JP5371881B2 - Cover material manufacturing method and cover material - Google Patents

Description

  The present invention relates to a cover material, and more particularly to a cover material containing polyurethane.

  Conventionally, polyurethane has been widely used for golf ball core cover materials, vehicle gear knob covers, door seal covers, cable covers, keyboard covers, audio covers, sports equipment grip covers, and the like.

  For example, when polyurethane is used for the core cover material of a golf ball, the scratch resistance, spin performance, feel at impact and controllability of the golf ball can be improved.

  As such a golf ball core cover material, in order to more easily cover the golf ball core with the cover material and improve the productivity of the golf ball, in particular, a thermoplastic polyurethane is included in the cover material. Has been proposed.

  The thermoplastic polyurethane contained in the cover material includes, for example, 4,4′-diphenylmethane diisocyanate, which is an aromatic isocyanate, in order to develop the resilience of the golf ball in addition to the above-mentioned various characteristics. The thermoplastic polyurethane used has been proposed.

  However, such polyurethane has insufficient light resistance (weather resistance) and easily yellows, so it is necessary to coat the surface of the golf ball with a white paint or the like. Therefore, when such a polyurethane resin is used, there is a problem that the productivity of the golf ball is lowered.

  Then, in order to eliminate such a malfunction, the method of using the thermoplastic polyurethane using alicyclic isocyanate for a cover material, for example is proposed (for example, refer patent documents 1-5).

Japanese Patent Laid-Open No. 9-271538 JP 2002-360740 A JP 2005-261444 A JP 2008-207019 A Japanese Patent No. 4340599

  However, thermoplastic polyurethanes using alicyclic isocyanates described in Patent Documents 1 to 5 (for example, 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, etc.) Compared with the above-mentioned thermoplastic polyurethane using 4,4'-diphenylmethane diisocyanate, it is excellent in light resistance (weather resistance) and hardly yellowed, but inferior in resilience.

  Therefore, with such polyurethane, physical properties as a cover material for the core of the golf ball may not be sufficiently obtained.

  Furthermore, since thermoplastic polyurethanes using these alicyclic isocyanates have low elasticity after thermoforming, for example, after heat compression molding or injection molding, the time required for demolding from the mold is long. There is a problem that the dimensional change rate of the later molded product is large.

  An object of the present invention is to provide a cover material containing polyurethane having good light resistance (weather resistance) and excellent rebound resilience and demoldability after thermoforming.

  In order to achieve the above object, a cover material of the present invention is a cover material containing polyurethane obtained by reacting an isocyanate component and an active hydrogen compound component, wherein the isocyanate component is 1,4-bis (isocyanato). It is characterized by containing methyl) cyclohexane.

  In the cover material of the present invention, it is preferable that the trans ratio of the 1,4-bis (isocyanatomethyl) cyclohexane is 80 mol% or more.

  In the cover material of the present invention, it is preferable that the trans ratio of the 1,4-bis (isocyanatomethyl) cyclohexane is 95 mol% or less.

  Moreover, in the cover material of this invention, it is suitable that the flow start temperature of the said polyurethane is 160-220 degreeC, the storage elastic modulus in 23 degreeC is 20-200 MPa, and a rebound resilience is 55% or more.

  Further, the cover material of the present invention is preferably used as a cover material for a core layer of a golf ball.

  The cover material of the present invention is also preferably used as a gear knob cover.

  The cover material of the present invention is also preferably used as a door seal cover.

  The cover material of the present invention is also preferably used as a cable cover.

  The cover material of the present invention is also preferably used as a keyboard cover.

  The cover material of the present invention is also preferably used as an audio cover.

  The cover material of the present invention is also preferably used as a grip cover.

  The cover material of the present invention has good light resistance (weather resistance), and excellent rebound resilience and demoldability after thermoforming such as thermal compression or injection molding, and thus can improve productivity. .

  Therefore, when the cover material of the present invention is used, for example, as a cover of a golf ball core, it provides a golf ball with little yellowing and excellent in abrasion resistance and productivity in addition to spinability and controllability. be able to.

  In addition, if the cover material of the present invention is used as, for example, a gear knob cover, door seal cover, cable cover, keyboard cover, audio cover, grip cover, etc., various covers with little yellowing and excellent scratch resistance and productivity. Can be provided.

  The cover material of the present invention contains polyurethane.

  Polyurethane can be obtained by reaction of an isocyanate component and an active hydrogen compound component.

  In the present invention, the isocyanate component contains 1,4-bis (isocyanatomethyl) cyclohexane as an essential component.

  1,4-bis (isocyanatomethyl) cyclohexane includes cis-1,4-bis (isocyanatomethyl) cyclohexane (hereinafter referred to as cis 1,4 isomer) and trans-1,4-bis ( There is a stereoisomer of isocyanatomethyl) cyclohexane (hereinafter referred to as trans 1,4 form), and in the present invention, 1,4-bis (isocyanatomethyl) cyclohexane represents trans 1,4 form, for example, It is 70% or more, preferably 80 mol% or more, more preferably 85 mol% or more, for example, 95 mol% or less, preferably 92 mol% or less.

  1,4-bis (isocyanatomethyl) cyclohexane is, for example, a two-stage method (direct method) or a salt formation method described in JP-A-7-309827, or Japanese Patent Application Laid-Open No. 2004-244349. It can be produced by a method that does not use phosgene described in Japanese Unexamined Patent Publication No. 2003-212835.

  The 1,4-bis (isocyanatomethyl) cyclohexane can be prepared as a modified product.

  Examples of the modified form of 1,4-bis (isocyanatomethyl) cyclohexane include, for example, a multimer of 1,4-bis (isocyanatomethyl) cyclohexane (dimer, trimer, etc.), a biuret modified form (for example, 1,4-bis Bis (isocyanatomethyl) cyclohexane and biuret-modified products produced by the reaction of water), allophanate-modified products (for example, 1,4-bis (isocyanatomethyl) cyclohexane and monools or low molecular weight polyols (described later) Allophanate-modified products produced from the reaction), polyol-modified products (for example, 1,4-bis (isocyanatomethyl) cyclohexane and low-molecular-weight polyol (described later) or polyol-modified product generated from the reaction of high molecular weight polyol (described later). Etc.), modified oxadiazine trione (for example, 1,4-bis (isocyanatomethyl) cyclohexane and carbon dioxide gas produced by the reaction of oxadiazine trione, etc.), modified carbodiimide (produced by decarboxylation condensation reaction of 1,4-bis (isocyanatomethyl) cyclohexane Carbodiimide modified products), uretdione modified products, and the like.

  In addition, as an isocyanate component, together with 1,4-bis (isocyanatomethyl) cyclohexane, for example, aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate excluding 1,4-bis (isocyanatomethyl) cyclohexane, An araliphatic polyisocyanate can also be used in combination.

