JP5564015B2 - Tube and tube manufacturing method - Google Patents

Description

  The present invention relates to a tube and a method for manufacturing the tube, and more particularly to a tube formed from a polyurethane elastomer and a method for manufacturing the tube.

  Conventionally, tubes used in various industrial fields such as medical and electric wires are required to have various mechanical properties such as flexibility and kink resistance. As a tube having such mechanical properties, for example, a tube made of a resin material such as polyurethane elastomer is known.

  Specifically, for example, the medical tube is formed from a mixed resin including a polyurethane resin obtained using 4,4-dicyclohexylmethane diisocyanate as a raw material and a styrene resin such as a styrene-isobutylene copolymer. A medical tube has been proposed (see, for example, Patent Document 1).

JP 2008-104766 A

  However, such a medical tube is excellent in mechanical properties such as kink resistance, but has surface tackiness, and therefore may cause blocking after production.

  Accordingly, an object of the present invention is to provide a tube having excellent mechanical properties and excellent blocking resistance, and a method for producing such a tube.

  In order to achieve the above object, the tube of the present invention is formed from a polyurethane elastomer obtained by a reaction between an isocyanate component containing 1,4-bis (isocyanatomethyl) cyclohexane and a polyol component, and has a hardness of 65A. It is over 95A or less.

  In the tube of the present invention, the polyol component contains a high molecular weight polyol and a low molecular weight polyol, and the high molecular weight polyol contains amorphous polytetramethylene ether glycol in a proportion of 20 to 80 mol%. Is preferred.

  The tube of the present invention is preferably a hose.

  The tube of the present invention is preferably a cable sheath.

  The tube manufacturing method of the present invention also includes a bismuth carboxylate, a zinc carboxylate, and zirconium, using an isocyanate component containing 1,4-bis (isocyanatomethyl) cyclohexane and a polyol component as catalysts. A step of preparing a polyurethane elastomer by reacting in the presence of at least one carboxylate selected from the group consisting of the following carboxylates, and a step of forming a tube from the polyurethane elastomer. It is said.

  Since the tube of the present invention is formed from a polyurethane elastomer obtained by the reaction of an isocyanate component containing 1,4-bis (isocyanatomethyl) cyclohexane and a polyol component, the hardness exceeds 65A and is 95A or less. In addition, the mechanical properties are excellent, and further, the blocking resistance can be improved.

  Further, in the method for producing a tube of the present invention, an isocyanate component containing 1,4-bis (isocyanatomethyl) cyclohexane and a polyol component are mixed with bismuth carboxylate, zinc carboxylate and zirconium carboxylic acid. Since the reaction is carried out in the presence of at least one carboxylate selected from the group consisting of salts, a tube having excellent mechanical properties and blocking resistance can be produced.

FIG. 1 is a schematic configuration diagram showing a kink resistance evaluation method.

  The tube of this invention is formed from the polyurethane elastomer obtained by reaction of an isocyanate component and a polyol component.

The isocyanate component contains 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ XDI) as an essential component.

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

  As 1,4-bis (isocyanatomethyl) cyclohexane, preferably, a trans 1,4 form is included.

  In the case where 1,4-bis (isocyanatomethyl) cyclohexane contains 1,4-trans, the content ratio is, for example, 80 mol with respect to the total mol of 1,4-bis (isocyanatomethyl) cyclohexane. % Or more, preferably 85 mol% or more.

  In addition, 1,4-bis (isocyanatomethyl) cyclohexane containing 1,4-bis (isocyanatomethyl) cyclohexane containing 80 mol% or more of trans 1,4 form is used as a raw material, 1,4-bis (aminomethyl) cyclohexane containing 80 mol% or more of trans form, For example, it is described in the phosgene method (cold heat two-stage method (direct method) or salt formation method) described in JP-A-7-309827, JP-A-2004-244349, JP-A-2003-212835, or the like. The non-phosgene method can be used.

  1,4-bis (isocyanatomethyl) cyclohexane can also be prepared as a derivative.

  Examples of derivatives of 1,4-bis (isocyanatomethyl) cyclohexane include, for example, multimers of 1,4-bis (isocyanatomethyl) cyclohexane (dimer, trimer (for example, isocyanurate modified, iminooxadiazine dione modified) Etc.), biuret-modified products (for example, biuret-modified products produced by the reaction of 1,4-bis (isocyanatomethyl) cyclohexane and water), allophanate-modified products (for example, 1,4-bis (isocyanate)). Natomethyl) cyclohexane and monools or low molecular weight polyols (described later) and polyol modified products (for example, 1,4-bis (isocyanatomethyl) cyclohexane and low molecular weight polyols (described later)). Or reaction with high molecular weight polyol (described later) Modified polyols, etc.), oxadiazine trione modified products (for example, oxadiazine trione produced by reaction of 1,4-bis (isocyanatomethyl) cyclohexane and carbon dioxide), carbodiimide modified products (1 , 4-bis (isocyanatomethyl) cyclohexane decarboxylation condensation product produced by decarboxylation condensation reaction, urea-modified product (for example, urea produced by reaction of 1,4-bis (isocyanatomethyl) cyclohexane and diamine) Modified body, etc.), uretdione modified body, uretonimine modified body and the like.

  Further, the isocyanate component can contain other polyisocyanate compounds (polyisocyanate compounds excluding 1,4-bis (isocyanatomethyl) cyclohexane) within a range that does not impair the excellent effects of the tube of the present invention.

  The other polyisocyanate compound is an organic compound containing two or more isocyanate groups, and examples thereof include polyisocyanate monomers such as aromatic polyisocyanate, araliphatic polyisocyanate, and aliphatic polyisocyanate.

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

  Examples of the araliphatic polyisocyanate include xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetra). Methyl xylylene diisocyanate or a mixture thereof (TMXDI), aromatic aliphatic diisocyanates such as ω, ω′-diisocyanate-1,4-diethylbenzene, and the like.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1 , 5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaproate, etc. Aliphatic diisocyanate and the like can be mentioned.

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

Examples of the alicyclic polyisocyanate excluding 1,4-bis (isocyanatomethyl) cyclohexane include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1, 3-cyclohexanediisocyanate), 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (isophorodiisocyanate) (IPDI), methylenebis (cyclohexylisocyanate) (4,4'-, 2,4'- or 2, 2'-methylenebis (cyclohexyl _isocyanate)) (H 12 _MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohex Diisocyanate), norbornane diisocyanate (various isomers or mixtures thereof) (NBDI), 1,3-bis (isocyanatomethyl) cyclohexane _{(1,3-H 6 XDI),} 1,3- bis (isocyanatomethyl) cyclohexane, And alicyclic diisocyanates such as 1,4-bis (isocyanatoethyl) cyclohexane.

