WO2012056939A1 - Hydrogenated block copolymer crumb and process for production thereof - Google Patents

Hydrogenated block copolymer crumb and process for production thereof Download PDF

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Publication number
WO2012056939A1
WO2012056939A1 PCT/JP2011/073909 JP2011073909W WO2012056939A1 WO 2012056939 A1 WO2012056939 A1 WO 2012056939A1 JP 2011073909 W JP2011073909 W JP 2011073909W WO 2012056939 A1 WO2012056939 A1 WO 2012056939A1
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Prior art keywords
crumb
block copolymer
mass
hydrogenated block
drying
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PCT/JP2011/073909
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French (fr)
Japanese (ja)
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伸明 久保
孝夫 山口
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日本エラストマー株式会社
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Priority to SG2013030341A priority Critical patent/SG189956A1/en
Priority to JP2012540785A priority patent/JP5591346B2/en
Priority to CN201180051908.XA priority patent/CN103189406B/en
Publication of WO2012056939A1 publication Critical patent/WO2012056939A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/06—Treatment of polymer solutions
    • C08F6/12—Separation of polymers from solutions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes

Definitions

  • the present invention relates to a hydrogenated block copolymer crumb and a method for producing the same.
  • a hydrogenated block copolymer which is a hydrogenated product of a block copolymer composed of a vinyl aromatic hydrocarbon and a conjugated diene, has excellent resilience and low-temperature properties. It is used as a modifier to improve impact resistance, low temperature characteristics, workability, and the like.
  • the composition of the hydrogenated block copolymer and the thermoplastic resin is widely used in the fields of electric / electronic parts, automobile parts, various industrial parts, daily necessities and the like.
  • the high molecular weight hydrogenated block copolymer is excellent in mechanical properties in addition to the various properties described above, and therefore, by combining with a liquid softener such as oil, a plasticizer and a thermoplastic resin such as polypropylene, It is used as a material for various industrial parts such as electric cables and automobile parts.
  • the above-mentioned high molecular weight hydrogenated block copolymer is generally handled in the form of porous dry crumbs, not pellets, in order to improve kneadability with oil and the like during compounding.
  • Many proposals have hitherto been made regarding methods for obtaining such porous dry crumbs of hydrogenated block copolymers.
  • the water content is 1% by mass by further dehydrating and drying with an extrusion dehydrator.
  • Methods for obtaining the following polymer crumb are known (see, for example, Patent Documents 1 and 2).
  • the operating temperature of the extruder for dehydrating the hydrogenated block copolymer crumb and the water content of the slurry before charging the extruder were adjusted.
  • Dehydration / drying method using an extrusion dehydrator for example, see Patent Document 3
  • a method for drying a hydrogenated block copolymer crumb with a hot air dryer under a specific temperature condition for example, see Patent Document 4
  • Patent Document 4 a specific temperature condition
  • Patent Documents 1 and 2 are preferable as a method for obtaining a low molecular weight hydrogenated block copolymer crumb, but for high molecular weight hydrogenated block copolymer crumbs, oil absorption during compounding is preferred. In terms of sex, sufficient characteristics have not yet been obtained.
  • the high molecular weight hydrogenated block copolymer crumb obtained by the methods disclosed in Patent Documents 3 and 4 does not uniformly disperse oil throughout the crumb when compounded with a thermoplastic resin or oil. Furthermore, there is a problem that the compound processability is still unstable, for example, the crumb does not completely melt and remains as an unmelted polymer.
  • the present inventor in a compound of a high molecular weight hydrogenated block copolymer crumb and a softening agent such as a thermoplastic resin or process oil, the oil is uniformly dispersed throughout the crumb and the residual amount of unmelted polymer is suppressed.
  • a high molecular weight hydrogenated block copolymer comprising a vinyl aromatic hydrocarbon and a conjugated diene having a specific range of crumb specific surface area and particle size distribution. It has been found that a method for producing crumb and its hydrogenated block copolymer crumb comprising a specific dehydration / drying step can solve the above-mentioned problems of the prior art, and has completed the present invention. That is, the present invention is as follows.
  • a hydrogenated block copolymer crumb comprising a hydrogenated product of a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene and satisfying the following (1) to (4): (1) Main peak molecular weight is 200,000 to 600,000 (2) Moisture content is 1% by mass or less (3) Specific surface area is 0.3 to 1.0 m 2 / g (4) A component that passes through a sieve having an opening of 3.35 mm and does not pass through a sieve having an opening of 0.425 mm is 80% by mass or more of the total crumb [2] A method for producing a hydrogenated block copolymer crumb according to [1] above, comprising the following ⁇ Step 1> to ⁇ Step 3>.
  • ⁇ Step 1> An aqueous slurry containing a hydrogenated block copolymer crumb is dehydrated, and all crumb components that have a moisture content of more than 60% by mass and not more than 80% by mass and do not pass through a sieve having an opening of 3.35 mm are included. Obtaining a crumb that is 60% by weight or more of the crumb.
  • ⁇ Step 2> A step of dehydrating and drying the crumb obtained in ⁇ Step 1> to obtain a crumb having a water content of 3 to 30% by mass.
  • ⁇ Step 3> A step of drying the crumb obtained in ⁇ Step 2> to obtain a crumb having a moisture content of 1% by mass or less.
  • a hydrogenated block copolymer having an excellent compound processability such as a uniform dispersion of oil throughout the crumb, good oil absorbability (oil retention), and reduction of unmelted polymer.
  • a crumb is obtained.
  • the hydrogenated block copolymer crumb of this embodiment is a crumb made of a hydrogenated block copolymer of vinyl aromatic hydrocarbon and conjugated diene, and satisfies the following (1) to (4).
  • Main peak molecular weight is 200,000 to 600,000
  • Water content is 1% by mass or less
  • Specific surface area is 0.3 to 1.0 m 2 / g (4)
  • a component that passes through a sieve having an opening of 3.35 mm and does not pass through a sieve having an opening of 0.425 mm is 80% by mass or more of the total crumb.
  • the hydrogenated block copolymer crumb in this embodiment is obtained by adding hydrogen to a block copolymer consisting of a vinyl aromatic hydrocarbon and a conjugated diene as described above, and as shown in the above (1),
  • the main peak molecular weight is 200,000 or more from the viewpoint of mechanical strength and impact resistance when a predetermined polymer composition is used, and 600,000 or less from the viewpoint of workability and compatibility with a high-molecular substance such as a thermoplastic resin. It is.
  • the main peak molecular weight is preferably 230,000 to 500,000, more preferably 250,000 to 450,000.
  • the molecular weight of the main peak of the hydrogenated block copolymer can be measured using GPC (gel permeation chromatography) measurement and a calibration curve obtained from measurement of commercially available standard polystyrene. Specifically, it can measure by the method as described in the Example mentioned later.
  • GPC gel permeation chromatography
  • the hydrogenated block copolymer crumb of the present embodiment has a water content of 1% by mass or less as shown in (2) above. Thereby, when it is compounded with a predetermined thermoplastic resin to obtain a thermoplastic resin composition, it is possible to prevent poor appearance due to foaming, generation of silver or the like.
  • the hydrogenated block copolymer crumb of this embodiment preferably has a moisture content of 0.9% by mass or less, and more preferably 0.8% by mass or less.
  • the hydrogenated block copolymer crumb of this embodiment has a specific surface area of 0.3 to 1.0 m 2 / g, preferably 0.35 to 0.8 m 2 / g, as shown in (3) above. Preferably, it is 0.4 to 0.7 m 2 / g.
  • the hydrogenated block copolymer crumb of the present embodiment has a crumb size that passes through a sieve having an opening of 3.35 mm and does not pass through a sieve having an opening of 0.425 mm, as shown in (4) above. It is assumed that the component is 80% by mass or more, preferably 82% by mass or more, more preferably 85% by mass or more of the total crumb.
  • the oil absorbability becomes good, the oil absorption unevenness can be suppressed, the plastic can be uniformly plasticized at the time of compound preparation, and the number of unmelted polymers can be reduced. Can do.
  • the water content, specific surface area, and size of the hydrogenated block copolymer crumb can be determined by the method described in the examples described later.
  • a hydrogenated block copolymer is prepared, and then a predetermined treatment is performed to obtain a hydrogenated block copolymer crumb.
  • a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene compound is obtained by a polymerization reaction, and then a hydrogenation reaction is performed to obtain a hydrogenated block copolymer.
  • the block copolymer can be produced by polymerizing vinyl aromatic hydrocarbon and conjugated diene in a hydrocarbon solvent using an organolithium compound as a polymerization initiator.
  • vinyl aromatic hydrocarbon examples include styrene, ⁇ -methylstyrene, p-methylstyrene, 2-vinylnaphthalene, divinylbenzene and the like.
  • conjugated diene examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3 butadiene, 1,3-pentadiene, 1,3-heptadiene, and the like.
  • the vinyl aromatic hydrocarbon content of the block copolymer is preferably 90% by mass or less, more preferably 60% by mass or less, and still more preferably 40% by mass or less, from the viewpoint of improving the impact resilience. .
  • Examples of the method for producing the block copolymer include Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-171979, Japanese Patent Publication No. 46-32415, Japanese Patent Publication No. 49-36957, and Japanese Patent Publication No. 48-2423. Examples thereof include the methods described in Japanese Patent Publication Nos. 48-4106, 51-49567, and 59-166518.
  • Examples of the structure of the block copolymer include those represented by general formulas (AB) n , (AB) n -A, and B- (AB) n .
  • A is a polymer block mainly composed of vinyl aromatic hydrocarbons
  • B is a polymer block mainly composed of conjugated diene. The boundary between the A block and the B block does not necessarily have to be clearly distinguished.
  • N is an integer of 1 or more, preferably an integer of 1 to 5.
  • the polymer block A mainly composed of vinyl aromatic hydrocarbons contains 50% by mass or more of vinyl aromatic hydrocarbons, preferably 70% by mass or more of vinyl aromatic hydrocarbons and conjugated dienes. These copolymer blocks and / or vinyl aromatic hydrocarbon homopolymer blocks are shown.
  • the polymer block B mainly composed of a conjugated diene contains a conjugated diene in an amount exceeding 50% by mass, preferably a copolymer block of a conjugated diene and a vinyl aromatic hydrocarbon containing 60% by mass or more, and And / or a conjugated diene homopolymer block.
  • the polymer block A and the polymer block B are a copolymer block of a vinyl aromatic hydrocarbon and a conjugated diene, even if the vinyl aromatic hydrocarbon in the copolymer block is uniformly distributed, It may be distributed in a tapered shape.
  • a plurality of portions where the vinyl aromatic hydrocarbons are uniformly distributed and / or a portion where the portions are distributed in a tapered shape may coexist. Further, a plurality of portions having different vinyl aromatic hydrocarbon contents may coexist in the copolymer block portion.
  • the block copolymer constituting the hydrogenated block copolymer crumb of this embodiment may be any mixture of block copolymers represented by the above general formula.
  • the ratio of the vinyl aromatic hydrocarbon polymer block incorporated in the block copolymer before hydrogenation to the total vinyl aromatic hydrocarbon (of vinyl aromatic hydrocarbon) is preferably 50% by mass or more, and more preferably 70 to 98% by mass.
  • the block ratio of vinyl aromatic hydrocarbons is measured by a method of oxidatively decomposing a block copolymer with tertiary butyl peroxide using osmium tetroxide as a catalyst (IM KOLTHOFF, et al., J. Polym. Sci). .1,429 (1946)).
  • the microstructure (ratio of cis, trans, vinyl) of the conjugated diene polymer incorporated in the block copolymer before hydrogenation can be arbitrarily changed by using a polar compound described later.
  • the 1,2-vinyl bond content of the block copolymer before hydrogenation is preferably 10 to 80%, more preferably 25 to 75%.
  • the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is 3 to 80%. Preferably, it is 5 to 70%.
  • the microstructure of the conjugated diene polymer incorporated in the block copolymer is that the block copolymer before hydrogenation is a carbon disulfide solution, and the infrared spectrum is in the range of 600 to 1000 cm ⁇ 1 using a solution cell. And can be determined according to the calculation formula of the method of Hampton (styrene-butadiene copolymer) by the absorbance at a predetermined wave number.
  • Hydrocarbon solvents used for the production of block copolymers include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc.
  • An alicyclic hydrocarbon or an aromatic hydrocarbon solvent such as benzene, toluene, ethylbenzene or xylene can be used. These may be used alone or in combination of two or more.
  • the organolithium compound used as a polymerization initiator for the polymerization of the block copolymer is a compound in which one or more lithium atoms are bonded in the molecule, for example, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium. Sec-butyl lithium, tert-butyl lithium, hexamethylene lithium, butadienyl dilithium, isoprenyl dilithium, and the like. These may be used alone or in combination of two or more. Further, the organolithium compound may be added in portions during the polymerization in the production of the block copolymer.
  • a predetermined polar compound can be used for the purpose of adjusting the polymerization rate, changing the microstructure of the polymerized conjugated diene moiety, and the like.
  • polar compounds include ethers such as tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, and 2,2-bis (2-oxolanyl) propane; Tertiary amine compounds such as methylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinuclidine; alkali metal alkoxide compounds such as potassium tert-amylate, potassium tert-butylate, sodium tert-butylate, sodium amylate A phosphine compound such as triphenylphosphin
  • the polymerization temperature for producing the block copolymer is preferably ⁇ 10 to 150 ° C., more preferably 30 to 120 ° C.
  • the time required for the polymerization varies depending on the conditions, but is preferably within 48 hours, more preferably 0.5 to 10 hours.
  • the polymerization atmosphere is preferably an inert gas atmosphere such as nitrogen gas.
  • the polymerization pressure is not particularly limited as long as it is carried out within a range of pressure sufficient to maintain the monomer and solvent in a liquid phase within the above polymerization temperature range.
  • impurities that inactivate the catalyst and the living polymer for example, water, oxygen, carbon dioxide gas, and the like are not mixed in the polymerization system.
  • the hydrogenation catalyst is not particularly limited and is conventionally known
  • a so-called Ziegler type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, Cr or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum (3) Ti, Ru Homogeneous hydrogenation catalysts such as so-called organometallic complexes such as organometallic compounds such as Rh and Zr are used.
  • Specific examples of the hydrogenation catalyst include Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No.
  • the hydrogenation catalyst described in JP-B-2-9041 can be used.
  • Preferred hydrogenation catalysts include a mixture with a titanocene compound and / or a reducing organometallic compound.
  • the titanocene compound compounds described in JP-A-8-109219 can be used.
  • (substituted) cyclopentadidi such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride.
  • Examples thereof include compounds having at least one ligand having an enyl skeleton, an indenyl skeleton, or a fluorenyl skeleton.
  • Examples of the reducing organometallic compound include organic alkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.
  • the hydrogenation reaction is preferably carried out in the temperature range of 0 to 200 ° C, more preferably 30 to 150 ° C.
  • the hydrogen pressure used for the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, and still more preferably 0.3 to 5 MPa.
  • the hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours.
  • the hydrogenation reaction can be any of a batch process, a continuous process, or a combination thereof.
  • the total hydrogenation rate after hydrogenation of the unsaturated double bond based on the conjugated diene compound incorporated in the block copolymer before hydrogenation can be arbitrarily selected according to the purpose and is not particularly limited.
  • 70% or more, more preferably 80% or more, and still more preferably 95% or more of the unsaturated double bond based on the conjugated diene compound in the block copolymer may be hydrogenated, and only a part is water. It may be attached.
  • the hydrogenation rate is preferably 10% or more and less than 70%, more preferably 15% or more and less than 65%, and further preferably 20% or more and less than 60%.
  • the hydrogenation rate of the hydrogenated block copolymer is measured by a nuclear magnetic resonance apparatus (NMR).
  • the hydrogenated block copolymer constituting the hydrogenated block copolymer crumb of this embodiment has a main peak molecular weight of 200,000 to 600,000.
  • the main peak molecular weight can be controlled by adjusting the amount of the polymerization initiator.
  • a crumbing agent may be used, and as the crumbing agent, an anionic surfactant, a cationic surfactant, or a nonionic surfactant is generally used.
