JP6962133B2 - Method for Producing Powder and Granules of Hydrogenated Block Copolymer and Resin Composition - Google Patents

Description

The present invention relates to a method for producing powder or granular material of a hydrogenated block copolymer and a resin composition containing a hydrogenated block copolymer.

A hydrogenated block copolymer obtained by hydrogenating a block copolymer of a vinyl aromatic compound and isobutylene is excellent in transparency and is a material suitable for optical materials, packaging materials, and the like. Such a hydrogenation block copolymer can be produced by a hydrogenation reaction using a hydrogenation catalyst in an organic solvent, but in order to use it as a molding material, it is volatile in the solution after the reaction such as an organic solvent. It is necessary to remove the components to recover the hydrogenated block copolymer, and to convert the recovered hydrogenated block copolymer into a molded product by heat melt molding or the like.

In the process of producing a synthetic polymer, as a method of removing volatile components such as a solvent from the solution after the reaction and recovering the polymer, a method of reprecipitation in a poor solvent (reprecipitation method) or a method of directly under heating is used. 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 precipitated polymer becomes highly viscous and it is difficult to remove the solvent, and if the solution concentration is too low, a large amount of poor solvent is required. Further, since the recovered solvent must be divided into a good solvent and a poor solvent, a multi-stage distillation apparatus is required in the subsequent process, which causes a problem that the process becomes complicated.

Further, in the direct solvent removal method, heating for a long time is required 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. be.

On the other hand, in the field of synthetic rubber, as a method of separating the polymer and the solvent from the reaction solution of the polymer, the polymer solution is injected into hot water, the solvent is distilled with steam, and the polymer is precipitated in the form of crumbs. The steam stripping method is known (Patent Document 1-3). Further, in Patent Document 4, it is possible to recover a hydrogenated block copolymer by allowing a polyoxyalkylene alkyl ether having an HLB value of 11 or more and 18 or less as a surfactant at the time of steam stripping. It is described that Patent Document 5 recovers a hydrogenated block copolymer by performing steam stripping in the presence of a polyoxyethylene sorbitan fatty acid ester as a surfactant.

Tokusho Sho 44-21346 Gazette Special Publication No. 57-47684 Special Publication No. 57-53363 Japanese Unexamined Patent Publication No. 2014-189664 Japanese Unexamined Patent Publication No. 2014-189665

After recovering the hydrogenated block copolymer obtained by the methods such as Patent Documents 1 to 5, it is obtained by the steam stripping method such as Patent Documents 4 and 5 in order to process it into a resin composition or a molded product thereof. It is necessary to use the crumb-shaped hydrogenated block copolymer as a powder. However, since the obtained hydrogenated block copolymer is soft and irregular, the obtained powder or granular material is liable to cause blocking, and the obtained powder or granular material is easily blocked by a recovery hopper for collecting the dried powder or granular material, or blocked in a flexible container. Trouble was occurring.

In view of the above situation, the present invention has a good balance of hydrogenated block copolymers, particularly transparency, optical properties, flexibility, mechanical properties, moldability, heat resistance, gas barrier properties, low moisture absorption, and chemical non-adsorption properties. For an excellent hydrogenated block copolymer, a method capable of stably producing powders and granules of a hydrogenated block copolymer having excellent anti-blocking properties without impairing the excellent transparency of the hydrogenated block copolymer. It is intended to be provided.

The present inventors have diligently studied to solve the above-mentioned problems, and have described the solid hydrogenated block copolymer obtained from the solution of the hydrogenated block copolymer as fumed silica, preferably a specific particle size and surface. We have found that by contacting with treated fumed silica, it is possible to produce powders and granules of hydrogenated block copolymers having excellent anti-blocking properties without impairing transparency, and have completed the present invention. ..
That is, the gist of the present invention is the following [1] to [8]. Describe the repetition of the claims.

[1] A solid hydride block copolymer from a solution containing a hydride block copolymer having a vinyl hydride aromatic polymer block A and a block B of a polymer mainly composed of isobutylene and a solvent. Is a method for producing powders and granules of the hydride block copolymer from the solid hydride block copolymer, wherein the solid hydride block copolymer and fumed silica are used. A method for producing powders and granules of a hydride block copolymer, which comprises a step of contacting them.

[2] The method for producing powder or granular material of a hydrogenated block copolymer according to [1], wherein the average particle size of the fumed silica is 100 nm or less.

[3] Granules of the hydrogenated block copolymer according to [1] or [2], wherein the amount of the fumed silica is 0.01 to 1% by mass with respect to the hydrogenated block copolymer. How to make a body.

[4] The method for producing powder or granular material of a hydrogenated block copolymer according to any one of [1] to [3], wherein the fumed silica is hydrophobic fumed silica.

