), 4,4'-, 2,4'- or 2,2'-dicyclohexylmethane diisocyanate or mixtures thereof (hydrogenated MDI , H ₁₂ MDI), 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or mixtures thereof (hydrogenated XDI, H ₆ XDI), bis (isocyanatomethyl) norbornane (NBDI), hexamethylene diisocyanate ( HDI), And derivatives thereof, more preferably m- or p-phenylene diisocyanate or a mixture thereof, 4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or a mixture thereof (MDI), 4,4'-, 2,4'- or 2,2'-dicyclohexylmethane diisocyanate or mixtures thereof (hydrogenated MDI, H ₁₂ MDI), 1,5-naphthalene diisocyanate (NDI), and their isocyanurate modification Body, polyol modified body (polyol adduct, urethane modified body), carbodiimide modified body, uretonimine modified body.

The high molecular weight polyol is an organic compound having two or more hydroxyl groups and a number average molecular weight of 400 or more. For example, polyether polyol, polyester polyol, polycarbonate polyol, acrylic polyol, epoxy polyol, natural oil polyol, silicone polyol, fluorine polyol , Macropolyols such as polyolefin polyol and polyurethane polyol.

The polyether polyol is, for example, a low molecular weight polyol (described later) and / or a low molecular weight polyamine (described later) as an initiator, and an alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, 3-methyltetrahydrofuran, Ring-opening addition polymerization of an alkylene oxide having 2 to 5 carbon atoms such as an oxetane compound (homopolymerization or copolymerization (when ethylene oxide and propylene oxide are used in combination as alkylene oxide, block copolymerization and / or random copolymerization) Polymerization)).

The low molecular weight polyol is an organic compound having two or more hydroxyl groups and a number average molecular weight of less than 400, such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butane. Diol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1, 5-pentanediol, 1,6-hexanediol, 2,6-dimethyl-1-octene-3,8-diol, alkane (carbon number 7 to 22) diol, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, bishydroxyethoxybenzene, xyl Glycol, bishydroxyethylene terephthalate, bisphenol A, diethylene glycol, trioxyethylene glycol, tetraoxyethylene glycol, pentaoxyethylene glycol, hexaoxyethylene glycol, dipropylene glycol, trioxypropylene glycol, tetraoxypropylene glycol, pentaoxypropylene Dihydric alcohols such as glycol and hexaoxypropylene glycol such as glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6- Hexanetriol, trimethylolpropane, 2,2-bis (hydroxymethyl) -3-butanol and other aliphatic triols ( A trihydric alcohol such as a prime number of 8 to 24), for example, tetramethylolmethane (pentaerythritol), a tetrahydric alcohol such as diglycerin, for example, a pentahydric alcohol such as xylitol, such as sorbitol, mannitol, allitol, iditol, dulcitol, Examples thereof include hexahydric alcohols such as altitol, inositol and dipentaerythritol, for example, 7-valent alcohols such as perseitol, and 8-valent alcohols such as sucrose. The polyhydric alcohol also includes an addition polymer (polyoxyalkylene polyol) obtained by adding an alkylene oxide such as propylene oxide or ethylene oxide to the above-mentioned mono- to octahydric alcohol.

Examples of the low molecular weight polyamine include ethylenediamine, 1,3-propanediamine, 1,3- or 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine, and 3-aminomethyl-3. , 5,5-trimethylcyclohexylamine (isophoronediamine), 4,4'-dicyclohexylmethanediamine, 2,5 (2,6) -bis (aminomethyl) bicyclo [2.2.1] heptane, 1,3- Low molecular weight diamines such as bis (aminomethyl) cyclohexane, hydrazine, o, m or p-tolylenediamine (TDA, OTD), for example, low molecular weight triamines such as diethylenetriamine, such as triethylenetetramine, tetraethylenepentamine, etc. Low molecular weight polyamines with 4 or more amino groups Is mentioned.

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

As the initiator, a low molecular weight polyol is preferably used.

More specifically, as the polyether polyol, polyethylene glycol, polypropylene glycol and / or polyethylene obtained by addition reaction of an alkylene oxide such as ethylene oxide and / or propylene oxide with the above-described low molecular weight glycol as an initiator. Polyoxy C2-3 alkylene (ethylene and / or propylene) glycols such as polypropylene glycol (random or block copolymers).

In addition, for example, polytetramethylene ether glycol (polyoxybutylene glycol) obtained by ring-opening polymerization of tetrahydrofuran, etc., and amorphous (liquid at room temperature) obtained by copolymerizing the above dihydric alcohol with a polymerization unit of tetrahydrofuran. Polytetramethylene ether glycol, and polyoxy C2-4 alkylene glycol obtained by copolymerizing tetrahydrofuran and alkylene oxide such as ethylene oxide and / or propylene oxide.

Examples of the polyester polyol include a condensation reaction or ester of a polyhydric alcohol selected from one or more of low molecular weight polyols, a polybasic acid, an alkyl ester thereof, an acid anhydride thereof, and an acid halide thereof. The polyester polyol obtained by exchange reaction is mentioned.

Examples of the low molecular weight polyol include the low molecular weight polyol described above.

Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, adipic acid, 2,2-dimethylmalonic acid, 2,2-dimethylglutaric acid, 1,1-dimethyl-1, 3-dicarboxypropane, 3-methyl-3-ethylglutaric acid, methylhexanedioic acid, suberic acid, azelaic acid, sebacic acid, other aliphatic dicarboxylic acids (11 to 20 carbon atoms), hydrogenated dimer acid, maleic Examples thereof include acid, fumaric acid, itaconic acid, citraconic acid, orthophthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, dimer acid and het acid.

Examples of the polybasic acid alkyl ester include the above-mentioned polybasic acid methyl ester and ethyl ester.

Examples of the acid anhydride include acid anhydrides derived from the above-mentioned polybasic acids. For example, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl anhydride (having 12 to 18 carbon atoms) ) Succinic acid, tetrahydrophthalic anhydride, trimellitic anhydride and the like.

Examples of the acid halide include acid halides derived from the polybasic acids described above, and examples include oxalic acid dichloride, adipic acid dichloride, and sebacic acid dichloride.

Examples of polyester polyols include hydroxyl group-containing vegetable oil fatty acids (for example, castor oil fatty acid containing ricinoleic acid, hydrogenated castor oil fatty acid containing 12-hydroxystearic acid, etc.) using the above-described low molecular weight polyol as an initiator. Examples thereof include vegetable oil-based polyester polyols obtained by subjecting hydroxycarboxylic acid to a condensation reaction under known conditions.

Examples of polyester polyols include polycaprolactone polyols and polyvalerolactone polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone using the above-described low molecular weight polyols as initiators. And lactone polyester polyols obtained by copolymerizing these dihydric alcohols with polycaprolactone polyols, polyvalerolactone polyols, and the like.

Examples of the polycarbonate polyol include polycarbonate polyol obtained by addition polymerization of carbonates such as ethylene carbonate and dimethyl carbonate using the above-described low molecular weight polyol as an initiator. The polycarbonate polyol includes an amorphous polycarbonate diol composed of a copolymer of 1,5-pentanediol and 1,6-hexanediol, and a copolymer of 1,4-butanediol and 1,6-hexanediol. An amorphous polycarbonate diol composed of 3-methyl-1,5-pentanediol, and an amorphous polycarbonate diol composed of 3-methyl-1,5-pentanediol.

Examples of the acrylic polyol include a copolymer obtained by copolymerizing a polymerizable monomer having one or more hydroxyl groups and another monomer copolymerizable therewith.

Examples of the polymerizable monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2,2-dihydroxymethylbutyl (meth) acrylate, polyhydroxy Examples thereof include alkyl maleates and polyhydroxyalkyl fumarate.

Further, as other monomers copolymerizable therewith, for example, (meth) acrylic acid, alkyl (meth) acrylate (C1-12), maleic acid, alkyl maleate, fumaric acid, fumaric acid Alkyl, itaconic acid, alkyl itaconate, styrene, α-methylstyrene, vinyl acetate, (meth) acrylonitrile, 3- (2-isocyanato-2-propyl) -α-methylstyrene, trimethylolpropane tri (meth) acrylate, Examples include pentaerythritol tetra (meth) acrylate.

The acrylic polyol can be obtained by copolymerizing these monomers in the presence of a suitable solvent and a polymerization initiator.

Examples of the epoxy polyol include an epoxy polyol obtained by reacting the above-described low molecular weight polyol with a polyfunctional halohydrin such as epichlorohydrin or β-methylepichlorohydrin.

Examples of the natural oil polyol include hydroxyl group-containing natural oils such as castor oil and coconut oil.

As the silicone polyol, for example, in the copolymerization of the acrylic polyol described above, a vinyl group-containing silicone compound such as γ-methacryloxypropyltrimethoxysilane is used as another copolymerizable monomer. Examples include coalesced and terminal alcohol-modified polydimethylsiloxane.

As the fluorine polyol, for example, in the copolymerization of the above-mentioned acrylic polyol, a copolymer containing a vinyl group-containing fluorine compound, for example, tetrafluoroethylene, chlorotrifluoroethylene, etc., as another copolymerizable monomer Etc.

Examples of the polyolefin polyol include polybutadiene polyol and partially saponified ethylene-vinyl acetate copolymer.