  In addition, 1,3-bis (isocyanatomethyl) cyclohexane includes cis-1,3-bis (isocyanatomethyl) cyclohexane (hereinafter referred to as cis 1,3 form), and trans-1,3- There is a geometric isomer of bis (isocyanatomethyl) cyclohexane (hereinafter referred to as trans 1,3).

  As 1,3-bis (isocyanatomethyl) cyclohexane, preferably, a trans 1,3 form is contained.

  In the case where 1,3-bis (isocyanatomethyl) cyclohexane contains trans 1,3-isomer, the content ratio is, for example, 50 moles relative to the total mole of 1,3-bis (isocyanatomethyl) cyclohexane. % Or more, preferably 70 mol% or more, more preferably 90 mol% or more.

  Moreover, as another polyisocyanate compound, the derivative | guide_body of the above-mentioned polyisocyanate monomer (The polyisocyanate monomer except 1, 4-bis (isocyanatomethyl) cyclohexane) is mentioned further.

  More specifically, as a derivative of the polyisocyanate compound, for example, a multimer of the above-mentioned polyisocyanate monomer (dimer, trimer (eg, isocyanurate-modified, iminooxadiazinedione-modified, etc.)), biuret, etc. Examples include modified products, allophanate modified products, polyol modified products, oxadiazine trione modified products, carbodiimide modified products, urea modified products, uretdione modified products, and uretonimine modified products.

  Furthermore, polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI) etc. are mentioned as a derivative of a polyisocyanate compound.

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

  The isocyanate component can further contain a monoisocyanate compound as an optional component from the viewpoint of adjusting the molecular weight of the polyurethane elastomer.

  The monoisocyanate compound is an organic compound containing one isocyanate group, and examples thereof include methyl isocyanate, ethyl isocyanate, n-hexyl isocyanate, cyclohexyl isocyanate, 2-ethylhexyl isocyanate, phenyl isocyanate, and benzyl isocyanate.

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

  In the isocyanate component, the content ratio of 1,4-bis (isocyanatomethyl) cyclohexane is, for example, 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more, and further preferably 90 mol%. % Or more, particularly preferably 100%.

  Examples of the polyol component include low molecular weight polyols and high molecular weight polyols.

  The low molecular weight polyol is a compound having two or more hydroxyl groups and a number average molecular weight of less than 400, preferably less than 300, such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol ( 1,4-butanediol), 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol 2,2,2-trimethylpentanediol, 3,3-dimethylolheptane, alkane (C7-20) diol, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1 , 4-cyclohexanediol and mixtures thereof, hydrogenated bisphenol 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol, dipropylene glycol and other dihydric alcohols such as glycerin, tri Trihydric alcohols such as methylolpropane and triisopropanolamine, for example tetramethylolmethane (pentaerythritol), tetrahydric alcohols such as diglycerin, for example pentavalent alcohols such as xylitol, such as sorbitol, mannitol, allitol, iditol, dulcitol And hexavalent alcohols such as altitol, inositol and dipentaerythritol, for example, 7-valent alcohols such as perseitol, and octavalent alcohols such as sucrose.

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

  The high molecular weight polyol is a compound having two or more hydroxyl groups and a number average molecular weight of 300 or more, preferably 400 or more. For example, polyether polyol, polyester polyol, polycarbonate polyol, polyurethane polyol, epoxy polyol, vegetable oil polyol, polyolefin Examples include polyols, acrylic polyols, and vinyl monomer-modified polyols.

  Examples of the polyether polyol include polyoxyalkylene polyols such as polypropylene polyol (polyoxypropylene polyol) and polytetramethylene ether polyol.

  Examples of the polypropylene polyol include, for example, the above-described low molecular weight polyols and the like, addition polymers of propylene oxide starting from aromatic polyamines, aliphatic polyamines, and the like (random and / or propylene oxide and alkylene oxides such as ethylene oxide). Or a block copolymer).

  Examples of the polytetramethylene ether polyol include a ring-opening polymer obtained by cationic polymerization of tetrahydrofuran, and an amorphous (non-crystalline) obtained by copolymerizing an alkyl-substituted tetrahydrofuran or the above-described dihydric alcohol with a polymerization unit such as tetrahydrofuran. Property) polytetramethylene ether glycol and the like.

  In addition, amorphous (noncrystalline) means that it is liquid at normal temperature (25 ° C.).

  Amorphous polytetramethylene ether glycol is, for example, a copolymer of tetrahydrofuran and alkyl-substituted tetrahydrofuran (for example, 3-methyltetrahydrofuran) (tetrahydrofuran / alkyl-substituted tetrahydrofuran (molar ratio)) = 15 / 85-85 / 15, a number average molecular weight of 500 to 4000, preferably 800 to 2500), for example, a copolymer of tetrahydrofuran and a branched glycol (such as neopentyl glycol) (tetrahydrofuran / branched glycol (molar ratio)) = 15/85 to 85/15, number average molecular weight 500 to 4000, preferably 800 to 2500).

  Examples of the polyester polyol include polycondensates obtained by reacting the above-described low molecular weight polyol and polybasic acid under known conditions.

  Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, and 3-methyl-3-ethylglutaric acid. , Azelaic acid, sebacic acid, other saturated aliphatic dicarboxylic acids (C11-13) such as maleic acid, fumaric acid, itaconic acid, other unsaturated aliphatic dicarboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid , Toluene dicarboxylic acid, naphthalene dicarboxylic acid, other aromatic dicarboxylic acids such as hexahydrophthalic acid, other alicyclic dicarboxylic acids such as dimer acid, hydrogenated dimer acid, het acid and other carboxylic acids, And acid anhydrides derived from these carboxylic acids, such as oxalic anhydride, succinic anhydride , Maleic anhydride, phthalic anhydride, 2-alkyl (C12-C18) succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, and acid halides derived from these carboxylic acids, such as oxalic acid Examples include dichloride, adipic acid dichloride, and sebacic acid dichloride.

  Further, as the polyester polyol, for example, a plant-derived polyester polyol, specifically, a hydroxyl group-containing vegetable oil fatty acid (for example, castor oil fatty acid containing ricinoleic acid, 12-hydroxystearic acid, using the above-described low molecular weight polyol as an initiator, And vegetable oil-based polyester polyols obtained by subjecting a hydroxycarboxylic acid such as hydrogenated castor oil fatty acid and the like to a condensation reaction under known conditions.

  Further, as the polyester polyol, for example, the above-described low molecular weight polyol (preferably dihydric alcohol) is used as an initiator, for example, lactones such as ε-caprolactone and γ-valerolactone, for example, L-lactide, D- Examples thereof include polycaprolactone polyol, polyvalerolactone polyol obtained by ring-opening polymerization of lactides such as lactide, and lactone polyester polyol obtained by copolymerizing the above-described dihydric alcohol.