[5] The powder or granular material of the hydrogenated block copolymer according to any one of [1] to [4], wherein the weight average molecular weight of the hydrogenated block copolymer is 10,000 or more and 200,000 or less. Manufacturing method.

[6] The powder or granule of the hydrogenated block copolymer according to any one of [1] to [5], wherein the hydrogenated block copolymer has two or more of the vinyl hydride aromatic polymer blocks A. Manufacturing method.

[7] A resin composition containing the following component (X) and component (Y).
Component (X): Hydrogenated block copolymer having a vinyl hydride aromatic polymer block A and a block B of a polymer mainly composed of isobutylene Component (Y): Fumed silica having an average particle size of 100 nm or less.

[8] The resin composition according to [7], wherein the weight average molecular weight of the component (X) is 10,000 or more and 200,000 or less.

According to the present invention, by contacting a solid hydrogenated block copolymer separated from the reaction solution of the hydrogenated block copolymer with fumed silica, the transparency is maintained and the anti-blocking property is excellent. It is possible to obtain powders and granules of a hydrogenated block copolymer. The resin composition using the powder or granular material of the hydrogenated block copolymer obtained by the present invention has excellent transparency, gas barrier property, water vapor impermeable property, etc., and therefore various containers, films, and other products. It can be used for a wide range of purposes as a molding material for.

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 carried out without departing from the gist of the present invention.

[Hydrogenation block copolymer]
First, the hydrogenated block copolymer according to the present invention (hereinafter referred to as "hydrogenated block copolymer of the present invention") will be described.
The hydrogenated block copolymer of the present invention is characterized by having a hydrogenated vinyl aromatic polymer block A and a block B of a polymer mainly composed of isobutylene.

The vinyl hydride aromatic polymer block A of the hydrogenated block copolymer of the present invention constitutes.
Examples of the vinyl aromatics of the monomer before hydrogenation include those in which a vinyl group is bonded to an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, or a phenanthrene ring, and this aromatic ring is vinyl. Substituents other than the group may be bonded. Specifically, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, 5- Styrenees such as t-butyl-2-methylstyrene, 4-monochromelostyrene, 4-chloromethylstyrene, 4-hydroxymethylstyrene, 4-t-butoxystyrene, dichlorostyrene, 4-monofluorostyrene, 4-phenylstyrene, etc. , Vinyl naphthalenes such as vinyl naphthalene, vinyl anthracenes such as vinyl anthracene, etc., and styrene, α-methylstyrene, 4-methylstyrene, 4-t-butylstyrene, 4-chloromethylstyrene, vinylnaphthalene are preferable. Further, styrene, α-methylstyrene, 4-methylstyrene, and 4-t-butylstyrene are preferably used. Most preferably, styrene is used. One of these vinyl aromatics may be used alone, or two or more thereof may be used in combination.

The vinyl hydride aromatic polymer block A is usually a block composed of only hydrogenated vinyl aromatics as a monomer, but it is within a range that does not impair the object of the present invention. For example, a monomer component 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 mass of the hydrogenated vinyl aromatic polymer block A.

On the other hand, the block B of the polymer mainly composed of isobutylene contains isobutylene as a monomer component in an amount more than 50% by mass of the total mass of the block B of the polymer mainly composed of isobutylene, preferably 55. It is contained in an amount of mass% or more, more preferably 70% by mass or more, still more preferably 80 to 100% by mass, and other monomers may be copolymerized in the above range. By including isobutylene as a monomer component in the block B of the polymer mainly composed of isobutylene in the above range, transparency, optical properties, flexibility, mechanical properties, gas barrier property, low hygroscopicity, and chemical non-adsorption property. A well-balanced and excellent hydrogenated block copolymer can be obtained. When the block B of the polymer mainly composed of isobutylene contains a monomer component other than isobutylene, the other monomer is not particularly limited as long as it is a monomer that can be cationically polymerized with isobutylene, but for example. , One or more of the above-mentioned vinyl aromatics, aliphatic olefins, dienes, vinyl ethers, β-pinenes 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 (block B of a polymer mainly composed of isobutylene). The combination is not particularly limited as long as the effect of the present invention can be obtained, and specifically, AB, AB- (BA) n, (AB) m, BA- (B-). A) Structures such as n-B (where n represents an integer of 1 or more and m represents an integer of 2 or more) can be mentioned.

Among these, it is preferable to have two or more segments A and one or more segments B in order to obtain the effect of the present invention, and among these, A- (BA) n, particularly ABA structure. It is more preferable to have.
Further, the molecular structure of the hydrogenated block copolymer of the present invention may be linear, branched, radial, or any combination thereof.