  Examples of aromatic polyisocyanates include 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, and isomer mixtures of these tolylene diisocyanates, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate. And 2,2'-diphenylmethane diisocyanate, and any isomer mixture of these diphenylmethane diisocyanates, toluylene diisocyanate, paraphenylene diisocyanate, naphthalene diisocyanate and the like.

  Examples of the aliphatic polyisocyanate include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2′-dimethylpentane diisocyanate, 2,2,4. -Trimethylhexane diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecamethylene triisocyanate, 1,3 , 6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 2,5,7 Trimethyl-1,8-diisocyanate-5-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butylene glycol dipropyl ether-ω, ω′-diisocyanate, lysine isocyania Natomethyl ester, lysine triisocyanate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, bis (4-isocyanate-n-butylidene) pentaerythritol Etc.

  Alicyclic polyisocyanates include, for example, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, trans, trans-, trans, cis-, and cis, cis-dicyclohexylmethane diisocyanate and mixtures thereof, 3- or 1,4-cyclohexane diisocyanate and mixtures thereof, 1,3- or 1,4-bis (isocyanatoethyl) cyclohexane, methylcyclohexane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, dimer acid diisocyanate, 2 , 5-diisocyanatomethylbicyclo [2,2,1] -heptane, its isomers 2,6-diisocyanatomethylbicyclo [2,2,1] -heptane, 2-isocyanatomethyl 2- 3-isocyanatopropyl) -5-isocyanatomethylbicyclo- [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6-isocyanatomethylbicyclo- [2, 2,1] -heptane, 2-isocyanatomethyl 3- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo- [2,2,1] -heptane, 2-isocyanatomethyl 3 -(3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo- [2,2,1] -heptane, 2-isocyanatomethyl 2- (3-isocyanatopropyl) -5- (2 -Isocyanatoethyl) -bicyclo- [2,2,1] -heptane, 2-isocyanatomethyl 2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bisi And chloro- [2,2,1] -heptane.

  Examples of the araliphatic polyisocyanate include 1,3- or 1,4-xylylene diisocyanate and a mixture thereof, 1,3- or 1,4-tetramethylxylylene diisocyanate and a mixture thereof.

  In addition, polyisocyanate modified products such as isocyanurates, allophanates, burettes, carbodiimides, oxadiazine triones and uretdione modified products of these polyisocyanates can be used in combination as long as the thermoformability of the polyurethane is not impaired.

  Furthermore, monoisocyanate can also be used in combination as long as the physical properties of the cover material molded from polyurethane, particularly the impact resilience is not impaired. Examples of the monoisocyanate include methyl isocyanate, ethyl isocyanate, n-hexyl isocyanate, cyclohexyl isocyanate, 2-ethylhexyl isocyanate, phenyl isocyanate, and benzyl isocyanate.

  The polyisocyanate that can be used in combination with 1,4-bis (isocyanatomethyl) cyclohexane is preferably 4,4′-diphenylmethane diisocyanate (MDI), 1,3- or 1,4-xylylene diisocyanate (XDI) and these. A mixture of the above, dicyclohexylmethane diisocyanate (hydrogenated MDI) and mixtures thereof, toluidine diisocyanate (TODI), 1,3-bis (isocyanatomethyl) cyclohexane, pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), 2,5-diisocyanatomethylbicyclo [2,2,1] -heptane, its isomer 2,6-diisocyanatomethylbicyclo [2,2,1] -heptane (NBDI), and their polyisocyanates Modified products of over bets are mentioned.

  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 stereoisomer of bis (isocyanatomethyl) cyclohexane (hereinafter referred to as trans 1,3), and 1,3-bis (isocyanatomethyl) cyclohexane and 1,4-bis (isocyanatomethyl) cyclohexane When used in combination, 1,3-bis (isocyanatomethyl) cyclohexane is trans 1,3, preferably 50 mol% or more, more preferably 70 mol% or more, particularly preferably 90 mol%. Contains above.

  Isocyanate component is 1,4-bis (isocyanatomethyl) cyclohexane and other isocyanates (for example, aromatic polyisocyanate, aliphatic polyisocyanate, 1,4-bis (isocyanatomethyl) cyclohexane except alicyclic polyisocyanate. 1,4-bis (isocyanatomethyl) cyclohexane with respect to the total number of moles of isocyanate groups in the isocyanate component when it contains isocyanates, araliphatic polyisocyanates and modified products of these polyisocyanates, monoisocyanates) Is contained in a proportion of 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more. Most preferably, 100 mol% is contained.

  Examples of the active hydrogen compound component include a polyol component.

  Examples of the polyol component include high molecular weight polyols.

  The high molecular weight polyol has two or more hydroxyl groups in one molecule, and the number average molecular weight is, for example, 400 to 8000, preferably 1400 to 4000, more preferably 1500 to 2500, and the hydroxyl value is For example, a compound of 10 to 125 mg KOH / g. The number average molecular weight of the polyol component can be calculated from the hydroxyl group equivalent of the polyol component (determined from JIS K1557-1 (2007)) and the average number of functional groups.

  Examples of the high molecular weight polyol include polyether polyol, polyester polyol, and polycarbonate polyol.

  Examples of the polyether polyol include polyoxyalkylene polyol and polytetramethylene ether glycol.

  The polyoxyalkylene polyol is, for example, an addition polymer of alkylene oxide using a low molecular weight polyol or a low molecular weight polyamine as an initiator.

  Examples of the alkylene oxide include propylene oxide, ethylene oxide, butylene oxide, styrene oxide, and the like. These alkylene oxides can be used alone or in combination of two or more. Of these, propylene oxide and ethylene oxide are preferable.

  Further, the polyoxyalkylene polyol has a primary hydroxylation rate at the molecular end of, for example, at least 50 mol%, and preferably 70 mol%. If the primary hydroxylation rate at the molecular end of the polyoxyalkylene polyol is the above value, the reaction completion rate with the polyisocyanate can be improved.

  Examples of the catalyst for preparing the polyoxyalkylene polyol include a phosphazenium compound described in Japanese Patent No. 3905638. If a polyoxyalkylene polyol is prepared using such a catalyst, a polyoxyalkylene polyol with a small amount of monool by-products can be obtained.

