JP6123415B2 - Method for recovering hydrogenated block copolymer and resin composition - Google Patents

Description

The present invention provides a hydrogenated block copolymer having excellent balance in transparency, optical properties, flexibility, mechanical properties, moldability, heat resistance, gas barrier properties, low hygroscopicity, and chemical non-adsorption properties, from a solution. The present invention relates to a recovery method and a resin composition containing the copolymer.

A hydrogenated block copolymer obtained by hydrogenating a block copolymer of a vinyl aromatic compound and isobutylene has excellent transparency and is a material suitable for optical materials and packaging materials. Such a hydrogenated block copolymer can be produced by a hydrogenation reaction using a hydrogenation catalyst in an organic solvent. However, in order to use it as a molding material, a volatile solvent such as an organic solvent is used from the solution after the reaction. After removing the components, it is necessary to form a molded body by heat-melt molding or the like.
In the synthetic polymer production process, the polymer can be recovered by removing volatile components such as solvent from the solution after the reaction, such as reprecipitation in a poor solvent (reprecipitation method) or direct heating. A method of removing only the solvent (direct solvent removal method) is known.
In the reprecipitation method, if the solution concentration is too high, the polymer deposited becomes highly viscous and the solvent is difficult to remove. If the solution concentration is too low, a large amount of poor solvent is required. Moreover, since the recovered solvent must be divided into a good solvent and a poor solvent, there is a problem that a multistage distillation apparatus is required in a subsequent process, and the process becomes complicated.
In the direct solvent removal method, heating for a long time is necessary to completely remove the solvent, and the molded product may be colored or the strength of the molded product may be reduced due to a decrease in molecular weight. is there.
On the other hand, in the field of synthetic rubber, as a method for separating the polymer and the solvent from the polymer reaction solution, the polymer solution is poured into hot water, the solvent is distilled with water vapor, and the polymer is precipitated in the form of crumbs. A steam stripping method is known (Patent Documents 1-3).

Japanese Patent Publication No.44-21346 Japanese Patent Publication No.57-47684 Japanese Patent Publication No.57-53363 Japanese Patent Laid-Open No. 11-100420

However, since the steam stripping method is performed in the presence of a surfactant, the surfactant remaining in the copolymer may adversely affect the transparency of the copolymer.
The present invention relates to a hydrogenated block copolymer having a good balance in transparency, optical properties, flexibility, mechanical properties, moldability, heat resistance, gas barrier properties, low hygroscopicity, and chemical non-adsorption properties. The object is to recover the crumb from the solution without damaging it.

The inventors of the present invention have intensively studied to solve the above-mentioned problems, and by performing steam stripping in the presence of a specific surfactant from a solution of a hydrogenated block copolymer, a crumb-like shape is obtained without impairing transparency. The present inventors have found that the copolymer can be recovered to solve the above problems, and the present invention has been completed.
That is, the gist of the present invention is the following [1] to [ 9 ].
[1] A hydrogenated block copolymer is recovered from a solution containing a hydrogenated block copolymer having a hydrogenated vinyl aromatic polymer block A and a block B of a polymer mainly composed of isobutylene and a solvent. A method for recovering a hydrogenated block copolymer, characterized by performing steam stripping in the presence of a polyoxyalkylene alkyl ether having an HLB value of 11 or more and 18 or less as a surfactant.
[ 2 ] The method for recovering a hydrogenated block copolymer according to [1] above, wherein the polyoxyalkylene alkyl ether has a cloud point not lower than the boiling point of the solvent or the azeotropic point of the solvent and water. .
[ 3 ] The method for recovering a hydrogenated block copolymer according to [1] or [2], wherein the solvent is a hydrocarbon solvent.
[ 4 ] The hydrogenated block copolymer according to any one of [1] to [ 3 ], wherein the polyoxyalkylene alkyl ether is added in an amount of 1 to 5000 ppm with respect to the water in the steam stripping tank. Recovery method.
[ 5 ] The recovery of the hydrogenated block copolymer according to any one of [1] to [ 4 ], wherein the hydrogenated block copolymer has a weight average molecular weight of 10,000 or more and 200,000 or less. Method.
[ 6 ] The hydrogenated block copolymer according to any one of [1] to [ 5 ], wherein the hydrogenated block copolymer has two or more hydrogenated vinyl aromatic polymer blocks A. How to recover coalescence.
[ 7 ] A resin composition comprising the following component (X) and component (Y).