The content of the vinyl hydride aromatic polymer block A of the hydride 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. It is preferably 95% by mass or less, more preferably 80% by mass or less, still more preferably 60% by mass or less, and particularly preferably 40% by mass or less. When the content of the hydrogenated vinyl aromatic polymer block A of the hydrogenated block copolymer is not more than the above upper limit value, the flexibility and elasticity are good, and the impact resistance tends to be excellent. When it is at least the above lower limit value, the heat resistance tends to be good.

The hydride block copolymer of the present invention may have a vinyl hydride aromatic polymer block A and a block B of a polymer mainly composed of isobutylene, and may be a vinyl hydride aromatic polymer block. It may have a polymer or a copolymer block C other than the block B of the polymer mainly composed of A and isobutylene. In this case, as the other block C, for example, in the block B of the polymer mainly composed of isobutylene, a polymer or copolymer block having an isobutylene content of less than 50% by mass, an aliphatic olefins, a diene, etc. Classes, vinyl ethers, polymers consisting of one or more of β-pinenes, or copolymer blocks.

However, if the content of the other block C in the hydride block copolymer of the present invention is too large, the vinyl hydride aromatic polymer block A and the block B of the polymer mainly composed of isobutylene may be contained. Therefore, the effect of the hydride block copolymer of the present invention may be impaired. Therefore, when the hydride block copolymer of the present invention contains another block C, the content thereof is the hydride block copolymer. It is preferably 40% by mass or less, particularly 20% by mass or less, based on the total mass of the above.

[Method for producing hydrogenated block copolymer]
As the method for producing the hydrogenated block copolymer of the present invention, any production method may be used as long as the above structure can be obtained. For example, the aromatic ring of a vinyl aromatic block copolymer obtained by performing cationic polymerization in an organic solvent using a Lewis acid catalyst or the like is hydrogenated by the method described in JP-A-11-100420. Can be obtained by

The hydrogenation method and reaction form 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 is cleaved. A hydrogenation method with less reaction is preferable. Such a preferable hydrogenation method includes 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 this hydrogenation catalyst, either a heterogeneous catalyst or a homogeneous catalyst can be used, and the hydrogenation reaction is preferably carried out in an organic solvent.

The heterogeneous catalyst can be used as it is as 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 amount of the catalyst component supported 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.

Homogeneous catalysts include catalysts that combine metal compounds such as nickel, cobalt, titanium or iron with organometallic compounds such as organoaluminum and organolithium; rhodium, palladium, ruthenium, renium, titanium, zirconium, hafnium and the like. The organometallic complex of the above can be used.
As the metal compound, an acetylacetone salt of each metal, a naphthenate, a cyclopentadienyl compound, a cyclopentadienyldichloro compound and the like are used. As the organoaluminum, alkylaluminum such as triethylaluminum and triisobutylaluminum; alkylaluminum halide such as diethylaluminum chloride and ethylaluminum dichloride; and alkylaluminum hydride such as diisobutylaluminum hydride are used.

Examples of the organic metal complex include a γ-dichloro-π-benzene complex of each of the above metals, a dichloro-tris (triphenylphosphine) complex, and a hydride-chloro-tris (triphenylphosphine) complex.

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, and more preferably 0.01 as the amount of the catalyst active component per 100 parts by mass of the vinyl aromatic block copolymer. It is 5 parts by mass or more, usually 50 parts by mass or less, preferably 30 parts by mass or less, and more preferably 15 parts by mass or less.

Hydrocarbon reactions of vinyl aromatic block copolymers include cyclohexane, methylcyclohexane, hexane, pentane, octane, decalin, tetralin, naphtha, etc. as solvents at a pressure of 5 to 25 MPa and a temperature of 100 to 250 ° C. It is preferable to use a hydrocarbon solvent, preferably a saturated hydrocarbon solvent. The amount of the solvent used is not particularly limited, but is usually 100 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the vinyl aromatic block copolymer.

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 at least the above lower limit value, the transparency, heat resistance, and moldability are excellent. The hydrogenation rate of the aromatic ring is calculated by, for example, ¹ H-NMR from the integrated value of the peak derived from the aliphatic around 0.5-2.5 ppm and the peak derived from the aromatic ring around 6.0-8.0 ppm. be able to.

The hydrogenated block copolymer of the present invention has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, preferably 10,000 or more, more preferably. Is 30,000 or more, more preferably 50,000 or more, preferably 200,000 or less, more preferably 150,000 or less, still more preferably 130,000 or less. When the Mw of the hydrogenated block copolymer is at least the above lower limit, the mechanical strength, heat resistance, and moldability of the obtained molded product are good, and when it is at least the above upper limit, it is melted during processing. The viscosity tends to decrease and the moldability tends to be good.