The polyurethane polyol reacts the above-mentioned macropolyol (for example, polyester polyol, polyether polyol, polycarbonate polyol, etc.) with the polyisocyanate at a ratio in which the equivalent ratio of hydroxyl group to isocyanate group (OH / NCO) exceeds 1. Thus, it can be obtained as a polyester polyurethane polyol, a polyether polyurethane polyol, a polycarbonate polyurethane polyol, or a polyester polyether polyurethane polyol.

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

As the high molecular weight polyol, from the viewpoint of moisture permeability, polyether polyol, polyester polyol, polycarbonate polyol, acrylic polyol, polyolefin polyol, and polyurethane polyol are preferable, and polyethylene glycol, polypropylene glycol, polyethylene polypropylene glycol, Examples thereof include polytetramethylene ether glycol, a copolymer of tetrahydrofuran and alkylene oxide, and polyester polyol.

The high molecular weight polyol is particularly preferably a polyether polyol having an oxyethylene group from the viewpoint of moisture permeability, and specifically, polyethylene glycol, polypropylene glycol, polyethylene polypropylene glycol (random or block copolymer). ), And a copolymer of tetrahydrofuran and ethylene oxide.

The number average molecular weight of the high molecular weight polyol is, for example, 400 to 5000, preferably 1000 to 4000, and more preferably 1500 to 3000.

The hydroxyl value of the high molecular weight polyol is, for example, 22 to 280 mgKOH / g, preferably 28 to 112 mgKOH / g, more preferably 37 to 75 mgKOH / g.

The hydroxyl value can be determined from an acetylation method, a phthalation method, or the like based on JIS K 1557-1 Method A or Method B.

The chain extender contains an amide group-containing diol.

The amide group-containing diol is an amide group-containing organic compound having two hydroxyl groups, and is represented by the following general formula (1).

HO—R ² —CO—NH—R ¹ —NH—CO—R ³ —OH (1)
(In the formula, R ¹ is a divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms, or a divalent aliphatic group having 7 to 8 carbon atoms. Represents an araliphatic hydrocarbon group, and R ² and R ³ are the same or different from each other and contain a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms or a divalent alicyclic ring having 3 to 5 carbon atoms Indicates a hydrocarbon group.)
In the above formula (1), R ¹ is a divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms, or a 7 to 8 carbon atom. A divalent araliphatic hydrocarbon group is shown.

In R ¹ , examples of the divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms include a divalent linear or branched aliphatic hydrocarbon group having 2 to 8 carbon atoms.

Examples of the linear aliphatic hydrocarbon group include an ethylene group, a propylene group, a butylene group (tetramethylene group), a pentylene group (pentamethylene group), a hexylene group (hexamethylene group), and a heptylene group (heptamethylene group). ), Linear alkylene groups having 2 to 8 carbon atoms such as octylene group (octamethylene group), for example, linear alkylene groups having 2 to 8 carbon atoms such as vinylene group, propenylene group, butenylene group, butadienylene group, octenylene group, etc. Examples thereof include alkenylene groups such as linear alkynylene groups having 2 to 8 carbon atoms such as ethynylene group, propynylene group, butynylene group, pentynylene group, octenylene group and the like.

Examples of the branched aliphatic hydrocarbon group include a branched alkylene group having 3 to 8 carbon atoms such as a methylethylene group, a methylpropylene group, an ethylpropylene group, a dimethylpropylene group, and a 2-ethylhexylene group, for example, Examples thereof include branched alkenylene groups having 3 to 8 carbon atoms such as methylethynylene group, methylpropenylene group and methylbutenylene group, for example, branched alkynylene groups having 4 to 8 carbon atoms such as methylpropynylene group and methylbutynylene group.

In R ¹ , the divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms may contain one or more alicyclic hydrocarbons in the hydrocarbon group. An aliphatic hydrocarbon group or the like may be bonded to the hydrocarbon. In such a case, the nitrogen atom (—NH—) bonded to R ¹ may be directly bonded to the alicyclic hydrocarbon, and the aliphatic hydrocarbon group bonded to the alicyclic hydrocarbon. Or both of them may be used.

More specifically, examples of the alicyclic hydrocarbon group include 3 to 8 carbon atoms such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and a cyclooctylene group. And the like.

Examples of the alicyclic hydrocarbon group containing an aliphatic hydrocarbon group include a methylcyclohexylene group, a hydrogenated xylylene group, a cyclohexylmethylene group, and a norbornylene group.

In R ¹ , the divalent araliphatic hydrocarbon group having 7 to 8 carbon atoms may contain an aromatic hydrocarbon in the hydrocarbon group. For example, the aromatic hydrocarbon includes an aliphatic hydrocarbon A hydrocarbon group or the like may be bonded. In such a case, the nitrogen atom (—NH—) bonded to R ¹ may be directly bonded to the aromatic hydrocarbon or bonded to the aliphatic hydrocarbon group bonded to the aromatic hydrocarbon. Or both of them.

As such aromatic ring-containing hydrocarbon group, more specifically, for example, a phenylenemonomethylene group (—C ₆ H ₄ —CH ₂ —), a xylylene group (phenylenebis (methylene) group (—CH ₂ —C)) _And an aralkylene group having 7 to 8 carbon atoms such as ₆ H ₄ —CH ₂ —)).

Further, the hydrocarbon group (aliphatic hydrocarbon group, alicyclic hydrocarbon group and araliphatic hydrocarbon group) can include a stable bond such as an ether bond, a thioether bond or an ester bond. .

More specifically, as such a hydrocarbon group, for example, an alkylene ether group (carbon containing an ether bond) such as a dimethylene ether group, a diethylene ether group, a triethylene ether group, a dipropylene ether group, or a tripropylene ether group. And divalent aliphatic hydrocarbon groups of 2 to 8).

R ¹ is preferably a divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms, more preferably a divalent linear aliphatic hydrocarbon group having 2 to 8 carbon atoms, from the viewpoint of heat resistance. More preferred are ethylene group, butylene group (tetramethylene group), hexylene group (hexamethylene group), and particularly preferred are ethylene groups.

In the above formula (1), R ² and R ³ are the same or different and contain a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms or a divalent alicyclic ring having 3 to 5 carbon atoms. A hydrocarbon group is shown.

Examples of the divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms include, for example, a divalent linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, such as a divalent branched chain having 2 to 5 carbon atoms. And an aliphatic hydrocarbon group in the form of a ring.

Examples of the divalent linear aliphatic hydrocarbon group having 1 to 5 carbon atoms include carbon such as methylene group, ethylene group, propylene group, butylene group (tetramethylene group), pentylene group (pentamethylene group), and the like. A linear alkylene group having 1 to 5 carbon atoms, for example, a linear alkenylene group having 2 to 5 carbon atoms such as vinylene group, propenylene group, butenylene group, butadienylene group, for example, ethynylene group, propynylene group, butynylene group, pentynylene, etc. And a straight-chain alkynylene group having 2 to 5 carbon atoms such as a group.

Examples of the divalent branched aliphatic hydrocarbon group having 2 to 5 carbon atoms include a branch having 2 to 5 carbon atoms such as a methylmethylene group, a methylethylene group, a methylpropylene group, an ethylpropylene group, and a dimethylpropylene group. A branched alkylene group such as a methyl ethynylene group, a methyl propenylene group and a methyl butenylene group, such as a branched alkenylene group having 3 to 5 carbon atoms, such as a branched alkynylene group having 4 to 5 carbon atoms such as a methyl propynylene group and a methyl butynylene group. Etc.

Examples of the divalent alicyclic hydrocarbon group having 3 to 5 carbon atoms include cycloalkylene groups having 3 to 5 carbon atoms such as cyclopropylene group, cyclobutylene group, and cyclopentylene group, such as methylcyclopropylene group. And an alicyclic hydrocarbon group having 3 to 5 carbon atoms containing an aliphatic hydrocarbon group such as an ethylcyclopropylene group and a methylcyclobutylene group.

R ² and R ³ are preferably a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms, more preferably a divalent linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, and more preferably Includes a linear alkylene group having 1 to 5 carbon atoms, particularly preferably a linear alkylene group having 5 carbon atoms.

In addition, from the viewpoint of thermal stability, R ² and R ³ are preferably atoms that bind the oxygen atom (O) of the hydroxyl group contained in the amide group-containing diol and the nitrogen atom (N) of the amide group in the shortest distance. A hydrocarbon group (—CH ₂ CO—) having 2 carbon atoms (including the carbon atom (C) of the amide group) or a hydrocarbon group having 5 or more (aliphatic hydrocarbon group, alicyclic hydrocarbon group) More preferably, a hydrocarbon group having 6 or more atoms that bond O and N at the shortest is mentioned.

Examples of R ² and R ³ include a butylene group (tetramethylene group) and a pentylene group (pentamethylene group), and a pentylene group (pentamethylene group) is preferable.

In the general formula (1), when R ² and R ³ are pentylene groups (pentamethylene groups), the amide group-containing diol is represented by the following general formula (2).

HO— (CH ₂ ) ₅ —CO—NH—R ¹ —NH—CO— (CH ₂ ) ₅ —OH (2)
(Wherein, ^{R 1} represents the same meaning as ^{R 1} in the formula (1).)
In the general formula (2), the oxygen atom (O) of the hydroxyl group contained in the amide group-containing diol and the nitrogen atom (N) of the amide group are (— (CH ₂ ) ₅ —CO—) or (—CO The number of atoms (that is, carbon atoms) bonded by a single route by — (CH ₂ ) ₅ —) and bonding them in the shortest is 6.