Component (X): Hydrogenated block copolymer having a hydrogenated vinyl aromatic polymer block A and a block B of a polymer mainly composed of isobutylene Component (Y): HLB value is 11 or more and 18 or less Polyoxyalkylene alkyl ether [ 8 ] The resin composition as described in [ 7 ] above, wherein the component (X) has a weight average molecular weight of 10,000 or more and 200,000 or less.
[ 9 ] The resin composition according to [ 7 ] or [ 8 ], wherein the component (X) has two or more hydrogenated vinyl aromatic polymer blocks A.

  According to the present invention, a hydrogenated block copolymer having excellent dispersibility can be obtained by steam stripping using a specific surfactant. In addition, since the hydrogenated block copolymer can be recovered without impairing transparency, the obtained hydrogenated block copolymer composition has excellent transparency, gas barrier properties, and water vapor impermeability, It can be used for a wide range of applications as molding materials for various containers, films, and other products.

Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description, and can be arbitrarily modified and implemented without departing from the gist of the present invention.
[Hydrogenated block copolymer]
The hydrogenated block copolymer of the present invention has a hydrogenated vinyl aromatic polymer block A and a polymer block B mainly composed of isobutylene.

The vinyl aromatics of the monomer before hydrogenation constituting the hydrogenated vinyl aromatic polymer block A of the hydrogenated block copolymer of the present invention include benzene ring, naphthalene ring, anthracene ring, fluorene ring, Examples include those in which a vinyl group is bonded to an aromatic ring such as a phenanthrene ring, and a substituent other than a vinyl group may be bonded to the aromatic ring. Specifically, styrene, α
-Methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene Styrenes such as 4-monochlorostyrene, 4-chloromethylstyrene, 4-hydroxymethylstyrene, 4-t-butoxystyrene, dichlorostyrene, 4-monofluorostyrene, 4-phenylstyrene, and vinyl naphthalenes such as vinylnaphthalene. Vinyl anthracene such as vinyl anthracene, and the like. Styrene, α-methyl styrene, 4-methyl styrene, 4-t-butyl styrene, 4-chloromethyl styrene, vinyl naphthalene are preferably used, and styrene, α- Methylstyrene, 4-methylstyrene 4-t-butylstyrene is preferably used. Most preferably styrene is used. These vinyl aromatics may be used individually by 1 type, and may use 2 or more types together.

The hydrogenated vinyl aromatic polymer block A is usually a block composed only of vinyl aromatics hydrogenated as a monomer, but within a range not impairing the object of the present invention, for example, Monomer components other than vinyl aromatics may be contained in a proportion of 50% by mass or less, preferably 30% by mass or less of the total weight of the hydrogenated vinyl aromatic polymer block A.
On the other hand, the polymer block B mainly composed of isobutylene contains isobutylene as a monomer component in an amount of more than 50 mass% of the total weight of the polymer block B mainly composed of isobutylene, preferably 55 It is contained in an amount of not less than mass%, more preferably not less than 70 mass%, still more preferably 80 to 100 mass%, and other monomers may be copolymerized within the above range. By including isobutylene as a monomer component in the above range in the block B of the polymer mainly composed of isobutylene, transparency, optical properties, flexibility, mechanical properties, gas barrier properties, low moisture absorption, non-chemical absorption A well-balanced and excellent hydrogenated block copolymer is obtained. When the block B of the polymer mainly composed of isobutylene contains other monomer components other than isobutylene, the other monomer is not particularly limited as long as it is a monomer that can be cationically polymerized with isobutylene. , One or more of the above-mentioned vinyl aromatics, aliphatic olefins, dienes, vinyl ethers, β-pinene and the like.

The hydrogenated block copolymer of the present invention has one or more segments A (hydrogenated vinyl aromatic polymer block A) and one or more segments B (polymer block B mainly composed of isobutylene), The combination is not particularly limited as long as the effects of the present invention can be obtained, and specifically, AB, A- (BA) _n , (AB) _m , BA- (B- A) _n- B (where n represents an integer of 1 or more, m represents an integer of 2 or more), and the like.

