JP2016037555A - Mixture having no stickiness and excellent long term storage stability and mixing method therefor, and production method for thermoplastic resin composition by melt-kneading said mixture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a mixture that has no stickiness and is excellent in long-term storage stability and a mixing method therefor, and a production method for a thermoplastic resin composition by melt-kneading said mixture.SOLUTION: The present invention provides: a mixture obtained by mixing (A) a hydrogenated product of a vinyl aromatic compound-conjugated diene compound copolymer having an average particle size of less than 1 mm, (B) 30 to 300 pts.mass of an oil per 100 pts.mass of the (A) component, and (C) 1.0 pts.mass or more of a resin incompatible with the oil per 100 pts.mass of the (A) component, and a mixing method therefor; and a production method for a thermoplastic resin composition by melt-kneading said mixture.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a mixture having no stickiness and excellent long-term storage stability, a method for mixing the mixture, and a method for producing a thermoplastic resin composition by melt-kneading the mixture.

Conventionally, various proposals have been made to melt and knead a resin composition containing a hydrogenated vinyl aromatic compound-conjugated diene compound copolymer so as to contain oil for the purpose of modifying the composition. Yes. For example, Patent Document 1 discloses a resin composition containing a polyamide resin, a polyphenylene ether resin, an elastomer (hydrogenated vinyl aromatic compound-conjugated diene compound copolymer), and oil. According to the article, it is said that the low temperature impact resistance can be greatly improved while maintaining the rigidity. Further, in Patent Document 2, the particle size is less than 1.4 mm, and 100 parts by weight of a hydrogenated block copolymer of a vinyl aromatic compound and a conjugated diene compound, and a non-aromatic rubber softener ( Oil) A thermoplastic elastomer composition containing 75 to 400 parts by weight is disclosed, and according to this thermoplastic elastomer composition, the composition is softened by a non-aromatic rubber softener (oil). It is said that the oil bleed out from the composition can be reduced.
Although not a resin composition, Patent Document 3 discloses a technique of mixing oil into an elastomer such as granular ethylene / propylene / diene rubber (EPDM) using a high-speed mixer before melt-kneading. Yes.

Japanese Patent Laid-Open No. 02-011656 JP 2006-160803 A JP-T-2001-525739

However, the technique of Patent Document 1 discloses a pellet containing an oil in a hydrogenated vinyl aromatic compound-conjugated diene compound copolymer, and a vinyl aromatic compound-conjugated diene compound containing no oil other than the pellet. The hydrogenated copolymer is melt kneaded with other resins and additives, but once the hydrogenated vinyl aromatic compound-conjugated diene compound copolymer hydrogenated without oil is melt kneaded, There was a problem that heat deterioration occurred and the physical properties were lowered.
The technique of Patent Document 2 aims to improve the stickiness of an elastomer after melt-kneading a specific hydrogenated block copolymer of a vinyl aromatic compound and a conjugated diene compound and oil. However, it does not disclose raw materials such as hydrogenated products before melt kneading. Further, this technique has a problem that the stickiness of the elastomer to which oil is added is insufficient, and the long-term storage stability is also insufficient.
Furthermore, in the technique of Patent Document 3, the oil may bleed out from the mixture of the elastomer and oil before melt kneading using the technique, and therefore the stickiness and handling properties of the elastomer deteriorate. When the mixture is stored for a long period of time, there is a problem that the elastomers containing the oil adhere to each other to form a large lump. Also, when melt-kneading a mixture of elastomer and oil, for example, using a feeder and supplying it to an extruder, a mixture that is not excellent in long-term storage becomes a large lump inside the hopper of the feeder, There was also a risk that production would become impossible.

  Accordingly, the present invention provides a mixture having no stickiness and excellent long-term storage stability, a method for mixing the mixture, and a method for producing a thermoplastic resin composition by melt-kneading the mixture.

  As a result of intensive studies to solve the above problems, the present inventors have adjusted the particle size of the hydrogenated product of the vinyl aromatic compound-conjugated diene compound copolymer and the oil content, and further, The inventors have found that the above problems can be solved by mixing compatible resins, and have completed the present invention.