  As the polycarbonate polyol, for example, a ring-opening polymer of ethylene carbonate using the above-described low molecular weight polyol (preferably a dihydric alcohol) as an initiator, for example, 1,4-butanediol, 1,5-pentanediol, Examples thereof include amorphous polycarbonate polyols obtained by copolymerizing a dihydric alcohol such as 3-methyl-1,5-pentanediol or 1,6-hexanediol with a ring-opening polymer.

  Further, the polyurethane polyol is a ratio in which the equivalent ratio (OH / NCO) of the hydroxyl group (OH) to the isocyanate group (NCO) of the polyester polyol, polyether polyol and / or polycarbonate polyol obtained as described above exceeds 1, By reacting with polyisocyanate, it can be obtained as polyester polyurethane polyol, polyether polyurethane polyol, polycarbonate polyurethane polyol, or polyester polyether polyurethane polyol.

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

  Examples of the vegetable oil polyol include hydroxyl group-containing vegetable oils such as castor oil and coconut oil. For example, castor oil polyol, or ester-modified castor oil polyol obtained by reaction of castor oil fatty acid and polypropylene polyol can be used.

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

  Examples of the acrylic polyol include a copolymer obtained by copolymerizing a hydroxyl group-containing acrylate and a copolymerizable vinyl monomer copolymerizable with the hydroxyl group-containing acrylate.

  Examples of the hydroxyl group-containing acrylate include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2,2-dihydroxymethylbutyl (meth) acrylate, polyhydroxyalkyl maleate, Examples thereof include polyhydroxyalkyl fumarate. Preferably, 2-hydroxyethyl (meth) acrylate etc. are mentioned.

  Examples of the copolymerizable vinyl monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and s-butyl ( Alkyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl acrylate, and the like ( (Meth) acrylate (C1-C12), for example, aromatic vinyl such as styrene, vinyltoluene, α-methylstyrene, for example, vinyl cyanide such as (meth) acrylonitrile, for example, ( A) Vinyl monomers containing a carboxyl group such as acrylic acid, fumaric acid, maleic acid, itaconic acid, or alkyl esters thereof such as ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di ( Alkane polyol poly (meth) acrylates such as meth) acrylate, oligoethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, for example 3- (2-isocyanate-2 And vinyl monomers containing isocyanate groups such as -propyl) -α-methylstyrene.

  The acrylic polyol can be obtained by copolymerizing these hydroxyl group-containing acrylate and copolymerizable vinyl monomer in the presence of a suitable solvent and polymerization initiator.

  The acrylic polyol includes, for example, silicone polyol and fluorine polyol.

  Examples of the silicone polyol include an acrylic polyol in which a silicone compound containing a vinyl group such as γ-methacryloxypropyltrimethoxysilane is blended as the copolymerizable vinyl monomer in the copolymerization of the acrylic polyol described above. .

  As the fluorine polyol, for example, in the copolymerization of the acrylic polyol described above, as the copolymerizable vinyl monomer, for example, an acrylic polyol in which a fluorine compound containing a vinyl group such as tetrafluoroethylene or chlorotrifluoroethylene is blended may be mentioned. .

  The vinyl monomer-modified polyol can be obtained by a reaction between the above-described high molecular weight polyol and a vinyl monomer.

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

  As the high molecular weight polyol, a polyether polyol is preferable, a polytetramethylene ether polyol is more preferable, and an amorphous polytetramethylene ether glycol is particularly preferable.

  As the amorphous polytetramethylene ether glycol, commercially available products can be used. Examples of such commercially available products include “PTXG” series manufactured by Asahi Kasei Corporation, “PTG-” manufactured by Hodogaya Chemical Co., Ltd. L ”series and the like.

  If amorphous polytetramethylene ether glycol is used as the high molecular weight polyol, flexibility and blocking resistance can be improved.

  Moreover, in the high molecular weight polyol, the content ratio of the amorphous polytetramethylene ether glycol is, for example, 10 to 90 mol%, preferably 20 to 80 mol%, more preferably, based on the total amount of the high molecular weight polyol. 30 to 80 mol%.

  When the content ratio of amorphous polytetramethylene ether glycol is in the above range, the extrusion stability in extrusion molding can be improved.

  In order to produce a tube, first, a polyurethane elastomer (specifically, a thermoplastic polyurethane elastomer: TPU, the same applies hereinafter) is prepared by a polymerization method such as bulk polymerization or solution polymerization.

  In bulk polymerization, for example, while stirring an isocyanate component under a nitrogen stream, a polyol component is added thereto, and the reaction temperature is 50 to 250 ° C., more preferably 50 to 200 ° C., for about 0.5 to 15 hours. React.

  In solution polymerization, an isocyanate component and a polyol component are added to an organic solvent and reacted at a reaction temperature of 50 to 120 ° C., more preferably 50 to 100 ° C. for about 0.5 to 15 hours.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, nitriles such as acetonitrile, alkyl esters such as methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate, such as n- Aliphatic hydrocarbons such as hexane, n-heptane, and octane, for example, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, for example, aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, such as methyl cellosolve acetate , Ethyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxy Glycol ether esters such as butyl acetate and ethyl-3-ethoxypropionate, for example, ethers such as diethyl ether, tetrahydrofuran and dioxane, such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, iodine Halogenated aliphatic hydrocarbons such as methylene chloride and dichloroethane, for example, polar aprotics such as N-methylpyrrolidone, dimethylformamide, N, N′-dimethylacetamide, dimethylsulfoxide, hexamethylphosphonylamide, etc. .

  Furthermore, as an organic solvent, a nonpolar solvent (nonpolar organic solvent) is mentioned, for example, As these nonpolar solvents, the aniline point containing an aliphatic and a naphthene type hydrocarbon organic solvent is 10--10, for example. Examples include non-polar organic solvents having low toxicity and weak dissolving power at 70 ° C., preferably 12 to 65 ° C., vegetable oils represented by terpene oil, and the like.

  Furthermore, in the above polymerization reaction, a catalyst (urethanization catalyst) is preferably added.

  Examples of the catalyst include carboxylates, amines, organometallic compounds, potassium salts and the like.

  Examples of the carboxylate include bismuth carboxylate, zinc carboxylate, zirconium carboxylate, tin carboxylate, lithium carboxylate, potassium carboxylate, sodium carboxylate, Examples include palladium carboxylate.

  In the carboxylate, the carboxylic acid includes, for example, methanoic acid, ethanoic acid, propanoic acid, isopropanoic acid, butanoic acid, isobutanoic acid, s-butanoic acid, t-butanoic acid, pentanoic acid, hexanoic acid, heptane Aliphatic carboxylic acids such as acid, octanoic acid, nonanoic acid, decanoic acid, neodecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid and octadecanoic acid, for example, aromatic carboxylic acids such as benzoic acid and phthalic acid, for example And dicarboxylic acids such as oxalic acid, succinic acid and fumaric acid.