  • the surfactant as the crumbing agent is generally added in an amount of 0.1 to 3000 ppm with respect to the water in the stripping zone.
  • water-soluble salts of metals such as Li, Na, K, Mg, Ca, Al, and Zn can also be used as a crumb dispersion aid.
  • ⁇ Step of recovering hydrogenated block copolymer crumb> As described above, an aqueous slurry obtained by dispersing a hydrogenated block copolymer crumb in water obtained by a steam stripping step is subjected to dehydration and drying treatments through the following steps to obtain a hydrogenated block copolymer crumb. Can be recovered. In the recovery step of the hydrogenated block copolymer crumb, ⁇ Step 1> dehydration treatment, ⁇ Step 2> dehydration treatment and drying treatment, and ⁇ Step 3> drying treatment described later are performed.
  • the dehydration process and the drying process may be performed by independent devices, each having a dehydration process unit and a drying process unit, and a so-called integrated type having a structure in which these units communicate with each other. You may perform using the following extrusion-type dryer.
  • the aqueous slurry is dehydrated to obtain a crumb having a moisture content of more than 60% by mass and 80% by mass or less and a crumb component not passing through a sieve having an opening of 3.35 mm is 60% by mass or more of the total crumbs.
  • the water content of the crumb after ⁇ Step 1> is preferably 62% by mass to 80% by mass, and more preferably 65% by mass to 75% by mass.
  • the crumb component which does not pass a sieve with a mesh opening of 3.35 mm after passing through ⁇ process 1> is 70 mass% or more of all crumbs, and it is more preferable that it is 80 mass% or more.
  • the dehydration treatment in ⁇ Step 1> can be performed by, for example, a rotary screen, a vibrating screen, a centrifugal dehydrator, or the like.
  • a decrease in polymer fluidity in the extruder in ⁇ Step 2> to be described later can be suppressed, and when the water content is 80% by mass or less, in Step 2 to be described later
  • the heat load on the polymer crumb in the extruder can be suppressed.
  • the dehydration and drying treatment in ⁇ Step 2> described later can be performed stably, and the desired crumb Specific surface area and particle size distribution can be obtained, and excellent compound workability can be achieved.
  • the crumb that has been dehydrated in ⁇ Step 1> and has a predetermined moisture content is made into a crumb having a moisture content of 3 to 30% by mass by performing the dehydration treatment and the drying treatment in ⁇ Step 2> It transfers to ⁇ process 3> mentioned later.
  • the water content of the crumb after the ⁇ Step 2> is preferably 3 to 25% by mass, and more preferably 3.2 to 20% by mass.
  • the dehydration treatment and the drying treatment may be performed by independent devices, but a so-called integrated extrusion dryer having a structure in which the dehydration treatment means and the drying treatment means are communicated with each other is used. You may go.
  • the extrusion dryer is a device that performs a dehydration process and a drying process, and includes a dehydration process unit and a drying process unit.
  • the dehydration process unit includes an extruder (an extruder-type water squeezer) and a drying process unit.
  • a kneader type dryer, a screw type expander type dryer or the like is employed.
  • the dehydrating means includes a single screw or twin screw multi-screw extruder and the drying means includes a screw dryer.
  • a combination of a single screw extruder and a screw dryer is particularly preferable.
  • a dehydrating apparatus and a drying apparatus for performing ⁇ Step 2> an extrusion dryer in which the dehydrating means and the drying means are integrated, specifically, a screw-type extruder,
  • the screw-type dryer, the integrated screw extruder-type dryer, and the like may be provided with a vent mechanism and a dewatering slit according to the purpose of use.
  • the moisture content of the crumb By setting the moisture content of the crumb to 3% by mass or more by ⁇ Step 2>, it is possible to prevent the crumb from gelling and / or decomposing by the shearing force of the extruder, and the moisture content is set to 30% by mass or less. Thus, it is possible to easily control the moisture content of the crumb obtained by ⁇ Step 3> described later to 1% by mass or less.
  • the outlet temperature of the apparatus that performs the drying process in ⁇ Step 2> that is, when the dehydration process and the drying process are performed separately, the outlet temperature of the apparatus that performs the dehydration process is set to 120 ° C. or less and the drying process is performed. It is preferable that the outlet temperature of the apparatus for performing the above is 135 to 175 ° C. More preferably, the outlet temperature of the apparatus for performing the dehydration treatment is 120 ° C. or less, the outlet temperature of the apparatus for performing the drying treatment is 138 to 172 ° C., and more preferably, the outlet temperature of the apparatus for performing the dehydration treatment is 118 ° C.
  • the outlet temperature of the drying apparatus is set to 140 to 172 ° C.
  • the temperature at the first stage outlet is set to 120 ° C. or lower, and the temperature at the second stage outlet. Is preferably 135 to 175 ° C. More preferably, the temperature at the first stage outlet is 120 ° C. or lower, the temperature at the second stage outlet is 138 to 172 ° C., more preferably the temperature at the first stage outlet is 118 ° C. or lower, and The temperature is 140-172 ° C.
  • the crumb obtained in ⁇ Step 2> is dried with a hot air dryer to obtain a crumb having a moisture content of 1% by mass or less.
  • the water content of the crumb after the ⁇ Step 3> is 1% by mass or less, preferably 0.95% by mass or less, and more preferably 0.9% by mass or less.
  • the aqueous slurry is dehydrated by ⁇ Step 1>, and the crumb component that has a moisture content of more than 60% by mass and not more than 80% by mass and does not pass through a sieve having an opening of 3.35 mm is 60% by mass of the total crumbs.
  • the crumb component that has a moisture content of more than 60% by mass and not more than 80% by mass and does not pass through a sieve having an opening of 3.35 mm is 60% by mass of the total crumbs.
  • the water content and size of the hydrogenated block copolymer crumb can be determined by the method described in the examples described later.
  • the crumb size and moisture content in the above ⁇ Step 1> and further defining the outlet temperature in the apparatus and the moisture content of the crumb at the outlet through ⁇ Step 1> to ⁇ Step 3>,
  • the pulsating flow in the device is also suppressed, and fine crumbs (passing through a sieve with an opening of 0.425 mm, sandy hard crumb) and large particle crumbs (passing through a sieve with an opening of 3.35 mm) Uniform crumbs with less foaming) are obtained.
  • the hydrogenated block copolymer crumb of this embodiment has a specific surface area of 0.3 to 1.0 m 2 / g. Moreover, the component which passes a sieve with an opening of 3.35 mm and does not pass a sieve with an opening of 0.425 mm is 80 mass% or more of the total crumbs. In order to obtain such a crumb, it is particularly effective to adjust the size and moisture content of the crumb before entering ⁇ Process 2> and optimize the dehydration and drying conditions in ⁇ Process 2>. is there. Specifically, if the water content of the crumb after passing through ⁇ Step 1> is too small as 60% or less, it will be dehydrated too much in ⁇ Step 2> and the fluidity will decrease.
  • ⁇ Step 2> if the water content is too high (over 80%) or the crumb size is too small to pass through a sieve having an opening of 3.35 mm, the dehydration and drying process can be stably performed in ⁇ Step 2>. It is not possible to obtain good fluidity.
  • ⁇ Step 2> if the water content of crumb is too high, the load in ⁇ Step 3> increases, and if the water content of crumb is too low, the fluidity of the crumb is lowered and foaming becomes uneven. The crumb size is uneven.
  • the outlet temperature of the apparatus in the drying process is set to 135 to 175 ° C. in ⁇ Step 2>. It is preferable. Therefore, as described above, in ⁇ Step 1>, the moisture content of the crumb is adjusted to be more than 60% by mass and 80% by mass or less, and the crumb component that does not pass through the sieve having a mesh size of 3.35 mm is 60% by mass of the total crumbs As described above, it is effective to control the water content of crumb to be 3 to 30% by mass in ⁇ Step 2>.
  • the hydrogenated block copolymer crumb of the present embodiment is prepared by using a predetermined thermoplastic resin or a softening agent such as process oil to produce a thermoplastic composition that can be used for various applications described later. it can.
  • a compound with a thermoplastic resin such as propylene and a softening agent such as process oil various additives can be blended depending on the purpose.
  • the type of additive is not particularly limited as long as it is generally used for blending thermoplastic resins and rubber-like polymers.
  • inorganic fillers such as metal hydroxides, silica-based inorganic fillers, metal oxides, organic fillers, antioxidants, UV absorbers and light stabilizers, stearic acid, behenic acid, zinc stearate, stear With lubricants such as calcium phosphate, magnesium stearate, ethylene bisstearamide, mold release agent, paraffin, plasticizer, flame retardant, antistatic agent, organic fiber, carbon fiber, metal whisker and other reinforcing materials, pigments, colorants, etc. is there.
  • lubricants such as calcium phosphate, magnesium stearate, ethylene bisstearamide, mold release agent, paraffin, plasticizer, flame retardant, antistatic agent, organic fiber, carbon fiber, metal whisker and other reinforcing materials, pigments, colorants, etc. is there.
  • additives may be added to the hydrogenated block copolymer crumb solution, or may be added in the dehydration step and / or the drying step, or may be added after the drying step.
  • the hydrogenated block copolymer crumb of this embodiment includes various thermoplastic resin modifiers, footwear materials, adhesive / adhesive materials, asphalt modifiers, industrial parts such as electric cables, automobile parts, and medical use. It can be used as a material for appliance materials, home appliances and parts thereof, electronic devices and parts thereof, household goods, toys and the like.
  • ⁇ Vinyl bond content> A carbon disulfide solution of a sample for measurement (a block copolymer produced according to Production Example 1 below) is prepared, and an infrared spectrum is 600 to 1000 cm ⁇ 1 using an infrared spectrophotometer (Spectraum 100 manufactured by PerkinElmer Japan). And the absorbance at a predetermined wave number was determined according to the formula for the method of Hampton (styrene-butadiene copolymer).
  • the hydrogenation rate of the hydrogenated block copolymer was measured using a nuclear magnetic resonance apparatus (DPX-400 manufactured by BRUCKER).
  • paraffinic process oil Diaffinic process oil (Diana Process Oil PW90 manufactured by Idemitsu Petrochemical Co., Ltd.) colored by dropping ink, and stirred so that the process oil was distributed throughout the crumb. Allowed to stand for 10 minutes. The image of the entire crumb after standing was binarized, and the area ratio of the colored portion (the ratio of the crumb that absorbed oil) was calculated.
  • paraffinic process oil colored with ink Diana Process Oil PW90 manufactured by Idemitsu Petrochemical Co., Ltd.
  • Oil holding power mass of paraffinic process oil (10 g) / [crumb total mass (10 g) ⁇ mass of crumb not colored with ink (g)]
  • the oil retention force is high, it means that the oil has accumulated above the crumb, and a certain amount of oil could be held with a small amount of crumb.
  • An unmelted polymer refers to a polymer in which crumbs are not completely melted and remain in the compound.
  • 24.57 g of paraffinic process oil (Diana Process Oil PW90 manufactured by Idemitsu Petrochemical Co., Ltd.) was added to 16.38 g of the hydrogenated block copolymer crumb and stirred so that the process oil spread evenly. Next, it was allowed to stand for 20 minutes at room temperature to absorb oil.
  • FIG. 1 shows a cross-sectional photograph of a sheet having the fish eye (unmelted polymer, diameter A). Actually, the fish eyes were observed as dots on the surface. The difference in the number of fish eyes (unmelted polymer) after 3 minutes (compound becomes uniform but unmelted polymer remains) and after 20 minutes (all unmelted polymer melts) is unmelted in the compound. The number of polymers.
  • 68 parts by mass of butadiene is supplied for polymerization, and finally, 16 parts by mass of styrene is supplied for polymerization to block the block copolymer of the SBS structure (S is a polystyrene block and B is a polybutadiene block). Coalescence was obtained.
  • the resulting block copolymer had a styrene content of 32% by mass, a main peak molecular weight of 280,000, and a vinyl bond content of the butadiene portion of 36%.
  • the steam stripping was carried out by adding the amount of styrene-maleic anhydride copolymer Na salt (hereinafter referred to as “crumbing agent A”) shown in Table 1 as a crumbing agent.
  • concentration of the hydrogenated block copolymer crumb in the obtained aqueous slurry was 5% by mass.
  • the aqueous slurry containing the hydrogenated block copolymer crumb obtained above is sent to a vibrating screen having a mesh opening of 1 mm and subjected to dehydration treatment ( ⁇ Step 1>), and then the method of (4) above
  • the water content of the hydrogenated block copolymer crumb that had undergone ⁇ Step 1> was measured, and the crumb size was measured by the method of (6) above.
  • Table 1 below shows the water content (% by mass) and the crumb size (ratio of components that do not pass through a sieve having an opening of 3.35 mm) (% by mass) of the hydrogenated block copolymer crumb obtained by ⁇ Step 1>. .
  • the crumbs of Examples 1 to 4 have good oil absorption uniformity, high oil retention, and the number of unmelted polymers in the compound is 10 or less, while the crumbs of Comparative Examples 1 to 4 are practical. Good oil absorption uniformity was not obtained, the oil retention was low, and the number of unmelted polymers in the compound was 15 or more.
  • Table 2 below shows the water content (% by mass) and the crumb size (ratio of components that do not pass through a sieve having an opening of 3.35 mm) (% by mass) of the hydrogenated block copolymer crumb obtained by ⁇ Step 1>.
  • the hydrogenated block copolymer crumb is supplied to a two-stage single-screw extruder in which a dehydrating means (first stage) and a drying means (second stage) are integrated, and the screw speed is about 80 rpm. Then, dehydration treatment and drying treatment were performed (first step and second step of ⁇ Step 2>).
  • the used two-stage single-screw extruder has a slit in the first-stage dewatering treatment means, but in order to keep the water in the crumb up to the second-stage drying treatment means, the slit is fully closed.
  • Table 2 below shows the respective outlet temperatures (first-stage outlet temperature, second-stage outlet temperature) of the dehydration treatment means and the drying treatment means, and the moisture content of the crumb obtained from the outlet of the drying treatment means.
  • the hydrogenated block copolymer crumb obtained above was dried with hot air of about 90 ° C. using a vibration transport dryer to obtain a dried crumb ( ⁇ Step 3>).
  • the water content, specific surface area, crumb size, oil absorption uniformity, oil retention, and number of unmelted polymers in the compound of the finally obtained hydrogenated block copolymer crumb are shown in Table 2 below.
  • the crumbs of Examples 5 to 8 have good oil absorption uniformity, high oil retention, and the number of unmelted polymers in the compound is 10 or less, while the crumbs of Comparative Examples 5 to 8 are practical. Good oil absorption uniformity was not obtained, oil retention was low, and the number of unmelted polymers in the compound was 15 or more. Moreover, the comparative example 9 had too much water content of the crumb, and could not be put into a dryer, and it was impossible to perform a dehydration process and a drying process.
  • Table 2 below shows the moisture content (% by mass) and the crumb size (ratio of components that do not pass through a sieve having an opening of 3.35 mm) (% by mass) of the crumb obtained in ⁇ Step 1>.
  • This crumb was subjected to a drying treatment with hot air of about 90 ° C. using a vibration transport dryer without performing the above-described ⁇ Step 2> to obtain a dried crumb ( ⁇ Step 3>).
  • the water content, specific surface area, crumb size, oil absorption uniformity, oil retention, and number of unmelted polymers in the compound of the finally obtained hydrogenated block copolymer crumb are shown in Table 2 below.
  • the crumb of Comparative Example 11 did not have a practically good oil absorption uniformity, had a low oil retention, and had 15 or more unmelted polymers in the compound.
  • Comparative Example 10 is an example in which ⁇ Step 3> was not performed after ⁇ Step 1> and ⁇ Step 2> under the same conditions as Comparative Example 8, and the crumb after ⁇ Step 2> was performed. The characteristics were shown. Moreover, in Table 2, Comparative Example 11 showed the characteristics of crumbs after performing ⁇ Step 3> without performing ⁇ Step 2> after performing ⁇ Step 1>.
  • the hydrogenated block copolymer crumb of the present invention is used industrially as a material for medical instrument materials, home appliances and parts thereof, electronic devices and parts thereof, various industrial parts such as electric cables, automobile parts, toys and the like. there is a possibility.