Among these, having two or more segments A and one or more segments B is preferable for obtaining the effects of the present invention, and among these, the structure of A- (BA) _n , particularly ABA, is used. More preferred are those having
The molecular structure of the hydrogenated block copolymer of the present invention may be any of linear, branched, radial, or any combination thereof.

  The content of the hydrogenated vinyl aromatic polymer block A in the hydrogenated block copolymer of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, Preferably it is 95 mass% or less, More preferably, it is 80 mass% or less, More preferably, it is 60 mass% or less, Most preferably, it is 40 mass% or less. When the content of the hydrogenated vinyl aromatic polymer block A in the hydrogenated block copolymer is not more than the above upper limit value, the flexibility and elasticity become good, and the impact resistance tends to be excellent. When the amount is not less than the above lower limit, the heat resistance tends to be good.

The hydrogenated block copolymer of the present invention may be any one having a hydrogenated vinyl aromatic polymer block A and a polymer block B mainly composed of isobutylene. You may have other polymer or copolymer block C other than the block B of the polymer which has A and isobutylene as a main component. In this case, as the other block C, for example, in the block B of a polymer mainly composed of isobutylene, a polymer or copolymer block having an isobutylene content of less than 50% by mass, aliphatic olefins, diene And a polymer or copolymer block composed of one kind or two or more kinds of vinyl ethers, vinyl ethers and β-pinene.

  However, if the content of the other block C in the hydrogenated block copolymer of the present invention is too large, it contains a hydrogenated vinyl aromatic polymer block A and a block B of a polymer mainly composed of isobutylene. Since the effect of the hydrogenated block copolymer of the present invention by the present invention may be impaired, when the hydrogenated block copolymer of the present invention contains another block C, the content thereof is the hydrogenated block copolymer. It is preferable that it is 40 mass% or less with respect to the total weight of this, especially 20 mass% or less.

  As a method for producing the hydrogenated block copolymer of the present invention, any production method may be used as long as the above structure is obtained. For example, a vinyl aromatic block copolymer obtained by performing cationic polymerization in an organic solvent using a Lewis acid catalyst or the like by the method described in the above-mentioned Patent Document 4 (Japanese Patent Laid-Open No. 11-100420). Can be obtained by hydrogenating the aromatic ring.

  The hydrogenation method and reaction mode of the aromatic ring of the vinyl aromatic block copolymer are not particularly limited and may be carried out according to a known method, but the hydrogenation rate can be increased, and the polymer chain scission can be performed. A hydrogenation process with little reaction is preferred. Examples of such a preferable hydrogenation method include a method using a catalyst containing at least one metal selected from nickel, cobalt, iron, titanium, rhodium, palladium, platinum, ruthenium, rhenium and the like. As the hydrogenation catalyst, either a heterogeneous catalyst or a homogeneous catalyst can be used, and the hydrogenation reaction is preferably performed in an organic solvent.

  The heterogeneous catalyst can be used in the form of a metal or a metal compound or supported on a suitable carrier. Examples of the carrier include activated carbon, silica, alumina, calcium carbonate, titania, magnesia, zirconia, diatomaceous earth, silicon carbide, calcium fluoride and the like. These may be used alone or in combination of two or more. The supported amount of the catalyst component is usually 0.1% by mass or more, preferably 1% by mass or more, and usually 60% by mass or less, preferably 50% by mass or less, based on the total amount of the catalyst component and the carrier.

As homogeneous catalysts, catalysts combining metal compounds such as nickel, cobalt, titanium or iron and organometallic compounds such as organoaluminum and organolithium; rhodium, palladium, ruthenium, rhenium, titanium, zirconium, hafnium, etc. An organometallic complex of the above can be used.
As said metal compound, the acetylacetone salt of each metal, a naphthenate, a cyclopentadienyl compound, a cyclopentadienyl dichloro compound, etc. are used. As the organic aluminum, alkyl aluminum such as triethylaluminum and triisobutylaluminum; alkylaluminum halide such as diethylaluminum chloride and ethylaluminum dichloride; alkylaluminum hydride such as diisobutylaluminum hydride and the like are used.