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

  Examples of the amines include tertiary amines such as triethylamine, triethylenediamine, bis- (2-dimethylaminoethyl) ether, N-methylmorpholine, and quaternary ammonium salts such as tetraethylhydroxylammonium, such as imidazole, Examples thereof include 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, for example And 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.

  Examples of the potassium salt include potassium carbonate, potassium acetate, and potassium octylate.

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

  The catalyst is preferably a carboxylate, more preferably a bismuth carboxylate, a zinc carboxylate, or a zirconium carboxylate.

  If these carboxylates are used, the kink resistance can be improved.

  The blending ratio of the catalyst is, for example, 1 to 5000 ppm, preferably 2 to 3000 ppm with respect to the total amount of the isocyanate component and the polyol component.

  In the polymerization reaction, the (unreacted) isocyanate component can be removed by a known removal means such as distillation or extraction.

  In the solution polymerization, the organic solvent after the reaction of the isocyanate component and the polyol component can also be removed by a known removal means such as distillation or extraction.

  In bulk polymerization and solution polymerization, for example, an isocyanate component and a polyol component have an equivalent ratio R (NCO / active hydrogen group) of the isocyanate group in the isocyanate component to the active hydrogen group (hydroxyl group) in the polyol component. It mix | blends so that it may become 0.75-1.3, Preferably 0.9-1.1.

  Further, when the above polymerization reaction is carried out more industrially, the polyurethane elastomer can be obtained by a known method such as a one-shot method or a prepolymer method, depending on the application.

  In the one-shot method, for example, an isocyanate component and a polyol component have an equivalent ratio R (NCO / active hydrogen group) of the isocyanate group in the isocyanate component to the active hydrogen group (hydroxyl group) in the polyol component, for example, 0.75. To 1.3, preferably 0.9 to 1.1, and then formulated (mixed), for example, at room temperature to 250 ° C., preferably at room temperature to 200 ° C., for example, 5 minutes to 72 hours, Preferably, the curing reaction is performed for 4 to 24 hours. The curing temperature may be a constant temperature, or may be raised or cooled stepwise.

  In such a one-shot method, preferably, the isocyanate component and / or the polyol component are heated to lower the viscosity and then mixed, and then defoamed as necessary, followed by preheating. It is poured into a mold and allowed to cure. Thereby, a polyurethane elastomer can be obtained.

  In the prepolymer method, for example, an isocyanate component and a part of the polyol component (preferably, a 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 and the remainder of the polyol component (preferably, a low molecular weight polyol) are reacted to cause a curing reaction. In the prepolymer method, the remainder of the polyol component is used as a chain extender.

  In order to synthesize an isocyanate group-terminated prepolymer, an isocyanate component and a part of the polyol component are equivalent ratio R (NCO / active hydrogen group) of the isocyanate group in the isocyanate component to the active hydrogen group in a part of the polyol component. Is, for example, 1.1-5.5, preferably 1.3-4.5, more preferably 1.5-3.5, and in a reaction vessel, For example, the reaction is performed at room temperature to 150 ° C., preferably 50 to 120 ° C., for example, for 0.5 to 18 hours, preferably 2 to 10 hours. In this reaction, it is preferable to add the above urethanization catalyst.

  Moreover, after completion | finish of reaction can also remove an unreacted isocyanate component by well-known removal means, such as distillation and extraction, as needed.

  Next, in order to react the obtained isocyanate group-terminated prepolymer with the remainder of the polyol component (chain extender), the isocyanate group-terminated prepolymer and the remainder of the polyol component (chain extender) are reacted with the polyol component. The equivalent ratio R (NCO / active hydrogen group) of the isocyanate group in the isocyanate group-terminated prepolymer to the active hydrogen group in the balance (chain extender) is, for example, 0.75 to 1.3, preferably 0.9. It is formulated (mixed) to be -1.1, and is allowed to undergo a curing reaction, for example, at room temperature to 250 ° C, preferably at room temperature to 200 ° C, for example, for 5 minutes to 72 hours, preferably 1 to 24 hours.

  Further, the polyurethane elastomer can further contain a heat stabilizer.

  Examples of the heat resistant stabilizer include hindered phenol antioxidants, phosphorus heat stabilizers, lactone heat stabilizers, sulfur heat stabilizers, and the like. Commercially available products of these heat stabilizers include, for example, Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1098, Irganox 1135, Irganox 1222, Irganox 1425WL, Irganox 1520L, Irganox 245, Irganox. 3790, Irganox 5057, Irganox 168, Irganox 126, HP-136, etc. (all manufactured by Ciba Specialty Chemicals).

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

  The blending ratio of the heat stabilizer is not particularly limited and is appropriately set according to the purpose and application.

  The heat resistance stabilizer can be added in advance to either or either of the isocyanate component and the polyol component, or can be added separately during the reaction of the isocyanate component and the polyol component.

  Further, the polyurethane elastomer can further contain a lubricant.

  Examples of the lubricant include fatty acid amide lubricants and montanic acid lubricants.

  Examples of the fatty acid amide-based lubricant include stearic acid amide, oleic acid amide, erucic acid amide, ethylene bis stearic acid amide, and preferably oleic acid amide and erucic acid amide.

  Examples of the montanic acid-based lubricant include montanic acid ester, montanic acid ester partial saponified product, montanic acid sodium salt, and montanic acid calcium salt, and preferably montanic acid ester and montanic acid ester partial saponified product. .

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

  The blending ratio of the lubricant is not particularly limited, and is appropriately set according to the purpose and application.

  The lubricant can be added in advance to either or either of the isocyanate component and the polyol component, or can be added separately during the reaction between the isocyanate component and the polyol component.

  The polyurethane elastomer may be a known additive, for example, a lubricant, further a plasticizer, an anti-blocking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a release agent, a pigment, a dye, if necessary. Fillers, hydrolysis inhibitors, flame retardants, and the like can be added.

  In addition, the mixture ratio of an additive is suitably set according to the objective and use.

  Such an additive can be added in advance to either or either of the isocyanate component and the polyol component, or can be added separately during the reaction of the isocyanate component and the polyol component.

  And a tube can be manufactured by shape | molding the polyurethane elastomer obtained by the above by well-known shaping | molding methods, such as extrusion molding and injection molding, for example after pelletizing.

  Further, the length, the outer diameter, and the inner diameter of the tube are not particularly limited, and are appropriately set according to the purpose and application.

  And according to such a tube, the improvement of a mechanical physical property can be aimed at.

  Specifically, the tube thus obtained has a hardness (conforming to JIS K7311 (1995), type A) exceeding 65A and 95A or less, preferably exceeding 70A and 93A or less, more preferably, Over 80A and below 90A.

  The hardness of the tube can be measured using, for example, a sample in which the above polyurethane elastomer is formed on a sheet.

  The tensile strength of the tube (according to JIS K7311 (1995), 23 ° C., 55% RH) is, for example, 10 to 50 MPa, preferably 15 to 50 MPa, and more preferably 20 to 50 MPa.