Such an amide group-containing diol can improve heat resistance and thermal stability.

The amide group-containing diol represented by the general formula (1) can be obtained, for example, by reacting a diamino compound with a hydroxycarboxylic acid or a derivative thereof.

The diamino compound is an organic compound having two amino groups, and examples thereof include aliphatic diamines, alicyclic diamines, and araliphatic diamines.

Examples of the aliphatic diamine include ethylenediamine, 1,3-propanediamine (propylenediamine), 1,4-butanediamine (tetramethylenediamine), 1,5-pentanediamine (pentamethylenediamine), and 1,6-hexane. Linear aliphatic diamines such as diamine (hexamethylenediamine), 1.7-heptanediamine (heptamethylenediamine), 1,8-octanediamine (octamethylenediamine), such as 1,2-propanediamine, Branched aliphatic diamines such as 1,3-butanediamine, 2,4-pentanediamine, and 1,6-octanediamine.

Examples of the alicyclic diamine include diamines having an amino group directly bonded to the alicyclic ring, such as cyclopropanediamine, cyclobutanediamine, cyclopentanediamine, cyclopentanediamine, and cyclohexanediamine, such as hydrogenated xylylenediamine and cyclohexylmethane. Examples include diamines such as diamines in which an amino group is bonded to an alicyclic ring via an aliphatic hydrocarbon group.

Examples of the araliphatic diamine include diamines in which an amino group is bonded to an aromatic ring via an aliphatic hydrocarbon group, such as phenylmethanediamine and xylylenediamine.

These diamino compounds can be used alone or in combination of two or more.

As the diamino compound, preferably, an aliphatic diamine is used, and more preferably, a linear aliphatic diamine is used.

Hydroxycarboxylic acid is an organic compound having one or more hydroxyl groups and one or more carboxyl groups, preferably an organic compound having one hydroxyl group and one carboxyl group, such as glycolic acid, 2- Examples thereof include hydroxypropanoic acid (lactic acid), 3-hydroxypropanoic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid and the like.

Further, examples of the hydroxycarboxylic acid derivative include alkyl esters and lactones of the above hydroxycarboxylic acid.

Examples of the alkyl ester of hydroxycarboxylic acid include, for example, methyl ester, ethyl ester, propyl ester and the like of the above-described hydroxycarboxylic acid.

Lactones are cyclic organic compounds containing an ester bond in the ring, and examples thereof include β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone (γ-methylbutyrolactone), and ε-caprolactone. Can be mentioned.

These hydroxycarboxylic acids or their derivatives can be used alone or in combination of two or more.

The hydroxycarboxylic acid or derivative thereof is preferably a hydroxycarboxylic acid derivative, more preferably a lactone.

In the production of the amide group-containing diol, for example, a diamino compound and a hydroxycarboxylic acid or a derivative thereof are mixed with, for example, 1.8 to 8 mol of a hydroxycarboxylic acid or a derivative thereof with respect to 1 mol of the diamino compound. Preferably, after formulation (mixing) to 2.0 to 6.0 mol, for example, 10 to 120 ° C., preferably 20 to 80 ° C., for example, 0.5 to 50 hours, preferably React for 2 to 24 hours. The reaction temperature can be a constant temperature, or can be raised or cooled stepwise.

The reaction may be solvent-free, but a known reaction solvent may be used if necessary.

The reaction solvent is not particularly limited, but alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 3-methyl-3-methoxybutanol, for example, ethylene glycol, diethylene glycol , Polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,4-butanediol, 1,5-pentanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, tripropylene glycol monomethyl ether, etc. Glycol solvents, for example, ketone solvents such as acetone, methyl ethyl ketone methyl isobutyl ketone, cyclohexanone, etc., ether solvents such as diethyl ether, tetrahydrofuran, dioxane, etc., such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, N-methyl Examples include organic solvents such as polar solvents such as pyrrolidone and hexamethylphosphonilamide.

These reaction solvents can be used alone or in combination of two or more.

Furthermore, in such a reaction, the amide group-containing diol can be separated from the obtained reaction mixture by a crystallization treatment such as recrystallization, if necessary.

Examples of the crystallization solvent used in the crystallization treatment include the same organic solvents as the above reaction solvent.

These crystallization solvents can be used alone or in combination of two or more.

The melting point of the amide group-containing diol thus obtained is, for example, 40 to 220 ° C., preferably 80 to 160 ° C.

Moreover, the chain extender should just contain the said amide group containing diol at least, for example, can also contain a low molecular-weight polyol as an arbitrary component.

Examples of the low molecular weight polyol include the low molecular weight polyol described above, and preferably a dihydric alcohol.

In the case where the chain extender contains a low molecular weight polyol, the content ratio is not particularly limited and is appropriately set according to the purpose and application.

In the method for producing a thermoplastic polyurethane resin of the present invention, at least the polyisocyanate, the high molecular weight polyol, and the chain extender are reacted.

That is, the thermoplastic polyurethane resin is synthesized by the reaction of polyisocyanate, high molecular weight polyol and chain extender.

And in the manufacturing method of the thermoplastic polyurethane resin of this invention, well-known methods, such as a prepolymer method and a one shot method, are employable, for example.

In the prepolymer method, for example, polyisocyanate and high molecular weight polyol are first reacted to synthesize an isocyanate group-terminated prepolymer having an isocyanate group at the molecular end. Next, the obtained isocyanate group-terminated prepolymer is reacted with a chain extender.

In order to synthesize an isocyanate group-terminated prepolymer, the equivalent ratio (NCO / OH) of the isocyanate group in the polyisocyanate with respect to the hydroxyl group in the high molecular weight polyol is 1.1 to 20 for example. Preferably, it is formulated (mixed) to be 1.3 to 10, more preferably 1.3 to 7, and is, for example, 40 to 150 ° C., preferably 50 to 120 ° C. in a reaction vessel. For example, the reaction is performed for 30 seconds to 8 hours, preferably 1 hour to 6 hours. In addition, after completion | finish of reaction can also remove unreacted polyisocyanate by well-known removal means, such as distillation and extraction, as needed.

Next, in order to react the obtained isocyanate group-terminated prepolymer with a chain extender, the isocyanate group-terminated prepolymer and the chain extender are reacted with an isocyanate in the isocyanate group-terminated prepolymer with respect to a hydroxyl group in the chain extender. Formulated (mixed) so that the equivalent ratio of groups (NCO / OH) is, for example, 0.8 to 1.2, preferably 0.9 to 1.1, more preferably 0.98 to 1.05. For example, at 40 to 280 ° C., preferably at 70 to 260 ° C., more preferably at 80 to 240 ° C., for example, for 30 seconds to 10 hours, preferably for 1 minute to 8 hours.

In the one-shot method, for example, polyisocyanate, high molecular weight polyol and chain extender are mixed with an equivalent ratio of isocyanate groups in the polyisocyanate (NCO / OH) to the total amount of hydroxyl groups in the high molecular weight polyol and chain extender. ) Is, for example, 0.8 to 1.2, preferably 0.9 to 1.1, more preferably 0.98 to 1.05. The reaction is carried out at 280 ° C., preferably 70 to 260 ° C., for example, for 30 seconds to 10 hours, preferably for 1 minute to 8 hours. The reaction temperature can be a constant temperature, or can be raised or cooled stepwise.

In the prepolymer method and the one-shot method, the mixing of the above components (polyisocyanate, high molecular weight polyol, amide group-containing diol, isocyanate group-terminated prepolymer, low molecular weight polyol, etc.) is not particularly limited, but preferably a dissolver. A mixing tank such as a circulating low-pressure or high-pressure impingement mixer, for example, a high-speed stirring mixer, a static mixer, a kneader, or a mixing device such as a single-screw or twin-screw extruder is used.

In the prepolymer method and the one-shot method, the compound containing a hydroxyl group (a high molecular weight polyol, an amide group-containing diol, and a low molecular weight polyol blended as necessary) is preferably subjected to a heat-reducing treatment as a pretreatment. , The water content is reduced.

The water content of each of these hydroxyl group-containing compounds (high molecular weight polyol, amide group-containing diol, and low molecular weight polyol blended as necessary) is, for example, 0.05% by mass or less, preferably Is 0.03% by mass or less, more preferably 0.02% by mass or less, and usually 0.005% by mass or more.

In addition, the method of reacting (polymerizing) each of the above components (polyisocyanate, high molecular weight polyol, amide group-containing diol, isocyanate group-terminated prepolymer, low molecular weight polyol, etc.) by the prepolymer method or the one-shot method is particularly limited However, known polymerization methods, more specifically, for example, solution polymerization, suspension polymerization in water, non-aqueous dispersion polymerization, melt polymerization (bulk polymerization) and the like can be mentioned. Preferably, solution polymerization, non-aqueous dispersion polymerization, and melt polymerization are exemplified.

In solution polymerization, the above components are added and dissolved in a polar organic solvent, and the above components are polymerized.

Examples of the polar organic solvent include aprotic polar solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, and hexamethylphosphonamide.

These polar organic solvents can be used alone or in combination of two or more.

The mixing ratio of the polar organic solvent is not particularly limited, and is appropriately set depending on the purpose and application, the viscosity of the reaction system, and the like.

In non-aqueous dispersion polymerization, for example, the above-described components are added to a low-polar organic solvent, and a dispersant is added to disperse the above-described components and polymerize.