Examples of organometallic complexes include γ-dichloro-π-benzene complexes, dichloro-tris (triphenylphosphine) complexes, hydrido-chloro-tris (triphenylphosphine) complexes of the above metals.
These hydrogenation catalysts can be used alone or in combination of two or more. The amount of the hydrogenation catalyst used is usually 0.001 part by mass or more, preferably 0.005 part by mass or more, more preferably 0.01 parts by mass, based on 100 parts by mass of the vinyl aromatic block copolymer. It is not less than 50 parts by mass, usually not more than 30 parts by mass, preferably not more than 30 parts by mass, more preferably not more than 15 parts by mass.

  The hydrogenation reaction is carried out at a pressure of 5 to 25 MPa at a temperature of 100 to 250 ° C., and as a solvent, a hydrocarbon solvent such as cyclohexane, methylcyclohexane, hexane, pentane, octane, decalin, tetralin or naphtha, preferably a saturated hydrocarbon It is preferable to use a system solvent. Although there is no restriction | limiting in particular in the usage-amount of a solvent, Usually, they are 100 mass parts or more and 1000 mass parts or less with respect to 100 mass parts of vinyl aromatic block copolymers.

The hydrogenation rate of the aromatic ring of the vinyl aromatic block copolymer is preferably 50 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more. When the hydrogenation rate is not less than the above lower limit, the transparency, heat resistance, and moldability are excellent. The hydrogenation rate of the aromatic ring is calculated from, for example, the integrated value of the peak derived from an aliphatic group near 0.5 to 2.5 ppm and the peak derived from an aromatic ring near 6.0 to 8.0 ppm by ¹ H-NMR. be able to.

  The hydrogenated block copolymer of the present invention has a polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, preferably 10,000 or more, more preferably 30000. More preferably, it is 50000 or more, preferably 200000 or less, more preferably 150,000 or less, and further preferably 130,000 or less. When the Mw of the hydrogenated block copolymer is not less than the above lower limit value, the mechanical strength, heat resistance, and moldability of the resulting molded article become favorable, and when it is not more than the above upper limit value, melting during processing Viscosity decreases and moldability tends to be good.

The molecular weight distribution of the hydrogenated block copolymer of the present invention can be appropriately selected according to the purpose of use, but the ratio (Mw / Mn) between the polystyrene-equivalent Mw and the number average molecular weight (Mn) measured by the above GPC. And is preferably 4 or less, more preferably 3 or less, and particularly preferably 2 or less. It is preferable for Mw / Mn to be equal to or less than the above upper limit value because a molded article excellent in moldability, heat resistance, transparency and the like can be easily obtained.
As a method of removing the organic solvent from the polymer solution obtained through the hydrogenation step and recovering the resin, it is preferable to perform steam stripping in the presence of the surfactant according to the present invention. The steam stripping method can be generally performed using a known method.

The hot water used in the steam stripping is preferably generated by blowing steam into the water. In addition, hot water may be generated by an external heat source such as a heat medium, an electric heater, or steam.
In the steam stripping, the polymer concentration in the hydrocarbon solvent solution of the hydrogenated block copolymer is preferably 5% by weight or more, more preferably 7% by weight or more, more preferably 60% by weight or less, and further preferably 40% by weight or less. preferable. The polymer concentration is adjusted to the above range and supplied into hot water. When the polymer concentration is 5% by weight or more, the amount of the solvent relative to the block copolymer is not too large, and the cost required for removing and collecting the solvent tends to be suppressed. On the other hand, when the polymer concentration is 60% by weight or less, the viscosity of the solution becomes too high, the fluidity does not deteriorate, and problems such as clogging during the process tend not to occur.
When the polymer concentration is less than 5% by weight, the concentration may be adjusted using a concentrator such as a flash tank or a stirring tank. On the contrary, when the polymer concentration exceeds 60% by weight, hydrocarbons are used. The concentration may be adjusted by diluting with a solvent.

  The concentration of the crumb-like polymer dispersed in water by steam stripping is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, more preferably 1% by weight with respect to the water in the steam stripping tank. The above is particularly preferable. Moreover, 50 weight% or less is preferable, 30 weight% or less is preferable, and 20 weight% or less is especially preferable. If it is this range, it will not cause trouble on operation, and a crumb having a good particle size can be obtained.