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Abstract

(Problem) To produce a hydrogenated block copolymer crumb which can exhibit excellent compounding properties including homogeneous dispersion of an oil throughout the crumb upon the compounding with the oil, the decrease of unmolten crumbs and the like. (Solution) A hydrogenated block copolymer crumb which comprises a hydrogenated product of a block copolymer of an aromatic vinyl hydrocarbon and a conjugated diene, and which fulfils the following requirements (1) to (4): (1) the main peak molecular weight is 200,000 to 600,000; (2) the water content is 1 mass% or less; (3) the specific surface area is 0.3-1.0 m2/g; and (4) a component that passes through a sieve having a mesh size of 3.35 mm but does not pass through a sieve having a mesh size of 0.425 mm is contained in an amount of 80 mass% or more relative to the total amount of all of the crumbs.

Description

水添ブロック共重合体クラム及びその製造方法Hydrogenated block copolymer crumb and process for producing the same
　本発明は、水添ブロック共重合体クラム、及びその製造方法に関する。 The present invention relates to a hydrogenated block copolymer crumb and a method for producing the same.
　従来から、ビニル芳香族炭化水素と共役ジエンとからなるブロック共重合体の水添物である水添ブロック共重合体は、反発弾性、低温特性に優れた特性を有することから、熱可塑性樹脂の耐衝撃性、低温特性、加工性等を改良する改質剤として使用されている。
　また、前記水添ブロック共重合体と熱可塑性樹脂との組成物は、電気・電子部品、自動車部品、各種工業部品、生活用品等の分野において広く利用されている。
　特に、高分子量の水添ブロック共重合体は、前記各種特性に加え、機械的特性に優れていることから、オイル等の液状軟化剤、可塑剤及びポリプロピレン等の熱可塑性樹脂と組み合わせることにより、電線ケーブル等の各種工業部品、自動車部品等の材料として用いられている。 Conventionally, a hydrogenated block copolymer, which is a hydrogenated product of a block copolymer composed of a vinyl aromatic hydrocarbon and a conjugated diene, has excellent resilience and low-temperature properties. It is used as a modifier to improve impact resistance, low temperature characteristics, workability, and the like.
The composition of the hydrogenated block copolymer and the thermoplastic resin is widely used in the fields of electric / electronic parts, automobile parts, various industrial parts, daily necessities and the like.
In particular, the high molecular weight hydrogenated block copolymer is excellent in mechanical properties in addition to the various properties described above, and therefore, by combining with a liquid softener such as oil, a plasticizer and a thermoplastic resin such as polypropylene, It is used as a material for various industrial parts such as electric cables and automobile parts.
　上述した高分子量の水添ブロック共重合体は、コンパウンド時のオイル等との混練性を良好にするため、一般的にはペレットではなく、多孔性乾燥クラムの形態で取り扱われることが多い。
　このような水添ブロック共重合体の多孔性乾燥クラムを得る方法に関しては、従来から多くの提案がなされている。 The above-mentioned high molecular weight hydrogenated block copolymer is generally handled in the form of porous dry crumbs, not pellets, in order to improve kneadability with oil and the like during compounding.
Many proposals have hitherto been made regarding methods for obtaining such porous dry crumbs of hydrogenated block copolymers.
　例えば、共重合工程及び水添工程により得られた水添ブロック共重合体の溶液からスチームストリッピングで溶媒を除去した後、さらに押出脱水機で脱水及び乾燥することにより、含水率が１質量％以下の重合体クラムを得る方法が知られている（例えば、特許文献１、２参照。）。 For example, after removing the solvent by steam stripping from the solution of the hydrogenated block copolymer obtained by the copolymerization step and the hydrogenation step, the water content is 1% by mass by further dehydrating and drying with an extrusion dehydrator. Methods for obtaining the following polymer crumb are known (see, for example, Patent Documents 1 and 2).
　また、高分子量の水添ブロック共重合体クラムのオイル吸油性を改良する方法として、水添ブロック共重合体クラムを脱水する押出機の運転温度や、押出機投入前のスラリー水分量を調節した押出脱水機による脱水・乾燥方法（例えば、特許文献３参照。）、さらには、特定の温度条件下で水添ブロック共重合体クラムを熱風乾燥機により乾燥処理する方法（例えば、特許文献４参照。）が提案されている。 In addition, as a method of improving the oil-absorbing property of the high molecular weight hydrogenated block copolymer crumb, the operating temperature of the extruder for dehydrating the hydrogenated block copolymer crumb and the water content of the slurry before charging the extruder were adjusted. Dehydration / drying method using an extrusion dehydrator (for example, see Patent Document 3), and further, a method for drying a hydrogenated block copolymer crumb with a hot air dryer under a specific temperature condition (for example, see Patent Document 4). .) Has been proposed.
特開昭６４－５６７１３号公報JP-A 64-56713 特開平２－１８９３０４号公報JP-A-2-189304 特表２００２－５４２９６３号公報Special Table 2002-542963 Publication 国際公開第９９／５５７５２号International Publication No. 99/55752
　しかしながら、特許文献１、２に開示されている方法は、低分子量の水添ブロック共重合体クラムを得る方法としては好ましいが、高分子量の水添ブロック共重合体クラムについてはコンパウンド時のオイル吸収性に関し、未だ十分な特性が得られていない。
　また、特許文献３、４に開示されている方法により得られる高分子量の水添ブロック共重合体クラムは、熱可塑性樹脂やオイル等とのコンパウンド時に、クラム全体にオイルが均一に分散しなかったり、さらにはクラムが完全に溶融しきらないことにより未溶融ポリマーとなって残留したりする等、コンパウンド加工性が未だ不安定であるという問題を有している。 However, the methods disclosed in Patent Documents 1 and 2 are preferable as a method for obtaining a low molecular weight hydrogenated block copolymer crumb, but for high molecular weight hydrogenated block copolymer crumbs, oil absorption during compounding is preferred. In terms of sex, sufficient characteristics have not yet been obtained.
In addition, the high molecular weight hydrogenated block copolymer crumb obtained by the methods disclosed in Patent Documents 3 and 4 does not uniformly disperse oil throughout the crumb when compounded with a thermoplastic resin or oil. Furthermore, there is a problem that the compound processability is still unstable, for example, the crumb does not completely melt and remains as an unmelted polymer.
　そこで本発明においては、上述したような従来技術の問題点に鑑みて、熱可塑性樹脂やプロセスオイル等とのコンパウンドに際し、クラム全体にオイルが均一に分散し、かつコンパウンド中における未溶融ポリマーの残存量が抑制される、優れたコンパウンド加工性を有する、水添ブロック共重合体クラム、及び当該水添ブロック共重合体クラムの製造方法を提供することを目的とする。 Therefore, in the present invention, in view of the problems of the prior art as described above, when compounding with a thermoplastic resin or process oil, the oil is uniformly dispersed throughout the crumb, and the unmelted polymer remains in the compound. It is an object of the present invention to provide a hydrogenated block copolymer crumb having an excellent compound processability in which the amount is suppressed, and a method for producing the hydrogenated block copolymer crumb.
　本発明者は、高分子量の水添ブロック共重合体クラムと、熱可塑性樹脂、プロセスオイル等の軟化剤とのコンパウンドにおいて、クラム全体にオイルが均一に分散し、未溶融ポリマーの残存量の抑制等、安定したコンパウンド加工性を得る手法について鋭意検討した結果、クラムの比表面積、粒子径分布が特定の範囲を有するビニル芳香族炭化水素と共役ジエンとからなる高分子量の水添ブロック共重合体クラム、及び特定の脱水・乾燥工程からなるその水添ブロック共重合体クラムの製造方法が、上述した従来技術の問題を解決できることを見出し、本発明を完成させるに至った。
　すなわち、本発明は下記の通りである。 The present inventor, in a compound of a high molecular weight hydrogenated block copolymer crumb and a softening agent such as a thermoplastic resin or process oil, the oil is uniformly dispersed throughout the crumb and the residual amount of unmelted polymer is suppressed. As a result of intensive studies on a method for obtaining stable compound processability, a high molecular weight hydrogenated block copolymer comprising a vinyl aromatic hydrocarbon and a conjugated diene having a specific range of crumb specific surface area and particle size distribution. It has been found that a method for producing crumb and its hydrogenated block copolymer crumb comprising a specific dehydration / drying step can solve the above-mentioned problems of the prior art, and has completed the present invention.
That is, the present invention is as follows.
〔１〕
　ビニル芳香族炭化水素と共役ジエンとのブロック共重合体の水添物からなる水添ブロック共重合体クラムであって、下記（１）～（４）を満たす水添ブロック共重合体クラム。
　（１）メインピーク分子量が２０万～６０万
　（２）含水率が１質量％以下
　（３）比表面積が０．３～１．０ｍ2／ｇ
　（４）目開き３．３５ｍｍの篩を通過し、かつ目開き０．４２５ｍｍの篩を通過しない成分が、全クラムの８０質量％以上
〔２〕
　前記〔１〕に記載の水添ブロック共重合体クラムの製造方法であって、下記＜工程１＞～＜工程３＞を含む、水添ブロック共重合体クラムの製造方法。
＜工程１＞：水添ブロック共重合体クラムを含有する水性スラリーを脱水処理し、含水率が６０質量％を超え８０質量％以下で、目開き３．３５ｍｍの篩を通過しないクラム成分が全クラムの６０質量％以上であるクラムを得る工程。
＜工程２＞：前記＜工程１＞で得られたクラムを、脱水処理及び乾燥処理し、含水率３～３０質量％のクラムを得る工程。
＜工程３＞：前記＜工程２＞で得られたクラムを乾燥処理し、含水率１質量％以下のクラムを得る工程。
〔３〕
　前記＜工程２＞において、前記乾燥処理における装置出口温度を１３５～１７５℃以下とする前記〔２〕に記載の水添ブロック共重合体クラムの製造方法。
〔４〕
　前記＜工程２＞において、脱水処理手段と乾燥処理手段とを具備し当該脱水処理手段と乾燥処理手段とが連通している押出式乾燥機を用い、
　前記脱水処理手段で前記脱水処理を行い、前記乾燥処理手段で前記乾燥処理を行う、前記〔２〕又は〔３〕に記載の水添ブロック共重合体クラムの製造方法。
〔５〕
　前記脱水処理手段の出口温度が１２０℃以下であり、前記乾燥処理手段の出口温度が１３５～１７５℃である、前記〔４〕に記載の水添ブロック共重合体クラムの製造方法。 [1]
A hydrogenated block copolymer crumb comprising a hydrogenated product of a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene and satisfying the following (1) to (4):
(1) Main peak molecular weight is 200,000 to 600,000 (2) Moisture content is 1% by mass or less (3) Specific surface area is 0.3 to 1.0 m 2 / g
(4) A component that passes through a sieve having an opening of 3.35 mm and does not pass through a sieve having an opening of 0.425 mm is 80% by mass or more of the total crumb [2]
A method for producing a hydrogenated block copolymer crumb according to [1] above, comprising the following <Step 1> to <Step 3>.
<Step 1>: An aqueous slurry containing a hydrogenated block copolymer crumb is dehydrated, and all crumb components that have a moisture content of more than 60% by mass and not more than 80% by mass and do not pass through a sieve having an opening of 3.35 mm are included. Obtaining a crumb that is 60% by weight or more of the crumb.
<Step 2>: A step of dehydrating and drying the crumb obtained in <Step 1> to obtain a crumb having a water content of 3 to 30% by mass.
<Step 3>: A step of drying the crumb obtained in <Step 2> to obtain a crumb having a moisture content of 1% by mass or less.
[3]
The method for producing a hydrogenated block copolymer crumb according to the above [2], wherein, in the <Step 2>, the apparatus outlet temperature in the drying treatment is set to 135 to 175 ° C. or lower.
[4]
In the <Step 2>, using an extrusion dryer that includes a dehydration treatment unit and a drying treatment unit, and the dehydration treatment unit and the drying treatment unit communicate with each other.
The method for producing a hydrogenated block copolymer crumb according to [2] or [3], wherein the dehydration process is performed by the dehydration process, and the drying process is performed by the drying process.
[5]
The method for producing a hydrogenated block copolymer crumb according to [4], wherein the outlet temperature of the dehydrating means is 120 ° C. or lower and the outlet temperature of the drying means is 135 to 175 ° C.
　本発明によれば、クラム全体にオイルが均一に分散し、オイル吸収性（オイル保持力）が良好で、未溶融ポリマーの減少化等の、優れたコンパウンド加工性を有する水添ブロック共重合体クラムが得られる。 According to the present invention, a hydrogenated block copolymer having an excellent compound processability such as a uniform dispersion of oil throughout the crumb, good oil absorbability (oil retention), and reduction of unmelted polymer. A crumb is obtained.
未溶融ポリマーを有するシートの断面写真を示す。The cross-sectional photograph of the sheet | seat which has an unmelted polymer is shown.
　以下、本発明を実施するための形態（以下、本実施形態と言う。）について説明する。
　なお、本発明は以下の実施形態に限定されるものではない。
　また、本明細書において、「略」を付した用語は、当業者の技術常識の範囲内でその「略」を除いた用語の意味を示すものであり、「略」を除いた意味自体をも含むものとする。 Hereinafter, modes for carrying out the present invention (hereinafter referred to as the present embodiment) will be described.
In addition, this invention is not limited to the following embodiment.
Further, in this specification, the term with “abbreviation” indicates the meaning of the term excluding the “abbreviation” within the technical common sense of those skilled in the art. Shall also be included.
〔水添ブロック共重合体クラム〕
　本実施形態の水添ブロック共重合体クラムは、ビニル芳香族炭化水素と共役ジエンとのブロック共重合体の水添物からなるクラムであり、下記（１）～（４）を満たす。
（１）メインピーク分子量が２０万～６０万
（２）含水率が１質量％以下
（３）比表面積が０．３～１．０ｍ2／ｇ
（４）目開き３．３５ｍｍの篩を通過し、かつ目開き０．４２５ｍｍの篩を通過しない成分が、全クラムの８０質量％以上 [Hydrogenated block copolymer crumb]
The hydrogenated block copolymer crumb of this embodiment is a crumb made of a hydrogenated block copolymer of vinyl aromatic hydrocarbon and conjugated diene, and satisfies the following (1) to (4).
(1) Main peak molecular weight is 200,000 to 600,000 (2) Water content is 1% by mass or less (3) Specific surface area is 0.3 to 1.0 m 2 / g
(4) A component that passes through a sieve having an opening of 3.35 mm and does not pass through a sieve having an opening of 0.425 mm is 80% by mass or more of the total crumb.
　本実施形態における水添ブロック共重合体クラムは、上記のようにビニル芳香族炭化水素と共役ジエンとからなるブロック共重合体に水素を添加したものであり、前記（１）に示すように、メインピーク分子量が、所定の重合体組成物とした場合の機械的強度及び耐衝撃性の観点から２０万以上、加工性や熱可塑性樹脂等の高分子物質との相溶性の観点から６０万以下である。
　メインピーク分子量は、好ましくは２３万～５０万であり、より好ましくは２５万～４５万である。
　水添ブロック共重合体のメインピークの分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）測定を行い、市販の標準ポリスチレンの測定から求めた検量線を使用して測定することができる。具体的には、後述する実施例に記載の方法により測定することができる。 The hydrogenated block copolymer crumb in this embodiment is obtained by adding hydrogen to a block copolymer consisting of a vinyl aromatic hydrocarbon and a conjugated diene as described above, and as shown in the above (1), The main peak molecular weight is 200,000 or more from the viewpoint of mechanical strength and impact resistance when a predetermined polymer composition is used, and 600,000 or less from the viewpoint of workability and compatibility with a high-molecular substance such as a thermoplastic resin. It is.
The main peak molecular weight is preferably 230,000 to 500,000, more preferably 250,000 to 450,000.
The molecular weight of the main peak of the hydrogenated block copolymer can be measured using GPC (gel permeation chromatography) measurement and a calibration curve obtained from measurement of commercially available standard polystyrene. Specifically, it can measure by the method as described in the Example mentioned later.