Examples of the low polar organic solvent include aliphatic hydrocarbons such as n-hexane and octane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, and aromatic hydrocarbons such as toluene, xylene and ethylbenzene. And the like.

These low polarity organic solvents can be used alone or in combination of two or more.

The mixing ratio of the low polarity organic solvent is not particularly limited, and is appropriately set depending on the purpose and application, the viscosity of the reaction system, and the like.

The dispersant is not particularly limited, and examples thereof include dispersants described in JP-A No. 2004-169011, and alkali metal salts such as sulfonic acid groups, carboxylic acid groups, and amino groups, ammonium salts, and inorganic acids. Known water-soluble polymers having ionic hydrophilic groups such as salts and organic acid salts, for example, known surfactants such as anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, etc. Is mentioned.

In melt polymerization (bulk polymerization), for example, while stirring the polyisocyanate under a nitrogen stream, a high molecular weight polyol and an amide group-containing diol (and a low molecular weight polyol blended as necessary) are added thereto, and the above reaction is performed. The components are heated and heated to melt and polymerize.

In the above polymerization method, a known urethanization catalyst such as amines or organometallic compounds can be added as necessary.

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

Examples of organometallic compounds include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dilaurate, dibutyltin Organic tin compounds such as dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, dibutyltin dichloride, for example, organic lead compounds such as lead octoate and lead naphthenate, for example, organic nickel compounds such as nickel naphthenate, Examples thereof include organic cobalt compounds such as cobalt naphthenate, organic copper compounds such as copper octenoate, and organic bismuth compounds such as bismuth octylate and bismuth neodecanoate.

Furthermore, examples of the urethanization catalyst 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 blending ratio of the urethanization catalyst is not particularly limited, but is, for example, 0.0001 to 0.05 parts by weight, preferably 0.001 to 0.03 parts by weight with respect to 100 parts by weight of the high molecular weight polyol. is there.

Furthermore, in such a thermoplastic polyurethane resin, if necessary, further known additives such as a plasticizer, a foaming agent, an antiblocking agent, a heat stabilizer, a light stabilizer, an antioxidant, a release agent are used. Agents, catalysts, and coupling agents, lubricants, rust inhibitors, opacifiers, pigments, dyes, lubricants, fillers, hydrolysis inhibitors, and the like can be blended in appropriate proportions. These additives may be added to one or more of each component, may be added during production of each component, may be added during mixing of each component, It can also be added to the resulting thermoplastic polyurethane resin.

In the thermoplastic polyurethane resin thus obtained, the concentration of the hard segment formed by the reaction between the polyisocyanate and the amide group-containing diol is 30 to 60% by mass, preferably 30 to 55% by mass, Preferably, it is 30 to 50% by mass.

When the hard segment (hard segment formed by the reaction of polyisocyanate and amide group-containing diol) is less than the lower limit, there is a problem that the heat resistance of the thermoplastic polyurethane resin is lowered.

On the other hand, when the hard segment (hard segment formed by reaction of polyisocyanate and amide group-containing diol) exceeds the above upper limit, there is a problem that the molding processability of the thermoplastic polyurethane resin is lowered.

In addition, the hard segment (hard segment formed by the reaction of polyisocyanate and amide group-containing diol) can be calculated, for example, from the blending ratio (preparation) of each component by the following formula.
[Mass of amide group-containing diol (g) + Mass of amide group-containing diol (g) / Molecular weight of amide group-containing diol) × Molecular weight of polyisocyanate] ÷ [(Mass of polyisocyanate (g) + mass of high molecular weight polyol) (G) + mass of amide group-containing diol (g) + mass of other components (low molecular weight polyols, additives, etc. as optional components (g))]] × 100
Further, in the thermoplastic polyurethane resin, when a low molecular weight polyol is blended as an optional component, the concentration of the hard segment formed by the reaction of the polyisocyanate and the low molecular weight polyol is, for example, 1 to 30% by mass, The content is preferably 1 to 25% by mass, more preferably 1 to 20% by mass.

In addition, the hard segment (hard segment formed by reaction of polyisocyanate and low molecular weight polyol) concentration can be calculated by the following formula from the blending ratio (preparation) of each component, for example.
[Mass of low molecular weight polyol (g) + mass of low molecular weight polyol (g) / molecular weight of low molecular weight polyol) × molecular weight of polyisocyanate] ÷ [(mass of polyisocyanate (g) + mass of high molecular weight polyol (g) + Mass (g) of low molecular weight polyol + mass of other components (amide group-containing diol, additive, etc. as essential components (g))]] × 100
The total amount of the hard segment concentration formed by the reaction of the polyisocyanate and the amide group-containing diol and the hard segment concentration formed by the reaction of the polyisocyanate and the low molecular weight polyol is, for example, 30 to 60 mass. %, Preferably 30 to 55% by mass, more preferably 30 to 50% by mass.

Further, the weight average molecular weight (weight average molecular weight by GPC measurement using standard polystyrene as a calibration curve) of such a thermoplastic polyurethane resin is, for example, 100,000 to 350,000, preferably 100,000 to 300,000, more preferably 120,000 to 250,000. It is.

If the weight average molecular weight is in the above range, excellent mechanical strength and heat resistance can be ensured, and excellent molding stability in thermoforming can be improved.

The softening temperature of such a thermoplastic polyurethane resin (softening temperature by thermomechanical analysis (TMA) measurement according to JIS K-7196) is, for example, 160 ° C. or higher, preferably 170 ° C. or higher, more preferably 180 ° C or higher, usually 230 ° C or lower.

When the softening temperature is in the above range, the heat resistance and thermal stability of the thermoplastic polyurethane resin can be improved, and excellent molding stability in thermoforming can be ensured.

Further, the 5% thermogravimetric decrease temperature (measurement method: thermogravimetric analysis (temperature increase rate 10 ° C./min, under nitrogen stream)) of such a thermoplastic polyurethane resin is, for example, 250 ° C. or higher, preferably 265 ° C. As mentioned above, More preferably, it is 300 degreeC or more, and is normally 340 degrees C or less.

In such a thermoplastic polyurethane resin, when the high molecular weight polyol contains an oxyethylene group, the content of the oxyethylene group is, for example, 10% by mass or more based on the total amount of the thermoplastic polyurethane resin. The amount is preferably 20% by mass or more, for example, 70% by mass or less, and preferably 60% by mass or less.

If the content of the oxyethylene group is not less than the above lower limit, the moisture permeability can be improved when the thermoplastic polyurethane resin is formed into a film having a thickness of 20 μm.

Such moisture permeability (according to JIS L-1099), for example, 4000g ^/ m 2 · 24h or more, preferably, 10000g ^/ m 2 · 24h or more, more preferably, be a 40000g ^/ m 2 · 24h or more Usually, it is 800,000 g / m ² · 24 h or less.

Such a thermoplastic polyurethane resin is not particularly limited, and is a known molding method, for example, a thermoplastic resin molding method such as injection molding, extrusion molding, press molding, cast molding, preferably extrusion molding, By press molding or cast formation, for example, it can be molded into various shapes such as pellets, plates, fibers, strands, films, sheets, pipes, hollows, boxes, and the like.

Among the above-mentioned molding methods, the molding temperature in the hot melt molding (injection molding, extrusion molding, press molding, etc.) of the thermoplastic polyurethane resin may be appropriately set according to the thermal characteristics of the thermoplastic polyurethane resin, and is not particularly limited. Is, for example, 160 to 260 ° C, preferably 175 to 245 ° C.

Further, in such a method, for example, in hot melt molding of a thermoplastic polyurethane resin, if supercritical carbon dioxide or the like is introduced and a supercritical fluid is diffused and dissolved in the thermoplastic polyurethane resin, supercritical carbon dioxide is obtained. Becomes a foaming agent, and the thermoplastic polyurethane resin can be formed as a microcellular foam composed of fine and uniform cells.

In addition, if a plasticizer (for example, aliphatic dibasic acid ester, phosphoric acid ester, epoxy plasticizer, etc.) is added to the thermoplastic polyurethane resin, the glass transition point of the thermoplastic polyurethane resin is lowered, Can reduce the viscosity.

Thereby, the injection moldability and extrusion moldability of the thermoplastic polyurethane resin can be improved, and the molded body can be made thinner, the surface accuracy of the molded body can be improved, and the molding temperature can be lowered.

In the cast molding, an organic solvent in which the thermoplastic polyurethane resin is soluble, for example, an aprotic polar organic solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. To prepare a solution of a thermoplastic polyurethane resin, and apply the solution to a substrate, for example, at a temperature below the boiling point of the aprotic polar organic solvent, in an inert gas stream, aprotic polarity By removing the organic solvent by volatilization, the thermoplastic polyurethane resin can be formed as a film (cast film).

The thermoplastic polyurethane resin thus obtained can be easily spun by, for example, a known spinning method (for example, wet spinning, dry spinning, melt spinning, etc.), and can be made into an elastic fiber.

Furthermore, after the molded product of the thermoplastic polyurethane resin obtained by the above method or the like is manufactured, the molded product can be further annealed.

In this method, for example, a molded product of a thermoplastic polyurethane resin is annealed at, for example, 70 to 190 ° C., preferably 80 to 180 ° C., for example, for 10 minutes to 24 hours, preferably 1 to 20 hours.

Thereby, the cohesion of the hard segment contained in the thermoplastic polyurethane resin can be improved, and a molded product having excellent mechanical strength and heat resistance can be obtained.