Examples of the surfactant that can be used in the present invention include polyoxyalkylene alkyl ethers which are nonionic surfactants. The oxyalkylene group of the polyoxyalkylene alkyl ether preferably has 2 or more carbon atoms, preferably 8 or less, more preferably 6 or less, and particularly preferably 4 or less. This is preferable because a balance between the dispersibility of the polymer and the transparency of the resulting polymer is obtained.
Representative examples of polyoxyalkylene alkyl ethers include polyoxyethylene lauryl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene Polyoxyethylene alkyl ethers such as ethylene polyoxypropylene alkyl ether and polyoxyethylene alkylene alkyl ether; polyoxypropylene lauryl ether, polyoxypropylene myristyl ether, polyoxypropylene cetyl ether, polyoxypropylene stearyl ether, and polyoxy Polyoxypropylene alcohol such as propylene polyoxypropylene alkyl ether Ethers; and the like.
Of these, polyoxyethylene alkyl ethers are preferred because of the excellent balance between crumb dispersibility and the transparency of the resulting polymer. Among these, polyoxyethylene lauryl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl are preferred. Most preferred are ether, polyoxyethylene stearyl ether and polyoxyethylene polyoxypropylene alkyl ether. These may be used singly or in combination of two or more.
The surfactant of the present invention may be used in combination with a nonionic surfactant, an anionic surfactant, a cationic surfactant, or the like as long as the effects of the present invention are not impaired.

  Further, among the surfactants of the present invention, the HLB value is preferably 11 or more, more preferably 12 or more, and particularly preferably 13 or more. Moreover, what is 18 or less is preferable, What is 17 or less is more preferable, What is 16 or less is especially preferable. Here, the HLB value indicates the balance of the amount of the hydrophilic group and the lipophilic group constituting the surfactant, and is generally a value that can be easily calculated by a known calculation formula in the field of surfactants. is there. When the HLB value is greater than 11, the lipophilicity as a surfactant does not become too strong, and the steam stripping temperature tends to function effectively without forming micelles. Moreover, when the HLB value is smaller than 18, the stabilization effect on the interface tends to increase. In the case of the same type of surfactant, for example, if it has polyoxyethylene units, the longer the polyoxyethylene chain, the higher the HLB value and the stronger the hydrophilicity.

  As the surfactant of the present invention, since it is necessary to stably liquid-liquid-disperse the polymer solution at a high temperature of 70 ° C. or higher, it is preferable to use a surfactant having a cloud point not lower than the solvent removal temperature.

The addition amount of the surfactant is preferably 1 ppm or more, more preferably 5 ppm or more, particularly preferably 10 ppm or more, and preferably 5000 ppm or less, and 3000 ppm or less, with respect to the water in the tank where steam stripping is performed. Is more preferable, and 1000 ppm or less is particularly preferable. When the addition amount is 1 ppm or more, crumbs are less likely to agglomerate and problems such as clogging tend not to occur during the steam stripping operation or the dehydration drying operation. By being 5000 ppm or less, stable operation of the steam stripping process due to foaming or the like hardly occurs, and the physical properties of the polymer tend not to be affected.

  The surfactant of the present invention may be added to water when performing steam stripping, or may be added to a hydrogenated block copolymer solution. Moreover, you may add to both.

  When the solvent is removed from the hydrogenated block copolymer solution by a steam stripping method to obtain a crumb-shaped hydrogenated copolymer, the temperature of water is equal to or higher than the boiling point of the solvent, or the solvent and water azeotrope. In such a case, it is preferable to carry out a temperature not lower than the azeotropic temperature and not higher than 120 ° C. When the boiling point is higher than the boiling point of the solvent or when the solvent and water are azeotroped, the removal of the solvent is facilitated and the residual solvent amount in the crumb tends to be reduced by carrying out at the azeotropic temperature or higher. Moreover, when the temperature at the time of steam stripping is 120 ° C. or less, a product having a small crumb particle size is obtained, and the production tends to be facilitated.