The molecular weight distribution of the hydrogenated block copolymer of the present invention can be appropriately selected depending on the intended use, but the ratio (Mw / Mn) of the polystyrene-equivalent Mw measured by the above GPC to the number average molecular weight (Mn). It is preferably 4 or less, more preferably 3 or less, and particularly preferably 2 or less. When Mw / Mn is not more than the above upper limit value, it is preferable because a molded product having excellent moldability, heat resistance, transparency and the like can be easily obtained.

[Recovery of solid hydrogenated block copolymer]
The method for recovering the solid hydrogenated block copolymer by removing the solvent from the hydrogenated block copolymer solution obtained through the above hydrogenation step is not particularly limited, but the presence of a surfactant is present. Below is a method of performing steam stripping. The steam stripping method can be carried out by using a generally known method.

The hot water used for 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.

When steam stripping is performed, the polymer (hydrogen block copolymer) concentration in the hydride block copolymer solution is preferably 5% by mass or more, more preferably 7% by mass or more, while the polymer concentration is 60% by mass. The following is preferable, and 40% by mass or less is more preferable. When the polymer concentration is 5% by mass or more, the amount of the solvent for the hydrogenated block copolymer is not too large, and the cost required for removing and recovering the solvent tends to be suppressed. On the other hand, when the polymer concentration is 60% by mass or less, the viscosity of the solution becomes too high and the fluidity does not deteriorate, and problems such as clogging during the process tend not to occur.
If the polymer concentration is less than 5% by mass, the concentration may be adjusted using a concentrator such as a flash tank or a stirring tank, and conversely, if the polymer concentration exceeds 60% by mass, hydrocarbons may be used. The concentration may be adjusted by diluting with a system solvent.

By supplying a hydrogenated block copolymer solution having a polymer concentration as described above into hot water by steam stripping, the concentration of the crumb-like polymer dispersed in the water is determined with respect to the water in the steam stripping tank. , 0.01% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 1% by mass or more. Further, 50% by mass or less is preferable, 30% by mass or less is preferable, and 20% by mass or less is particularly preferable. Within this range, a crumb having a good particle size can be obtained without causing any trouble in operation.

During steam stripping, a surfactant such as the following polyoxyalkylene alkyl ether or polyoxyethylene sorbitan fatty acid ester may be present.

Preferred surfactants to be present during steam stripping include polyoxyalkylene alkyl ethers, which are nonionic surfactants. The carbon number of the oxyalkylene group of the polyoxyalkylene alkyl ether is preferably 2 or more, preferably 8 or less, further preferably 6 or less, and particularly preferably 4 or less. It is preferable from the viewpoint of the balance between the dispersibility of the polymer and the transparency of the obtained polymer.

Typical examples of polyoxyalkylene alkyl ethers are polyoxyethylene lauryl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, and polyoxy. Polyoxyethylene alkyl ethers such as ethylene polyoxypropylene alkyl ethers and polyoxyethylene alkylene alkyl ethers; polyoxypropylene lauryl ethers, polyoxypropylene myristyl ethers, polyoxypropylene cetyl ethers, polyoxypropylene stearyl ethers, and polyoxy. Polyoxypropylene alkyl ethers such as propylene polyoxypropylene alkyl ether; and the like.

Among these, polyoxyethylene alkyl ethers are preferable because they have an excellent balance between the dispersibility of crumbs and the transparency of the obtained polymer. Among them, polyoxyethylene lauryl ether, polyoxyethylene myristyl ether, and polyoxyethylene cetyl are preferable. Most preferred are ethers, polyoxyethylene stearyl ethers and polyoxyethylene polyoxypropylene alkyl ethers.

Preferred nonionic surfactants as surfactants to be present during steam stripping also include polyoxyethylene sorbitan fatty acid esters. Typical examples of polyoxyethylene sorbitan fatty acid ester are polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, and polyoxyethylene sorbitan tristearate. And so on. Of these, polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monopalmitate are the most preferable.

The above-mentioned preferable nonionic surfactant may be used alone or in combination of two or more.

The above-mentioned preferable nonionic surfactant may be used in combination with other nonionic surfactants, anionic surfactants, cationic surfactants and the like as long as the effects are not impaired. ..

The surfactant used in the present invention preferably has an HLB value of 11 or more, more preferably 12 or more, and particularly preferably 13 or more. Further, the HLB value is preferably 18 or less, more preferably 17 or less, and particularly preferably 16 or less. Here, the HLB value indicates the balance between the amounts of the hydrophilic groups and the lipophilic groups constituting the surfactant, and is a value that can be easily calculated by a calculation formula generally known in the field of surfactants. be. When the HLB value is larger than 11, the lipophilicity as a surfactant does not become too strong, and it tends to function effectively without forming micelles at the steam stripping temperature. Further, when the HLB value is smaller than 18, the stabilizing effect on the interface tends to be large. If the same type of surfactant has a polyoxyethylene unit, for example, the longer the polyoxyethylene chain, the larger the HLB value and the stronger the hydrophilicity.