  In addition, the tensile strength of a tube can be measured using the sample which formed said polyurethane elastomer in the sheet | seat, for example.

  Moreover, the extrudability of the tube is excellent in extrudability.

  The extrudability of a tube is an index indicating stability in extrusion molding and can be evaluated by the following method.

  That is, the extrusion molding is started, and after a predetermined time T1 (for example, 0.5 hours) has elapsed and after a predetermined time T2 (for example, 1.5 hours) longer than T1, a predetermined length L (for example, 200 mm) ) (Tube 1 after T1 and tube 2 after T2).

Next, with respect to each of the obtained two tubes, the inner diameter and outer diameter at both ends are measured, the average values are obtained, and the inner diameter retention ratio and outer diameter retention ratio are calculated by the following equations.
[Inner diameter retention ratio (%)] = 100 × (inner diameter of tube 1) / (inner diameter of tube 2)
[Outer diameter retention ratio (%)] = 100 × (outer diameter of tube 1) / (outer diameter of tube 2)
If the inner diameter retention ratio and the outer diameter retention ratio are close to 100%, it is determined that the extrudability (stability in extrusion molding) is good.

  Specifically, in the evaluation under the above conditions, the inner diameter retention of the tube is, for example, 99 to 106%, preferably 99 to 103%, and the outer diameter retention of the tube is, for example, 99 to 108%, preferably 99 to 103%.

  The tube is also excellent in kink resistance.

  FIG. 1 is a schematic configuration diagram showing a kink resistance evaluation method.

  The kink resistance can be evaluated by the following method.

  That is, as shown in FIG. 1, extrusion molding is started, and after a predetermined time T1 (for example, 0.5 hour) has elapsed, a tube having a predetermined length L (for example, 30 cm) is formed and both ends thereof are gripped. Thus, a ring having a predetermined diameter (for example, a diameter of 50 mm) is formed.

  Thereafter, when both ends of the tube are crossed and pulled in a direction in which the ring becomes smaller, the ring becomes elliptical and a kink (folded line) is generated (see the phantom line in FIG. 1). At this time, the distance (D in FIG. 1) between the tube intersection (point C in FIG. 1) and the kink point (point K in FIG. 1) is measured.

  Note that the smaller the distance between the tube intersection and the kink point, the better the kink resistance.

  Specifically, in the evaluation under the above conditions, the distance between the tube intersection and the kink point is, for example, 10 to 45 mm, preferably 15 to 35 mm.

  Furthermore, the tube is also excellent in blocking resistance.

  Specifically, a tube is extruded and a tube after a predetermined time has elapsed since the extrusion was started (for example, 0.5 hours from 0.5 hour to 1 hour after the start of molding) These tubes can be easily peeled even when they are accumulated in the shape of a spider having a diameter (for example, 25 cm in diameter) and left for 12 to 24 hours.

  Therefore, such a tube can be used for various industrial uses. Preferably, a medical tube (for example, an infusion set or transfusion set used in human administration of infusion or blood, for example, a blood circuit used for extracorporeal circulation of blood in hemodialysis or heart-lung machine, enteral nutrition, central vein, etc. It is used as various systems such as nutrition, for example, drainage / perfusion systems such as gastric tubes and suction catheters, urine management systems such as urinary bags, and peritoneal dialysis systems.

  In addition to the above medical tubes (catheters, etc.), such tubes are also used for packing, cable sheaths, conveyor belts, air tubes, hydraulic tubes, electric wire tubes, wire harnesses, hoses, fire hoses, telecommunications cables , Industrial products such as automobile wiring, computer wiring, curl cords, care products such as sheets and films, hot melt films used for industrial or clothing, stretch fibers, water absorbent fibers and other fibers, leisure products, miscellaneous goods , Anti-vibration / vibration isolation materials, shock absorbers, optical materials, automotive parts, surface protection sheets, films, tape members, semiconductor protection tapes, watch bands, outsole, golf ball members, tennis racket strings and other sports equipment, For belts such as endless belts Rukoto can. Preferably, it is used as a hose or a cable sheath.

  If a tube is used as a hose, a hose excellent in various mechanical strengths, flexibility, kink resistance, and blocking resistance can be provided.

  If the tube is used as a cable sheath, a cable sheath excellent in various mechanical strengths, flexibility, kink resistance, and blocking resistance can be provided.

  The tube of the present invention is formed from a polyurethane elastomer obtained by a reaction between an isocyanate component containing 1,4-bis (isocyanatomethyl) cyclohexane and a polyol component, and the hardness exceeds 65A and is 95A or less. Therefore, the mechanical properties are excellent, and further, the blocking resistance can be improved.

Next, although this invention is demonstrated based on an Example and a comparative example, this invention is not limited by the following Example.
Production of 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ XDI) (measurement of hydrolyzable chlorine concentration of polyisocyanate)
The concentration of hydrolyzable chlorine contained in each 1,4-bis (isocyanatomethyl) cyclohexane (hereinafter abbreviated as HC) is the water content described in Annex 3 of JIS K-1556 (2000). It was measured according to the test method for degradable chlorine.

Production Example 1 (Method for producing 1,4-bis (isocyanatomethyl) cyclohexane 1 (hereinafter referred to as 1,4-BIC1))
Using 1,4-bis (aminomethyl) cyclohexane (produced by Mitsubishi Gas Chemical Co., Inc.) having a trans / cis ratio of 93/7 by ¹³ C-NMR measurement as a raw material, a cold two-stage phosgenation method was carried out under pressure.

  Into a jacketed pressure reactor equipped with an electromagnetic induction stirrer, an automatic pressure control valve, a thermometer, a nitrogen introduction line, a phosgene introduction line, a condenser and a raw material feed pump, 2500 parts by mass of orthodichlorobenzene were charged. Subsequently, 1425 mass parts of phosgene was added from the phosgene introduction line, and stirring was started. Cold water was passed through the reactor jacket to maintain the internal temperature at about 10 ° C. A solution obtained by dissolving 400 parts by mass of 1,4-bis (aminomethyl) cyclohexane in 2500 parts by mass of orthodichlorobenzene was fed with a feed pump over 60 minutes, and cold phosgenation was performed at 30 ° C. or less under normal pressure. Carried out. After the feed was completed, the inside of the flask became a pale brown white slurry.

  Next, the temperature in the reactor was increased to 140 ° C. in 60 minutes while being pressurized to 0.25 MPa, and further heat phosgenated at a pressure of 0.25 MPa and a reaction temperature of 140 ° C. for 2 hours. Further, 480 parts by mass of phosgene was added during the thermal phosgenation. During the thermal phosgenation, the liquid in the flask became a light brown clear solution. After completion of the thermal phosgenation, nitrogen gas was aerated at 100 to 140 ° C. at 100 L / hour for degassing.