  The low molecular weight polyol is a compound having two or more hydroxyl groups and a number average molecular weight of less than 60 to 400, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1, 3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, alkane (7-22) diol, diethylene glycol, triethylene glycol, dipropylene glycol, 1, 3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,4-cyclohexanediol, alkane-1,2-diol (C17-20), hydrogenated bisphenol F, hydrogenated bisphenol A, 1,4-dihydroxy -2-butene, p-ki Rylene glycol, bis (2-hydroxyethyl) terephthalate, bis (2-hydroxyethyl) isophthalate, 1,4-bis (2-hydroxyethoxy) benzene, 1,3-bis (2-hydroxyethoxy) benzene, resorcin, Hydroquinone, 2,2'-bis (4-hydroxycyclohexyl) propane, 2,6-dimethyl-1-octene-3,8-diol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl)- Dihydric alcohols such as 2,4,8,10-tetraoxaspiro [5,5] undecane, bisphenol F and bisphenol A, for example, trihydric alcohols such as glycerin and trimethylolpropane, such as tetramethylolmethane, pentaerythritol Dipentaerythritol, D-sorbitol, Ki Examples thereof include polyhydric alcohols having four or more hydroxyl groups such as sitolitol, D-mannitol and D-mannitol.

  Examples of the low molecular weight polyamine include aliphatic diamines such as ethylenediamine, and aromatic diamines such as tolylenediamine.

  The number average molecular weight of the polyoxyalkylene polyol is preferably 200 to 8000, and more preferably 500 to 5000.

  Examples of the polytetramethylene ether glycol include a ring-opening polymer obtained by cationic polymerization of tetrahydrofuran, and an amorphous (room temperature liquid) polytetramethylene ether glycol obtained by copolymerizing the above-described dihydric alcohol with a polymerization unit of tetrahydrofuran. Is mentioned.

  In addition, the number average molecular weight of polytetramethylene ether glycol is preferably 250 to 8000, and more preferably 250 to 3000.

  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 aliphatic dicarboxylic acids (carbon number 11-13), suberic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, octadecanedioic acid, nonadecanedioic acid Carboxylic acids such as acid, eicosane diacid, methylhexane diacid, citraconic acid, hydrogenated dimer acid, maleic acid, fumaric acid, itaconic acid, orthophthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, dimer acid and het acid And acid anhydrides, acid halides, ricinoleic acid derived from these carboxylic acids, 1 - such as hydroxy stearic acid.

  Specific examples of polycondensates of low molecular weight polyols and polybasic acids include poly (ethylene butylene adipate) polyol, poly (ethylene adipate) polyol, poly (ethylene propylene adipate) polyol, poly (propylene adipate) polyol, poly (Butylene hexane adipate) polyol, poly (butylene adipate) polyol, etc. are mentioned.

  Examples of the polyester polyol include castor oil polyol, or a modified castor oil polyol via an ester bond obtained by reacting castor oil polyol and polypropylene glycol.

  Further, as the polyester polyol, for example, polycaprolactone polyol, polyvalerolactone polyol obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone, using the above-described low molecular weight polyol as an initiator, Furthermore, the lactone type | system | group polyol which copolymerized said dihydric alcohol to them etc. are mentioned. Moreover, for example, adipic acid-based polyester polyol obtained by copolymerizing glycol with adipic acid can be used.

  In addition, the number average molecular weight of the polyester polyol is preferably 500 to 4000, and more preferably 800 to 3000.

  Moreover, when the high molecular weight polyol is a polyester polyol, it is preferable to add a carbodiimide group-containing compound having a carbodiimide group to the polyester polyol. By adding a carbodiimide group-containing compound, the hydrolysis resistance of the thermoplastic polyurethane resin can be improved.

  Examples of the carbodiimide group-containing compound include carbodiimides described in JP-A-9-208649. More specific commercial products include, for example, Carbodilite (manufactured by Nisshinbo Industries, Inc.), Starbuxol I (manufactured by Rhein Chemie), stabilizer 7000 (manufactured by RASCHIG GmbH), and the like.

  Moreover, it is preferable to add 0.01-2 mass parts of carbodiimide group containing compounds with respect to 100 mass parts of polyester polyols, for example.

  Examples of the polycarbonate polyol include a ring-opening polymer of ethylene carbonate using the above dihydric alcohol as an initiator, and examples thereof include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1 Polycarbonate diols obtained by condensation reaction of dihydric alcohols such as 1,6-hexanediol and carbonates such as dimethyl carbonate, diethyl carbonate and diphenyl carbonate, and amorphous (room temperature liquid) polycarbonate polyols.

  The number average molecular weight of the polycarbonate polyol is preferably 500 to 3000, and more preferably 800 to 2000.

  These high molecular weight polyols can be used alone or in combination of two or more. Of these, adipic acid-based polyester polyols, polytetramethylene ether glycols, polycarbonate polyols copolymerized with glycol, and amorphous polytetramethylene ether glycols and amorphous polycarbonate polyols are preferable. More preferably, they are the above-mentioned polytetramethylene ether glycol and amorphous polytetramethylene ether glycol, and the number average molecular weight thereof is preferably 1000 to 3000.

  In the present invention, the above-described low molecular weight polyol can be used in combination with the high molecular weight polyol as the polyol component.

  In the present invention, examples of the active hydrogen compound component further include a chain extender and a crosslinking agent.

  In the present invention, the chain extender is, for example, a compound having a number average molecular weight of 40 to 600, for example, a low molecular weight polyol such as the above dihydric alcohol, an aromatic diamine, an araliphatic diamine, an alicyclic group. Examples include diamines such as diamines and aliphatic diamines.

  Examples of the aromatic diamine include 4,4′-diphenylmethanediamine, 3,3′-dichloro-4,4′-diphenylmethanediamine, Etacure 300 (trade name: manufactured by Albemarle), and TCCAM (trade name: Ihara Chemical Co., Ltd.). Manufactured).

  Examples of the araliphatic diamine include 1,3- or 1,4-xylylenediamine or a mixture thereof.

  Examples of the alicyclic diamine include 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis- (4-aminocyclohexyl) methane, diaminocyclohexane, and 3,9-bis (3-aminopropyl). ) -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,3- and 1,4-bis (aminomethyl) cyclohexane and mixtures thereof, 1,3- and 1,4-bis (Aminoethyl) cyclohexane and mixtures thereof.

  Examples of the aliphatic diamine include ethylene diamine, propylene diamine, pentamethylene diamine, hexamethylene diamine, hydrazine, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopentane, and the like.

  These chain extenders can be used alone or in combination of two or more. Of these, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-bis (2 -Hydroxyethoxy) benzene, 1,4-bis (hydroxyethyl) terephthalate, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,4-cyclohexanediol. Particularly preferred is 1,4-butanediol.

  Moreover, as a crosslinking agent, it is a compound with a number average molecular weight of 40-800, for example, Comprising: For example, above-mentioned trihydric alcohol etc. are mentioned.

  Usually, when a bifunctional chain extender is used as the active hydrogen compound component, a polyurethane exhibiting thermoplasticity is obtained, and when a trifunctional crosslinking agent is used, a thermosetting polyurethane is obtained.