Further, as the surfactant used for steam stripping, since it is necessary to stably disperse the polymer solution in a liquid-liquid manner at a high temperature of 70 ° C. or higher, the surfactant may have a cloud point equal to or higher than the solvent removal temperature. preferable.

The amount of the surfactant added to the water in the tank for steam stripping is preferably 1 ppm or more, more preferably 5 ppm or more, particularly preferably 10 ppm or more, preferably 5000 ppm or less, still more preferably 3000 ppm or less. , 1000 ppm or less is particularly preferable. When the addition amount is 1 ppm or more, agglutination between crumbs is less likely to occur, and problems such as clogging during the steam stripping operation and the dehydration drying operation tend not to occur. On the other hand, when the addition amount is 5000 ppm or less, unstable operation of the steam stripping step due to foaming or the like is unlikely to occur, and the physical properties of the polymer tend not to be affected.

The surfactant may be added to the water used for steam stripping, or may be added to the hydrogenated block copolymer solution. Moreover, you may add it to both.

The temperature of water when the solvent is removed from the solution of the hydride block copolymer by the steam stripping method to obtain a crumb-like hydride copolymer is equal to or higher than the boiling point of the solvent, or the solvent and water azeotrope. In this case, it is preferable to carry out the process at a temperature equal to or higher than the azeotropic temperature and lower than 120 ° C. When the solvent is azeotropically heated or higher than the boiling point of the solvent or when the solvent and water are azeotropically heated, the solvent can be easily removed and the amount of residual solvent in the crumb tends to be reduced. Further, when the temperature at the time of steam stripping is 120 ° C. or lower, a product having a small crumb particle size can be obtained, and the production tends to be easy.

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

The recovery of the solid hydrogenated block copolymer from the hydrogenated block copolymer solution may be performed by a reprecipitation method or a direct solvent removal method, not by the steam stripping described above.

[Manufacture of hydrogenated block copolymer powder and granules]
In the method for producing powder or granules of a hydride block copolymer of the present invention, the solid hydride block copolymer recovered from the hydride block copolymer solution as described above is brought into contact with fumed silica. A powder or granule of a hydrogenated block copolymer having excellent anti-blocking properties can be obtained.

As the fumed silica, fumed silica obtained by a known method can be used. The silicon dioxide used in fumed silica is colloidal silicon dioxide. Colloidal silicon dioxide is generally fumed silica prepared by suitable methods to reduce particle size and modify surface properties. Humed silica can be roughly classified into hydrophilic fumed silica and hydrophobic fumed silica, but since it is possible to obtain powders and granules of hydrogenated block copolymers having more excellent anti-blocking properties. In the present invention, it is preferable to use hydrophobic fumed silica.

A common method in the art of modifying surface properties to obtain hydrophobic fumed silica is silica under conditions of high temperature vapor phase hydrolysis with a surface modified silicon compound such as silicon dimethyl chloride. Fumed silica is produced by producing a material. Such products are described in Cabot Corporation [Tuscola, Illinois] (trade name CAB-O-SIL), and Degussa, Inc. It is commercially available from a number of sources, including [Piscataway, NJ] (trade name AEROSIL).

Suitable hydrophobic modified fumed silica particles are commercially available from Degussa Corporation, trade name for R-series AEROSIL® and AEROXIDE® LE. Not limited to these. Hydrophobic coating, BET surface area, average primary particle size, carbon content, etc. are different for each type of AEROSIL® R and AEROXIDE® LE. The hydrophobicity of the fumed silica particles is imparted by a suitable hydrophobizing treatment, such as surface treatment with at least one compound of the group of organic silanes, alkylsilanes, fluorinated silanes, and / or disilazane.

Commercially available hydrophobic fumed silica particles include AEROSIL® R976S, AEROSIL® RX300-5, AEROSIL® RY300, AEROSIL® R202, AEROSIL® R805, AEROSIL (registered trademark). Registered Trademarks) R812, AEROSIL® R812S, AEROSIL® R972, AEROSIL® R974, AEROSIL® R8200, AEROXIDE® LE-1, and AEROXIDE® LE- There are two.

The average particle size of fumed silica used in the present invention is preferably 100 nm or less. This is because if the average particle size is larger than 100 nm, the transparency of the molded product deteriorates. The average particle size of fumed silica is more preferably 80 nm or less, and particularly preferably 60 nm or less. However, since fumed silica having an average particle size smaller than 3 nm has poor handleability, the average particle size of fumed silica is usually 3 nm or more.
Here, the average particle size of fumed silica is the average particle size of the primary particles converted from the BET specific surface area.