　本実施形態の水添ブロック共重合体クラムは、前記（２）に示すように、含水率が１質量％以下であるものとする。これにより、所定の熱可塑性樹脂とコンパウンドし、熱可塑性樹脂組成物を得た場合に、発泡やシルバー等の発生による外観不良を防止できる。
　本実施形態の水添ブロック共重合体クラムは、含水率が０．９質量％以下であることが好ましく、０．８質量％以下であることがより好ましい。 The hydrogenated block copolymer crumb of the present embodiment has a water content of 1% by mass or less as shown in (2) above. Thereby, when it is compounded with a predetermined thermoplastic resin to obtain a thermoplastic resin composition, it is possible to prevent poor appearance due to foaming, generation of silver or the like.
The hydrogenated block copolymer crumb of this embodiment preferably has a moisture content of 0.9% by mass or less, and more preferably 0.8% by mass or less.
　本実施形態の水添ブロック共重合体クラムは、前記（３）に示すように、比表面積が０．３～１．０ｍ2／ｇ、好ましくは０．３５～０．８ｍ２／ｇ、より好ましくは０．４～０．７ｍ２／ｇである。
　また、本実施形態の水添ブロック共重合体クラムは、前記（４）に示すように、クラムサイズを、目開き３．３５ｍｍの篩を通過し、かつ目開き０．４２５ｍｍの篩を通過しない成分が、全クラムの８０質量％以上、好ましくは８２質量％以上、より好ましくは８５質量％以上であるものとする。前記（３）、（４）の要件を満たすことにより、オイル吸収性が良好なものとなり、オイル吸収ムラを抑制でき、コンパウンド作製時に均一に可塑化でき、未溶融ポリマー数の低減化を図ることができる。　
　水添ブロック共重合体クラムの含水率、比表面積、サイズについては、後述する実施例に記載の方法により求めることができる。 The hydrogenated block copolymer crumb of this embodiment has a specific surface area of 0.3 to 1.0 m 2 / g, preferably 0.35 to 0.8 m 2 / g, as shown in (3) above. Preferably, it is 0.4 to 0.7 m 2 / g.
In addition, the hydrogenated block copolymer crumb of the present embodiment has a crumb size that passes through a sieve having an opening of 3.35 mm and does not pass through a sieve having an opening of 0.425 mm, as shown in (4) above. It is assumed that the component is 80% by mass or more, preferably 82% by mass or more, more preferably 85% by mass or more of the total crumb. By satisfying the requirements of (3) and (4) above, the oil absorbability becomes good, the oil absorption unevenness can be suppressed, the plastic can be uniformly plasticized at the time of compound preparation, and the number of unmelted polymers can be reduced. Can do.
The water content, specific surface area, and size of the hydrogenated block copolymer crumb can be determined by the method described in the examples described later.
〔水添ブロック共重合体クラムの製造方法〕
　先ず、後述するように水添ブロック共重合体を作製し、その後、所定の処理を行うことにより、水添ブロック共重合体クラムを得る。
（水添ブロック共重合体の製造工程）
　重合反応によりビニル芳香族炭化水素と共役ジエン化合物のブロック共重合体を得、その後、水添反応を行い、水添ブロック共重合体を得る。
　＜重合反応＞
　ブロック共重合体は、炭化水素溶媒中、有機リチウム化合物を重合開始剤として、ビニル芳香族炭化水素及び共役ジエンを重合することにより作製できる。
　ビニル芳香族炭化水素としては、例えば、スチレン、α－メチルスチレン、ｐ－メチルスチレン、２－ビニルナフタレン、ジビニルベンゼン等が挙げられる。
　共役ジエンとしては、例えば、１，３－ブタジエン、イソプレン、２，３－ジメチル－１，３ブタジエン、１，３－ペンタジエン、１，３－ヘプタジエン等が挙げられる。
　ブロック共重合体のビニル芳香族炭化水素含有量は、反発弾性の改良効果の観点から、９０質量％以下であることが好ましく、より好ましくは６０質量％以下、さらに好ましくは４０質量％以下である。 [Method for producing hydrogenated block copolymer crumb]
First, as described later, a hydrogenated block copolymer is prepared, and then a predetermined treatment is performed to obtain a hydrogenated block copolymer crumb.
(Production process of hydrogenated block copolymer)
A block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene compound is obtained by a polymerization reaction, and then a hydrogenation reaction is performed to obtain a hydrogenated block copolymer.
<Polymerization reaction>
The block copolymer can be produced by polymerizing vinyl aromatic hydrocarbon and conjugated diene in a hydrocarbon solvent using an organolithium compound as a polymerization initiator.
Examples of the vinyl aromatic hydrocarbon include styrene, α-methylstyrene, p-methylstyrene, 2-vinylnaphthalene, divinylbenzene and the like.
Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3 butadiene, 1,3-pentadiene, 1,3-heptadiene, and the like.
The vinyl aromatic hydrocarbon content of the block copolymer is preferably 90% by mass or less, more preferably 60% by mass or less, and still more preferably 40% by mass or less, from the viewpoint of improving the impact resilience. .
　ブロック共重合体の製造方法としては、例えば、特公昭３６－１９２８６号公報、特公昭４３－１７９７９号公報、特公昭４６－３２４１５号公報、特公昭４９－３６９５７号公報、特公昭４８－２４２３号公報、特公昭４８－４１０６号公報、特公昭５１－４９５６７号公報、特開昭５９－１６６５１８号公報等に記載された方法が挙げられる。
　ブロック共重合体の構造としては、例えば、一般式（Ａ－Ｂ）ｎ、（Ａ－Ｂ）ｎ－Ａ、Ｂ－（Ａ－Ｂ）ｎで表されるものが挙げられる。
　なお、Ａはビニル芳香族炭化水素を主体とする重合体ブロックであり、Ｂは共役ジエンを主体とする重合体ブロックである。ＡブロックとＢブロックとの境界は必ずしも明瞭に区別される必要はない。また、ｎは１以上の整数、好ましくは１～５の整数である。 Examples of the method for producing the block copolymer include Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-171979, Japanese Patent Publication No. 46-32415, Japanese Patent Publication No. 49-36957, and Japanese Patent Publication No. 48-2423. Examples thereof include the methods described in Japanese Patent Publication Nos. 48-4106, 51-49567, and 59-166518.
Examples of the structure of the block copolymer include those represented by general formulas (AB) n , (AB) n -A, and B- (AB) n .
A is a polymer block mainly composed of vinyl aromatic hydrocarbons, and B is a polymer block mainly composed of conjugated diene. The boundary between the A block and the B block does not necessarily have to be clearly distinguished. N is an integer of 1 or more, preferably an integer of 1 to 5.
　上記において、ビニル芳香族炭化水素を主体とする重合体ブロックＡは、ビニル芳香族炭化水素を５０質量％以上含有するものとし、好ましくは７０質量％以上含有するビニル芳香族炭化水素と共役ジエンとの共重合体ブロック及び／又はビニル芳香族炭化水素単独重合体ブロックを示す。
　共役ジエンを主体とする重合体ブロックＢは、共役ジエンを５０質量％を超える量で含有するものとし、好ましくは６０質量％以上含有する共役ジエンとビニル芳香族炭化水素との共重合体ブロック及び／又は共役ジエン単独重合体ブロックを示す。 In the above, the polymer block A mainly composed of vinyl aromatic hydrocarbons contains 50% by mass or more of vinyl aromatic hydrocarbons, preferably 70% by mass or more of vinyl aromatic hydrocarbons and conjugated dienes. These copolymer blocks and / or vinyl aromatic hydrocarbon homopolymer blocks are shown.
The polymer block B mainly composed of a conjugated diene contains a conjugated diene in an amount exceeding 50% by mass, preferably a copolymer block of a conjugated diene and a vinyl aromatic hydrocarbon containing 60% by mass or more, and And / or a conjugated diene homopolymer block.
　重合体ブロックＡ、重合体ブロックＢが、ビニル芳香族炭化水素と共役ジエンとの共重合体ブロックである場合、当該共重合体ブロック中のビニル芳香族炭化水素は均一に分布していても、テーパー状に分布していてもよい。
　また、共重合体ブロック部分には、ビニル芳香族炭化水素が均一に分布している部分及び／又はテーパー状に分布している部分がそれぞれ複数個共存していてもよい。
　さらに、共重合体ブロック部分には、ビニル芳香族炭化水素含有量が異なる部分が複数個共存していてもよい。
　本実施形態の水添ブロック共重合体クラムを構成するブロック共重合体は、上記一般式で表されるブロック共重合体の任意の混合物でもよい。 When the polymer block A and the polymer block B are a copolymer block of a vinyl aromatic hydrocarbon and a conjugated diene, even if the vinyl aromatic hydrocarbon in the copolymer block is uniformly distributed, It may be distributed in a tapered shape.
In the copolymer block portion, a plurality of portions where the vinyl aromatic hydrocarbons are uniformly distributed and / or a portion where the portions are distributed in a tapered shape may coexist.
Further, a plurality of portions having different vinyl aromatic hydrocarbon contents may coexist in the copolymer block portion.
The block copolymer constituting the hydrogenated block copolymer crumb of this embodiment may be any mixture of block copolymers represented by the above general formula.
　本実施形態の水添ブロック共重合体クラムの、水添前のブロック共重合体に組み込まれているビニル芳香族炭化水素重合体ブロックの全ビニル芳香族炭化水素に対する割合（ビニル芳香族炭化水素のブロック率という）は、５０質量％以上が好ましく、より好ましくは７０～９８質量％に調整することが推奨される。これにより、所定の材料と混合して重合体組成物としたとき、柔軟性の良好なゴム状重合体組成物や、耐衝撃性と剛性とのバランスに優れた重合体組成物が得られる。
　なお、ビニル芳香族炭化水素のブロック率は、（ビニル芳香族炭化水素重合体ブロック）／（ブロック共重合体を構成する全ビニル芳香族炭化水素含有量）×１００により求められる。
　ビニル芳香族炭化水素のブロック率は、四酸化オスミウムを触媒としてターシャリブチルパーオキサイドによりブロック共重合体を酸化分解する方法により測定される（Ｉ．Ｍ．ＫＯＬＴＨＯＦＦ，ｅｔａｌ．，Ｊ．Ｐｏｌｙｍ．Ｓｃｉ．１，４２９（１９４６）に記載の方法）。 In the hydrogenated block copolymer crumb of this embodiment, the ratio of the vinyl aromatic hydrocarbon polymer block incorporated in the block copolymer before hydrogenation to the total vinyl aromatic hydrocarbon (of vinyl aromatic hydrocarbon The block ratio is preferably 50% by mass or more, and more preferably 70 to 98% by mass. Thereby, when it mixes with a predetermined material and it is set as a polymer composition, a rubber-like polymer composition with favorable softness | flexibility and a polymer composition excellent in the balance of impact resistance and rigidity are obtained.
The block ratio of the vinyl aromatic hydrocarbon is determined by (vinyl aromatic hydrocarbon polymer block) / (total vinyl aromatic hydrocarbon content constituting the block copolymer) × 100.
The block ratio of vinyl aromatic hydrocarbons is measured by a method of oxidatively decomposing a block copolymer with tertiary butyl peroxide using osmium tetroxide as a catalyst (IM KOLTHOFF, et al., J. Polym. Sci). .1,429 (1946)).
　水添前のブロック共重合体に組み込まれている共役ジエン系重合体のミクロ構造（シス、トランス、ビニルの比率）は、後述する極性化合物等の使用により任意に変えることができる。
　共役ジエンとして、１，３－ブタジエンを使用した場合には、水添前のブロック共重合体の１，２－ビニル結合量は１０～８０％であることが好ましく、より好ましくは２５～７５％であり、共役ジエンとして、イソプレンを使用した場合又は１，３－ブタジエンとイソプレンを使用した場合には、１，２－ビニル結合と３，４－ビニル結合の合計量は３～８０％であることが好ましく、より好ましくは５～７０％である。
　ブロック共重合体に組み込まれている共役ジエン系重合体のミクロ構造は、水添前のブロック共重合体を二硫化炭素溶液とし、溶液セルを用いて、赤外線スペクトルを６００～１０００ｃｍ－１の範囲で測定し、所定の波数における吸光度によりハンプトン（スチレン－ブタジエン共重合体）の方法の計算式に従い求めることができる。 The microstructure (ratio of cis, trans, vinyl) of the conjugated diene polymer incorporated in the block copolymer before hydrogenation can be arbitrarily changed by using a polar compound described later.
When 1,3-butadiene is used as the conjugated diene, the 1,2-vinyl bond content of the block copolymer before hydrogenation is preferably 10 to 80%, more preferably 25 to 75%. When isoprene is used as the conjugated diene or when 1,3-butadiene and isoprene are used, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is 3 to 80%. Preferably, it is 5 to 70%.
The microstructure of the conjugated diene polymer incorporated in the block copolymer is that the block copolymer before hydrogenation is a carbon disulfide solution, and the infrared spectrum is in the range of 600 to 1000 cm −1 using a solution cell. And can be determined according to the calculation formula of the method of Hampton (styrene-butadiene copolymer) by the absorbance at a predetermined wave number.
　ブロック共重合体の製造に用いられる炭化水素溶媒としては、ブタン、ペンタン、ヘキサン、イソペンタン、ヘプタン、オクタン、イソオクタン等の脂肪族炭化水素、シクロペンタン、メチルシクロペンタン、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン等の脂環式炭化水素、あるいはベンゼン、トルエン、エチルベンゼン、キシレン等の芳香族炭化水素溶媒が使用できる。
　これらは一種のみを単独で用いてもよく、二種以上を混合して用いてもよい。 Hydrocarbon solvents used for the production of block copolymers include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc. An alicyclic hydrocarbon or an aromatic hydrocarbon solvent such as benzene, toluene, ethylbenzene or xylene can be used.
These may be used alone or in combination of two or more.
　重合開始剤としてブロック共重合体の重合に用いられる有機リチウム化合物は、分子中に一個以上のリチウム原子を結合した化合物であり、例えば、エチルリチウム、ｎ－プロピルリチウム、イソプロピルリチウム、ｎ－ブチルリチウム、ｓｅｃ－ブチルリチウム、ｔｅｒｔ－ブチルリチウム、ヘキサメチレンリチウム、ブタジエニルジリチウム、イソプレニルジリチウム等が挙げられる。
　これらは一種のみを単独で用いてもよく、二種以上を使用してもよい。
　また、有機リチウム化合物は、ブロック共重合体の製造において重合途中で分割添加してもよい。 The organolithium compound used as a polymerization initiator for the polymerization of the block copolymer is a compound in which one or more lithium atoms are bonded in the molecule, for example, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium. Sec-butyl lithium, tert-butyl lithium, hexamethylene lithium, butadienyl dilithium, isoprenyl dilithium, and the like.
These may be used alone or in combination of two or more.
Further, the organolithium compound may be added in portions during the polymerization in the production of the block copolymer.
　ブロック共重合体の製造時に、重合速度の調整、重合した共役ジエン部分のミクロ構造の変更等を目的として、所定の極性化合物を使用することができる。
　極性化合物としては、例えば、テトラヒドロフラン、ジエチルエーテル、ジオキサン、エチレングリコールジメチルエーテル、エチレングリコールジブチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジブチルエーテル、ジメトキシベンゼン、２，２－ビス（２－オキソラニル）プロパン等のエーテル類；テトラメチルエチレンジアミン、ジピペリジノエタン、トリメチルアミン、トリエチルアミン、ピリジン、キヌクリジン等の３級アミン化合物；カリウム－ｔ－アミラート、カリウム－ｔ－ブチラート、ナトリウム－ｔ－ブチラート、ナトリウムアミラート等のアルカリ金属アルコキシド化合物；トリフェニルホスフィン等のホスフィン化合物等が挙げられる。 In the production of the block copolymer, a predetermined polar compound can be used for the purpose of adjusting the polymerization rate, changing the microstructure of the polymerized conjugated diene moiety, and the like.