According to the thermoplastic polyurethane resin of the present invention, a film having excellent moisture permeability can be formed. Therefore, it is suitably used in the manufacture of moisture permeable films for clothing, specifically, for example, raincoats and windbreakers. It is done.

Furthermore, the thermoplastic polyurethane resin of the present invention is not limited to the above-mentioned applications. For example, automotive parts, electronic parts, mechanical / industrial parts, electric wires / cables, rolls, hoses / tubes, belts, films / sheets, laminates, etc. In various industrial fields such as coatings, adhesives, sealing materials, sports / leisure products, shoe-related parts, sundries, nursing care products, housing supplies, medical care, building materials, civil engineering, waterproofing / paving materials, foams, slush powders, etc. Can be used.

And in the thermoplastic polyurethane resin of this invention, while the chain extender which is a raw material contains the amide group containing diol shown by the said General formula (1), it is obtained by reaction of the chain extender and polyisocyanate. Since the content of the hard segment is adjusted to 30 to 60% by mass with respect to the total amount of the thermoplastic polyurethane resin, it is possible to ensure excellent mechanical strength and to have excellent heat resistance and thermal stability. .

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited thereto. In the following description, “part” and “%” are based on mass unless otherwise specified. Moreover, the measuring method used for an Example etc. is shown below.

<Weight average molecular weight (Mw)>
A solution in which lithium bromide (manufactured by Junsei Kagaku) was dissolved in N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for liquid chromatography) at a concentration of 0.01 mmol / L was used as an eluent.

The measurement sample solution was prepared by dissolving the measurement sample at a concentration of 0.25% by mass in a solvent having the same composition as the eluent. A GPC column (Showa Denko, trade name: KD-G, KD-806M) is mounted in series with a GPC measurement device (Showa Denko, trade name: Shodex GPC-101), the column temperature is 45 ° C., and the eluent flow rate. The weight average molecular weight (Mw) was calculated from a standard polystyrene calibration curve prepared in advance using a differential refractometer (RI) detector under the conditions of 0.7 mL / min.
<Thermal weight reduction temperature (unit: ° C)>
Using a thermal analyzer (trade name: TGA-50, manufactured by Shimadzu Corporation), about 5 mg of a sample was weighed in a platinum cell and heated from room temperature to 700 ° C. at a temperature increase rate of 10 ° C./min in a nitrogen atmosphere. It was measured. Based on 200 ° C., a 5% weight loss temperature was measured.
<Flow start temperature (unit: ° C)>
1 g of the sample is filled in an elevated flow tester (model: CFT-500, manufactured by Shimadzu Corporation), using a nozzle of 1 mm (diameter) × 10 mm (length), under the conditions of a heating rate of 5 ° C./min and a load of 100 kgf. The flow start temperature was measured.
<Softening temperature (unit: ° C)>
Using a thermomechanical analysis (TMA) apparatus (trade name: TMA4000S, manufactured by Mac Science), the softening temperature was measured according to JIS K-7196, “Softening temperature test method by thermomechanical analysis of thermoplastic film and sheet”.

The diameter of the indenter used was 1.0 mm, and the softening temperature was maintained at 25 ° C. for 30 minutes under a nitrogen stream under a load of 50 gf, and then at a temperature increase rate of 5 ° C./min. It was measured.
<Moisture permeability ^{(unit: g / m 2 · 24h)} >
In accordance with the method described in JIS L-1099 B-1 method (potassium acetate method), measurement was performed after a nylon taffeta was placed on the surface where the film and water were in contact. Thereafter, the moisture permeability was converted to a value for 24 hours.
<Tensile strength (unit: MPa), elastic modulus (unit: MPa), elongation at break (unit:%)>
The elastic modulus (MPa), tensile strength (MPa) and elongation at break (%) at 23 ° C. and 50% relative humidity were measured according to JIS K-7311 using a tensile tester (tensile tester INSTRON 1123 manufactured by Instron). Measured according to the method.
<Hardness: Shore A, Shore D>
Based on the method described in JIS K 7311, Shore A hardness was measured, and the result was shown as a numerical value.

For those having a Shore A hardness of 95 or more, the hardness was measured using a Shore D durometer in accordance with the method described in JIS K 7311, and the results were shown as numerical values.
(Amido group-containing diol)
Production Example 1 (Production of amide group-containing diol 1)
Under a nitrogen atmosphere, a reactor equipped with a stirrer was charged with 30.1 parts of ethylenediamine, and sufficiently purged with nitrogen while stirring. Thereafter, the temperature was raised to 50 ° C., and 172.2 parts of ε-caprolactone was gradually added at the same temperature, and then 234 parts of acetonitrile was added and reacted for 20 hours.

After completion of the reaction, the mixture was allowed to stand at room temperature to precipitate crystals. The obtained crystals were washed with acetonitrile, and N, N′-bis- (6-hydroxycaproyl) ethylenediamine (amide group-containing diol 1). Of white powder (yield 58%, melting point 152 ° C.) was obtained.

Production Example 2 (Production of amide group-containing diol 2)
Under a nitrogen atmosphere, 44.9 parts of 1,4-butanediamine were charged into a reactor equipped with a stirrer, and the nitrogen was sufficiently substituted while stirring. Thereafter, the temperature was raised to 50 ° C., and 245.0 parts of ε-caprolactone was gradually added at the same temperature, and then 134 parts of tetrahydrofuran was added and reacted for 6 hours.

After completion of the reaction, crystallization was performed using isopropyl alcohol, and the precipitated product was washed with isopropyl alcohol, and white, N, N′-bis- (6-hydroxycaproyl) butanediamine (amide group-containing diol 2) was obtained. 49.2 parts of powder (yield 31%, melting point 134 ° C.) were obtained.

Production Example 3 (Production of amide group-containing diol 3)
Under a nitrogen atmosphere, a reactor equipped with a stirrer was charged with 18.1 parts of ethylenediamine, and sufficiently purged with nitrogen while stirring. Thereafter, 156.0 parts of γ-butyrolactone was gradually added at room temperature and allowed to react for 20 hours.

After completion of the reaction, crystallization was performed using isopropyl alcohol, the precipitated product was washed with isopropyl alcohol, and white powder of N, N′-bis- (4-hydroxybutyroyl) ethylenediamine (amide group-containing diol 3) 28.6 parts (yield 41%, melting point 142 ° C.) were obtained.

Production Example 4 (Production of amide group-containing diol 4)
Under a nitrogen atmosphere, a reactor equipped with a stirrer was charged with 18.1 parts of ethylenediamine, and sufficiently purged with nitrogen while stirring. Thereafter, the temperature was raised to 80 ° C., 120.2 parts of δ-valerolactone was gradually added at the same temperature, 79 parts of isopropyl alcohol was added, and the mixture was reacted for 2 hours.

After completion of the reaction, the precipitated product was washed with isopropyl alcohol, and 44.9 parts of white powder of N, N′-bis- (5-hydroxyvaleroyl) ethylenediamine (amide group-containing diol 4) (57% yield, Melting point 140 ° C.).

Production Example 5 (Production of amide group-containing diol 5)
In a nitrogen atmosphere, 135 parts of methyl glycolate was charged into a reactor equipped with a stirrer, and then cooled in an ice-water bath, and 36 parts of ethylenediamine was gradually added dropwise. Subsequently, it stirred for 30 minutes, Then, it heated up at 100 degreeC and stirred for 5 hours and made it react at the same temperature.

After completion of the reaction, crystallization treatment was performed with 250 parts of methanol, and the resulting white powder was vacuum-dried at 40 ° C. for 7 hours to obtain N, N′-bis- (hydroxyacetyl) ethylenediamine (amide group facial oil diol). 5) of white powder (yield 76%, melting point 143 ° C.) was obtained.
(Thermoplastic polyurethane resin and molded product)
Example 1 (Production of thermoplastic polyurethane resin 1)
Under a nitrogen atmosphere, 53.46 parts of polyethylene glycol (trade name: PEG # 2000U, hydroxyl value: 54.8 mgKOH / g, manufactured by NOF Corporation) was added to a reactor equipped with a stirrer, and heated at 80 ° C. for 1 hour.

Next, 25.12 parts of 4,4′-diphenylmethane diisocyanate was added and reacted at 80 ° C. for 2 hours to synthesize an isocyanate group-terminated urethane prepolymer (hereinafter abbreviated as prepolymer).

70 parts of dimethylacetamide (hereinafter abbreviated as DMAc) was added to the obtained prepolymer and stirred sufficiently so that the prepolymer was uniformly dissolved. Next, the DMAc solution of the prepolymer was heated to 100 ° C., and the DMAc solution of amide group-containing diol 1 (previously 21.42 parts of amide group-containing diol 1 was dissolved in 30 parts of DMAc at 100 ° C. The solution was added dropwise over 5 minutes.

Next, after reacting at 100 ° C. for 30 minutes, 200 parts of DMAc was gradually added and reacted for 1 hour. The obtained reaction solution was reprecipitated with 2000 parts of acetonitrile, washed repeatedly with acetonitrile, and then suction filtered.

Then, 92.1 parts of thermoplastic polyurethane resin (polyurethane elastomer) 1 was obtained by drying the obtained white solid under reduced pressure at 80 ° C.