The amount of fumed silica, preferably hydrophobic fumed silica, is preferably 0.01 to 1% by mass with respect to the hydrogenated block copolymer. If the amount of fumed silica added is less than 0.01% by mass, it may not be possible to sufficiently obtain the anti-blocking property by adding fumed silica. Therefore, the amount of fumed silica added is preferably 0.01% by mass or more, particularly 0.02% by mass or more, particularly 0.03% by mass or more, based on the hydrogenated block copolymer. On the other hand, if the amount of fumed silica added is too large, the transparency of the molded product deteriorates due to the aggregation of fumed silica, or the fumed silica that cannot be completely adhered to the surface of the powdered granules of the hydride block copolymer. The amount of fumed silica added to the hydride block copolymer is preferably 1% by mass or less, particularly 0.7% by mass or less, and particularly preferably 0.5% by mass or less because it accumulates.

[Resin composition]
The resin composition of the present invention contains the following component (X) and component (Y).
Component (X): Hydrogenated block copolymer having a vinyl hydride aromatic polymer block A and a block B of a polymer mainly composed of isobutylene Component (Y): Fumed silica having an average particle size of 100 nm or less.

The hydrogenated block copolymer of the component (X) has the above-mentioned vinyl hydride aromatic polymer block A and block B of a polymer mainly composed of isobutylene, and includes block A, block B and these. Hydrogenated block copolymers having are synonymous with.
The fumed silica of the component (Y) is also synonymous with the fumed silica described above.

The resin composition of the present invention is produced by the above-mentioned method for producing powder or granular material of a hydrogenated block copolymer of the present invention.
Alternatively, the resin composition of the present invention can also be produced by blending the hydrogenated block copolymer of the component (X) produced by an arbitrary method with the fumed silica of the component (Y).

The ratio of the component (Y) to the component (X) contained in the resin composition of the present invention is fumed with respect to the hydrogenated block copolymer in the above-mentioned method for producing powder or granules of the hydrogenated block copolymer of the present invention. Similar to the amount of silica added, the ratio of the component (Y) to the component (X) is 0.01 to 1% by mass, particularly 0.02 to 0.7% by mass, especially 0.03 to 0.5% by mass. It is preferable to have.

The method for confirming that the resin composition contains the component (X) and the component (Y) is not particularly limited, but can be confirmed by NMR, mass spectrometry, or the like.

The resin composition of the present invention may be a resin composition containing the above-mentioned component (X) and component (Y), as well as other resin components other than the component (X), various additives, and the like, if necessary. can.

Other resin components that can 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, and the like. 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, nylon 66, aramid Aromatic polyester resins such as resins, polyethylene terephthalates and polybutylene terephthalates, polylactic acid, polybutylene succinates, aliphatic polyester resins such as polycaprolactone, polycarbonate resins, polyarylate resins, modified polyphenylene oxide resins and polysulphon resins. , Polyphenylene sulfide resin, polyether sulfone resin, polyether ketone resin, polyether ether ketone resin, polyimide resin, polyoxymethylene homopolymer, polyoxymethylene copolymer such as polyoxymethylene copolymer, polymethylmethacrylate resin, dimethyl Silicon-containing soft polymers such as polysiloxane, diphenylpolysiloxane, and dihydroxypolysiloxane, vinyl aromatic polymers such as polystyrene, ethylene / propylene copolymer rubber (EPM), ethylene / propylene / non-conjugated diene copolymer rubber (EPDM) , Ethylene / butene copolymer rubber (EBM), ethylene / propylene / butene copolymer rubber and other ethylene-based elastomers, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene / butylene Others containing-styrene block copolymers, styrene elastomers such as styrene-ethylene / propylene-styrene block copolymers, polybutadiene, vinyl hydride aromatic polymers, hydride hydride / butadiene or styrene / isoprene block copolymers Examples thereof include vinyl hydride aromatic block copolymers, cycloolefin copolymers, cycloolefin copolymers, etc. (However, among the above resin components, those contained in the component (X) are excluded). One of these may be used alone, or two or more thereof may be used in combination.

Among them, all of vinyl hydride aromatic polymers, vinyl hydride aromatic block copolymers, cycloolefin polymers, and cycloolefins have an excellent balance of transparency, heat resistance, gas barrier properties, and non-adsorption of chemicals. Polymers and polyolefin resins are preferable, and vinyl hydride aromatic polymers are particularly preferable.