  By the steam stripping step, a slurry in which crumbs made of a hydrogenated block copolymer are dispersed in water is obtained. The water-containing crumb is first dehydrated to about 30 to 60% by weight with a vibrating screen, a centrifugal dehydrator or the like, and further dehydrated to about 1 to 20% by weight with a dehydrator such as a screw type extrusion dehydrator. The dehydrated crumb has a moisture content of less than 1% by weight by a dryer such as a hot air dryer, a vacuum dryer, an extrusion dryer, or an expansion dryer.

  Examples of the resin composition obtained by the above method include resin compositions containing the following component (X) and component (Y).

Component (X): Hydrogenated block copolymer having hydrogenated vinyl aromatic polymer block A and block B of polymer mainly composed of isobutylene Component (Y): Polyoxyalkylene alkyl ether

The hydrogenated block copolymer of component (X) has the above-described hydrogenated vinyl aromatic polymer block A and a block B of a polymer mainly composed of isobutylene. The block A, the block B, and these The hydrogenated block copolymer having the same meaning is used.
The polyoxyalkylene alkyl ether of component (Y) is also synonymous with the polyoxyalkylene alkyl ether described above.
Moreover, the resin composition of this invention can be made into the resin composition containing the hydrogenated block copolymer of this invention, another resin component, various additives as needed.
The method for confirming that the component (X) and the component (Y) are contained from the resin composition is not particularly limited, but can be confirmed by NMR, mass spectrometry, or the like.

Other resin components that may be contained in the resin composition of the present invention include ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / acrylic acid ester copolymer, Ethylene / α-olefin copolymer such as ethylene / methacrylic acid ester copolymer, polyolefin resin such as polyethylene, polypropylene, polybutene-1 resin, polyphenylene ether resin, polyamide resin such as nylon 6 and nylon 66, aramid Resins, aromatic polyester resins such as polyethylene terephthalate and polybutylene terephthalate, aliphatic polyester resins such as polylactic acid, polybutylene succinate and polycaprolactone, polycarbonate resins, polyarylate resins, modified polyphenylene oxide trees , Polysulfone resin, polyphenylene sulfide resin, polyether sulfone resin, polyether ketone resin, polyether ether ketone resin, polyimide resin, polyoxymethylene homopolymer, polyoxymethylene copolymer and other polyoxymethylene resins, polymethyl methacrylate Resins, silicon-containing soft polymers such as dimethylpolysiloxane, diphenylpolysiloxane, dihydroxypolysiloxane, vinyl aromatic polymers such as polystyrene, ethylene / propylene copolymer rubber (EPM), ethylene / propylene / nonconjugated diene copolymer rubber (EPDM), ethylene elastomer such as ethylene / butene copolymer rubber (EBM), ethylene / propylene / butene copolymer rubber, styrene-butadiene-styrene block copolymer, Styrene elastomer such as styrene-isoprene-styrene block copolymer, styrene-ethylene / butylene-styrene block copolymer, styrene-ethylene / propylene-styrene block copolymer, polybutadiene, vinyl hydride aromatic polymer, hydrogen And other hydrogenated vinyl aromatic block copolymers including cyclostyrene / butadiene or styrene / isoprene block copolymers, cycloolefin polymers, cycloolefin copolymers, etc. (however, among the above resin components, Excluding those contained in component (X)). These may be used alone or in combination of two or more.

Among these, it is excellent in the balance of transparency, heat resistance, gas barrier property, and non-adsorbing property for chemicals, so that it can be used as a hydrogenated vinyl aromatic polymer, a hydrogenated vinyl aromatic block copolymer, a cycloolefin polymer, a cycloolefin copolymer. Polymers and polyolefin resins are preferred, and vinyl hydride aromatic polymers are particularly preferred.
Examples of the vinyl aromatics constituting the above-mentioned hydrogenated vinyl aromatic polymer and vinyl hydrogenated aromatic block copolymer include styrene, α-methylstyrene, 2-methylstyrene, 3-methyl. Styrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, 4-monochlorostyrene, dichlorostyrene, 4-mono Fluorostyrene, 4-phenylstyrene vinyl naphthalene, vinyl anthracene and the like can be mentioned. Among them, styrene, α-methylstyrene and 4-methylstyrene are preferably used. These vinyl aromatics may be used individually by 1 type, and may use 2 or more types together.