Examples of polar compounds include ethers such as tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, and 2,2-bis (2-oxolanyl) propane; Tertiary amine compounds such as methylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinuclidine; alkali metal alkoxide compounds such as potassium tert-amylate, potassium tert-butylate, sodium tert-butylate, sodium amylate A phosphine compound such as triphenylphosphine;
　ブロック共重合体の製造する際の重合温度は、－１０～１５０℃が好ましく、より好ましくは３０～１２０℃である。
　重合に要する時間は条件によって異なるが、４８時間以内が好ましく、より好ましくは０．５～１０時間である。
　また、重合系の雰囲気は、窒素ガス等の不活性ガス雰囲気にすることが好ましい。
　重合圧力は、上記重合温度範囲でモノマー及び溶媒を液相に維持するに充分な圧力の範囲で行えばよく、特に限定されるものでない。
　さらに、重合系内は触媒及びリビングポリマーを不活性化させるような不純物、例えば、水、酸素、炭酸ガス等が混入しないようにすることが好ましい。 The polymerization temperature for producing the block copolymer is preferably −10 to 150 ° C., more preferably 30 to 120 ° C.
The time required for the polymerization varies depending on the conditions, but is preferably within 48 hours, more preferably 0.5 to 10 hours.
The polymerization atmosphere is preferably an inert gas atmosphere such as nitrogen gas.
The polymerization pressure is not particularly limited as long as it is carried out within a range of pressure sufficient to maintain the monomer and solvent in a liquid phase within the above polymerization temperature range.
Furthermore, it is preferable that impurities that inactivate the catalyst and the living polymer, for example, water, oxygen, carbon dioxide gas, and the like are not mixed in the polymerization system.
＜水添反応＞
　上述した＜重合反応＞によりブロック共重合体を得た後、アルコール、水等のプロトン供与体を添加し、その後、後述する水添触媒を用いて水素添加反応を行うことにより、水添ブロック共重合体を得ることができる。 <Hydrogenation reaction>
After obtaining the block copolymer by the above <polymerization reaction>, a proton donor such as alcohol or water is added, and then a hydrogenation reaction is performed using a hydrogenation catalyst to be described later. A polymer can be obtained.
　水添触媒としては、特に制限されず、従来から公知である（１）Ｎｉ、Ｐｔ，Ｐｄ、Ｒｕ等の金属をカーボン、シリカ、アルミナ、ケイソウ土等に担持させた担持型不均一系水素触媒、（２）Ｎｉ、Ｃｏ，Ｆｅ、Ｃｒ等の有機酸塩又はアセチルアセトン塩等の遷移金属塩と有機アルミニウム等の還元剤とを用いる、いわゆるチ－グラ型水添触媒、（３）Ｔｉ、Ｒｕ、Ｒｈ、Ｚｒ等の有機金属化合物等のいわゆる有機金属錯体等の均一系水添触媒が用いられる。
　具体的な水添触媒としては、例えば、特公昭４２－８７０４号公報、特公昭４３－６６３６号公報、特公昭６３－４８４１号公報、特公平１－３７９７０号公報、特公平１－５３８５１号公報、特公平２－９０４１号公報に記載された水添触媒を使用することができる。好ましい水添触媒としてはチタノセン化合物及び／又は還元性有機金属化合物との混合物が挙げられる。
　前記チタノセン化合物としては、特開平８－１０９２１９号公報に記載された化合物が使用でき、例えば、ビスシクロペンタジエニルチタンジクロライド、モノペンタメチルシクロペンタジエニルチタントリクロライド等の（置換）シクロペンタジエニル骨格、インデニル骨格、あるいはフルオレニル骨格を有する配位子を少なくとも一つ以上もつ化合物が挙げられる。
　また、前記還元性有機金属化合物としては、例えば、有機リチウム等の有機アルカリ金属化合物、有機マグネシウム化合物、有機アルミニウム化合物、有機ホウ素化合物、あるいは有機亜鉛化合物等が挙げられる。 The hydrogenation catalyst is not particularly limited and is conventionally known (1) A supported heterogeneous hydrogen catalyst in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like. (2) a so-called Ziegler type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, Cr or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum, (3) Ti, Ru Homogeneous hydrogenation catalysts such as so-called organometallic complexes such as organometallic compounds such as Rh and Zr are used.
Specific examples of the hydrogenation catalyst include Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-337970, Japanese Patent Publication No. 1-53851. The hydrogenation catalyst described in JP-B-2-9041 can be used. Preferred hydrogenation catalysts include a mixture with a titanocene compound and / or a reducing organometallic compound.
As the titanocene compound, compounds described in JP-A-8-109219 can be used. For example, (substituted) cyclopentadidi such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. Examples thereof include compounds having at least one ligand having an enyl skeleton, an indenyl skeleton, or a fluorenyl skeleton.
Examples of the reducing organometallic compound include organic alkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.
　水添反応は、好ましくは０～２００℃、より好ましくは３０～１５０℃の温度範囲で実施する。
　水添反応に使用される水素の圧力は、好ましくは０．１～１５ＭＰａ、より好ましくは０．２～１０ＭＰａ、さらに好ましくは０．３～５ＭＰａとする。
　また、水添反応時間は、好ましくは３分～１０時間、より好ましくは１０分～５時間である。
　水添反応は、バッチプロセス、連続プロセス、あるいはそれらの組み合わせのいずれでも用いることができる。 The hydrogenation reaction is preferably carried out in the temperature range of 0 to 200 ° C, more preferably 30 to 150 ° C.
The hydrogen pressure used for the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, and still more preferably 0.3 to 5 MPa.
The hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours.
The hydrogenation reaction can be any of a batch process, a continuous process, or a combination thereof.
　水添前のブロック共重合体に組み込まれている共役ジエン化合物に基づく不飽和二重結合の、水添後におけるトータル水素添加率は、目的に合わせて任意に選択でき、特に限定されない。ブロック共重合体中の共役ジエン化合物に基づく不飽和二重結合の好ましくは７０％以上、より好ましくは８０％以上、さらに好ましくは９５％以上が水添されていてもよく、一部のみが水添されていてもよい。
　一部のみが水添されている場合には、水添率は１０％以上７０％未満であることが好ましく、より好ましくは１５％以上６５％未満、さらに好ましくは２０％以上６０％未満である。
　水添ブロック共重合体の水添率は核磁気共鳴装置（ＮＭＲ）により測定される。 The total hydrogenation rate after hydrogenation of the unsaturated double bond based on the conjugated diene compound incorporated in the block copolymer before hydrogenation can be arbitrarily selected according to the purpose and is not particularly limited. Preferably 70% or more, more preferably 80% or more, and still more preferably 95% or more of the unsaturated double bond based on the conjugated diene compound in the block copolymer may be hydrogenated, and only a part is water. It may be attached.
When only a part is hydrogenated, the hydrogenation rate is preferably 10% or more and less than 70%, more preferably 15% or more and less than 65%, and further preferably 20% or more and less than 60%. .
The hydrogenation rate of the hydrogenated block copolymer is measured by a nuclear magnetic resonance apparatus (NMR).
　上述したように、本実施形態の水添ブロック共重合体クラムを構成する水添ブロック共重合体は、メインピーク分子量が２０万～６０万である。
　メインピーク分子量は、重合開始剤量を調整することにより制御することができる。 As described above, the hydrogenated block copolymer constituting the hydrogenated block copolymer crumb of this embodiment has a main peak molecular weight of 200,000 to 600,000.
The main peak molecular weight can be controlled by adjusting the amount of the polymerization initiator.
（水添ブロック共重合体クラムを得る処理）
　＜水性スラリーを得る工程＞　
　上述のようにして水添ブロック共重合体の溶液を得た後、必要に応じて触媒残差を除去し、続いて水添ブロック共重合体の溶液を、撹拌下熱湯中に投入し、スチームストリッピングにより溶媒を除去することにより、水添ブロック共重合体クラムが水中に分散した水性スラリーを得る。
　スチームストリッピングにおける処理方法は、特に限定するものでなく従来知られている方法を採用できる。
　スチームストリッピングの際、クラム化剤を使用してもよく、クラム化剤としては、アニオン界面活性剤、カチオン界面活性剤、非イオン界面活性剤が一般的に使用される。
　前記クラム化剤としての界面活性剤は、ストリッピング帯の水に対して一般に０．１～３０００ｐｐｍ添加される。これらの界面活性剤に加えてＬｉ，Ｎａ，Ｋ、Ｍｇ、Ｃａ、Ａｌ、Ｚｎ等の金属の水溶性塩をクラムの分散助剤として用いることもできる。 (Process to obtain hydrogenated block copolymer crumb)
<Step of obtaining an aqueous slurry>
After obtaining the hydrogenated block copolymer solution as described above, the catalyst residue is removed as necessary. Subsequently, the hydrogenated block copolymer solution is poured into hot water with stirring, and steam is added. By removing the solvent by stripping, an aqueous slurry in which the hydrogenated block copolymer crumb is dispersed in water is obtained.
The processing method in the steam stripping is not particularly limited, and a conventionally known method can be adopted.
In the steam stripping, a crumbing agent may be used, and as the crumbing agent, an anionic surfactant, a cationic surfactant, or a nonionic surfactant is generally used.
The surfactant as the crumbing agent is generally added in an amount of 0.1 to 3000 ppm with respect to the water in the stripping zone. In addition to these surfactants, water-soluble salts of metals such as Li, Na, K, Mg, Ca, Al, and Zn can also be used as a crumb dispersion aid.
　＜水添ブロック共重合体クラムを回収する工程＞　
　上述したように、スチームストリッピング工程により得られる、水添ブロック共重合体クラムが水中に分散した水性スラリーは、以下の工程を経て脱水・乾燥処理を施すことにより、水添ブロック共重合体クラムを回収することができる。
　水添ブロック共重合体クラムの回収工程は、後述する＜工程１＞脱水処理、＜工程２＞脱水処理及び乾燥処理、＜工程３＞乾燥処理を行う。
　なお、＜工程２＞においては、脱水処理と乾燥処理とをそれぞれ独立した装置により行ってもよく、脱水処理手段と乾燥処理手段とを具備し、これらが連通している構造の、いわゆる一体型の押出式乾燥機を用いて行ってもよい。 <Step of recovering hydrogenated block copolymer crumb>
As described above, an aqueous slurry obtained by dispersing a hydrogenated block copolymer crumb in water obtained by a steam stripping step is subjected to dehydration and drying treatments through the following steps to obtain a hydrogenated block copolymer crumb. Can be recovered.
In the recovery step of the hydrogenated block copolymer crumb, <Step 1> dehydration treatment, <Step 2> dehydration treatment and drying treatment, and <Step 3> drying treatment described later are performed.
In <Step 2>, the dehydration process and the drying process may be performed by independent devices, each having a dehydration process unit and a drying process unit, and a so-called integrated type having a structure in which these units communicate with each other. You may perform using the following extrusion-type dryer.
　[工程１]
　水性スラリーを脱水処理し、含水率が６０質量％を超え８０質量％以下で、目開き３．３５ｍｍの篩いを通過しないクラム成分が全クラムの６０質量％以上であるクラムを得る。
　＜工程１＞を経た後のクラムの含水率は、６２質量％～８０質量％であることが好ましく、６５質量％～７５質量％であることがより好ましい。
　また、＜工程１＞を経た後、目開き３．３５ｍｍの篩いを通過しないクラム成分が全クラムの７０質量％以上であることが好ましく、８０質量％以上であることがより好ましい。
　かかる＜工程１＞における脱水処理は、例えば、回転式スクリーン、振動スクリーン、遠心脱水機等により行うことができる。
　得られるクラムの含水率が６０質量％を超えると、後述する＜工程２＞における押出機内でのポリマー流動性の低下を抑制でき、また含水率が８０質量％以下とすると、後述する工程２における押出機内での、重合体クラムに対する熱負荷を抑制できる。
　さらに、目開き３．３５ｍｍの篩いを通過しないクラム成分が全クラムの６０質量％以上とすることにより、後述する＜工程２＞における脱水及び乾燥処理を安定して行うことができ、所望のクラムの比表面積、粒子径分布が得られ、優れたコンパウンド加工性が達成できる。 [Process 1]
The aqueous slurry is dehydrated to obtain a crumb having a moisture content of more than 60% by mass and 80% by mass or less and a crumb component not passing through a sieve having an opening of 3.35 mm is 60% by mass or more of the total crumbs.
The water content of the crumb after <Step 1> is preferably 62% by mass to 80% by mass, and more preferably 65% by mass to 75% by mass.
Moreover, it is preferable that the crumb component which does not pass a sieve with a mesh opening of 3.35 mm after passing through <process 1> is 70 mass% or more of all crumbs, and it is more preferable that it is 80 mass% or more.
The dehydration treatment in <Step 1> can be performed by, for example, a rotary screen, a vibrating screen, a centrifugal dehydrator, or the like.
When the water content of the obtained crumb exceeds 60% by mass, a decrease in polymer fluidity in the extruder in <Step 2> to be described later can be suppressed, and when the water content is 80% by mass or less, in Step 2 to be described later The heat load on the polymer crumb in the extruder can be suppressed.
Furthermore, when the crumb component that does not pass through a sieve having a mesh opening of 3.35 mm is 60% by mass or more of the total crumb, the dehydration and drying treatment in <Step 2> described later can be performed stably, and the desired crumb Specific surface area and particle size distribution can be obtained, and excellent compound workability can be achieved.
　[工程２]
　上述したように、＜工程１＞により脱水処理され、所定の含水率となったクラムは、＜工程２＞において脱水処理及び乾燥処理を行うことにより含水率が３～３０質量％のクラムとし、後述する＜工程３＞に移送する。
　当該＜工程２＞を経た後のクラムの含水率は３～２５質量％であることが好ましく、３．２～２０質量％であることがより好ましい。
　前記脱水処理と乾燥処理は、それぞれ独立した装置により行ってもよいが、脱水処理手段と乾燥処理手段とを具備し、これらが連通している構造の、いわゆる一体型の押出式乾燥機を用いて行ってもよい。
　前記押出式乾燥機は、脱水処理及び乾燥処理を行う装置であり、脱水処理手段と乾燥処理手段とを具備し、脱水処理手段としては押出機（押出機型水搾り機）、乾燥処理手段としてはニーダー型乾燥機、スクリュー型エキスパンダー式乾燥機等が採用される。特に、脱水処理手段として一軸又は二軸等の多軸スクリュー型押出機を具備し、乾燥処理手段としてスクリュー型乾燥機を具備する構成のものが、脱水効率及び作業性の観点で好ましい。
　クラムの脱水を緩やかに制御するには、一軸のスクリュー型押出機、スクリュー型乾燥機の組み合わせが特に好ましい。 [Process 2]
As described above, the crumb that has been dehydrated in <Step 1> and has a predetermined moisture content is made into a crumb having a moisture content of 3 to 30% by mass by performing the dehydration treatment and the drying treatment in <Step 2> It transfers to <process 3> mentioned later.
The water content of the crumb after the <Step 2> is preferably 3 to 25% by mass, and more preferably 3.2 to 20% by mass.
The dehydration treatment and the drying treatment may be performed by independent devices, but a so-called integrated extrusion dryer having a structure in which the dehydration treatment means and the drying treatment means are communicated with each other is used. You may go.
The extrusion dryer is a device that performs a dehydration process and a drying process, and includes a dehydration process unit and a drying process unit. The dehydration process unit includes an extruder (an extruder-type water squeezer) and a drying process unit. A kneader type dryer, a screw type expander type dryer or the like is employed. In particular, it is preferable from the viewpoints of dewatering efficiency and workability that the dehydrating means includes a single screw or twin screw multi-screw extruder and the drying means includes a screw dryer.
In order to moderately control crumb dewatering, a combination of a single screw extruder and a screw dryer is particularly preferable.
　また、＜工程２＞を実施するための脱水装置、乾燥装置、さらには、脱水処理手段と乾燥処理手段とが一体型となっている押出式乾燥機、具体的には、スクリュー型押出機、スクリュー型乾燥機、一体型スクリュー押出機型乾燥機等は、それぞれ使用目的に応じてベント機構、脱水用スリットを取り付けたものであってもよい。 In addition, a dehydrating apparatus and a drying apparatus for performing <Step 2>, an extrusion dryer in which the dehydrating means and the drying means are integrated, specifically, a screw-type extruder, The screw-type dryer, the integrated screw extruder-type dryer, and the like may be provided with a vent mechanism and a dewatering slit according to the purpose of use.