Table 1 shows the weight average molecular weight (Mw), 5% thermogravimetric decrease temperature and flow start temperature of the obtained thermoplastic polyurethane resin 1.
<Manufacture of hot press sheet>
A hot press sheet of thermoplastic polyurethane resin 1 was molded using a vacuum press machine (manufactured by Kansai Roll Co., Ltd.) set at 240 ° C.

That is, in a 0.3 mm-thick sheet (spacer shape; 80 × 80 × 0.3 mm on a 240 × 240 × 0.3 mm thick plate, four pieces are taken), each 80 × 80 × 0.3 mm 5 parts of the thermoplastic polyurethane resin 1 was preheated for 5 minutes, pressurized at 5 MPa for 2 minutes, and then pressurized at 2.5 MPa using a press plate set at 20 ° C. installed in the same press. A sheet sample for measurement was prepared by cooling for a minute. The hot plate was a 5 mm thick brass plate.

The softening temperature of the obtained sheet sample for measurement was measured by thermomechanical analysis (TMA). The results are shown in Table 1.

Further, the tensile strength (unit: MPa), elastic modulus (unit: MPa), elongation at break (unit:%), and hardness (Shore A, Shore D) of the measurement sheet sample were measured. The results are shown in Table 1.
<Manufacture of solvent cast film>
25 parts of the thermoplastic polyurethane resin 1 was dissolved in 75 parts of DMAc to prepare a thermoplastic polyurethane resin solution. The solution was coated on a polypropylene plate using an applicator so as to have a thickness of 160 μm, and then DMAc was volatilized and removed for 1 hour in a nitrogen atmosphere with a dryer set at 100 ° C. Thus, a cast film of the thermoplastic polyurethane resin 1 having a thickness of 20 μm was formed.

Further, the moisture permeability (unit: g / m ² · 24 h), tensile strength (unit: MPa), elastic modulus (unit: MPa), and elongation at break (unit:%) of the cast film were measured. The results are shown in Table 1.

Example 2 (Production of thermoplastic polyurethane resin 2)
Under a nitrogen atmosphere, a reactor equipped with a stirrer was charged with 32.08 parts of polyethylene glycol (trade name: PEG # 2000U, hydroxyl value of 54.8 mgKOH / g manufactured by NOF) and 21.03 parts of poly (ethylene oxide). -Tetrahydrofuran) copolymer (trade name: Polyserine DC-1800E, hydroxyl value 63.3 mgKOH / g) manufactured by NOF Corporation was added and heated at 80 ° C. for 1 hour.

Next, 25.47 parts of 4,4′-diphenylmethane diisocyanate was added and reacted at 80 ° C. for 2 hours to synthesize a prepolymer.

70 parts of DMAc was added to the obtained prepolymer and stirred sufficiently so that the prepolymer was uniformly dissolved. Next, the DMAc solution of the prepolymer was heated to 100 ° C., and the DMAc solution of amide group-containing diol 1 (previously 21.42 parts of amide group-containing diol 1 was dissolved in 30 parts of DMAc at 100 ° C. The solution was added dropwise over 5 minutes.

Thereafter, the obtained white solid was dried under reduced pressure at 80 ° C. to obtain 94.2 parts of a thermoplastic polyurethane resin (polyurethane elastomer) 2.

Table 1 shows the weight average molecular weight (Mw), 5% thermogravimetric decrease temperature and flow start temperature of the obtained thermoplastic polyurethane resin 2.
<Manufacture of hot press sheet>
A hot press sheet of the thermoplastic polyurethane resin 2 was molded by the same operation as in Example 1.

Further, the tensile strength (unit: MPa), elastic modulus (unit: MPa), elongation at break (unit:%), and hardness (Shore A, Shore D) of the measurement sheet sample were measured. The results are shown in Table 1.
<Manufacture of solvent cast film>
A cast film of thermoplastic polyurethane resin 2 having a thickness of 20 μm was formed in the same manner as in Example 1.

Example 3 (Production of thermoplastic polyurethane resin 3)
Under a nitrogen atmosphere, 58.71 parts of a poly (ethylene oxide-tetrahydrofuran) copolymer (trade name: Polyserine DC-1800E, hydroxyl value 63.3 mgKOH / g) manufactured by NOF CORPORATION was added to a reactor equipped with a stirrer. And heated at 80 ° C. for 1 hour.

Next, 23.62 parts of 4,4′-diphenylmethane diisocyanate was added and reacted at 80 ° C. for 2 hours to synthesize a prepolymer.

70 parts of DMAc was added to the obtained prepolymer and stirred sufficiently so that the prepolymer was uniformly dissolved. Subsequently, the DMAc solution of the prepolymer was heated to 100 ° C., and the DMAc solution of amide group-containing diol 1 (previously 17.67 parts of amide group-containing diol 1 was dissolved in 30 parts of DMAc at 100 ° C. The solution was added dropwise over 5 minutes.

Thereafter, the obtained white solid was dried at 80 ° C. under reduced pressure to obtain 93.0 parts of a thermoplastic polyurethane resin (polyurethane elastomer) 3.

Table 1 shows the weight average molecular weight (Mw), 5% thermogravimetric decrease temperature and flow start temperature of the obtained thermoplastic polyurethane resin 3.
<Manufacture of hot press sheet>
A hot press sheet of thermoplastic polyurethane resin 3 was molded by the same operation as in Example 1.

Also, the tensile strength (unit: MPa), elastic modulus (unit: MPa), elongation at break (unit:%), and hardness (Shore A, Shore D) of the sheet sample for measurement were measured. The results are shown in Table 1.

Example 4 (Production of thermoplastic polyurethane resin 4)
Under a nitrogen atmosphere, a reactor equipped with a stirrer was charged with 29.85 parts of polyethylene glycol (trade name: PEG # 2000U, hydroxyl value of 54.8 mgKOH / g manufactured by NOF) and 29.36 parts of poly (ethylene oxide). -Tetrahydrofuran) copolymer (trade name: Polyserine DC-1800E, hydroxyl value 63.3 mgKOH / g) manufactured by NOF Corporation was added and heated at 80 ° C. for 1 hour.

Next, 23.12 parts of 4,4′-diphenylmethane diisocyanate was added and reacted at 80 ° C. for 2 hours to synthesize a prepolymer.

Thereafter, the obtained white solid was dried under reduced pressure at 80 ° C. to obtain 88.2 parts of thermoplastic polyurethane resin (polyurethane elastomer) 4.

Table 1 shows the weight average molecular weight (Mw), 5% thermogravimetric decrease temperature and flow start temperature of the obtained thermoplastic polyurethane resin 4.
<Manufacture of hot press sheet>
A hot press sheet of thermoplastic polyurethane resin 4 was molded by the same operation as in Example 1.

Example 5 (Production of thermoplastic polyurethane resin 5)
Under a nitrogen atmosphere, 59.44 parts of polytetraethylene ether glycol (trade name: PTG-2000SN, hydroxyl value: 57.0 mgKOH / g) manufactured by Hodogaya Chemical Co., Ltd. was added to a reactor equipped with a stirrer, and the mixture was heated at 80 ° C. for 1 hour. Heated.

Next, 22.89 parts of 4,4′-diphenylmethane diisocyanate was added and reacted at 80 ° C. for 2 hours to synthesize a prepolymer.

The obtained white solid was dried under reduced pressure at 80 ° C. to obtain 93 parts of a thermoplastic polyurethane resin (polyurethane elastomer) 5.

Table 2 shows the weight average molecular weight (Mw), 5% thermogravimetric decrease temperature and flow start temperature of the obtained thermoplastic polyurethane resin 5.
<Manufacture of hot press sheet>
A hot press sheet of the thermoplastic polyurethane resin 5 was molded by the same operation as in Example 1.

The softening temperature of the obtained sheet sample for measurement was measured by thermomechanical analysis (TMA). The results are shown in Table 2.

Also, the tensile strength (unit: MPa), elastic modulus (unit: MPa), elongation at break (unit:%), and hardness (Shore A, Shore D) of the sheet sample for measurement were measured. The results are shown in Table 2.

Example 6 (Production of thermoplastic polyurethane resin 6)
In a reactor equipped with a stirrer under a nitrogen atmosphere, 56.5 parts of polyester polyol (trade name: Takelac U-2024, hydroxyl value 56.3 mgKOH / g, manufactured by Mitsui Chemicals)
And heated at 80 ° C. for 1 hour.

Next, 22.81 parts of 4,4′-diphenylmethane diisocyanate was added and reacted at 80 ° C. for 2 hours to synthesize a prepolymer.

The obtained white solid was dried under reduced pressure at 80 ° C. to obtain 92 parts of a thermoplastic polyurethane resin (polyurethane elastomer) 6.

Table 2 shows the weight average molecular weight (Mw), 5% thermogravimetric decrease temperature and flow start temperature of the obtained thermoplastic polyurethane resin 6.
<Manufacture of hot press sheet>
A hot press sheet of thermoplastic polyurethane resin 6 was molded by the same operation as in Example 1.

Example 7 (Production of thermoplastic polyurethane resin 7)
In a reactor equipped with a stirrer under a nitrogen atmosphere, 30.07 parts of the amide group-containing diol 1, 101.3 parts of polycaprolactone polyol (trade name: PLACEL220 manufactured by Daicel Chemical Industries), and 170 parts of dehydrated dimethyl Acetamide (manufactured by Wako Pure Chemical Industries, Ltd.) was added and heated and stirred at 100 ° C. to obtain a uniform solution.