  From the viewpoint of improving the productivity of the cover material, polyurethane exhibiting thermoplasticity is preferably used. Therefore, a chain extender is preferably used as the active hydrogen compound component.

  For example, thermoplastic polyurethane is produced by using the above-described components (that is, isocyanate component, active hydrogen compound component (polyol component and chain extender)), for example, by a known synthesis method such as a one-shot method or a prepolymer method. Can be synthesized.

  In any of the above methods, preferably, the high molecular weight polyol is preliminarily heated under reduced pressure to reduce its water content. The water content of the high molecular weight polyol after the treatment is, for example, 0.05% by mass or less, and preferably 0.03% by mass or less. More preferably, it is 0.02 mass% or less.

  In the one-shot method, the isocyanate component, the polyol component, and the chain extender are mixed in an equivalent ratio of the isocyanate group of the isocyanate component (isocyanate group / active hydrogen) to the active hydrogen group (hydroxyl group and amino group) of the polyol component and the chain extender. At the same time, for example, 0.9 to 1.2, preferably 0.95 to 1.1, and more preferably 0.98 to 1.08.

  This stirring and mixing is performed, for example, in an inert gas (for example, nitrogen) atmosphere at a reaction temperature of 40 to 280 ° C., preferably 100 to 260 ° C., for a reaction time of about 30 seconds to 1 hour.

  The method for stirring and mixing is not particularly limited, but for example, a mixing tank such as a disper, a dissolver, a turbine blade, a circulating low-pressure or high-pressure collision mixing device, a high-speed stirring mixer, a static mixer, a kneader, a single screw or a twin screw Examples thereof include a method of stirring and mixing using a known mixing apparatus such as a rotary extruder and a belt conveyor type. Preferably, the isocyanate component, the polyol component and the chain extender are sufficiently mixed with a high-speed stirring mixer, and then mixed with a static mixer, a single screw extruder or a kneader, or the isocyanate component with a high-speed stirring mixer. A method in which a reaction mixture in which a polyol component and a chain extender are sufficiently mixed is allowed to flow continuously on a belt conveyor to cause a reaction. If each component is stirred and mixed by such a method, the resulting thermoplastic polyurethane can be reduced in size and gel.

  Further, at the time of stirring and mixing, a catalyst such as amines and metal compounds and a solvent can be added as necessary.

  Preferred examples of the catalyst include organometallic compounds. Examples of such organometallic compounds include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, and dibutyltin. Examples include dilaurate, dioctyltin dilaurate, dibutyltin dichloride, lead octoate, lead naphthenate, nickel naphthenate, cobalt naphthenate, copper octenoate, and bismuth catalysts.

  These catalysts can be used alone or in combination of two or more. For example, for example, 0.001 to 0.5 parts by mass, preferably 0.01 to 0.3 parts by mass with respect to 100 parts by mass of the polyol component. Part is added.

  In the prepolymer method, an isocyanate component and a polyol component are first reacted to synthesize an isocyanate group-terminated prepolymer, and then the isocyanate group-terminated prepolymer and a chain extender are reacted.

  In order to synthesize the isocyanate group-terminated prepolymer, the ratio by which the equivalent ratio of the isocyanate component of the isocyanate component to the active hydrogen group (hydroxyl group) of the polyol component (isocyanate group / active hydrogen group) exceeds 1.0, for example, It mixes simultaneously in the ratio used as 1.1-20, Preferably 1.3-10, More preferably, 1.3-6, It stirs and mixes and is made to react.

  In this reaction, for example, a polyisocyanate and a polyol component other than the chain extender are stirred and mixed in an inert gas (eg, nitrogen) atmosphere at a reaction temperature of 40 to 150 ° C. for a reaction time of about 30 seconds to 8 hours. . In addition, the above-described catalyst and solvent can be added to the reaction as necessary.

  Next, the isocyanate group-terminated prepolymer and the chain extender have an equivalent ratio (active hydrogen group / isocyanate group) of the active hydrogen group (amino group and hydroxyl group) of the chain extender to the isocyanate group of the isocyanate group-terminated prepolymer, for example, , 0.9 to 1.2, preferably 0.95 to 1.1, and more preferably 0.98 to 1.08, and the mixture is stirred and mixed.

  This stirring and mixing is performed, for example, at a reaction temperature of 40 to 280 ° C, preferably 100 to 270 ° C, more preferably 120 to 260 ° C, and a reaction time of about 0.5 minutes to 10 minutes. Moreover, at the time of stirring and mixing, the above-described catalyst and solvent can be added as necessary.

  Examples of the stirring and mixing method in the prepolymer method include the stirring and mixing method described above.

  As a method for synthesizing a polyurethane according to the present invention, a prepolymer method is preferable from the viewpoint of improving mechanical properties including rebound resilience.

  The obtained thermoplastic polyurethane is pulverized and pulverized using, for example, a cutter, a pellet manufacturing apparatus (pelletizer), etc., and then used in a desired shape (for example, pellets) using a molding machine such as an extrusion molding machine. Shape).

  The thermoplastic polyurethane may be added to other known additives such as a heat stabilizer, a light stabilizer (ultraviolet absorber), a plasticizer, an antiblocking agent, a mold release agent, and an oxidation agent as necessary. Inhibitors, ultraviolet absorbers, pigments, dyes, lubricants, fillers, hydrolysis inhibitors, rust inhibitors, fillers, and the like can be added. These additives may be added at the time of synthesizing each component, or may be added at the time of mixing each component.

  Examples of the heat resistant stabilizer include hindered phenol antioxidants, phosphorus heat stabilizers, lactone heat stabilizers, sulfur heat stabilizers, and the like. Examples of commercially available products of these heat stabilizers include IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1098, IRGANOX 1135, IRGANOX 1222, IRGANOX 1425WL, IRGANOX 1520L, IRGANOX 245, IRGANOX 3790, IRGANOX 36126, IRGANOX 36126, IRGAFOS 168 Manufactured).

  Examples of the light-resistant stabilizer (ultraviolet absorber) include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzoate-based light stabilizers, hindered amine-based light stabilizers, and the like. Examples of commercially available light stabilizers include TINUVIN P, TINUVIN 234, TINUVIN 326, TINUVIN 327, TINUVIN 328, TINUVIN 329, TINUVIN 571, TINUVIN 144, TINUVIN 765, and TINUVINB 75 (all manufactured by Ciba Specialty Chemicals LA, Inc.). -52, LA-62, LA-72 (manufactured by Adeka).

  These heat-resistant stabilizer and light-resistant stabilizer are added to the thermoplastic polyurethane in a proportion of, for example, 0.01 to 1.2% by mass, preferably 0.1 to 1% by mass.