　＜工程２＞によりクラムの含水率を３質量％以上とすることにより、押出機のせん断力によりクラムがゲル化及び／又は分解してしまうことを防止でき、含水率を３０質量％以下とすることにより、後述する＜工程３＞により得られるクラムの含水率を１質量％以下に制御することを容易にすることができる。 By setting the moisture content of the crumb to 3% by mass or more by <Step 2>, it is possible to prevent the crumb from gelling and / or decomposing by the shearing force of the extruder, and the moisture content is set to 30% by mass or less. Thus, it is possible to easily control the moisture content of the crumb obtained by <Step 3> described later to 1% by mass or less.
　＜工程２＞における乾燥処理を行う装置の出口温度、すなわち、脱水処理と乾燥処理とをそれぞれ別個の装置で行う場合には、脱水処理を行う装置の出口温度を１２０℃以下とし、かつ乾燥処理を行う装置の出口温度を１３５～１７５℃とすることが好ましい。
　より好ましくは脱水処理を行う装置の出口温度を１２０℃以下とし、かつ乾燥処理を行う装置の出口温度を１３８～１７２℃とし、さらに好ましくは脱水処理を行う装置の出口温度を１１８℃以下とし、かつ乾燥処理を行う装置の出口温度を１４０～１７２℃とする。
　脱水処理手段と乾燥処理手段とが一体型となっている、いわゆる２段階構成の押出式乾燥機で処理する場合には１段目出口の温度を１２０℃以下とし、かつ２段目出口の温度を１３５～１７５℃とすることが好ましい。
　より好ましくは１段目出口の温度を１２０℃以下とし、かつ２段目出口の温度を１３８～１７２℃とし、さらに好ましくは１段目出口の温度を１１８℃以下とし、かつ２段目出口の温度を１４０～１７２℃とする。
　上記温度範囲に設定することにより、脱水処理、乾燥処理を安定して行うことができ、所望のクラムの比表面積、粒子径分布が得られ、優れたコンパウンド加工性が達成できる。 In the case where the outlet temperature of the apparatus that performs the drying process in <Step 2>, that is, when the dehydration process and the drying process are performed separately, the outlet temperature of the apparatus that performs the dehydration process is set to 120 ° C. or less and the drying process is performed. It is preferable that the outlet temperature of the apparatus for performing the above is 135 to 175 ° C.
More preferably, the outlet temperature of the apparatus for performing the dehydration treatment is 120 ° C. or less, the outlet temperature of the apparatus for performing the drying treatment is 138 to 172 ° C., and more preferably, the outlet temperature of the apparatus for performing the dehydration treatment is 118 ° C. or less In addition, the outlet temperature of the drying apparatus is set to 140 to 172 ° C.
In the case of processing with a so-called two-stage extrusion dryer in which the dehydrating means and the drying means are integrated, the temperature at the first stage outlet is set to 120 ° C. or lower, and the temperature at the second stage outlet. Is preferably 135 to 175 ° C.
More preferably, the temperature at the first stage outlet is 120 ° C. or lower, the temperature at the second stage outlet is 138 to 172 ° C., more preferably the temperature at the first stage outlet is 118 ° C. or lower, and The temperature is 140-172 ° C.
By setting to the above temperature range, the dehydration treatment and the drying treatment can be performed stably, the desired specific surface area and particle size distribution of crumb can be obtained, and excellent compound workability can be achieved.
　[工程３]
　上述したように、＜工程２＞で得られたクラムを、熱風乾燥機で乾燥処理を行い、含水率１質量％以下のクラムとする。
　当該＜工程３＞を経た後のクラムの含水率は、１質量％以下とし、０．９５質量％以下であることが好ましく、０．９質量％以下であることがより好ましい。
　乾燥クラムの含水率を１質量％以下とすることにより、コンパウンド工程後に得られる熱可塑性樹脂組成物において、発泡やシルバー等の発生による外観不良を防止できる。 [Process 3]
As described above, the crumb obtained in <Step 2> is dried with a hot air dryer to obtain a crumb having a moisture content of 1% by mass or less.
The water content of the crumb after the <Step 3> is 1% by mass or less, preferably 0.95% by mass or less, and more preferably 0.9% by mass or less.
By setting the moisture content of the dried crumb to 1% by mass or less, in the thermoplastic resin composition obtained after the compounding process, it is possible to prevent poor appearance due to foaming, generation of silver or the like.
　上述したように、＜工程１＞により水性スラリーを脱水処理し、含水率が６０質量％を超え８０質量％以下で、目開き３．３５ｍｍの篩いを通過しないクラム成分が全クラムの６０質量％以上であるクラムを得、＜工程２＞により、脱水処理及び乾燥処理を行うことにより含水率が３～３０質量％のクラムとし、＜工程３＞により熱風乾燥機で乾燥処理を行うことにより、クラムの含水率を１質量％以下に調整できる。 As described above, the aqueous slurry is dehydrated by <Step 1>, and the crumb component that has a moisture content of more than 60% by mass and not more than 80% by mass and does not pass through a sieve having an opening of 3.35 mm is 60% by mass of the total crumbs. By obtaining the crumb as described above, by performing dehydration treatment and drying treatment in <Step 2> to obtain a crumb having a moisture content of 3 to 30% by mass, and by performing drying treatment in a hot air dryer in <Step 3> The water content of crumb can be adjusted to 1% by mass or less.
　なお、水添ブロック共重合体クラムの含水率、サイズについては、後述する実施例に記載の方法により求めることができる。
　前記＜工程１＞によりクラムのサイズ及び含水率を規定し、さらには、＜工程１＞～＜工程３＞を通して装置内の出口温度及び出口におけるクラムの含水率を規定することにより、クラムの流動性が高まり、適度に発泡した（比表面積の大きい）クラムを得ることができる。さらに、装置内での脈流も抑制され、微粉状クラム（目開き０．４２５ｍｍの篩を通過し、砂状の硬いクラム）や大粒径クラム（目開き３．３５ｍｍの篩を通過せず、発泡が不均一なクラム）の少ない、均一なクラムが得られる。
　本実施形態の水添ブロック共重合体クラムは、比表面積が０．３～１．０ｍ2／ｇである。また、目開き３．３５ｍｍの篩を通過し、かつ目開き０．４２５ｍｍの篩を通過しない成分が、全クラムの８０質量％以上である。
　このようなクラムを得るためには、特に、＜工程２＞に入る前段階のクラムのサイズと含水率を調整し、かつ＜工程２＞での脱水・乾燥条件を最適化することが有効である。
　詳細には、＜工程１＞を経た後のクラムの含水率が６０％以下と少な過ぎると、＜工程２＞で脱水されすぎて流動性が低下してしまう。一方、含水率が８０％超と多過ぎたり、クラムサイズが目開き３．３５ｍｍの篩を通過しないクラム成分が少な過ぎたりすると、＜工程２＞で安定的に脱水・乾燥処理を行うことができず、やはり良好な流動性が得られない。
　また、＜工程２＞において、クラムの含水率が高すぎると＜工程３＞での負荷が大きくなり、クラムの含水率が低すぎると、クラムの流動性が低下し、発泡が不均一となり、クラムサイズが不均一化する。さらに乾燥しすぎてクラムの流動性が低下、発泡が不均一となり、クラムサイズが不均一化することを防止するため、＜工程２＞において乾燥処理における装置の出口温度を１３５～１７５℃とすることが好ましい。
　よって、上述したように、＜工程１＞でクラムの含水率を、６０質量％を超え８０質量％以下に調整し、目開き３．３５ｍｍの篩を通過しないクラム成分が全クラムの６０質量％以上とし、＜工程２＞でクラムの含水率を３～３０質量％になるように制御することが有効である。 The water content and size of the hydrogenated block copolymer crumb can be determined by the method described in the examples described later.
By defining the crumb size and moisture content in the above <Step 1>, and further defining the outlet temperature in the apparatus and the moisture content of the crumb at the outlet through <Step 1> to <Step 3>, Thus, it is possible to obtain a crumb that is foamed moderately (having a large specific surface area). Furthermore, the pulsating flow in the device is also suppressed, and fine crumbs (passing through a sieve with an opening of 0.425 mm, sandy hard crumb) and large particle crumbs (passing through a sieve with an opening of 3.35 mm) Uniform crumbs with less foaming) are obtained.
The hydrogenated block copolymer crumb of this embodiment has a specific surface area of 0.3 to 1.0 m 2 / g. Moreover, the component which passes a sieve with an opening of 3.35 mm and does not pass a sieve with an opening of 0.425 mm is 80 mass% or more of the total crumbs.
In order to obtain such a crumb, it is particularly effective to adjust the size and moisture content of the crumb before entering <Process 2> and optimize the dehydration and drying conditions in <Process 2>. is there.
Specifically, if the water content of the crumb after passing through <Step 1> is too small as 60% or less, it will be dehydrated too much in <Step 2> and the fluidity will decrease. On the other hand, if the water content is too high (over 80%) or the crumb size is too small to pass through a sieve having an opening of 3.35 mm, the dehydration and drying process can be stably performed in <Step 2>. It is not possible to obtain good fluidity.
In <Step 2>, if the water content of crumb is too high, the load in <Step 3> increases, and if the water content of crumb is too low, the fluidity of the crumb is lowered and foaming becomes uneven. The crumb size is uneven. Furthermore, in order to prevent the crumb fluidity from being lowered too much, resulting in non-uniform foaming and non-uniform crumb size, the outlet temperature of the apparatus in the drying process is set to 135 to 175 ° C. in <Step 2>. It is preferable.
Therefore, as described above, in <Step 1>, the moisture content of the crumb is adjusted to be more than 60% by mass and 80% by mass or less, and the crumb component that does not pass through the sieve having a mesh size of 3.35 mm is 60% by mass of the total crumbs As described above, it is effective to control the water content of crumb to be 3 to 30% by mass in <Step 2>.
〔水添ブロック共重合体クラムを用いた重合体組成物〕
　本実施形態の水添ブロック共重合体クラムは、所定の熱可塑性樹脂や、プロセスオイル等の軟化剤を用いてコンパウンドすることにより、後述する各種用途に利用できる素材となる熱可塑性組成物が作製できる。
　なお、プロピレン等の熱可塑性樹脂やプロセスオイル等の軟化剤とのコンパウンドにおいては、目的に応じて種々の添加剤を配合することができる。添加剤の種類は、熱可塑性樹脂やゴム状重合体の配合に一般的に用いられるものであれば特に制限されるものではない。例えば、金属水酸化物、シリカ系無機充填剤、金属酸化物等の無機充填剤や、有機充填剤、酸化防止剤、紫外線吸収剤や光安定剤、ステアリン酸、ベヘニン酸、ステアリン酸亜鉛、ステアリン酸カルシウム、ステアリン酸マグネシウム、エチレンビスステアロアミド等の滑剤、離型剤、パラフィン、可塑剤、難燃剤、帯電防止剤、有機繊維、炭素繊維、金属ウィスカー等の補強材、顔料、着色剤等である。
　これらの添加剤は、水添ブロック共重合体クラムの溶液に添加してもよく、又は前記脱水工程及び／又は乾燥工程において添加してもよく、あるいは乾燥工程後に添加してもよい。 [Polymer composition using hydrogenated block copolymer crumb]
The hydrogenated block copolymer crumb of the present embodiment is prepared by using a predetermined thermoplastic resin or a softening agent such as process oil to produce a thermoplastic composition that can be used for various applications described later. it can.
In addition, in a compound with a thermoplastic resin such as propylene and a softening agent such as process oil, various additives can be blended depending on the purpose. The type of additive is not particularly limited as long as it is generally used for blending thermoplastic resins and rubber-like polymers. For example, inorganic fillers such as metal hydroxides, silica-based inorganic fillers, metal oxides, organic fillers, antioxidants, UV absorbers and light stabilizers, stearic acid, behenic acid, zinc stearate, stear With lubricants such as calcium phosphate, magnesium stearate, ethylene bisstearamide, mold release agent, paraffin, plasticizer, flame retardant, antistatic agent, organic fiber, carbon fiber, metal whisker and other reinforcing materials, pigments, colorants, etc. is there.
These additives may be added to the hydrogenated block copolymer crumb solution, or may be added in the dehydration step and / or the drying step, or may be added after the drying step.
〔水添ブロック共重合体クラムの用途〕
　本実施形態の水添ブロック共重合体クラムは、各種熱可塑性樹脂の改質剤、履物用素材、粘・接着材用素材、アスファルト改質剤、電線ケーブル等の工業部品、自動車部品、医療用器具材料、家電製品及びその部品、電子デバイス及びその部品、家庭用品、玩具等の素材として利用できる。 [Use of hydrogenated block copolymer crumb]
The hydrogenated block copolymer crumb of this embodiment includes various thermoplastic resin modifiers, footwear materials, adhesive / adhesive materials, asphalt modifiers, industrial parts such as electric cables, automobile parts, and medical use. It can be used as a material for appliance materials, home appliances and parts thereof, electronic devices and parts thereof, household goods, toys and the like.
　以下、本発明を実施例に基づいて説明する。なお、本発明は、以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described based on examples. The present invention is not limited to the following examples.
　実施例における試料の分析は以下に示す方法によって行った。
＜（１）結合スチレン量＞
　測定用試料（下記製造例１により作製するブロック共重合体）のクロロホルム溶液を調製し、分光光度計（ＪＡＳＣＯ製：Ｖ－５５０）を用いて、スチレンのフェニル基によるＵＶ２５４ｎｍの吸収を検出することにより、結合スチレン量（質量％）を測定した。 The analysis of the sample in an Example was performed by the method shown below.
<(1) Bonded styrene content>
Prepare a chloroform solution of a sample for measurement (block copolymer prepared according to Production Example 1 below), and detect UV 254 nm absorption by the phenyl group of styrene using a spectrophotometer (manufactured by JASCO: V-550). The amount of bound styrene (% by mass) was measured.
＜（２）メインピーク分子量＞
　水添ブロック共重合体のテトラヒドロフラン溶液を調製し、ポリスチレン系ゲル（昭和電工製：Ｓｈｏｄｅｘ）のＧＰＣ（東ソー製：ＨＬＣ－８３２０）を使用して、試料のクロマトグラムを測定した。
　メインピーク分子量は、市販の標準ポリスチレンのピーク分子量を使用して作成した検量線を用いて求めた。 <(2) Main peak molecular weight>
A tetrahydrofuran solution of the hydrogenated block copolymer was prepared, and the chromatogram of the sample was measured using GPC (manufactured by Tosoh: HLC-8320) of polystyrene gel (manufactured by Showa Denko: Shodex).
The main peak molecular weight was calculated | required using the analytical curve created using the peak molecular weight of a commercially available standard polystyrene.
＜ビニル結合含有量＞
　測定用試料（下記製造例１により作製するブロック共重合体）の二硫化炭素溶液を調製し、赤外分光光度計（パーキンエルマージャパン社製Ｓｐｅｃｔｒｕｍ１００）を用いて、赤外線スペクトルを６００～１０００ｃｍ－１の範囲で測定し、所定の波数における吸光度によりハンプトン（スチレン－ブタジエン共重合体）の方法の計算式に従い求めた。 <Vinyl bond content>
A carbon disulfide solution of a sample for measurement (a block copolymer produced according to Production Example 1 below) is prepared, and an infrared spectrum is 600 to 1000 cm −1 using an infrared spectrophotometer (Spectraum 100 manufactured by PerkinElmer Japan). And the absorbance at a predetermined wave number was determined according to the formula for the method of Hampton (styrene-butadiene copolymer).
＜（３）水添率＞
　水添ブロック共重合体の水添率を、核磁気共鳴装置（ＢＲＵＣＫＥＲ社製ＤＰＸ－４００）を用いて測定した。 <(3) Hydrogenation rate>
The hydrogenation rate of the hydrogenated block copolymer was measured using a nuclear magnetic resonance apparatus (DPX-400 manufactured by BRUCKER).