  Additives include antioxidants, heat stabilizers, light stabilizers, UV absorbers, fillers such as fillers, neutralizers, lubricants, antifogging agents, antiblocking agents, slip agents, dispersants, colorants, Flame retardants, antistatic agents, conductivity-imparting agents, cross-linking agents, cross-linking aids, metal deactivators, molecular weight regulators, antibacterial agents, antifungal agents, fluorescent whitening agents, organic diffusing agents, inorganic diffusing agents, etc. And the like.

EXAMPLES Hereinafter, although this invention is demonstrated still in detail using an Example, this invention is not limited by a following example, unless the summary is exceeded.
In the following Examples and Comparative Examples, various physical properties were measured according to the following methods.
(1) Molecular weight:
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the hydrogenated block copolymer or block copolymer are measured by gel permeation chromatography (GPC) and calculated in terms of standard polystyrene under the following conditions. It was.
Apparatus: Waters 2690 manufactured by Nihon Waters Co., Ltd. Detector (RI detection): Waters 2410 manufactured by Nihon Waters Co., Ltd.
Column: Showa Denko Co., Ltd. Shodex KF-604, KF-603, KF-602.50 each connected in series was used.
Solvent: Tetrahydrofuran Flow rate: 0.7 mL / min
Temperature: 40 ° C

(2) Hydrogenation rate:
The hydrogenation rate (mol%) of the aromatic ring of the hydrogenated block copolymer was calculated by measuring a ¹ H-NMR spectrum.

<Evaluation of hydrogenated block copolymer or hydrogenated block copolymer composition>
[Production example]
In a stainless steel autoclave equipped with a stirrer, a polystyrene block content of 30% by mass, a weight average molecular weight (Mw) = 111000, and a number average molecular weight (Mn) = 82100 styrene-isobutylene-styrene copolymer 25 parts by mass And the solution which consists of 75 mass parts of cyclohexane and 4 mass parts of 5 mass% palladium carrying activated carbon catalyst as a hydrogenation catalyst were put and mixed. The inside of the reactor was replaced with hydrogen gas, and hydrogen gas was supplied while stirring the solution, and a hydrogenation reaction was performed at a temperature of 180 ° C. and a pressure of 10 MPa for 6 hours.

After completion of the hydrogenation reaction, the reaction solution was diluted with 100 parts by mass of cyclohexane, and the solution was filtered to remove the hydrogenation catalyst to obtain a hydrogenated block copolymer solution having a solid content concentration of 12.5% by mass. .
The hydrogenated block copolymer thus obtained was represented by the following formula, the weight average molecular weight (Mw) was 100,000, and the number average molecular weight (Mn) was 76000 (Mw / Mn = 1.3). . The hydrogenation rate was 99.7%.

[Example 1]
Into a 1 L separable flask is placed 300 mL of an aqueous solution containing 300 ppm of HLB15.3 and a polyoxyethylene lauryl ether having a cloud point of 98 ° C., heated to 78 ° C. and stirred at 780 rpm, and the polymer solution shown in the production example is injected at a rate of 2 mL. Infused at / min. The dispersibility of the produced polymer crumb was evaluated as follows. The results are shown in Table 1.
The dispersibility of the crumb was classified according to the following by visual judgment with respect to the state in the steam stripping tank.
○: A state in which crumbs having a particle size of about 10 mm or less are uniformly dispersed in water, and aggregation between the crumbs does not occur.
X: Formation of crumbs having a particle size exceeding 10 mm, polymer adhesion to the inner wall of the tank and the stirring blade, or aggregation between crumbs, resulting in a lump.

  The slurry was filtered and then dried with a vacuum dryer at 80 ° C. to obtain a composition containing a hydrogenated block copolymer and a surfactant. About this hydrogenated block copolymer composition, compression molding is performed at a temperature of 230 ° C. in a compression molding machine under conditions of preheating for 3 minutes, press for 3 minutes, and cooling press for 2 minutes, forming a sheet having a thickness of 0.5 mm, Transparency was evaluated as follows. The results are shown in Table 1.