  Such polyurethane has a flow starting temperature of, for example, 160 to 220 ° C, preferably 160 to 220 ° C, more preferably 170 to 220 ° C, and particularly preferably 180 to 210 ° C.

  If the flow start temperature of polyurethane is within the above range, the molding cycle time of hot compression molding or injection molding can be shortened.

  In addition, the flow start temperature of a polyurethane can be measured with an elevated flow tester (for example, Shimadzu Corporation make, model: CFT-500).

  Further, the storage elastic modulus at 23 ° C. of polyurethane (polyurethane thermoformed into a film or sheet having a thickness of about 0.1 to 1 mm) is, for example, 20 to 200 MPa, preferably 30 to 200 MPa, and more preferably 60 to 180 MPa. It is.

  The range of the storage elastic modulus includes, for example, 25D to 60D as hardness measured at 23 ° C. using a Shore D type durometer. Alternatively, 87A to 95A are included as hardness measured at 23 ° C. using a Shore A type durometer.

  If the storage modulus of polyurethane is in the above range, when the cover material is used as a cover material for the core of a golf ball, the resilience and feel at impact can be compatible.

  In addition, a storage elastic modulus is a value in 23 degreeC when the temperature dependence (1 rad / s (10 Hz)) of dynamic viscoelasticity is measured.

  Moreover, the impact resilience of polyurethane is, for example, 55% or more, preferably 58% or more, and more preferably 60% or more. The upper limit of the resilience of polyurethane is about 80%.

  When the rebound resilience is not less than the above lower limit, when the cover material is used as a cover material for the core of the golf ball, the restitution coefficient is improved, and a golf ball excellent in spin property and controllability can be obtained.

  The impact resilience can be measured according to the method described in JIS K-7311.

  Further, the color difference (ΔE) of the polyurethane after the light resistance test due to the xenon irradiation of the polyurethane is, for example, 3 or less, preferably 2.5 or less, more preferably 2 or less, and particularly preferably 1 or less.

  When the color difference is within the above range, a golf ball, a gear knob cover, a door seal cover, a cable cover, a keyboard cover, an audio cover, a grip cover, and the like having a good design property with little yellowing of the cover material can be obtained.

  The abrasion resistance of polyurethane can be measured by, for example, the Taber abrasion test method described in JIS K-7311. For example, the wear amount (unit: mg) measured with a wear wheel (model: H-22 wheel) is, for example, 50 mg or less, preferably 45 mg or less, more preferably 35 mg or less.

  Furthermore, the thermoformability of polyurethane is based on, for example, the ease of demolding the molded product from the mold after injection molding and the dimensional change rate of the molded product after demolding. If the rubber elasticity is low after injection molding, the molded product is tacky, so that it is difficult to remove the mold, and even if it can be removed, the molded product is easily deformed and the rate of dimensional change increases. Furthermore, after the heat compression molding, a polishing mark may be observed on the surface of the molded product in the process of cutting and polishing the resin piece (burr) protruding from the mold or the resin piece of the injection gate attached after the injection molding. .

  In the polyurethane according to the present invention, the concentration of the hard segment formed by the reaction of the polyisocyanate and the chain extender is, for example, 15 to 40% by mass, preferably 18 to 35% by mass, and particularly preferably 19 to 19%. 32% by mass. If the hard segment concentration of the thermoplastic polyurethane is in the above range, suitable storage elastic modulus, rebound resilience, tensile and tear strength can be expressed.

In addition, a hard segment density | concentration can be calculated by following Formula from the compounding prescription (preparation) of each component, for example.
[Chain extender (g) + (chain extender (g) / molecular weight of chain extender (g / mol)) × average molecular weight of polyisocyanate (g / mol)] ÷ (high molecular weight polyol (g) + polyisocyanate (G) + chain extender (g) + optional component (low molecular weight polyol (g)) × 100
The hard segment concentration can also be measured by, for example, measuring solid polyurethane or solution NMR of thermoplastic polyurethane. Specific measurement methods are described in, for example, Satoshi Yamazaki et. al "Effect of aggregation structure on rheological properties of thermoplastic poly- ethanes" magazine name Polymer, 48, 4793-4803, 2007.

  Moreover, the cover material of this invention can contain another resin component as a resin component in the range which does not impair the effect of this invention other than the said polyurethane.

  Examples of the method for containing other resin components include the method disclosed in Japanese Patent No. 4021176. By applying such a method, it is possible to improve the scuff resistance of the cover material and durability in repeated use.

  Examples of other resin components include ionomer resins, thermoplastic elastomers, diene block copolymers, and the like.

  Examples of the ionomer resin include a polymer obtained by neutralizing at least a part of a carboxyl group in a copolymer of ethylene and an α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms with a metal ion, ethylene and 3 carbon atoms. A polymer in which at least a part of carboxyl groups in a terpolymer of 8 α, β-unsaturated carboxylic acids and α, β-unsaturated carboxylic acid esters is neutralized with a metal ion, or these A mixture is mentioned.

  Examples of the α, β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid, and the like, and preferably acrylic acid or methacrylic acid.

  Examples of the α, β-unsaturated carboxylic acid ester include methyl, ethyl, propyl, n-butyl, and isobutyl esters such as acrylic acid, methacrylic acid, fumaric acid, and maleic acid. An acid ester or a methacrylic acid ester is mentioned.

  In addition, a carboxyl group in a copolymer of ethylene and α, β-unsaturated carboxylic acid or a terpolymer of ethylene, α, β-unsaturated carboxylic acid and α, β-unsaturated carboxylic acid ester Examples of the metal ions that neutralize at least a part of the alkali metal ions include alkali metal ions such as sodium, potassium and lithium; divalent metal ions such as magnesium, calcium, zinc, barium and cadmium; trivalent metal ions such as aluminum; Other ions such as tin and zirconium can be mentioned. From the viewpoint of improving the resilience, sodium, zinc, and magnesium ions are preferable.

  Specific examples of the ionomer resin include Himiran (trade name) commercially available from Mitsui DuPont Polychemical Co., Ltd. and Surlyn (trade name) commercially available from DuPont Co., Ltd.

  Specific examples of the thermoplastic elastomer include, for example, a thermoplastic polyamide elastomer (trade name: Pevacs) commercially available from Arkema Co., Ltd., and a thermoplastic polyester elastomer (trade name: Hytrel) commercially available from Toray DuPont Co., Ltd. And thermoplastic polystyrene elastomer (trade name: Lavalon) commercially available from Mitsubishi Chemical Corporation.

  When the cover material of the present invention contains other resin components of the polyurethane, the polyurethane content is, for example, 50% by mass or more, preferably, based on the total amount of polyurethane and other resin components, It is 60 mass% or more, More preferably, it is 70 mass% or more. Furthermore, it is also a preferable aspect that it consists only of the said polyurethane.