Examples of the vinyl aromatics of the monomers constituting the above-mentioned vinyl hydride aromatic polymer and vinyl hydride aromatic block copolymer include styrene, α-methylstyrene, 2-methylstyrene, and 3-methyl. Styrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, 4-monochromelostyrene, dichlorostyrene, 4-mono Fluorostyrene, 4-phenylstyrene, vinylnaphthalene, vinylanthracene and the like can be mentioned, and among them, styrene, α-methylstyrene and 4-methylstyrene are preferably used. One of these vinyl aromatics may be used alone, or two or more thereof may be used in combination.

Additives include antioxidants, heat stabilizers, light stabilizers, UV absorbers, fillers such as fillers, neutralizers, lubricants, antifogging agents, antiblocking agents, slip agents, dispersants, colorants, etc. Flame retardant, antistatic agent, conductivity imparting agent, cross-linking agent, cross-linking aid, metal inactivating agent, molecular weight modifier, antibacterial agent, anti-mold material, fluorescent whitening agent, organic diffusing agent, inorganic diffusing agent, etc. Examples include the light diffusing agent of.

Hereinafter, the present invention will be described in more detail with reference to Examples, Reference Examples and Comparative Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. The values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable ranges are the above-mentioned upper limit or lower limit values and the following. It may be in the range specified by the value of Examples or the combination of the values of Examples.

In the following Examples, Reference 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 hydride block copolymer or block copolymer are measured by gel permeation chromatography (GPC) under the following conditions in terms of standard polystyrene. rice field.
Equipment: Waters 2690 manufactured by Japan Waters Corp.
Detector (RI detection): Waters 2410 manufactured by Japan Waters Corp.
Column: A series of three Shodex KF-604, KF-603, and KF-602.50 manufactured by Showa Denko KK 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 the 1H-NMR spectrum.

(3) Anti-blocking property Approximately 40 g of the sample is weighed into "Unipack C-4" manufactured by Seinichi Co., Ltd., and after the sample is filled in the bag, pressures of ^{46 g / cm 2} and 31 g / cm ^{2 are applied, respectively.} A weight (load: 19.3 kg or 13 kg) was placed therein and allowed to stand in an oven at 40 ° C. for a certain treatment time, then taken out of the oven and adjusted for 24 hours at room temperature. Then, the pellets were taken out from the bag, the blocking state of the pellets was visually observed, and the judgment was made according to the following criteria 1 to 5. The results are shown in Table 1.
1: No blocking 2: Blocking / Unraveling by own weight 3: Blocking / Unraveling by lightly pressing, Partially unraveling by own weight 4: Blocking / Unraveling by own weight 5: Veil-like

(4) Total light transmittance Using a test piece obtained by injection molding a sample, the total light transmittance was measured and the transparency of the injection molded product was evaluated in accordance with JIS K7361-1.

[Example 1]
A stainless steel autoclave equipped with a stirrer has a polystyrene block content (hereinafter sometimes referred to as PS content) of 30% by mass, a weight average molecular weight (Mw) = 111,000, and a number average molecular weight (Mn). A solution consisting of 25 parts by mass of a styrene-isobutylene-styrene copolymer and 75 parts by mass of tetrahydrofuran was added and mixed with 4 parts by mass of a 5% by mass palladium-supported activated carbon catalyst as a hydrogenation catalyst. The inside of the reactor was replaced with hydrogen gas, hydrogen gas was further supplied while stirring the solution, and a hydrogenation reaction was carried out at a temperature of 170 ° C. and a pressure of 10 MPa for 4.5 hours.

After completion of the hydrogenation reaction, the reaction solution was diluted with 100 parts by mass of tetrahydrofuran, and the solution was filtered to remove the hydrogenation catalyst. The filtrate was poured into 1200 parts by mass of methanol with stirring, and the precipitated hydrogenated block copolymer was separated by filtration and dried under a vacuum drier.

The hydrogenated block copolymer thus obtained was represented by the following formula, and had a weight average molecular weight (Mw) of 103,000 and a number average molecular weight (Mn) of 78,200 (Mw / Mn =). 1.3). The hydrogenation rate was 97%. Hereinafter, this hydrogenated block copolymer may be referred to as (X-1). This hydrogenated block copolymer (X-1) was soft, amorphous, and blocked.

The obtained blocked crumb-shaped hydrogenated block copolymer (X-1) was kneaded at 140 to 180 ° C. using a single-screw extruder "Thermo 40φ" (manufactured by Yoshii Iron Works Co., Ltd.). After extruding and cooling, pellets were obtained using a strand cutter. Hydrophobic fumed silica "AEROSIL (registered trademark) R976S" (average particle size: 7 nm, dimethylsilane surface-treated product) manufactured by Nippon Aerosil Co., Ltd. was added to the obtained pellets as an anti-blocking agent in an amount of 0.05% by mass based on the resin. The anti-blocking property was evaluated.