That is, the present invention is as follows.
[1] A hydrogenated vinyl aromatic compound-conjugated diene compound copolymer (A) having an average particle size of less than 1 mm;
30 to 300 parts by mass of oil (B) with respect to 100 parts by mass of component (A),
A mixture obtained by mixing 1.0 part by mass or more of the oil and the incompatible resin (C) with respect to 100 parts by mass of the component (A).
[2] The mixture according to [1], wherein the resin that is incompatible with the oil of the component (C) is a polyphenylene ether resin.
[3] The mixture according to any one of [1] and [2], wherein the vinyl aromatic compound in the component (A) is styrene.
[4] The mixture according to any one of [1] to [3], wherein the conjugated diene compound in the component (A) is butadiene.
[5] The mixture according to any one of [1] to [3], wherein the conjugated diene compound in the component (A) is isoprene.
[6] The mixture according to any one of [1] to [5] above, wherein the vinyl aromatic compound-conjugated diene compound copolymer is a block copolymer.
[7] In any one of the above [1] to [6], the vinyl aromatic compound-conjugated diene compound copolymer of the component (A) is a vinyl aromatic compound in an amount of 5 to 95% by mass, and a conjugated diene compound. Containing 95 to 5% by mass.
[8] In any one of the above [1] to [7], the hydrogenated structure of the vinyl aromatic compound-conjugated diene compound copolymer is a hydrogenated vinyl aromatic compound-conjugated diene compound copolymer. A mixture that is a thing.
[9] In any one of the above [1] to [7], the structure of the hydrogenated product of the vinyl aromatic compound-conjugated diene compound copolymer is vinyl aromatic compound-conjugated diene compound copolymer-vinyl aromatic. A mixture which is a hydrogenated product of a group compound.
[10] The mixture according to any one of [1] to [9], wherein a weight average molecular weight of the hydrogenated vinyl aromatic compound-conjugated diene compound copolymer is 50,000 to 400,000.
[11] The mixture according to any one of [1] to [10], wherein the oil is a paraffinic oil and / or a naphthenic oil.
[12] The mixture according to any one of [1] to [11], wherein the oil has a weight average molecular weight of 400 to 3000.
[13] In any one of the above [1] to [12], the resin incompatible with the oil of the component (C) is a polyphenylene ether resin having an average particle size in the range of 0.05 to 1.0 mm Is a mixture.
[14] The polyphenylene ether resin according to any one of [1] to [12], wherein the resin that is incompatible with the oil of the component (C) has an average particle size of 0.1 to 6.0 mm. And
The mixture in which the polyphenylene ether resin of the component (C) contains 10 to 90% by mass of a polyphenylene ether resin and 90 to 10% by mass of a polystyrene resin.
[15] The mixture according to any one of [1] to [14] above, wherein the component (A), the component (B), and the component (C) are sequentially supplied to the mixing device and mixed. Mixing method.
[16] The component (A) and the component (B) are sequentially supplied to the mixing device and mixed, and then the component (C) is supplied to the mixing device and further mixed. [1] A method for mixing the mixture according to any one of [14].
[17] 60 to 80 parts by mass of 100 parts by mass of the component (A), the component (B), and the rest of the component (A) are sequentially supplied to the mixing device, and then mixed. The method for mixing a mixture according to any one of the above [1] to [14], wherein the component (C) is supplied to the mixing device and further mixed.
[18] Supplying the component (A) to a mixing device, stirring and mixing the component (A), supplying and mixing the component (B), and then supplying the component (C) A mixing method of the mixture according to any one of the above [1] to [14].
[19] The mixing method according to any one of [16] to [18], wherein the mixing of the component (A) and the component (B) is carried out until substantially no leaching occurs in an oil bleed-out test. .
[20] The mixing method according to any one of [15] to [19], wherein the oil of the component (B) is supplied while being dispersed by a disperser attached to the mixing device.
[21] In any one of the above [15] to [20], the mixing device is a mixing device with a vertical stirring blade, a mixing device with a horizontal stirring blade, a vertical tank rotating mixing device, or a horizontal rotating mixing device. A mixing method comprising any one of them.
[22] A method for producing a thermoplastic resin composition, wherein a mixture mixed by using the mixing method of any one of [15] to [21] is melt kneaded with a thermoplastic resin using a melt kneader.
[23] The method for producing a thermoplastic resin composition according to [22], wherein the melt kneader is any one of a single screw extruder and a twin screw extruder.