  Further, the cover material of the present invention has a specific gravity such as, for example, pigment components such as zinc oxide, titanium oxide, and blue pigment, for example, calcium carbonate and barium sulfate, in addition to the above resin component, as long as the performance of the cover material is not impaired For example, an anti-aging agent, an ultraviolet absorber, a light stabilizer, a fluorescent material, a fluorescent brightening agent, and the like can be contained.

  Examples of the pigment component include titanium oxide as a white pigment.

  When titanium oxide is blended, the content thereof is, for example, 0. 100 parts by mass with respect to 100 parts by mass of a resin component (polyurethane as an essential component and other resin components as an optional component, the same shall apply hereinafter). 5 parts by mass or more, preferably 1 part by mass or more, and usually 8 parts by mass or less.

  When the content of titanium oxide is within the above range, it is possible to ensure concealability, rebound resilience, and durability of physical properties as a cover material.

  The cover material of the present invention is manufactured by thermoforming a resin component mainly composed of the above polyurethane. For example, it is possible to cite heat compression molding using a specific mold or injection molding directly on the core layer.

  The thermoforming temperature is, for example, 180 to 240 ° C, preferably 185 to 230 ° C. The molding pressure is, for example, 0.5 to 25 MPa, or preferably 1 to 20 MPa. A cover material having a uniform thickness can be obtained by thermoforming under the above conditions.

  The thickness of the cover material of the present invention is, for example, 1.0 mm or less, preferably 0.9 mm or less, more preferably 0.6 mm or less, and usually 0.3 mm or more.

  In particular, when the cover material of the present invention is used for a golf ball, the thickness thereof is, for example, 5 mm or less, preferably 3 mm or less, more preferably 2 mm or less, and usually 0.1 mm or more.

  If the thickness of the cover material is within the above range, for example, when the cover material is used as a cover material for the core of a golf ball, the outer diameter of the core can be increased, so that the resilience performance of the golf ball can be improved.

  Cover materials obtained in this way include, for example, golf ball core covers, soccer, baseball, basket or volleyball cover materials, vehicle gear knob covers, door seal covers, tail lamp covers, spring covers, console box covers, electric wires, Suitable for fiber optic cable covers, keyboard covers, audio covers, glove covers for sports equipment such as tennis rackets, door mirror covers, various covers such as tubes and hoses, and various sheets and films with a thickness of several millimeters to several microns. Can be used.

  And since the cover material of this invention is excellent in light resistance (weather resistance), and is excellent in rebound resilience and demoldability after thermoforming, such as thermal compression or injection molding, it improves productivity. Can do.

  Therefore, when the cover material of the present invention is used, for example, as a cover of a golf ball core, it provides a golf ball with little yellowing and excellent in abrasion resistance and productivity in addition to spinability and controllability. be able to.

  A golf ball using the cover material of the present invention usually has a structure having a core and a cover material.

  The core is not particularly limited, and various known cores such as a core made of a plurality of rubber layers, a core made of a plurality of resin intermediate layers, and a thread wound core having a thread rubber layer can be used.

  Examples of the rubber used for the rubber layer of the core include natural rubber and synthetic rubber. Examples of the synthetic rubber include polybutadiene-based synthetic rubber, polyisoprene-based synthetic rubber, and ethylene-propylene-diene-based synthetic rubber.

  From the viewpoint of improving the resilience, the rubber is preferably a cis-rich polybutadiene rubber having a cis bond rate of 40% by mass or more.

  Further, for example, a crosslinking initiator such as an organic peroxide, a co-crosslinking agent and a filler made of a metal salt, an organic sulfur compound, an antiaging agent, and the like can be blended with the rubber as necessary. .

  The hardness of the rubber layer is not particularly limited, but the hardness measured at 23 ° C. using a Shore D type durometer is preferably 25D to 55D.

  The diameter of the rubber layer is not particularly limited, but is, for example, 36 to 42 mm.

  Examples of the resin used for the core intermediate layer include thermoplastic elastomers such as ionomer resins, amides, and esters, and vulcanized rubbers.

  The hardness of the intermediate layer is not particularly limited, but is preferably 40D to 60D as the hardness measured at 23 ° C. using a Shore D type durometer.

  The golf ball in which the cover material of the present invention is used is preferably a two-piece golf ball or a three-piece golf ball.

  In addition, if the cover material of the present invention is used as, for example, a gear knob cover, door seal cover, cable cover, keyboard cover, audio cover, grip cover, etc., various covers with little yellowing and excellent scratch resistance and productivity. Can be provided.

Next, although this invention is demonstrated based on a manufacture example, a reference example, an Example, and a comparative example, this invention is not limited by the following Example. In the following description, “part” and “%” are based on mass unless otherwise specified. Moreover, the measuring method used for a synthesis example etc. is shown below.

Production Example 1 (Production method of 1,4-bis (isocyanatomethyl) cyclohexane 1 (hereinafter 1,4-BIC1))
^A cold two-stage phosgenation method was carried out under pressure using 1,4-bis (aminomethyl) cyclohexane (manufactured by Mitsubishi Gas Chemical Company) having a trans / cis ratio of 93/7 as measured by ¹³ C-NMR.

  Into a jacketed pressure reactor equipped with an electromagnetic induction stirrer, automatic pressure control valve, thermometer, nitrogen introduction line, phosgene introduction line, condenser, and raw material feed pump, 2500 parts of orthodichlorobenzene were charged. Next, 1425 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 prepared by dissolving 400 parts of 1,4-bis (aminomethyl) cyclohexane in 2500 parts of orthodichlorobenzene was fed with a feed pump over 60 minutes, and cold phosgenation was performed at 30 ° C. or lower and normal pressure. did. 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 of phosgene were 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 to degas.

  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 to 143 ° C., 0.7 to 1 KPa Under the conditions, rectification was further performed while refluxing to obtain 382 parts 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.

Production Example 2 (Method for producing 1,4-bis (isocyanatomethyl) cyclohexane 2 (hereinafter 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 the same method 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.

Production Example 3 (Method for producing 1,4-bis (isocyanatomethyl) cyclohexane 3 (hereinafter, 1,4-BIC3))
A four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen inlet tube was charged with 846 parts of 1,4-BIC1 of Production Example 1 and 154 parts of 1,4-BIC2 of Production Example 2. The mixture was stirred at room temperature for 1 hour 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 85/15.