＜（４）クラム中の含水率＞
　水添ブロック共重合体クラムを、ハロゲン水分計にて１５０℃で８分間加熱し、その質量減少量を求め、下記式により算出した。
　含水率（質量％）＝前後における質量減少量（クラム中の含水量）／加熱前の水添ブロック共重合体クラムの質量×１００ <(4) Moisture content in crumb>
The hydrogenated block copolymer crumb was heated with a halogen moisture meter at 150 ° C. for 8 minutes to determine its mass loss, and calculated according to the following formula.
Moisture content (mass%) = mass decrease before and after (water content in crumb) / mass of hydrogenated block copolymer crumb before heating × 100
＜（５）クラムの比表面積＞
　水添ブロック共重合体の窒素による吸着等温線を測定し、ＢＥＴ多点法により比表面積を求めた。
　装置はＢＥＬＳＯＲＰ－ｍｉｎｉ（日本ＢＥＬ社製）を使用し、吸着温度７７Ｋで測定を行った。 <(5) Specific surface area of crumb>
The adsorption isotherm of the hydrogenated block copolymer by nitrogen was measured, and the specific surface area was determined by the BET multipoint method.
The apparatus used was BELSORP-mini (manufactured by BEL Japan) and the measurement was performed at an adsorption temperature of 77K.
＜（６）クラムサイズ＞
　ふるい振とう機（セイシン企業社製オクタゴンデジタル）を用い、目開き０．４２５ｍｍの篩の上に目開き３．３５ｍｍの篩を重ね、目開き３．３５ｍｍの篩の上からクラムを投入して１５分間振動させ、各篩上に残ったクラム量、及び通過したクラム量を測定し、目開き３．３５ｍｍの篩を通過しないクラムの割合（質量％）及びクラムサイズが０．４２５～３．３５ｍｍであるクラムの割合（質量％）を算出した。 <(6) Clam size>
Using a sieve shaker (Ocagon Digital, manufactured by Seishin Enterprise Co., Ltd.), a sieve with a mesh opening of 3.35 mm is stacked on a sieve with a mesh opening of 0.425 mm, and crumbs are put on the sieve with a mesh opening of 3.35 mm. Vibrate for 15 minutes, measure the amount of crumbs remaining on each sieve and the amount of crumbs that have passed through. The proportion (mass%) of crumbs that was 35 mm was calculated.
＜（７）オイル吸収均一性＞
　水添ブロック共重合体クラム１００ｇに、インクを滴下して着色したパラフィン系プロセスオイル（出光石油化学社製ダイアナプロセスオイルＰＷ９０）１００ｇを投入し、クラム全体にプロセスオイルが行きわたるように攪拌後、１０分間静置した。
　静置後のクラム全体の画像を２値化し、着色部分の面積比率（オイルを吸収したクラムの比率）を算出した。 <(7) Oil absorption uniformity>
100 g of hydrogenated block copolymer crumb was charged with 100 g of paraffinic process oil (Diana Process Oil PW90 manufactured by Idemitsu Petrochemical Co., Ltd.) colored by dropping ink, and stirred so that the process oil was distributed throughout the crumb. Allowed to stand for 10 minutes.
The image of the entire crumb after standing was binarized, and the area ratio of the colored portion (the ratio of the crumb that absorbed oil) was calculated.
＜（８）オイル保持力＞
　直径約３ｃｍの円筒形の容器に水添ブロック共重合体クラム１０ｇを入れ、この水添ブロック共重合体の上から、インクで着色したパラフィン系プロセスオイル（出光石油化学社製ダイアナプロセスオイルＰＷ９０）１０ｇを投入し、５分間静置し、インクにより着色されていないクラムの質量を測定した。
　前記インクで着色したパラフィン系プロセスオイルの質量（１０ｇ）と、インクにより着色されたクラムの質量の比を下記の式により算出し、オイル保持力とした。
　オイル保持力＝パラフィン系プロセスオイルの質量（１０ｇ）／〔クラム全質量（１０ｇ）－インクにより着色されていないクラムの質量（ｇ）〕
　この評価では、円筒形容器内に積層したクラムのうち、上の方だけがオイルの色に染まり、下の方はオイルの色に染まっていない状態となる。前記オイル保持力が高いと、オイルがクラムの上方に溜まっており、一定量のオイルを少ないクラムで保持できたことを意味する。 <(8) Oil holding power>
10 g of hydrogenated block copolymer crumb is placed in a cylindrical container having a diameter of about 3 cm, and paraffinic process oil colored with ink (Diana Process Oil PW90 manufactured by Idemitsu Petrochemical Co., Ltd.) is placed on the hydrogenated block copolymer. 10 g was added and allowed to stand for 5 minutes, and the mass of crumbs not colored with ink was measured.
The ratio of the mass (10 g) of the paraffinic process oil colored with the ink and the mass of the crumb colored with the ink was calculated according to the following formula to obtain the oil retention force.
Oil holding power = mass of paraffinic process oil (10 g) / [crumb total mass (10 g) −mass of crumb not colored with ink (g)]
In this evaluation, among the crumbs stacked in the cylindrical container, only the upper part is stained with the oil color, and the lower part is not stained with the oil color. When the oil retention force is high, it means that the oil has accumulated above the crumb, and a certain amount of oil could be held with a small amount of crumb.
＜（９）コンパウンド中未溶融ポリマー数＞
　未溶融ポリマーとは、コンパウンドにおいてクラムが完全に溶融しきらず、残留した状態となっているものを言う。
　水添ブロック共重合体クラム１６．３８ｇに、パラフィン系プロセスオイル（出光石油化学社製ダイアナプロセスオイルＰＷ９０）２４．５７ｇを添加して、プロセスオイルが均一に展着するように攪拌した。
　次に、室温で２０分間静置して吸油させた。
　その後、ポリプロピレン（サンアロマー社製ＰＬ５００Ａ）９．０１ｇ、ｎ－オクタデシル－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）－プロピオネート（製品名イルガノックス１０７６）０．０４ｇを添加し、ラボプラストミル（東洋精機社製４Ｍ１５０）を用いて１６０℃、７０ｒｐｍで２０分間混練した。
　前記混練開始３分後と２０分後に、それぞれコンパウンドサンプル２ｇを採取し、圧縮成形によって直径約１５ｃｍ、厚さ約６０μｍのシートを作製し、拡大鏡（アズワン株式会社製「マイスタールーペＬＢ」の倍率３．５倍）を用いて、前記シート中の径が約１００μｍ以上のフィッシュアイ（未溶融ポリマー）の数をカウントした。
　図１に、前記フィッシュアイ（未溶融ポリマー、径Ａ）を有するシートの断面写真を示す。実際には、当該フィッシュアイが表面に点状となって観察された。
　３分後（コンパウンドは均一に状態になるが、未溶融ポリマーが残留）と２０分後（未溶融ポリマーが全て溶融）の、それぞれにおけるフィッシュアイ（未溶融ポリマー）数の差をコンパウンド中未溶融ポリマー数とした。 <(9) Number of unmelted polymers in compound>
An unmelted polymer refers to a polymer in which crumbs are not completely melted and remain in the compound.
24.57 g of paraffinic process oil (Diana Process Oil PW90 manufactured by Idemitsu Petrochemical Co., Ltd.) was added to 16.38 g of the hydrogenated block copolymer crumb and stirred so that the process oil spread evenly.
Next, it was allowed to stand for 20 minutes at room temperature to absorb oil.
Thereafter, 9.01 g of polypropylene (PL500A manufactured by Sun Allomer Co.) and 0.04 g of n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate (product name Irganox 1076) were added. The mixture was kneaded at 160 ° C. and 70 rpm for 20 minutes using a Laboplast mill (4M150, manufactured by Toyo Seiki Co., Ltd.).
After 3 minutes and 20 minutes from the start of the kneading, 2 g of the compound sample was collected, and a sheet having a diameter of about 15 cm and a thickness of about 60 μm was prepared by compression molding. A magnifier (“Meister Loupe LB” manufactured by ASONE CORPORATION) The number of fish eyes (unmelted polymer) having a diameter of about 100 μm or more in the sheet was counted.
FIG. 1 shows a cross-sectional photograph of a sheet having the fish eye (unmelted polymer, diameter A). Actually, the fish eyes were observed as dots on the surface.
The difference in the number of fish eyes (unmelted polymer) after 3 minutes (compound becomes uniform but unmelted polymer remains) and after 20 minutes (all unmelted polymer melts) is unmelted in the compound. The number of polymers.
（製造例１：ブロック共重合体の製造方法）
　撹拌機及びジャケットを付けた温度制御が可能なオートクレーブを反応器として使用し、窒素ガス雰囲気下において、不純物を除去したスチレン１６質量部、テトラヒドロフラン０．１４質量部、テトラメチルエチレンジアミン０．０３質量部のシクロヘキサン溶液を調製し、反応器内温を５０℃に保持した後、重合開始剤としてｎ－ブチルリチウム０．０６質量部を反応器に供給して重合した。
　次に、ブタジエン６８質量部を供給して重合し、最後にスチレン１６質量部を供給して重合することにより、Ｓ－Ｂ－Ｓ構造（Ｓはポリスチレンブロック、Ｂはポリブタジエンブロック）のブロック共重合体を得た。
　得られたブロック共重合体のスチレン含有量は３２質量％、メインピーク分子量は２８万、ブタジエン部分のビニル結合含有量は３６％であった。 (Production Example 1: Production method of block copolymer)
Using a temperature-controllable autoclave with a stirrer and a jacket as a reactor, in a nitrogen gas atmosphere, 16 parts by mass of styrene from which impurities have been removed, 0.14 parts by mass of tetrahydrofuran, 0.03 parts by mass of tetramethylethylenediamine A cyclohexane solution was prepared, and the reactor internal temperature was maintained at 50 ° C., and then 0.06 parts by mass of n-butyllithium as a polymerization initiator was supplied to the reactor for polymerization.
Next, 68 parts by mass of butadiene is supplied for polymerization, and finally, 16 parts by mass of styrene is supplied for polymerization to block the block copolymer of the SBS structure (S is a polystyrene block and B is a polybutadiene block). Coalescence was obtained.
The resulting block copolymer had a styrene content of 32% by mass, a main peak molecular weight of 280,000, and a vinyl bond content of the butadiene portion of 36%.
（製造例２：水添ブロック共重合体の製法）
　上記の製造例１により得られたブロック共重合体の溶液に、シクロヘキサンに、ビス（シクロペンタジエニル）チタンジクロライドと、トリメチルアルミニウムを含むｎ－ヘキサン溶液とを混合し、室温にて３日間反応させて得た水添触媒（ビス（η５－シクロペンタジエニル）チタニウムジクロリド／トリメチルアルミニウムのモル比＝１／２）を、Ｔｉとして１００ｐｐｍ添加し、水素圧０．７ＭＰａ、温度９５℃で１時間水添反応を行った。得られた水添ブロック共重合体のブタジエン部分の水添率は９８％であった。 (Production Example 2: Method for producing hydrogenated block copolymer)
To a solution of the resultant block copolymer by the above Production Example 1, in cyclohexane, bis mixed with (cyclopentadienyl) titanium dichloride, and n- hexane solution containing trimethylaluminum, 3 days at room temperature the reaction A hydrogenation catalyst (bis (η5-cyclopentadienyl) titanium dichloride / trimethylaluminum molar ratio = 1/2) obtained by adding 100 ppm as Ti, hydrogen pressure 0.7 MPa, temperature 95 ° C. for 1 hour Hydrogenation reaction was performed. The hydrogenation rate of the butadiene portion of the obtained hydrogenated block copolymer was 98%.
〔実施例１～４〕、〔比較例１～４〕
　前記製造例１、２により得られた水添ブロック共重合体の溶液に、反応停止剤として、水を、重合に使用したｎ－ブチルリチウム量に対し５倍モル添加した後、安定剤としてｎ－オクタデシル－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）－プロピオネート（製品名イルガノックス１０７６）を水添ブロック共重合体１００質量部に対して０．２５質量部添加した。
　この水添ブロック共重合体溶液を９５℃で１時間スチームストリッピングした。スチームストリッピングは、クラム化剤として、表１に示す量のスチレン－無水マレイン酸共重合体Ｎａ塩（以下、クラム化剤Ａ）を添加して実施した。
　得られた水性スラリー中の、水添ブロック共重合体クラムの濃度は５質量％であった。
　次に、上記で得られた水添ブロック共重合体クラムを含有する水性スラリーを目開き１ｍｍの振動型スクリーンに送り、脱水処理（＜工程１＞）を行い、その後、上記（４）の方法により＜工程１＞を経た水添ブロック共重合体クラムの含水率を測定し、上記（６）の方法によりクラムサイズを測定した。
　＜工程１＞により得られた水添ブロック共重合体クラムの含水率（質量％）及びクラムサイズ（目開き３．３５ｍｍの篩を通過しない成分の割合）（質量％）を下記表１に示す。 [Examples 1 to 4], [Comparative Examples 1 to 4]
Water was added as a reaction terminator to the hydrogenated block copolymer solution obtained in the above Production Examples 1 and 2 at a 5-fold mole to the amount of n-butyllithium used for polymerization, and then n as a stabilizer. -Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate (product name Irganox 1076) was added in an amount of 0.25 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer. .
The hydrogenated block copolymer solution was steam stripped at 95 ° C. for 1 hour. The steam stripping was carried out by adding the amount of styrene-maleic anhydride copolymer Na salt (hereinafter referred to as “crumbing agent A”) shown in Table 1 as a crumbing agent.
The concentration of the hydrogenated block copolymer crumb in the obtained aqueous slurry was 5% by mass.
Next, the aqueous slurry containing the hydrogenated block copolymer crumb obtained above is sent to a vibrating screen having a mesh opening of 1 mm and subjected to dehydration treatment (<Step 1>), and then the method of (4) above The water content of the hydrogenated block copolymer crumb that had undergone <Step 1> was measured, and the crumb size was measured by the method of (6) above.
Table 1 below shows the water content (% by mass) and the crumb size (ratio of components that do not pass through a sieve having an opening of 3.35 mm) (% by mass) of the hydrogenated block copolymer crumb obtained by <Step 1>. .
　この水添ブロック共重合体クラムに対して、実施例１～４、比較例１～４においては、脱水処理と乾燥処理とを、それぞれ別個の装置を用いて行った。
　先ず、１軸スクリュー押出機型水絞り機に供給し、スクリュー回転数約８０ｒｐｍで押し出して脱水処理を行った（＜工程２＞の１段目）。
　当該１軸スクリュー押出機型水絞り機の出口温度を下記表１に示した。
　次に、前記で得られた水添ブロック共重合体クラムを、１軸スクリュー型エキスパンダー乾燥機に供給し、スクリュー回転数約８０ｒｐｍで押し出して乾燥処理をした（＜工程２＞の２段目）。
　当該１軸スクリュー型エキスパンダー乾燥機の出口の温度及び得られたクラムの含水率を下記表１に示した。 With respect to this hydrogenated block copolymer crumb, in Examples 1 to 4 and Comparative Examples 1 to 4, dehydration treatment and drying treatment were performed using separate apparatuses.
First, it was supplied to a single screw extruder type water squeezer and extruded at a screw rotation speed of about 80 rpm for dehydration treatment (first stage of <Step 2>).
The outlet temperature of the single screw extruder type water squeezer is shown in Table 1 below.
Next, the hydrogenated block copolymer crumb obtained above was supplied to a single screw type expander dryer and extruded at a screw rotation speed of about 80 rpm for drying treatment (second stage of <Step 2>). .
The temperature at the outlet of the single screw type expander dryer and the moisture content of the obtained crumb are shown in Table 1 below.
　その後、前記で得られた水添ブロック共重合体クラムに対し、振動輸送乾燥機を用いて約９０℃の熱風で乾燥処理を行った。（＜工程３＞）。
　最終的に得られた乾燥クラムの含水率、比表面積、クラムサイズ、オイル吸収均一性、オイル保持力、及びコンパウンド中の未溶融ポリマー数を下記表１に示した。 Thereafter, the hydrogenated block copolymer crumb obtained above was dried with hot air of about 90 ° C. using a vibration transport dryer. (<Step 3>).