  If the mixture of the present invention, the mixing method thereof and the method for producing a thermoplastic resin composition by melting and kneading the mixture are employed, the mixture has no stickiness and is excellent in long-term storage and performs a stable melt-kneading operation. Thus, a resin composition having various physical properties can be produced.

It is a figure which shows the outline | summary of the mixing apparatus with a vertical stirring blade which can be used in order to mix the mixture of this invention, or can be used for the mixing method of this invention. It is a figure which shows the twin-screw extruder outline | summary which can be used for the manufacturing method of the thermoplastic resin composition of this invention.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following description, It can implement by changing variously within the range of the summary.

〔blend〕
The mixture of the present embodiment comprises a hydrogenated compound (A) of vinyl aromatic compound-conjugated diene compound copolymer having an average particle size of less than 1 mm, and an oil (B) 30 to 100 parts by mass of the component (A). 300 parts by mass and 1.0 part by mass or more of the resin (C) incompatible with the oil are mixed (dry blended) with 100 parts by mass of the component (A).

(Hydrogenated product of vinyl aromatic compound-conjugated diene compound copolymer (A))
The hydrogenated vinyl aromatic compound-conjugated diene compound copolymer used in the present invention is a copolymer of a vinyl aromatic compound and a conjugated diene compound, preferably a block copolymer in each monomer unit. The polymer block A is composed of a polymer block A mainly composed of a vinyl aromatic compound and a polymer block B mainly composed of a conjugated diene compound.

  In the block copolymer, the vinyl aromatic compound in the random copolymer portion may be distributed uniformly or in a tapered shape. In the block copolymer, a plurality of portions where the vinyl aromatic compound is uniformly distributed and / or a portion where the vinyl aromatic compound is distributed in a tapered shape may coexist. Further, a plurality of portions having different vinyl aromatic compound contents may coexist in the block copolymer.

As the block copolymer composed of the polymer block A mainly composed of a vinyl aromatic compound and the polymer block B mainly composed of a conjugated diene compound, a block copolymer having the following structure is generally exemplified.
(AB) _n , A- (BA) _n , B- (AB) _{n + 1} , [(AB) _k ] _{m + 1-} Z,
[(A−B) _k −A] _{m + 1} −Z, [(B−A) _k ] _{m + 1} −Z, [(B−A) _k −B] _{m + 1} −Z
In the above formula, Z represents a residue of a coupling agent or a residue of an initiator of a polyfunctional organolithium compound. N, k, and m are integers of 1 or more, and are generally 1 to 5.

  Examples of the vinyl aromatic compound used in the hydrogenated product of the vinyl aromatic compound-conjugated diene compound copolymer include, but are not limited to, for example, styrene, α-methylstyrene, vinyl toluene, p-tert. -Butylstyrene, diphenylethylene, etc. are mentioned. These may be used alone or in combination of two or more. In particular, styrene is preferable as the vinyl aromatic compound.

  The vinyl aromatic compound content of the vinyl aromatic compound-conjugated diene compound copolymer is 5 to 95 mass%, and the conjugated diene compound content is 95 to 5 mass%. By setting it as such content, impact resistance can be provided. Moreover, 10-60 mass% is preferable and, as for content of a vinyl aromatic compound, 20-60 mass% is more preferable. 90-40 mass% is preferable and, as for content of a conjugated diene compound, 80-40 mass% is more preferable.

  The vinyl aromatic compound content in the block copolymer of hydrogenated vinyl aromatic compound-conjugated diene compound is usually preferably 10 to 90% by mass, more preferably 15 to 85% by mass, More preferably, it is 20-80 mass%. Moreover, it is preferable that content of a conjugated diene compound is 90-10 mass%, More preferably, it is 85-15 mass%, More preferably, it is 80-20 mass%.