Production Example 4 (Method for producing 1,4-bis (isocyanatomethyl) cyclohexane 4 (hereinafter, 1,4-BIC4))
1,4-BIC4 was obtained in the same manner as in Production Example 3, except that 558 parts of 1,4-BIC1 of Production Example 1 and 442 parts of 1,4-BIC2 of Production Example 2 were used. The purity of the obtained 1,4-BIC4 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 70/30.
(Isocyanate group content / unit: mass% contained in the isocyanate group-terminated prepolymer solution)
The isocyanate group content of the isocyanate group-terminated prepolymer solution was measured by an n-dibutylamine method according to JIS K-1556 using a potentiometric titrator.

Reference Example 1 (Preparation of polyurethane (A))
In a four-necked flask equipped with a stirrer, thermometer, reflux tube, and nitrogen introduction tube, 283 parts of 1,4-BIC1 of Production Example 1 and a polytetramethylene ether glycol having a number average molecular weight of 2000 (trade name: PTG2000SN, 314 parts of Hodogaya Chemical Co., Ltd. (hereinafter abbreviated as PTG2000SN) and 314 parts of polytetramethylene ether glycol (trade name: PTG1000, manufactured by Hodogaya Chemical Co., Ltd.) (hereinafter abbreviated as PTG1000). Partially charged and reacted at 80 ° C. in a nitrogen atmosphere until the isocyanate group content was 9.08% by mass to obtain an isocyanate group-terminated polyurethane prepolymer A (hereinafter abbreviated as prepolymer).

  Prepolymer (A) 1000 parts adjusted to 80 ° C., heat stabilizer (trade name: Irganox 245, manufactured by Ciba Japan Co., Ltd.) 0.3 parts, UV absorber (trade names: chinuvin 234, Ciba Japan) 0.2 part, light-resistant stabilizer (trade name: ADK STAB LA-62, manufactured by ADEKA) 0.2 part, ethylene bisstearylamide (trade name: Alflow H-50S, manufactured by Nippon Oil & Fats) as lubricant , 0.12 parts by mass of a catalyst solution obtained by diluting a catalyst (trade name: Stanocto, manufactured by API Corporation) to 4% by mass using diisononyl adipate (trade name: DINA, manufactured by JPlus) is placed in a stainless steel container. Using a high speed disper, the mixture was stirred and mixed for about 2 minutes under stirring at 800 rpm. Subsequently, 88.7 parts of 1,4-butanediol (manufactured by Mitsubishi Chemical Corporation) adjusted to 80 ° C. in advance was added as a chain extender. The mixture was further stirred for about 4 minutes until the whole became uniform. The aforementioned reaction mixture was poured into a SUS pad whose temperature was adjusted to 100 ° C. in advance, and reacted at 150 ° C. for 2 hours and then at 100 ° C. for 22 hours. Thereafter, the polyurethane A was removed from the vat and cured for 7 days under a constant temperature and humidity condition of a room temperature of 23 ° C. and a relative humidity of 50%.

  The obtained polyurethane 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. Polyurethane A pellets were obtained by extruding strands at a cylinder temperature range of 185 to 225 ° C. using a single screw extruder (model: SZW40-28MG, manufactured by Technobel) and cutting it. The obtained pellets were further dried overnight at 80 ° C. under a nitrogen stream.

  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 200 to 220 ° C., a mold temperature of 30 ° C., an injection time of 10 seconds, and an injection speed Injection molding was performed under the conditions 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 a constant temperature and humidity condition at a room temperature of 23 ° C. and a relative humidity of 50%, and then physical properties were evaluated. The physical property evaluation results are shown in Table 1.

Reference Example 2 (Preparation of polyurethane (B))
The same formulation as in Reference Example 1 except that 288 parts of 1,4-BIC3 of Production Example 3, 310 parts of PTG2000SN and 310 parts of PTG1000 were used and reacted until the isocyanate group content was 9.44% by mass. And the operation yielded Prepolymer B. Furthermore, polyurethane B was obtained by the same formulation and operation as in Reference Example 1 except that 91.9 parts of 1,4-butanediol was added. Tables 1 and 2 show the physical property evaluation results.

Reference Example 3 (Preparation of polyurethane (C))
Formulation similar to Reference Example 1 except that 255 parts of 1,4-BIC3 of Production Example 3, 336 parts of PTG2000SN and 336 parts of PTG1000 were used and reacted until the isocyanate group content was 7.33% by mass. The prepolymer C was obtained by the operation. Furthermore, polyurethane C was obtained by the same formulation and operation as in Reference Example 1 except that 72.9 parts of 1,4-butanediol was added. The physical property evaluation results are shown in Table 1.

Reference Example 4 (Preparation of polyurethane (D))
The same formulation as in Reference Example 1 except that 300 parts of 1,4-BIC4 of Production Example 4, 301 parts of PTG2000SN and 301 parts of PTG1000 were used and reacted until the isocyanate group content was 10.16% by mass. And the operation yielded prepolymer D. Furthermore, polyurethane D was obtained in the same formulation and operation as in Reference Example 1 except that 98.3 parts of 1,4-butanediol was added. The physical property evaluation results are shown in Table 1.

Example 5
100 parts of the polyurethane (B) of Reference Example 2 and 10 parts of a thermoplastic polyester elastomer (Hytrel 4047 manufactured by Toray DuPont) were dry blended.

  Next, the blended pellets are put into a hopper of a twin-screw extruder (Ikegai Iron Works, PCM-30, L / D = 41.5), and 5 parts of isocyanate monomer 1,4-BIC3 from the vent port of the extruder. Was added, and uniform pellets were obtained while continuously melting and kneading at a rotation speed of 25 rpm and a barrel temperature of 200 to 220 ° C.

Thereafter, using the obtained pellets, injection molding was performed in the same manner as in Reference Example 1 to obtain a sheet having a thickness of 2 mm. The physical property evaluation results are shown in Table 2.

Comparative Example 1 (Preparation of polyurethane (E))
402 parts of 4,4′-methylenebis (cyclohexyl isocyanate) (trade name: Vestanut H12MDI, manufactured by Evonik), 246 parts of PTG2000SN, 247 parts of PTG1000, and 0.12 parts of catalyst solution, Prepolymer E was obtained by the same formulation and operation as in Reference Example 1 except that the reaction was carried out until the content became 10.92% by mass. Furthermore, polyurethane E was obtained in the same formulation and operation as in Reference Example 1 except that 104.8 parts of 1,4-butanediol and 0.32 parts of catalyst solution were added. The physical property evaluation results are shown in Table 1.