Next, a solution in which 38.80 parts of 4,4'-diphenylmethane diisocyanate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 35 parts of dehydrated dimethylacetamide was added dropwise thereto, and after completion of the addition, the mixture was heated and stirred for 2 hours.

Thereafter, reprecipitation was performed with 3000 parts of acetonitrile, and the obtained solid was separated by filtration and then washed twice with 500 parts of acetonitrile.

The obtained white solid was heated and dried overnight at 70 ° C. under a nitrogen stream to obtain 159.1 parts of a thermoplastic polyurethane resin (polyurethane elastomer) 7.

Table 2 shows the weight average molecular weight (Mw), 5% thermogravimetric decrease temperature and flow start temperature of the obtained thermoplastic polyurethane resin 7.
<Manufacture of hot press sheet>
A hot press sheet of the thermoplastic polyurethane resin 7 was molded by the same operation as in Example 1.

Example 8 (Production of thermoplastic polyurethane resin 8)
Under a nitrogen atmosphere, a reactor equipped with a stirrer was charged with 35.31 parts of amide group-containing diol 1, 118.90 parts of polycarbonate polyol (trade name: Duranol T5652 manufactured by Asahi Kasei Chemicals), and 200 parts of dehydrated dimethyl. Acetamide (manufactured by Wako Pure Chemical Industries, Ltd.) was added and heated and stirred at 100 ° C. to obtain a uniform solution.

Next, a solution in which 46.52 parts of 4,4′-diphenylmethane diisocyanate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 45 parts of dehydrated dimethylacetamide was added dropwise thereto. After completion of the dropwise addition, heating and stirring were continued for 2 hours. did.

Thereafter, reprecipitation was performed with 4000 parts of acetonitrile, and the obtained solid was separated by filtration and then washed twice with 1000 parts of acetonitrile.

The obtained white solid was heated and dried overnight at 70 ° C. under a nitrogen stream to obtain 182.0 parts of a thermoplastic polyurethane resin (polyurethane elastomer) 8.

Table 2 shows the weight average molecular weight (Mw), 5% thermogravimetric decrease temperature and flow start temperature of the obtained thermoplastic polyurethane resin 8.
<Manufacture of hot press sheet>
A hot press sheet of thermoplastic polyurethane resin 8 was molded by the same operation as in Example 1.

Example 9 (Production of thermoplastic polyurethane resin 9)
Under a nitrogen atmosphere, a reactor equipped with a stirrer was charged with 32.08 parts of polyethylene glycol (trade name: PEG # 2000U, hydroxyl value of 54.8 mgKOH / g manufactured by NOF) and 21.03 parts of poly (ethylene oxide). -Tetrahydrofuran) copolymer (trade name: Polyserine DC-1800E, hydroxyl value 63.3 mgKOH / g) manufactured by NOF Corporation was added and heated at 80 ° C. for 1 hour.

Next, 24.55 parts of 4,4'-diphenylmethane diisocyanate was added thereto and reacted at 80 ° C. for 2 hours to synthesize a prepolymer.

70 parts of DMAc was added to the resulting prepolymer and stirred sufficiently to dissolve the prepolymer uniformly. Next, the DMAc solution of the prepolymer was heated to 100 ° C.,
A DMAc solution of amide group-containing diol 2 (a solution obtained by previously dissolving 22.34 parts of amide group-containing diol 2 in 30 parts of DMAc at 100 ° C.) was added dropwise over 5 minutes.

The obtained white solid was dried under reduced pressure at 80 ° C. to obtain 92 parts of a thermoplastic polyurethane resin (polyurethane elastomer) 9.

Table 3 shows the weight average molecular weight (Mw), 5% thermogravimetric decrease temperature and flow start temperature of the obtained thermoplastic polyurethane resin 9.
<Manufacture of hot press sheet>
A hot press sheet of the thermoplastic polyurethane resin 9 was formed by the same operation as in Example 1.

The softening temperature of the obtained sheet sample for measurement was measured by thermomechanical analysis (TMA). The results are shown in Table 3.

Also, the tensile strength (unit: MPa), elastic modulus (unit: MPa), elongation at break (unit:%), and hardness (Shore A, Shore D) of the sheet sample for measurement were measured. The results are shown in Table 3.

Example 10 (Production of thermoplastic polyurethane resin 10)
Under a nitrogen atmosphere, a reactor equipped with a stirrer was charged with 29.85 parts of polyethylene glycol (trade name: PEG # 2000U, hydroxyl value of 54.8 mgKOH / g manufactured by NOF) and 29.36 parts of poly (ethylene oxide). -Tetrahydrofuran) copolymer (trade name: Polyserine DC-1800E, hydroxyl value 63.3 mgKOH / g) manufactured by NOF Corporation was added and heated at 80 ° C. for 1 hour.

Next, 24.91 parts of 4,4′-diphenylmethane diisocyanate was added and reacted at 80 ° C. for 2 hours to synthesize a prepolymer.

70 parts of DMAc was added to the obtained prepolymer and stirred sufficiently so that the prepolymer was uniformly dissolved. Subsequently, the DMAc solution of the prepolymer was heated to 100 ° C., and the amide group-containing diol 3 DMAc solution (15.89 parts of the amide group-containing diol 3 was previously dissolved in 30 parts of DMAc at 100 ° C. The solution was added dropwise over 5 minutes.

Thereafter, the obtained white solid was dried at 80 ° C. under reduced pressure to obtain 89.6 parts of a thermoplastic polyurethane resin (polyurethane elastomer) 10.

Table 3 shows the weight average molecular weight (Mw), 5% thermogravimetric decrease temperature and flow start temperature of the obtained thermoplastic polyurethane resin 10.
<Manufacture of hot press sheet>
A hot press sheet of the thermoplastic polyurethane resin 10 was formed by the same operation as in Example 1.

Example 11 (Production of thermoplastic polyurethane resin 11)
Under a nitrogen atmosphere, a reactor equipped with a stirrer was charged with 29.85 parts of polyethylene glycol (trade name: PEG # 2000U, hydroxyl value of 54.8 mgKOH / g manufactured by NOF) and 29.36 parts of poly (ethylene oxide). -Tetrahydrofuran) copolymer (manufactured by NOF Corporation, trade name: Polyserine DC-1800E, hydroxyl value 63.3 mgKOH / g) was added and heated at 80 ° C. for 1 hour.

Next, 23.97 parts of 4,4′-diphenylmethane diisocyanate was added and reacted at 80 ° C. for 2 hours to synthesize a prepolymer.

70 parts of DMAc was added to the obtained prepolymer and stirred sufficiently so that the prepolymer was uniformly dissolved. Next, the DMAc solution of the prepolymer was heated to 100 ° C., and the DMAc solution of amide group-containing diol 4 (16.83 parts of amide group-containing diol 4 was previously dissolved in 30 parts of DMAc at 100 ° C. The solution was added dropwise over 5 minutes.

The white solid obtained was dried under reduced pressure at 80 ° C. to obtain 72.6 parts of a thermoplastic polyurethane resin (polyurethane elastomer) 11.

Table 3 shows the weight average molecular weight (Mw), 5% thermogravimetric decrease temperature and flow start temperature of the obtained thermoplastic polyurethane resin 11.
<Manufacture of hot press sheet>
A hot press sheet of thermoplastic polyurethane resin 11 was formed by the same operation as in Example 1.

Example 12 (Production of thermoplastic polyurethane resin 12)
In a nitrogen atmosphere, a reactor equipped with a stirrer was charged with 29.85 parts of polyethylene glycol (manufactured by NOF Corporation, trade name: PEG # 2000U, hydroxyl value 54.8 mgKOH / g), and 29.36 parts of poly ( An ethylene oxide-tetrahydrofuran) copolymer (manufactured by NOF Corporation, trade name: Polyserine DC-1800E, hydroxyl value 63.3 mgKOH / g) was added, and the mixture was heated at 80 ° C. for 1 hour.

Next, 27.16 parts of 4,4′-diphenylmethane diisocyanate was added and reacted at 80 ° C. for 2 hours to synthesize a prepolymer.

70 parts of DMAc was added to the obtained prepolymer and stirred sufficiently so that the prepolymer was uniformly dissolved. Next, the DMAc solution of the prepolymer was heated to 100 ° C., and the DMAc solution of amide group-containing diol 5 (previously 13.63 parts of amide group-containing diol 5 was dissolved in 30 parts of DMAc at 100 ° C. The solution was added dropwise over 5 minutes.

The obtained white solid was dried under reduced pressure at 80 ° C. to obtain 86 parts of a thermoplastic polyurethane resin (polyurethane elastomer) 12.

Table 3 shows the weight average molecular weight (Mw), 5% thermogravimetric decrease temperature and flow start temperature of the obtained thermoplastic polyurethane resin 12.
<Manufacture of hot press sheet>
A hot press sheet of the thermoplastic polyurethane resin 12 was molded by the same operation as in Example 1.

Comparative Example 1 (Production of thermoplastic polyurethane resin 13)
Under a nitrogen atmosphere, 53.46 parts of polyethylene glycol (trade name: PEG # 2000U, hydroxyl value: 54.8 mgKOH / g, manufactured by NOF Corporation) was added to a reactor equipped with a stirrer, and heated at 80 ° C. for 1 hour.

Next, 35.95 parts of 4,4′-diphenylmethane diisocyanate was added and reacted at 80 ° C. for 2 hours to synthesize a prepolymer.