Further, the amount of the antiblocking agent added to the resin was set to 1% by mass, and a cylinder temperature of 220 ° C. and a mold temperature of 40 were used using an injection molding machine (an injection molding unit was connected to a "Xplore microcompounder" manufactured by DSM). A test piece having a size of 80 mm × 30 mm and a thickness of 2 mm was produced by injection molding at ° C. The total light transmittance was evaluated using this test piece.
The evaluation results are shown in Table-1.

[Example 2]
The same procedure as in Example 1 was carried out except that hydrophobic fumed silica "AEROSIL (registered trademark) RX300-5" (average particle size: 7 nm, trimethylsilane surface-treated product) manufactured by Nippon Aerosil Co., Ltd. was used as the anti-blocking agent. ..

[Example 3]
The same procedure as in Example 1 was carried out except that hydrophobic fumed silica “AEROSIL (registered trademark) RY300” (average particle size: 7 nm, silicone oil surface-treated product) manufactured by Nippon Aerosil Co., Ltd. was used as the anti-blocking agent.

[Example 4]
The same procedure as in Example 1 was carried out except that the hydrophobic fumed silica “AEROSIL (registered trademark) R805” (average particle size: 20 nm, alkylsilane surface-treated product) manufactured by Nippon Aerosil Co., Ltd. was used as the antiblocking agent.

[Comparative Example 1]
It was carried out in the same manner as in Example 1 except that the anti-blocking agent was not added.

[Reference example 1]
The same procedure as in Example 1 was carried out except that the hydrophilic fumed silica “AEROSIL (registered trademark) 300” (average particle size: 7 nm, non-surface treated product) manufactured by Nippon Aerosil Co., Ltd. was used as the antiblocking agent.

[Reference example 2]
The same procedure as in Example 1 was carried out except that the hydrophilic fumed silica “AEROSIL (registered trademark) 90G” (average particle size: 20 nm, non-surface treated product) manufactured by Nippon Aerosil Co., Ltd. was used as the blocking inhibitor.

[Reference example 3]
The same procedure as in Example 1 was carried out except that the hydrophilic fumed silica “AEROSIL (registered trademark) 50” (average particle size: 30 nm, non-surface treated product) manufactured by Nippon Aerosil Co., Ltd. was used as the antiblocking agent.

[Reference example 4]
The same procedure as in Example 1 was carried out except that the hydrophilic fumed silica “AEROSIL (registered trademark) OX50” (average particle size: 40 nm, non-surface treated product) manufactured by Nippon Aerosil Co., Ltd. was used as the anti-blocking agent.

[Evaluation results]
As shown in Table 1, in the case of Comparative Example 1 to which the anti-blocking agent was not added, the treatment was completely blocked in 1 hour, whereas Examples 1 to 4 to which the anti-blocking agent was added, Reference Example. It can be seen that the anti-blocking property is improved in 1 to 4. However, in Reference Examples 1 to 4 in which hydrophilic fumed silica which has not been surface-treated as an anti-blocking agent is used, although the anti-blocking property is improved, hydrophobic fumed silica which has been subjected to hydrophobic treatment is used. A decrease in the total light transmittance is observed as compared with Examples 1 to 4.

Claims (6)

The solid hydride block copolymer is separated from the solution containing the hydride block copolymer having the vinyl hydride aromatic polymer block A and the block B of the polymer mainly composed of isobutylene and the solvent. , A method for producing powders and granules of the hydride block copolymer from the solid hydride block copolymer, which is a step of bringing the solid hydride block copolymer into contact with fumed silica. only including,
A method for producing powder or granular material of a hydrogenated block copolymer, wherein the fumed silica is hydrophobic fumed silica having an average particle diameter of 100 nm or less. The method for producing powder or granular material of a hydrogenated block copolymer according to claim 1, wherein the amount of the fumed silica is 0.01 to 1% by mass with respect to the hydrogenated block copolymer. The method for producing powder or granular material of a hydrogenated block copolymer according to claim 1 or 2 , wherein the weight average molecular weight of the hydrogenated block copolymer is 10,000 or more and 200,000 or less. The method for producing powder or granules of a hydrogenated block copolymer according to any one of claims 1 to 3 , wherein the hydrogenated block copolymer has two or more of the vinyl hydride aromatic polymer blocks A. .. A resin composition containing the following component (X) and component (Y).
Component (X): Hydrogenated block copolymer having a vinyl hydride aromatic polymer block A and a block B of a polymer mainly composed of isobutylene Component (Y): Hydrophobic fume having an average particle size of 100 nm or less Hydrogenation The resin composition according to claim 5 , wherein the weight average molecular weight of the component (X) is 10,000 or more and 200,000 or less.