  Next, after distilling off the solvent orthodichlorobenzene under reduced pressure, a glass flask was packed with 4 elements of packing (Sumitomo Heavy Industries, Ltd., trade name: Sumitomo / Sulzer Lab Packing EX type). Using a rectifying apparatus equipped with a tube, a distillation column equipped with a reflux ratio adjusting timer (manufactured by Shibata Kagaku Co., Ltd., trade name: distillation head K type) and a cooler, 138-143 ° C., 0.7-1 KPa Under the conditions, rectification was further performed while refluxing to obtain 382 parts by mass of 1,4-BIC1.

The purity of the obtained 1,4-BIC1 as measured by gas chromatography was 99.9%, the hue as measured by APHA was 5, and the trans / cis ratio as determined by ¹³ C-NMR was 93/7. Hydrolyzable chlorine (HC) was 19 ppm.

Production Example 2 (Production method of 1,4-bis (isocyanatomethyl) cyclohexane 2 (hereinafter referred to as 1,4-BIC2))
Using 1,4-bis (aminomethyl) cyclohexane (produced by Tokyo Chemical Industry Co., Ltd.) having a trans / cis ratio of 41/59 by ¹³ C-NMR measurement as a raw material, 388 parts by mass in the same manner as 1,4-BIC1 1,4-BIC2 was obtained. The purity of the obtained 1,4-BIC2 as measured by gas chromatography was 99.9%, the hue as measured by APHA was 5, and the trans / cis ratio as determined by ¹³ C-NMR was 41/59. HC was 22 ppm.

Production Example 3 (Production method of 1,4-bis (isocyanatomethyl) cyclohexane 3 (hereinafter referred to as 1,4-BIC3))
In a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, 865 parts by mass of 1,4-BIC1 of Production Example 1 and 135 parts by mass of 1,4-BIC2 of Production Example 2 were installed. The mixture was stirred for 1 hour at room temperature under a nitrogen atmosphere. The purity of the obtained 1,4-BIC3 as measured by gas chromatography was 99.9%, the hue as measured by APHA was 5, and the trans / cis ratio as determined by ¹³ C-NMR was 86/14. HC was 19 ppm.

Synthesis Example 1 (Synthesis of prepolymer (a))
In a four-necked flask equipped with a stirrer, a thermometer, a reflux tube and a nitrogen introduction tube, PTMEG-2 (manufactured by BASF, trade name: polyTHF2000S, number average molecular weight 2000, polytetramethylene ether glycol consisting of tetrahydrofuran), Polymerized PTMEG-1 (product name: PTXG, number average molecular weight 1,800, amorphous polytetramethylene ether glycol obtained by copolymerization of tetrahydrofuran and neopentyl glycol) is 90 mol% and 10 mol%, respectively. Then, a high molecular weight polyol prepared so as to become was charged, and then 1,4-BIC3 was charged so that the equivalent ratio R (NCO / OH) was 2.5. Under a nitrogen atmosphere, the reaction was carried out at 80 ° C. until the isocyanate group content was 5.11% by mass to obtain an isocyanate group-terminated polyurethane prepolymer (hereinafter abbreviated as prepolymer) (a).

Synthesis Example 2 (Synthesis of prepolymer (b))
The high molecular weight polyol is made of PTMEG-1 (manufactured by BASF, trade name: polyTHF1000S, number average molecular weight 1000, polytetramethylene ether glycol made of tetrahydrofuran) and copolymerized PTMEG-1 at 20 mol% and 80 mol%, respectively. The prepolymer (b) was prepared in the same manner as in Synthesis Example 1 except that 1,4-BIC3 was charged so that the equivalent ratio R (NCO / OH) was 1.45. Got.

Synthesis Example 3 (Synthesis of prepolymer (c))
A high molecular weight polyol was prepared such that PTMEG-1 and copolymerized PTMEG-1 were 20 mol% and 80 mol%, respectively, and the equivalent ratio R (NCO / OH) was 1.39 so as to be 2.39. The prepolymer (c) was obtained in the same manner as in Synthesis Example 1, except that 4-BIC3 was charged.

Synthesis Example 4 (Synthesis of prepolymer (d))
A high molecular weight polyol was prepared such that PTMEG-1 and copolymerized PTMEG-1 were 70 mol% and 30 mol%, respectively, and the equivalent ratio R (NCO / OH) was 1.48. The prepolymer (d) was obtained in the same manner as in Synthesis Example 1, except that 4-BIC3 was charged.

Synthesis Example 5 (Synthesis of prepolymer (e))
A high molecular weight polyol was prepared such that PTMEG-1 and copolymerized PTMEG-1 were 70 mol% and 30 mol%, respectively, and the equivalent ratio R (NCO / OH) was 3.84. The prepolymer (e) was obtained in the same manner as in Synthesis Example 1, except that 4-BIC3 was charged.

Synthesis Example 6 (Synthesis of prepolymer (f))
A high molecular weight polyol was prepared such that PTMEG-1 and copolymerized PTMEG-1 were 80 mol% and 20 mol%, respectively, and the equivalent ratio R (NCO / OH) was 1.93. The prepolymer (f) was obtained in the same manner as in Synthesis Example 1 except that 4-BIC3 was charged.

Synthesis Example 7 (Synthesis of prepolymer (g))
A high molecular weight polyol was prepared such that PTMEG-1 and copolymerized PTMEG-1 were 50 mol% and 50 mol%, respectively, and the equivalent ratio R (NCO / OH) was 2.4. The prepolymer (g) was obtained in the same manner as in Synthesis Example 1 except that 4-BIC3 was charged.

Synthesis Example 8 (Synthesis of prepolymer (h))
A high molecular weight polyol is copolymerized with PTMEG-1 and PTMEG-2 (made by Hodogaya Chemical Co., Ltd., trade name: PTG-L (number average molecular weight 1000, amorphous polytetramethylene copolymerized with tetrahydrofuran and 3-methyltetrahydrofuran). Ether glycol) is 20 mol% and 80 mol%, respectively, and 1,4-BIC3 is charged so that the equivalent ratio R (NCO / OH) is 2.33. Prepolymer (h) was obtained in the same manner as in Synthesis Example 1.

Synthesis Example 9 (Synthesis of prepolymer (i))
The same procedure as in Synthesis Example 1 was repeated, except that only copolymer PTMEG-1 was used and 1,4-BIC3 was charged so that the equivalent ratio R (NCO / OH) was 1.68. Polymer (i) was obtained.

Synthesis Example 10 (Synthesis of prepolymer (j))
PEs-OH (trade name: Takelac U-2024, number average molecular weight 2000, adipic acid-based polyester polyol) and copolymer PTMEG-1 are 70 mol% and 30 mol% respectively. The prepolymer (j) was prepared in the same manner as in Synthesis Example 1, except that 1,4-BIC3 was charged so that the equivalent ratio R (NCO / OH) was 2.47. )

Synthesis Example 11 (Synthesis of prepolymer (k))
A high molecular weight polyol was prepared such that PTMEG-1 and copolymerized PTMEG-1 were 50 mol% and 50 mol%, respectively, and the equivalent ratio R (NCO / OH) was 3.54. , 4′-methylenebis (cyclohexyl isocyanate) (H ₁₂ MDI) was used in the same manner as in Synthesis Example 1 to obtain a prepolymer (k).