Comparative Example 2 (Preparation of polyurethane (F))
^From the analysis results of ¹ H-NMR and ¹³ C-NMR, commercially available TPU (trade name: trade name: MDI as an isocyanate component, polytetramethylene ether glycol as a polyol component, and 1,4-butanediol as a chain extender. Using Elastollan 1195ATR (manufactured by BASF), injection molding was carried out in the same manner as in Reference Example 1 to obtain polyurethane F. Tables 1 and 2 show the physical property evaluation results.
Physical property evaluation 1
The storage elastic modulus at 23 ° C., hardness, flow start temperature, rebound resilience, color difference and thermoformability of the polyurethanes obtained in each of the reference examples, examples and comparative examples were measured by the following methods. The results are shown in Table 1.
<Storage elastic modulus at 23 ° C. (unit: MPa)>
Using an injection-molded polyurethane sheet, the measurement was performed with a solid viscoelastic device (Rheometrics Far East, RSA-II). The storage elastic modulus at 23 ° C. was measured under conditions of a temperature rising rate of 3 ° C./min, a frequency of 1 rad / s, and a temperature range of −100 to 250 ° C.
<Hardness: Shore A (unit: none)>
The Shore A hardness was measured according to “JIS K-7311 polyurethane thermoplastic elastomer test method”, and the result was shown as a numerical value.
<Flow start temperature (unit: ° C)>
Using a capillary rheometer (model: CFT-500D, manufactured by Shimadzu Corporation) under a nitrogen stream in advance under the conditions of a die having a diameter of 1 mm, a length of 10 mm, a load of 20 kgf, and a heating rate of 2.5 ° C./min. The flow start temperature of the pellets dried overnight at 80 ° C. was measured.
<Rebound resilience (unit:%)>
The impact resilience was measured according to "JIS K-7311 polyurethane thermoplastic elastomer test method", and the results were shown as numerical values.
<Color difference (ΔE / unit: none)>
The ΔL, Δa, and Δb values of the strip-shaped polyurethane sheets before and after the xenon irradiation test were measured using a color pigment meter (model: CR-200, manufactured by Minolta Camera Co., Ltd.). From these values, the ΔE value was determined. A smaller ΔE value represents less discoloration.

The xenon irradiation test was conducted using a super xenon weather meter (manufactured by Suga Test Instruments Co., Ltd., model: SX75-AP) with a black panel temperature of 89 ° C., a relative humidity of 50%, and a xenon lamp irradiance of 100 W / m ² (irradiation). Irradiation was performed for 480 hours under the condition of a wavelength of 300 to 400 nm.
<Thermoformability>
A polyurethane sheet was injection molded into a mold having a smooth surface using the injection molding machine and injection conditions described in Reference Example 1. It is a system that automatically molds after injection molding and cooling for 45 seconds. Thermoformability was evaluated according to the following evaluation criteria. The dimensional change rate was measured after the injection-molded sheet was left in an oven at 23 ° C. and 50% relative humidity for 12 hours.
(Evaluation criteria)
When the mold is opened, the sheet is easily removed from the mold, and the absolute value of the value obtained by multiplying the ratio of the length of the sheet immediately after injection molding to the length of the same position of the mold by 100 (change in dimensions) Rate) is less than 1.5%: ○
When the mold is opened, the sheet is removed from the mold, and the absolute value of the value obtained by multiplying the ratio of the length of the sheet immediately after injection molding and the length of the same position of the mold by 100 (dimensional change rate) Is over 1.5% and less than 2%:
When the mold is opened, the sheet cannot be removed from the mold, and the absolute value of the value obtained by multiplying the ratio of the length of the sheet immediately after injection molding and the length of the same position of the mold by 100 (the rate of change in dimensions) ) Exceeds 2%: ×

Physical property evaluation 2
The polyurethanes obtained in Reference Example 2, Example 5 and Comparative Example 2 were subjected to a gravel test and a dematch test, and evaluated for scuff resistance and durability. The results are shown in Table 2.
<Grabber test>
Using a gravelometer (Q Panel, model: QGR), the injection pressure after fixing the sheet surface so that the crushed stone that injects in the horizontal direction collides with the sheet surface at an angle of 45 ° 50 g of No. 7 crushed stone was sprayed on the sheet surface at 0.2 MPa for about 5 seconds. After spraying, the scratched area on the sheet surface, the depth of the scratches and the number of scratches were evaluated visually. The evaluation criteria are shown below.
(Evaluation criteria)
A: The scratched area is small and the scratch is shallow.
○: Scratched area is slightly large, but scratch is shallow.
X: A lot of scratched areas and deep scratches.
<Demacha test>
A test piece was prepared by the method described in JIS K 6260, and a reciprocating motion was added 300 times / minute in an atmosphere of 23 ° C. using a Demacha bending tester (model: FT1503, manufactured by Ueshima Seisakusho). The bending test was performed 100,000 times.

  Thereafter, by observing cracks in the test piece, grades from grade 1 to grade 6 were determined according to the method described in the same JIS. The first grade refers to the case where a crack like a needle hole is seen with the naked eye, and in this case, it refers to the case of 10 needle holes or less. On the other hand, grade 6 refers to a crack length of 3.0 mm or more. If the series number increases, it is judged that the degree of cracking is large, that is, the durability is lowered.

  The second grade is when the number of needle holes is 11 or more, or when there are one or more cracks larger than the needle holes even when the number of needle holes is 10 or less, the crack length is 0.5 mm. The fourth grade refers to the case where the crack length is 1.0 mm or more and less than 1.5 mm.

From the results of the gravel test and the demacha test , it was found that in Example 5 , a cover material excellent in scratch resistance and durability was obtained.

Claims (12)

A polyurethane obtained by reacting an isocyanate component containing 1,4-bis (isocyanatomethyl) cyclohexane and an active hydrogen compound component, a thermoplastic elastomer, and 1,4-bis (isocyanatomethyl) cyclohexane are kneaded. And forming the cover material. The method for producing a cover material according to claim 1, wherein a trans ratio of the 1,4-bis (isocyanatomethyl) cyclohexane contained in the isocyanate component is 80 mol% or more. The method for producing a cover material according to claim 1 or 2, wherein a trans ratio of the 1,4-bis (isocyanatomethyl) cyclohexane contained in the isocyanate component is 95 mol% or less. The flow start temperature of the polyurethane is 160 to 220 ° C, the storage elastic modulus at 23 ° C is 20 to 200 MPa, and the rebound resilience is 55% or more. The manufacturing method of the cover material of description.   A cover material obtained by the method for manufacturing a cover material according to claim 1. The cover material according to claim 5 , wherein the cover material is used as a cover material for a core layer of a golf ball. The cover material according to claim 5 , wherein the cover material is used as a gear knob cover. The cover material according to claim 5 , wherein the cover material is used as a door seal cover. The cover material according to claim 5 , wherein the cover material is used as a cable cover. The cover material according to claim 5 , wherein the cover material is used as a keyboard cover. The cover material according to claim 5 , wherein the cover material is used as an audio cover. The cover material according to claim 5 , wherein the cover material is used as a grip cover.