70 parts of DMAc was added to the obtained prepolymer and stirred sufficiently so that the prepolymer was uniformly dissolved. Next, the DMAc solution of the prepolymer was heated to 100 ° C., and the DMAc solution of 1,4-butanediol (previously dissolved 10.59 parts of 1,4-butanediol in 30 parts of DMAc at 100 ° C.) The solution was added dropwise over 5 minutes.

The obtained white solid was dried at 80 ° C. under reduced pressure to obtain 96.7 parts of a thermoplastic polyurethane resin (polyurethane elastomer) 13.

Table 4 shows the weight average molecular weight (Mw), 5% thermogravimetric decrease temperature and flow start temperature of the obtained thermoplastic polyurethane resin 13.
<Manufacture of hot press sheet>
A hot press sheet of thermoplastic polyurethane resin 13 was molded by the same operation as in Example 1.

The softening temperature of the obtained sheet sample for measurement was measured by thermomechanical analysis (TMA). The results are shown in Table 4.

Further, the tensile strength (unit: MPa), elastic modulus (unit: MPa), elongation at break (unit:%), and hardness (Shore A, Shore D) of the measurement sheet sample were measured. The results are shown in Table 4.
<Manufacture of solvent cast film>
A cast film of a thermoplastic polyurethane resin 13 having a thickness of 20 μm was formed by the same operation as in Example 1.

Further, the moisture permeability (unit: g / m ² · 24 h), tensile strength (unit: MPa), elastic modulus (unit: MPa), and elongation at break (unit:%) of the cast film were measured. The results are shown in Table 4.

Comparative Example 2 (Production of thermoplastic polyurethane resin 14)
Under a nitrogen atmosphere, 70.11 poly (ethylene oxide-tetrahydrofuran) copolymer (trade name: Polyserine DC-1800E, hydroxyl value 63.3 mgKOH / g, manufactured by NOF) was added to a reactor equipped with a stirrer. Heated at 80 ° C. for 1 hour.

Next, 19.19 parts of 4,4′-diphenylmethane diisocyanate was added and reacted at 80 ° C. for 2 hours to synthesize a prepolymer.

70 parts of DMAc was added to the obtained prepolymer and stirred sufficiently so that the prepolymer was uniformly dissolved. Next, the DMAc solution of the prepolymer was heated to 100 ° C., and the DMAc solution of amide group-containing diol 1 (preliminarily dissolved 10.71 parts of amide group-containing diol 1 in 100 parts of DMAc at 100 ° C.) The solution was added dropwise over 5 minutes.

After reacting at 100 ° C. for 30 minutes, 200 parts of DMAc was gradually added and reacted for 1 hour. The obtained reaction solution was reprecipitated with 2000 parts of acetonitrile, washed repeatedly with acetonitrile, and then suction filtered.

The obtained white solid was dried under reduced pressure at 80 ° C. to obtain 91 parts of a thermoplastic polyurethane resin (polyurethane elastomer) 14.

Table 4 shows the weight average molecular weight (Mw), 5% thermogravimetric decrease temperature and flow start temperature of the obtained thermoplastic polyurethane resin 14.
<Manufacture of hot press sheet>
A hot press sheet of the thermoplastic polyurethane resin 14 was molded by the same operation as in Example 1.

Also, the tensile strength (unit: MPa), elastic modulus (unit: MPa), elongation at break (unit:%), and hardness (Shore A, Shore D) of the sheet sample for measurement were measured. The results are shown in Table 4.

Comparative Example 3 (Production of thermoplastic polyurethane resin 15)
Under a nitrogen atmosphere, 30.7 parts of a poly (ethylene oxide-tetrahydrofuran) copolymer (trade name: polyserine DC-1800E, hydroxyl value 63.3 mgKOH / g) manufactured by NOF CORPORATION was added to a reactor equipped with a stirrer. And heated at 80 ° C. for 1 hour.

Next, 34.5 parts of 4,4′-diphenylmethane diisocyanate was added and reacted at 80 ° C. for 2 hours to synthesize a prepolymer.

70 parts of DMAc was added to the obtained prepolymer and stirred sufficiently so that the prepolymer was uniformly dissolved. Next, the DMAc solution of the prepolymer was heated to 100 ° C., and the DMAc solution of amide group-containing diol 1 (previously 34.8 parts of amide group-containing diol 1 was dissolved in 30 parts of DMAc at 100 ° C. The solution was added dropwise over 5 minutes.

Thereafter, the obtained white solid was dried under reduced pressure at 80 ° C. to obtain 96 parts of a thermoplastic polyurethane resin (polyurethane elastomer) 15.

Table 4 shows the weight average molecular weight (Mw), 5% thermogravimetric decrease temperature and flow start temperature of the obtained thermoplastic polyurethane resin 15.
<Manufacture of hot press sheet>
A hot press sheet of thermoplastic polyurethane resin 15 was molded by the same operation as in Example 1.

The abbreviations and product names in the table are as follows (the same applies hereinafter).
PEG # 2000U: polyethylene glycol, number average molecular weight 2000, hydroxyl value 54.8 mgKOH / g, NOF PC-DC-1800E: polyether polyol (polyserine DC-1800E), poly (ethylene oxide-tetrahydrofuran) copolymer, Number average molecular weight 1,800, hydroxyl value 63.3 mg KOH / g, NOF PTG-2000SN: polytetraethylene ether glycol, number average molecular weight 2000, hydroxyl value 57.0 mg KOH / g, Hodogaya Chemical Takelac U-2024: polyester polyol, Number average molecular weight 2000, hydroxyl value 56 mgKOH / g, Mitsui Chemicals PACCEL220: polycaprolactone polyol, number average molecular weight 2000, hydroxyl value 56 mgKOH / g, Daicel Chemical Duranol T 652: Polycarbonate polyol, number average molecular weight 2000, hydroxyl value 56 mg KOH / g, MDI manufactured by Asahi Kasei Chemicals: 4,4′-diphenylmethane diisocyanate 1,4-BG: 1,4-butanediol The above invention is an example of the present invention However, this is merely an example and should not be construed as limiting. Modifications of the present invention apparent to those skilled in the art are intended to be included within the scope of the following claims.

The thermoplastic polyurethane resin of the present invention can be used in various industrial fields, and is particularly effective in industrial fields where moisture permeability is required.

Claims

A thermoplastic polyurethane resin obtained by reacting at least a polyisocyanate, a high molecular weight polyol, and a chain extender,
The chain extender contains an amide group-containing diol represented by the following general formula (1),
A thermoplastic, characterized in that the content of hard segments formed by the reaction of the polyisocyanate and the amide group-containing diol is 30 to 60% by mass with respect to the total amount of the thermoplastic polyurethane resin. Polyurethane resin.
HO—R 2 —CO—NH—R 1 —NH—CO—R 3 —OH (1)
(In the formula, R 1 is a divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms, or a divalent aliphatic group having 7 to 8 carbon atoms. Each represents an araliphatic hydrocarbon group, and R 2 and R 3 are the same or different from each other and represent a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms or a divalent fatty acid having 3 to 5 carbon atoms. Indicates a ring-containing hydrocarbon group.)
The thermoplastic polyurethane resin according to claim 1, wherein the amide group-containing diol is represented by the following general formula (2).
HO— (CH 2 ) 5 —CO—NH—R 1 —NH—CO— (CH 2 ) 5 —OH (2)
(Wherein, R 1 represents the same meaning as R 1 in the formula (1).)
The thermoplastic polyurethane resin according to claim 1, wherein the amide group-containing diol is obtained by a reaction between an aliphatic diamine and a hydroxycarboxylic acid or a derivative thereof.
The high molecular weight polyol contains an oxyethylene group,
2. The thermoplastic polyurethane resin according to claim 1, wherein a content of the oxyethylene group is 20% by mass or more and 60% by mass or less with respect to a total amount of the thermoplastic polyurethane resin.
5. The thermoplastic polyurethane resin according to claim 4, wherein the moisture permeability when formed into a film having a thickness of 20 μm is 10,000 g / m 2 · 24 h or more.
The thermoplastic polyurethane resin according to claim 1, wherein the softening temperature is 160 ° C or higher.
A thermoplastic polyurethane resin obtained by reacting at least a polyisocyanate, a high molecular weight polyol, and a chain extender,
The chain extender contains an amide group-containing diol represented by the following general formula (1),
Molding a thermoplastic polyurethane resin in which the content of hard segments formed by the reaction of the polyisocyanate and the amide group-containing diol is 30 to 60% by mass with respect to the total amount of the thermoplastic polyurethane resin. A molded article characterized by being obtained by
HO—R 2 —CO—NH—R 1 —NH—CO—R 3 —OH (1)
(In the formula, R 1 is a divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms, or a divalent aliphatic group having 7 to 8 carbon atoms. Each represents an araliphatic hydrocarbon group, and R 2 and R 3 are the same or different from each other and represent a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms or a divalent fatty acid having 3 to 5 carbon atoms. Indicates a ring-containing hydrocarbon group.)
The molded article according to claim 7, which is obtained by molding the thermoplastic polyurethane resin into a film.
The molded article according to claim 7, wherein the molded article is obtained by extruding the thermoplastic polyurethane resin.
The thermoplastic polyurethane resin is dissolved in an aprotic polar solvent to prepare a solution of the thermoplastic polyurethane resin, and then the aprotic polar organic solvent is removed from the solution to form a film. The molded article according to claim 8, wherein