Synthesis Example 12 (Synthesis of prepolymer (l))
A high molecular weight polyol was prepared such that PTMEG-1 and copolymerized PTMEG-1 were 50 mol% and 50 mol%, respectively, and the equivalent ratio R (NCO / OH) was 2.7. , 3-bis (isocyanatomethyl) cyclohexane (1,3-H ₆ XDI) was used in the same manner as in Synthesis Example 1 to obtain a prepolymer (1).

Synthesis Example 13 (Synthesis of prepolymer (m))
A high molecular weight polyol is prepared so that the copolymerized PTMEG-1 and copolymerized PTMEG-2 are 50 mol% and 50 mol%, respectively, and the equivalent ratio R (NCO / OH) is 1.30. A prepolymer (m) was obtained in the same manner as in Synthesis Example 1, except that 1,4-BIC3 was charged into the reactor.

Synthesis Example 14 (Synthesis of prepolymer (n))
A high molecular weight polyol was prepared such that PTMEG-1 and copolymerized PTMEG-1 were 50 mol% and 50 mol%, respectively, and the equivalent ratio R (NCO / OH) was 6, A prepolymer (n) was obtained in the same manner as in Synthesis Example 1, except that -BIC3 was charged.

  Table 1 shows the formulation for each synthesis example.

Details of the abbreviations in Table 1 will be described below.
1,4-H ₆ XDI: 1,4-BIC3 obtained in Production Example 3
PTMEG-1: manufactured by BASF, trade name: polyTHF1000S, number average molecular weight 1000, polytetramethylene ether glycol PTMEG-2: manufactured by BASF, trade name: polyTHF2000S, number average molecular weight 2000, polytetramethylene composed of tetrahydrofuran Ether glycol PEs-OH: manufactured by Mitsui Chemicals, Inc., trade name: Takelac U-2024, number average molecular weight 2000, adipic acid polyester polyol copolymer PTMEG-1: manufactured by Asahi Kasei Fibers, Inc., trade name: PTXG, number average molecular weight 1800, Amorphous polytetramethylene ether glycol copolymerized by copolymerization of tetrahydrofuran and neopentyl glycol PTMEG-2: manufactured by Hodogaya Chemical Co., Ltd., trade name: PTG-L, number average molecular weight 100 , Amorphous polytetramethylene ether glycol obtained by copolymerizing tetrahydrofuran and 3-methyltetrahydrofuran
Reference Example 1 (Synthesis of polyurethane elastomer (A))
To 100 parts by mass of the prepolymer (a) previously adjusted to 80 ° C., 0.3 parts by mass of a heat stabilizer (trade name: Irganox 245, manufactured by BASF Japan), NDB (bismuth neodecanoate (manufactured by Shepherd Chemical Co.) as a catalyst) , Trade name: BiCAT-8124)) 500 ppm was put into a stainless steel container, and stirred and mixed for about 2 minutes under stirring at 800 rpm using a high-speed disper. Next, 1,4-BD (1,4-butanediol (manufactured by Mitsubishi Chemical Corporation)) adjusted to 80 ° C. in advance as a chain extender so that the equivalent ratio R (NCO / OH) is 1.01. Added.

  Next, the mixture is sufficiently stirred for about 10 minutes until the whole becomes uniform, and the reaction mixture is poured into a SUS pad that has been temperature-controlled at 150 ° C. in advance, and allowed to react at 150 ° C. for 1 hour and then at 100 ° C. for 23 hours. A polyurethane elastomer (A) was obtained.

  Thereafter, the polyurethane elastomer (A) was removed from the vat and cured for 7 days under constant temperature and humidity conditions of room temperature 23 ° C. and relative humidity 50%.

  The obtained polyurethane elastomer (A) was cut into a dice with a bale cutter, and the dice-like resin was pulverized with a pulverizer. The pulverized pellets were dried overnight at 80 ° C. under a nitrogen stream. Using a single screw extruder (model: SZW40-28MG, manufactured by Technobel), a strand was extruded at a cylinder temperature in the range of 185 to 245 ° C. and cut to obtain polyurethane elastomer (A) pellets. The obtained pellets were further dried overnight at 80 ° C. under a nitrogen stream.

  Next, using an injection molding machine (model: NEX-140, manufactured by Nissei Plastic Industry Co., Ltd.), with a screw rotation speed of 80 rpm and a barrel temperature of 210 to 235 ° C., a mold temperature of 30 ° C., an injection time of 10 seconds, Injection molding was performed under conditions of an injection speed of 60 mm / s and a cooling time of 45 seconds. The obtained sheet having a thickness of 2 mm was cured for 7 days under constant temperature and humidity conditions of room temperature 23 ° C. and relative humidity 55% to obtain an elastomer sheet. The hardness and tear strength of the obtained sheet were evaluated by the following methods.

  Further, using a single screw extruder (model: SZW40-28MG, manufactured by Technobel) equipped with a tube forming die having an inner diameter of 2.5 mm and an outer diameter of 4.0 mm, the above dried pellets were removed. The tube was extruded at a barrel temperature of 210 to 235 ° C. The continuously extruded tube was cooled through a water bath. Then, the extrusion moldability and blocking resistance of the obtained tube were evaluated by the following methods.

  The obtained tube was cured for 7 days under constant temperature and humidity conditions of room temperature 23 ° C. and relative humidity 55%, and then kink resistance was evaluated by the following method.

Example 2 (Synthesis of polyurethane elastomer (B))
A polyurethane elastomer (B), an elastomer sheet thereof and a tube were obtained by the same formulation and operation as in Reference Example 1 except that the prepolymer (b) was used.

Example 3 (Synthesis of polyurethane elastomer (C))
The same prescription and operation as in Reference Example 1 except that prepolymer (c) was used and 500 ppm of NDZ (neodecanoic acid zinc (product name: BiCAT-1365)) was used as the catalyst. A polyurethane elastomer (C), its elastomer sheet and tube were obtained.

Example 4 (Synthesis of polyurethane elastomer (D))
A polyurethane elastomer (D), an elastomer sheet thereof and a tube were obtained by the same formulation and operation as in Reference Example 1 except that the prepolymer (d) was used.

Example 5 (Synthesis of polyurethane elastomer (E))
The same formulation and operation as in Reference Example 1 except that the prepolymer (e) was used and 10 ppm of DBTDL (dibutyltin dilaurate (trade name: Stan BL) manufactured by Sankyo Co., Ltd. was used as the catalyst. Polyurethane elastomer (E), its elastomer sheet and tube were obtained.