The moisture content, specific surface area, crumb size, oil absorption uniformity, oil retention, and number of unmelted polymers in the compound of the finally obtained dried crumb are shown in Table 1 below.
　実施例１～４のクラムはオイル吸収均一性が良好であり、オイル保持力が高く、コンパウンド中の未溶融ポリマー数が１０個以下であるのに対し、比較例１～４のクラムは実用上良好なオイル吸収均一性が得られず、オイル保持力が低く、コンパウンド中の未溶融ポリマー数が１５個以上であった。 The crumbs of Examples 1 to 4 have good oil absorption uniformity, high oil retention, and the number of unmelted polymers in the compound is 10 or less, while the crumbs of Comparative Examples 1 to 4 are practical. Good oil absorption uniformity was not obtained, the oil retention was low, and the number of unmelted polymers in the compound was 15 or more.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
〔実施例５～８〕、〔比較例５～９〕
　前記製造例１、２により得られた水添ブロック共重合体の溶液に、反応停止剤として、水を、重合に使用したｎ－ブチルリチウム量に対し５倍モル添加した後、安定剤としてｎ－オクタデシル－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）－プロピオネート（製品名イルガノックス１０７６）を水添ブロック共重合体１００質量部に対して０．２５質量部添加した。
　この水添ブロック共重合体溶液を９５℃で１時間スチームストリッピングした。スチームストリッピングは、クラム化剤として、表２に示す量のクラム化剤Ａを添加して実施した。
　得られた水性スラリー中の、水添ブロック共重合体クラムの濃度は５質量％であった。
　次に、上記で得られた水添ブロック共重合体クラムを含有する水性スラリーを目開き１ｍｍの振動型スクリーンに送り、脱水処理（＜工程１＞）を行い、その後、上記（４）の方法により含水率を測定し、上記（６）の方法によりクラムサイズを測定した。＜工程１＞により得られた水添ブロック共重合体クラムの含水率（質量％）及びクラムサイズ（目開き３．３５ｍｍの篩を通過しない成分の割合）（質量％）を下記表２に示す。
　この水添ブロック共重合体クラムに対し、脱水処理手段（１段目）と乾燥処理手段（２段目）とが一体化された２段１軸スクリュー押出機に供給し、スクリュー回転数約８０ｒｐｍで押し出して脱水処理及び乾燥処理を行った（＜工程２＞の１段目、２段目）。
　使用した２段１軸スクリュー押出機は、１段目脱水処理手段にスリットを有しているが、クラム中の水分を２段目の乾燥処理手段まで保持させるために、スリットを全閉にして運転した。
　脱水処理手段及び乾燥処理手段のそれぞれの出口温度（１段目出口温度、２段目出口温度）、及び乾燥処理手段の出口から得られたクラムの含水率を下記表２に示した。 [Examples 5 to 8], [Comparative Examples 5 to 9]
Water was added as a reaction terminator to the hydrogenated block copolymer solution obtained in the above Production Examples 1 and 2 at a 5-fold mole to the amount of n-butyllithium used for polymerization, and then n as a stabilizer. -Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate (product name Irganox 1076) was added in an amount of 0.25 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer. .
The hydrogenated block copolymer solution was steam stripped at 95 ° C. for 1 hour. Steam stripping was performed by adding the amount of crumbing agent A shown in Table 2 as the crumbing agent.
The concentration of the hydrogenated block copolymer crumb in the obtained aqueous slurry was 5% by mass.
Next, the aqueous slurry containing the hydrogenated block copolymer crumb obtained above is sent to a vibrating screen having a mesh opening of 1 mm and subjected to dehydration treatment (<Step 1>), and then the method of (4) above Then, the water content was measured, and the crumb size was measured by the method (6) above. Table 2 below shows the water content (% by mass) and the crumb size (ratio of components that do not pass through a sieve having an opening of 3.35 mm) (% by mass) of the hydrogenated block copolymer crumb obtained by <Step 1>. .
The hydrogenated block copolymer crumb is supplied to a two-stage single-screw extruder in which a dehydrating means (first stage) and a drying means (second stage) are integrated, and the screw speed is about 80 rpm. Then, dehydration treatment and drying treatment were performed (first step and second step of <Step 2>).
The used two-stage single-screw extruder has a slit in the first-stage dewatering treatment means, but in order to keep the water in the crumb up to the second-stage drying treatment means, the slit is fully closed. Drove.
Table 2 below shows the respective outlet temperatures (first-stage outlet temperature, second-stage outlet temperature) of the dehydration treatment means and the drying treatment means, and the moisture content of the crumb obtained from the outlet of the drying treatment means.
　その後、前記で得られた水添ブロック共重合体クラムを、振動輸送乾燥機を用いて約９０℃の熱風で乾燥処理を行い、乾燥クラムを得た（＜工程３＞）。
　最終的に得られた水添ブロック共重合体クラムの含水率、比表面積、クラムサイズ、オイル吸収均一性、オイル保持力、及びコンパウンド中の未溶融ポリマー数を下記表２に示した。 Thereafter, the hydrogenated block copolymer crumb obtained above was dried with hot air of about 90 ° C. using a vibration transport dryer to obtain a dried crumb (<Step 3>).
The water content, specific surface area, crumb size, oil absorption uniformity, oil retention, and number of unmelted polymers in the compound of the finally obtained hydrogenated block copolymer crumb are shown in Table 2 below.
　実施例５～８のクラムはオイル吸収均一性が良好であり、オイル保持力が高く、コンパウンド中の未溶融ポリマー数が１０個以下であるのに対し、比較例５～８のクラムは実用上良好なオイル吸収均一性が得られず、オイル保持力も低く、コンパウンド中の未溶融ポリマー数が１５個以上であった。
　また、比較例９は、クラムの水分量が多すぎ、乾燥機に投入できず、脱水処理及び乾燥処理を行うことが不可能であった。 The crumbs of Examples 5 to 8 have good oil absorption uniformity, high oil retention, and the number of unmelted polymers in the compound is 10 or less, while the crumbs of Comparative Examples 5 to 8 are practical. Good oil absorption uniformity was not obtained, oil retention was low, and the number of unmelted polymers in the compound was 15 or more.
Moreover, the comparative example 9 had too much water content of the crumb, and could not be put into a dryer, and it was impossible to perform a dehydration process and a drying process.
〔比較例１０〕
　比較例８と同じ条件で＜工程１＞及び＜工程２＞を行った後、＜工程３＞を行わず、水添ブロック共重合体クラムを得た。
　得られたクラムの含水率、比表面積、クラムサイズ、オイル吸収均一性、オイル保持力、及びコンパウンド中の未溶融ポリマー数を下記表２に示した。
　比較例１０は、実用上良好なオイル吸収均一性が得られず、オイル保持力も低く、コンパウンド中の未溶融ポリマー数が１５個以上であった。 [Comparative Example 10]
After performing <Step 1> and <Step 2> under the same conditions as in Comparative Example 8, <Step 3> was not performed, and a hydrogenated block copolymer crumb was obtained.
The water content, specific surface area, crumb size, oil absorption uniformity, oil retention, and number of unmelted polymers in the compound of the obtained crumb are shown in Table 2 below.
In Comparative Example 10, practically good oil absorption uniformity was not obtained, the oil retention was low, and the number of unmelted polymers in the compound was 15 or more.
〔比較例１１〕
　前記製造例１、２により得られた水添ブロック共重合体の溶液に、反応停止剤として、水を、重合に使用したｎ－ブチルリチウム量に対し５倍モル添加した後、安定剤としてｎ－オクタデシル－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）－プロピオネート（製品名イルガノックス１０７６）を水添ブロック共重合体１００質量部に対して０．２５質量部添加した。
　この水添ブロック重合体溶液を９５℃で１時間スチームストリッピングした。スチームストリッピングは、クラム化剤として、ポリオキシエチレンアルキルエーテルリン酸（以下、クラム化剤Ｂ）を水添ブロック共重合体に対して８００ｐｐｍ添加して実施した。
　得られた水性スラリー中の水添ブロック共重合体クラムの濃度は５質量％であった。
　次に、上記で得られた水添ブロック共重合体クラムを含有する水性スラリーを目開き１ｍｍの振動型スクリーンに送り、脱水処理（＜工程１＞）を行い、その後、上記（４）の方法により含水率を測定し、上記（６）の方法によりクラムサイズを測定した。＜工程１＞により得られたクラムの含水率（質量％）及びクラムサイズ（目開き３．３５ｍｍの篩を通過しない成分の割合）（質量％）を下記表２に示した。
　このクラムに対し、上述した＜工程２＞を行わず、振動輸送乾燥機を用いて約９０℃の熱風で乾燥処理を行い、乾燥クラムを得た（＜工程３＞）。
　最終的に得られた水添ブロック共重合体クラムの含水率、比表面積、クラムサイズ、オイル吸収均一性、オイル保持力、及びコンパウンド中の未溶融ポリマー数を下記表２に示した。 [Comparative Example 11]
Water was added as a reaction terminator to the hydrogenated block copolymer solution obtained in the above Production Examples 1 and 2 at a 5-fold mole to the amount of n-butyllithium used for polymerization, and then n as a stabilizer. -Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate (product name Irganox 1076) was added in an amount of 0.25 parts by mass with respect to 100 parts by mass of the hydrogenated block copolymer. .
This hydrogenated block polymer solution was steam stripped at 95 ° C. for 1 hour. Steam stripping was carried out by adding 800 ppm of polyoxyethylene alkyl ether phosphoric acid (hereinafter referred to as crumbing agent B) as a crumbing agent to the hydrogenated block copolymer.
The concentration of the hydrogenated block copolymer crumb in the obtained aqueous slurry was 5% by mass.
Next, the aqueous slurry containing the hydrogenated block copolymer crumb obtained above is sent to a vibrating screen having a mesh opening of 1 mm and subjected to dehydration treatment (<Step 1>), and then the method of (4) above Then, the water content was measured, and the crumb size was measured by the method (6) above. Table 2 below shows the moisture content (% by mass) and the crumb size (ratio of components that do not pass through a sieve having an opening of 3.35 mm) (% by mass) of the crumb obtained in <Step 1>.
This crumb was subjected to a drying treatment with hot air of about 90 ° C. using a vibration transport dryer without performing the above-described <Step 2> to obtain a dried crumb (<Step 3>).
The water content, specific surface area, crumb size, oil absorption uniformity, oil retention, and number of unmelted polymers in the compound of the finally obtained hydrogenated block copolymer crumb are shown in Table 2 below.
　比較例１１のクラムは実用上良好なオイル吸収均一性が得られず、オイル保持力も低く、コンパウンド中の未溶融ポリマー数が１５個以上であった。 The crumb of Comparative Example 11 did not have a practically good oil absorption uniformity, had a low oil retention, and had 15 or more unmelted polymers in the compound.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２中、比較例１０は、比較例８と同条件で＜工程１＞及び＜工程２＞を経た後、＜工程３＞を行わなかった例であり、＜工程２＞を経た後のクラムの特性を示した。
　また、表２中、比較例１１は、＜工程１＞を経た後、＜工程２＞を行わず、＜工程３＞を行った後のクラムの特性を示した。 In Table 2, Comparative Example 10 is an example in which <Step 3> was not performed after <Step 1> and <Step 2> under the same conditions as Comparative Example 8, and the crumb after <Step 2> was performed. The characteristics were shown.
Moreover, in Table 2, Comparative Example 11 showed the characteristics of crumbs after performing <Step 3> without performing <Step 2> after performing <Step 1>.
　本出願は、２０１０年１０月２８日に日本国特許庁へ出願された、日本特許出願（特願２０１０－２４２３１３）に基づくものであり、その内容はここに参照として取り込まれる。 This application is based on a Japanese patent application (Japanese Patent Application No. 2010-242313) filed with the Japan Patent Office on October 28, 2010, the contents of which are incorporated herein by reference.
　本発明の水添ブロック共重合体クラムは、医療用器具材料、家電製品及びその部品、電子デバイス及びその部品、電線ケーブル等の各種工業部品、自動車部品、玩具等の材料として、産業上の利用可能性がある。 The hydrogenated block copolymer crumb of the present invention is used industrially as a material for medical instrument materials, home appliances and parts thereof, electronic devices and parts thereof, various industrial parts such as electric cables, automobile parts, toys and the like. there is a possibility.

Claims (5)

  1. 　ビニル芳香族炭化水素と共役ジエンとのブロック共重合体の水添物からなる水添ブロック共重合体クラムであって、下記（１）～（４）を満たす水添ブロック共重合体クラム。
    （１）メインピーク分子量が２０万～６０万
    （２）含水率が１質量％以下
    （３）比表面積が０．３～１．０ｍ2／ｇ
    （４）目開き３．３５ｍｍの篩を通過し、かつ目開き０．４２５ｍｍの篩を通過しない成分が、全クラムの８０質量％以上     A hydrogenated block copolymer crumb comprising a hydrogenated product of a block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene and satisfying the following (1) to (4):
    (1) Main peak molecular weight is 200,000 to 600,000 (2) Water content is 1% by mass or less (3) Specific surface area is 0.3 to 1.0 m 2 / g
    (4) A component that passes through a sieve having an opening of 3.35 mm and does not pass through a sieve having an opening of 0.425 mm is 80% by mass or more of the total crumb.
  2. 　請求項１に記載の水添ブロック共重合体クラムの製造方法であって、下記＜工程１＞～＜工程３＞を含む、水添ブロック共重合体クラムの製造方法。
    ＜工程１＞：水添ブロック共重合体クラムを含有する水性スラリーを脱水処理し、含水率が６０質量％を超え８０質量％以下で、目開き３．３５ｍｍの篩を通過しないクラム成分が全クラムの６０質量％以上であるクラムを得る工程。
    ＜工程２＞：前記＜工程１＞で得られたクラムを、脱水処理及び乾燥処理し、含水率３～３０質量％のクラムを得る工程。
    ＜工程３＞：前記＜工程２＞で得られたクラムを乾燥処理し、含水率１質量％以下のクラムを得る工程。     The method for producing a hydrogenated block copolymer crumb according to claim 1, comprising the following <Step 1> to <Step 3>.
    <Step 1>: An aqueous slurry containing a hydrogenated block copolymer crumb is dehydrated, and all crumb components that have a moisture content of more than 60% by mass and not more than 80% by mass and do not pass through a sieve having an opening of 3.35 mm are included. Obtaining a crumb that is 60% by weight or more of the crumb.
    <Step 2>: A step of dehydrating and drying the crumb obtained in <Step 1> to obtain a crumb having a water content of 3 to 30% by mass.
    <Step 3>: A step of drying the crumb obtained in <Step 2> to obtain a crumb having a moisture content of 1% by mass or less.
  3. 　前記＜工程２＞において、前記乾燥処理における装置出口温度を１３５～１７５℃以下とする請求項２に記載の水添ブロック共重合体クラムの製造方法。 The method for producing a hydrogenated block copolymer crumb according to claim 2, wherein, in the <Step 2>, an apparatus outlet temperature in the drying treatment is set to 135 to 175 ° C or lower.
  4. 　前記＜工程２＞において、脱水処理手段と乾燥処理手段とを具備し当該脱水処理手段と乾燥処理手段とが連通している押出式乾燥機を用い、前記脱水処理手段で前記脱水処理を行い、前記乾燥処理手段で前記乾燥処理を行う、請求項２又は３に記載の水添ブロック共重合体クラムの製造方法。 In the <Step 2>, using an extrusion drier having a dehydrating means and a drying means, and the dehydrating means and the drying means communicating with each other, the dehydrating means performs the dehydrating process, The method for producing a hydrogenated block copolymer crumb according to claim 2 or 3, wherein the drying treatment is performed by the drying treatment means.
  5. 　前記脱水処理手段の出口温度が１２０℃以下であり、前記乾燥処理手段の出口温度が１３５～１７５℃である、請求項４に記載の水添ブロック共重合体クラムの製造方法。 The method for producing a hydrogenated block copolymer crumb according to claim 4, wherein the outlet temperature of the dehydrating means is 120 ° C or lower and the outlet temperature of the drying means is 135 to 175 ° C.
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