  Examples of the conjugated diene compound include, but are not limited to, butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and the like. You may use, and may use 2 or more types together. In particular, as the conjugated diene compound, butadiene, isoprene and a combination thereof are preferable.

  Moreover, the microstructure which is a polymerization form of the conjugated diene compound in the vinyl aromatic compound-conjugated diene compound block copolymer can be arbitrarily selected. For example, in butadiene, the 1,2-vinyl bond is preferably 2 to 85%, more preferably 10 to 85%, and still more preferably 35 to 85%.

  In isoprene, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is preferably 2 to 85%, more preferably 3 to 75%, and still more preferably 3 to 60%. is there. The 1,2-vinyl bond and 3,4-vinyl bond may be uniformly distributed in the conjugated diene compound polymer block or may be distributed in a tapered shape.

  In addition, the conjugated diene compound polymer is a polymer portion having a different 1,2-vinyl bond content or a total amount of 1,2-vinyl bond and 3,4-vinyl bond, for example, 1,2-vinyl bond content or There may be a polymer block portion having a total amount of 1,2-vinyl bonds and 3,4-vinyl bonds of less than 30%, and a polymer block portion of 30% or more, and further, the amount of these vinyl bonds. A plurality of polymer block portions of conjugated diene compounds having different numbers may coexist.

  The weight average molecular weight (polystyrene conversion molecular weight by gel permeation chromatography) of the vinyl aromatic compound-conjugated diene compound block copolymer is preferably 50,000 to 500,000, more preferably 55,000 to 400. , 000, more preferably 60,000 to 400,000.

Here, the vinyl aromatic compound-conjugated diene compound block copolymer as described above is present in the polymer by adding a hydrogenation catalyst and hydrogen gas in a hydrocarbon solvent and performing a hydrogenation reaction. A hydrogenated block copolymer in which the olefinic unsaturated bond derived from the conjugated diene compound is preferably reduced to 90% or less, more preferably 55% or less, and even more preferably 5% or less can be obtained.
The hydrogenation reaction is not limited in its production method as long as it can reduce the olefinic unsaturated bond derived from the conjugated diene compound present in the vinyl aromatic compound-conjugated diene compound block copolymer, and any production method can be used. It may be a method.

The average particle diameter of the vinyl aromatic compound-conjugated diene compound hydrogenated product is less than 1 mm, preferably less than 0.8 mm, more preferably less than 0.6 mm. This is because by making the average particle size less than 1 mm, the oil of component (B) can easily penetrate into the hydrogenated product.
In addition, in this invention, the measuring method of the average particle diameter of the hydrogenated substance of a vinyl aromatic compound-conjugated diene compound is a value measured with a laser diffraction type particle size meter.

(Oil (B))
The oil that can be used in the mixture of the present invention is not limited to the following, but for example, paraffinic oil and naphthenic oil are preferably used from the viewpoint of compatibility with the conjugated diene compound.

  Examples of the paraffinic oil include, but are not limited to, paraffinic compounds having 4 to 155 carbon atoms, preferably paraffinic compounds having 4 to 50 carbon atoms. These paraffinic oils are preferably used in a mixture and liquid at room temperature. Specific examples of the paraffinic oil include, but are not limited to, K-350 (liquid paraffin 99.9995%) manufactured by Kaneda Corporation, and PW-90 (n-paraffin manufactured by Idemitsu Kosan Co., Ltd.). System process oil), Sanko Chemical Co., Ltd. neothiozole (n-paraffin process oil), and the like.

Naphthenic oils are cyclic saturated hydrocarbons and include, but are not limited to, for example, cyclopentane C ₅ H ₁₀ , cyclohexane C ₆ H ₁₂ , fuchtelite C ₁₉ H ₃₄ and oleanane C ₃₀ H _52. Etc. alone or as a mixture. These naphthenic oils are preferably used in a mixture and are liquid at room temperature. Specific naphthenic oils include Diana process oil NS90S and Diana process oil NS100 manufactured by Idemitsu Kosan.

  Specific examples of the mixture of paraffinic oil and naphthenic oil include Diana Process Oil NP250 and Diana Process Oil PW380 manufactured by Idemitsu Kosan.