Example 6 (Synthesis of polyurethane elastomer (F))
The same prescription and operation as in Reference Example 1 except that prepolymer (f) was used and 500 ppm of NDZr (zirconium neodecanoate (trade name: BiCAT-4130M)) was used as the catalyst. Polyurethane elastomer (F), its elastomer sheet and tube were obtained.

Example 7 (Synthesis of polyurethane elastomer (G))
The same composition as in Reference Example 1 except that the prepolymer (g) was used, and 1,4-butanediol and neopentyl glycol were used as the chain extenders so as to be 70 mol% and 30 mol%, respectively. A polyurethane elastomer (G), an elastomer sheet thereof and a tube were obtained by formulation and operation.

Example 8 (Synthesis of polyurethane elastomer (H))
A polyurethane elastomer (H), its elastomer sheet, and a tube were obtained by the same formulation and operation as in Reference Example 1 except that the prepolymer (h) was used.

Example 9 (Synthesis of polyurethane elastomer (I))
A polyurethane elastomer (I), its elastomer sheet, and a tube were obtained by the same formulation and operation as in Reference Example 1 , except that the prepolymer (i) was used.

Example 10 (Synthesis of polyurethane elastomer (J))
A polyurethane elastomer (J), an elastomer sheet thereof, and a tube were obtained by the same formulation and operation as in Reference Example 1 except that the prepolymer (j) was used.

Comparative Example 1 (Synthesis of polyurethane elastomer (K))
A polyurethane elastomer (K), its elastomer sheet, and a tube were obtained by the same formulation and operation as in Reference Example 1 except that the prepolymer (k) was used.

Comparative Example 2 (Synthesis of polyurethane elastomer (L))
A polyurethane elastomer (L), an elastomer sheet thereof and a tube were obtained by the same formulation and operation as in Reference Example 1 except that the prepolymer (l) was used.

Comparative Example 3 (Synthesis of polyurethane elastomer (M))
A polyurethane elastomer (M), an elastomer sheet thereof and a tube were obtained by the same formulation and operation as in Reference Example 1 except that the prepolymer (m) was used.

Comparative Example 4 (Synthesis of polyurethane elastomer (N))
A polyurethane elastomer (N), its elastomer sheet and a tube were obtained by the same formulation and operation as in Reference Example 1 except that the prepolymer (n) was used.

Tables 2, 3 and 4 show the formulation of each example , each reference example and each comparative example.

The details of the abbreviations in Tables 2 to 4 are described below.
1,4-BG: 1,4-butanediol NPG: neopentyl glycol NDB: bismuth neodecanoate (trade name: BiCAT-8124, manufactured by Shepherd Chemical Co., Ltd.)
NDZ: zinc neodecanoate (manufactured by Shepherd Chemical Co., Ltd., trade name: BiCAT-1365)
NDZr: zirconium neodecanoate (manufactured by Shepherd Chemical Co., Ltd., trade name: BiCAT-4130M)
DBTDL: Dibutyltin dilaurate (trade name: Stan BL)
Evaluation The elastomer sheets and tubes obtained in each Example and each Comparative Example were evaluated by the following methods. The result is combined with Tables 2-4, and is shown.
<Hardness>
Using the sheet obtained by injection molding, A hardness was measured using an Asker rubber hardness meter (manufactured by Kobunshi Keiki Co., Ltd., type A) in accordance with JIS K-7311 (1995).
<Tensile strength (unit: MPa)>
Using a sheet obtained by injection molding, in accordance with JIS K-7311 (1995), using a tensile tester (Orientec Co., Model U-4400) at 23 ° C. and 55% relative humidity, The tensile strength (unit: MPa) of the sheet was measured.
<Extrudability of tube (unit:%)>
The tube 0.5 hours after the start of molding and that 1.5 hours after were sampled so that each length would be 200 mm. The outer diameter of both ends of each tube was measured using a laser dimension measuring device (trade name LS-31000, manufactured by Keyence Corporation), and the average value was obtained. On the other hand, the inner diameter of the tube was measured by using a dimension measuring instrument (trade name: Master Pin Gauge, manufactured by Eisen Co., Ltd.), and the average value was obtained.

The retention ratio of the inner and outer diameters was calculated by the following formula, and the tube extrudability was evaluated. In addition, if the retention rate of the inner diameter and the outer diameter was close to 100%, it was judged that the extrusion stability was good.
Inner diameter retention ratio (%) = {(Inner diameter of tube after forming 0.5 hour) / (Inner diameter of tube after forming 1.5 hour)} × 100
Outer diameter retention ratio (%) = {(outer diameter of tube after 0.5 hours of molding) / (outer diameter of tube after 1.5 hours of molding)} × 100
<Blocking resistance of tube>
Tubes were continuously molded under the conditions described in <Extrusion Stability of Tube> above. The tube was accumulated in a round shape so as to form a circular shape having a diameter of about 25 cm for 0.5 hour from 0.5 hour to 1 hour after the start of molding.

  The next day after molding (after 24 hours), the resistance when pulling the tubes apart was evaluated by palpation.

The evaluation criteria are as follows.
○: The tubes were easily separated.
Δ: A slight resistance was felt to the peeling between the tubes.
X: The tubes adhered to each other and could not be easily peeled off.
<Kink resistance of tube (unit: mm)>
As shown in FIG. 1, a ring having a diameter of 50 mm was formed by holding both ends of a tube (length: 30 cm) 0.5 hours after molding. Next, when both ends of the tube were slowly pulled so as to cross the tubes, the ring became elliptical, and when pulled as it was, kinks (folds) occurred at the top of the elliptical ring. At that time, the length (unit: mm) of the point of the tube where the crease occurred from the point where the tubes crossed each other was measured. The smaller this value, the better the kink resistance.

C Tube intersection K Kink point

Claims (4)

Formed from a polyurethane elastomer obtained by reaction of an isocyanate component containing 1,4-bis (isocyanatomethyl) cyclohexane and a polyol component;
Hardness exceeds the 65A, Ri der below 95A,
The polyol component contains a high molecular weight polyol and a low molecular weight polyol,
The tube , wherein the high molecular weight polyol contains 20 to 80 mol% of amorphous polytetramethylene ether glycol . The tube according to claim 1 , wherein the tube is a hose.   The tube according to claim 1, wherein the tube is a cable sheath. An isocyanate component containing 1,4-bis (isocyanatomethyl) cyclohexane, a high molecular weight polyol and a low molecular weight polyol, and the high molecular weight polyol contains 20 to 80 mol% of amorphous polytetramethylene ether glycol. A polyol component containing at a ratio of
Preparing a polyurethane elastomer by reacting as a catalyst in the presence of at least one carboxylate selected from the group consisting of bismuth carboxylate, zinc carboxylate and zirconium carboxylate; and,
A method for producing a tube, comprising the step of forming a tube from the polyurethane elastomer.

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