The transparency of the sheet was visually compared with a pressed sheet of a hydrogenated block copolymer containing no surfactant (Comparative Example 4) and classified according to the following.
○: Transparency equal to or higher than the case of no surfactant (Comparative Example 4) ×: White turbidity compared to the case of no surfactant (Comparative Example 4)

[Example 2]
The crumb dispersibility and sheet transparency were evaluated in the same manner as in Example 1 except that the surfactant was changed to polyoxyethylene lauryl ether having an HLB of 13.6 and a cloud point of 83 ° C. The results are shown in Table 1.

[Example 3]
The crumb dispersibility and sheet transparency were evaluated in the same manner as in Example 1 except that the surfactant was changed to HLB14.2 and polyoxyethylene cetyl ether having a cloud point of 98 ° C. The results are shown in Table 1.

[Example 4]
Evaluation of crumb dispersibility and sheet transparency was carried out in the same manner as in Example 1 except that the surfactant was changed to polyoxyethylene polyoxypropylene alkyl (C12-14) ether having an HLB of 14.0 and a cloud point of 88 ° C. It was. The results are shown in Table 1.

[Comparative Example 1]
Clam dispersibility and sheet transparency were evaluated in the same manner as in Example 1 except that the surfactant was changed to polyoxyethylene monostearate having an HLB of 16.9 and a cloud point of 100 ° C. or higher. The results are shown in Table 1.

[Comparative Example 2]
Evaluation of crumb dispersibility and sheet transparency was performed in the same manner as in Example 1 except that the surfactant was changed to polyoxyethylene monostearate having an HLB of 15.6 and a cloud point of 90 ° C. The results are shown in Table 1.

[Comparative Example 3]
The crumb dispersibility and sheet transparency were evaluated in the same manner as in Example 1 except that the surfactant was changed to a polyoxyethylene polyoxypropylene block polymer having a cloud point of 100 ° C. or higher. The results are shown in Table 1.

[Comparative Example 4]
The crumb dispersibility was evaluated in the same manner as in Example 1 except that the surfactant was not used. The results are shown in Table 1.

  As shown in Examples 1 to 4, when polyoxyalkylene alkyl ether was used as the surfactant, when other surfactants (Comparative Examples 1 to 3) were used, and when no surfactant was used Compared with (Comparative Example 4), it was found that the balance between crumb dispersibility and sheet transparency was excellent, and a good crumb could be obtained without impairing the transparency of the hydrogenated block copolymer.

Claims (9)

A method of recovering a hydrogenated block copolymer from a solution containing a hydrogenated block copolymer having a hydrogenated vinyl aromatic polymer block A and a block B of a polymer mainly composed of isobutylene and a solvent. A method for recovering a hydrogenated block copolymer, characterized by performing steam stripping in the presence of a polyoxyalkylene alkyl ether having an HLB value of 11 or more and 18 or less as a surfactant. The polyoxyalkylene alkyl ether, a method of recovering the hydrogenated block copolymer according to claim 1, characterized in that it has a clouding point equal to or higher than the azeotropic point and the boiling point or a solvent and water of the solvent. The method for recovering a hydrogenated block copolymer according to claim 1 or 2 , wherein the solvent is a hydrocarbon solvent. The method for recovering a hydrogenated block copolymer according to any one of claims 1 to 3 , wherein the polyoxyalkylene alkyl ether is added in an amount of 1 to 5000 ppm based on water in the steam stripping tank. The method for recovering a hydrogenated block copolymer according to any one of claims 1 to 4 , wherein the hydrogenated block copolymer has a weight average molecular weight of 10,000 or more and 200,000 or less. The method for recovering a hydrogenated block copolymer according to any one of claims 1 to 5 , wherein the hydrogenated block copolymer has two or more hydrogenated vinyl aromatic polymer blocks A. The resin composition containing the following component (X) and component (Y).
Component (X): Hydrogenated block copolymer having a hydrogenated vinyl aromatic polymer block A and a block B of a polymer mainly composed of isobutylene Component (Y): HLB value is 11 or more and 18 or less Polyoxyalkylene alkyl ether The weight average molecular weight of the said component (X) is 10,000 or more and 200,000 or less, The resin composition of Claim 7 characterized by the above-mentioned. The resin composition according to claim 7 or 8 , wherein the component (X) has two or more hydrogenated vinyl aromatic polymer blocks A.