  The weight average molecular weight (polystyrene conversion molecular weight by gel permeation chromatography) of oil is 400-3000 normally, Preferably it is 450-2500, More preferably, it is 500-2000. When the weight average molecular weight is less than 400, the oil blended with the hydrogenated vinyl aromatic compound-conjugated diene compound copolymer tends to bleed out from the hydrogenated vinyl aromatic compound-conjugated diene compound copolymer. When the weight average molecular weight exceeds 3000, the viscosity is too high and the hydrogenated vinyl aromatic compound-conjugated diene compound copolymer tends not to be impregnated easily.

  The amount of the oil is 30 to 300 parts by mass, preferably 35 to 250 parts by mass, and more preferably 40 to 100 parts by mass of the hydrogenated product of the vinyl aromatic compound-conjugated diene compound copolymer. -200 parts by mass. When the amount exceeds 300 parts by mass, the oil cannot be absorbed into the hydrogenated product of the vinyl aromatic compound-conjugated diene compound copolymer. Moreover, if it is less than 30 mass parts, the workability of the hydrogenated product of the vinyl aromatic compound-conjugated diene compound copolymer, for example, during melt kneading is lowered.

(Resin incompatible with oil (C))
The oil-incompatible resin that can be used in the mixture of the present invention is not limited to the following as long as it is incompatible with the oil. For example, polyphenylene ether resin, polycarbonate resin, polyamide Resin and polyester resin, and polyphenylene ether resin is preferable.

  The polyphenylene ether-based resin that can be used in the mixture of the present invention is not limited to the following, but may be, for example, a polyphenylene ether resin or a mixture of a polyphenylene ether resin and a polystyrene-based resin.

  Examples of the polyphenylene ether resin include, but are not limited to, poly (2,6-dimethyl-1,4-phenylene ether) and poly (2-methyl-6-ethyl-1,4-phenylene ether). ), Poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other Polyphenylene ether copolymers such as copolymers with phenols (for example, 2,3,6-trimethylphenol and 2-methyl-6-butylphenol) are also included. The polyphenylene ether resin is particularly preferably poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, and poly (2 , 6-dimethyl-1,4-phenylene ether) is more preferable.

The reduced viscosity of the polyphenylene ether resin (unit: g / dl, measured in chloroform at 30 ° C.) is preferably 0.10 to 0.7, more preferably 0.2 to 0.65, even more preferably. Is 0.3 to 0.6. When the reduced viscosity of the polyphenylene ether resin is 0.10 or more, the mechanical strength can be maintained, and when the reduced viscosity of the polyphenylene ether resin is 0.7 or less, the fluidity can be maintained.
The reduced viscosity is measured with a chloroform solvent, 30 ° C., and a 0.5 g / dl solution using an Ubbelohde viscometer.

The average particle size of the polyphenylene ether resin is preferably 0.01 to 1.5 mm, more preferably 0.020 to 1.3 mm, and still more preferably 0.03 to 1.0 mm. By setting the average particle size to 0.01 mm or more, the carrying ability is improved, and by setting the average particle size to 1.5 mm or less, it is possible to prevent the occurrence of unmelted polyphenylene-tere resin.
In the present invention, the method for measuring the average particle size of the polyphenylene ether resin is a value measured with a laser diffraction particle size meter.

Further, we are preferable that the static bulk density of the polyphenylene ether resin is 0.40~0.70kg / m ^3, more preferably 0.42~65kg / m ^3, more preferably 0.45 to 0. 6 kg / m ³ . By setting the bulk density to 0.40 kg / m ³ or more, it is possible to improve the conveyance capacity, and by setting the bulk density to 0.70 kg / m ³ or less, generation of unmelted polyphenylene ether resin is prevented. can do.

Here, the polystyrene-based resin that can be used for the polyphenylene ether-based resin is not limited to the following, but, for example, general-purpose polystyrene resin, high-impact polystyrene-based resin, styrene / acrylic copolymer-based resin, and styrene / acrylic resin Acrylic / butadiene copolymer resins and the like may be used in combination. Particularly preferred polystyrene resins are general purpose polystyrene (hereinafter also referred to as “GPPS”) and high impact polystyrene (hereinafter also referred to as “HIPS”).
In addition, it is preferable that the rubber average particle diameter of high impact polystyrene is 1.0-2.0 micrometers, and it is preferable that a rubber concentration is 8-15 weight%. The high impact polystyrene rubber is not limited, but for example, high cis butadiene rubber is preferable.

  Here, in the case of using a polyphenylene ether resin as the component (C), the mixture of the polyphenylene ether resin and the polystyrene resin may be a once melt-kneaded pellet and / or a pulverized one thereof. It may be a mixture obtained by mixing the system resin without melt-kneading. When a mixture of a polyphenylene ether resin and a polystyrene resin is used, when the polyphenylene ether resin and the polystyrene resin are supplied to the mixing device, they may be supplied separately and mixed by the mixing device.

  The content of each of the polyphenylene ether resin and the polystyrene resin is preferably 10 to 90% by mass and 90 to 10% by mass, respectively, more preferably 15 to 85% by mass and 85 to 15% by mass, respectively. More preferably, they are 20-80 mass% and 80-20 mass%, respectively. When the polyphenylene ether resin is less than 10% by mass, the heat resistance is lowered, and when it exceeds 90% by mass, the workability tends to be inferior.

The average particle size of the mixture of the polyphenylene ether resin and the polystyrene resin is preferably 0.1 mm to 6.0 mm, more preferably 0.2 to 5.0 mm, and particularly preferably 0.3 to 4 mm. 0.0 mm. An arithmetic calculation of the average particle diameter of the polyphenylene ether resin and the average particle diameter of the polystyrene resin may be performed, or the particle diameter of the melt-kneaded pellet (in the case of a pellet, the average value of the length and diameter of the pellet) may be used.
The amount of the polyphenylene ether-based resin is preferably 1.0 part by mass or more, preferably 10 parts by mass or more, with respect to 100 parts by mass of the hydrogenated product of the vinyl aromatic compound-conjugated diene compound copolymer. More preferably, it is 30 parts by mass or more.

From the above, the mixture of the present invention is an oil (B) with respect to 100 parts by mass of the hydrogenated vinyl aromatic compound-conjugated diene compound copolymer (A) having an average particle size of less than 1 mm and the component (A). 30 to 300 parts by mass and 100 parts by mass of the component (A) are mixed with 1.0 part by mass or more of the incompatible resin (C), so there is no stickiness and excellent long-term storage In addition, when the mixture is melt-kneaded, a stable melt-kneading operation can be performed, and a resin composition having various physical properties can be produced.
Specifically, since the hydrogenated product has an average particle size of less than 1 mm and the oil is mixed in the above amount, the oil easily and sufficiently permeates the hydrogenated product. Moreover, the long-term storage property of a mixture can be improved by including incompatible resin with the said oil in a mixture. Specifically, when the hydrogenated product that has sucked in oil has a possibility that the particles adhere to each other and become a lump when stored for a long time, the oil and the incompatible resin are included in the lump. Therefore, long-term storage stability is improved, and a stable melt-kneading operation can be performed when the mixture is melt-kneaded.
In addition, since the hydrogenated product contains oil, the melting temperature thereof is lowered, and therefore, thermal degradation of the hydrogenated product during melt kneading can be prevented. In particular, the high molecular weight hydrogenated product is effective because the melting temperature tends to increase.
Furthermore, since the resin composition obtained from the said mixture contains oil, it can improve a physical property.

  The mixture obtained by the present invention can be used after being melt-kneaded with a thermoplastic resin. The type of the thermoplastic resin is not limited to the following, but for example, a known resin can also be used. Preferable specific examples include polyphenylene ether resins (for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-dimethylphenylene ether-co-2,3,6-trimethylphenylene ether). ), Etc.), melt-kneaded product of polyphenylene ether resin and polystyrene resin, polycarbonate resin, polyolefin resin (high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, ethylene / propylene copolymer) ), Polystyrene resin (polystyrene, high impact polystyrene, acrylonitrile / styrene copolymer, syndiotactic polystyrene, acrylonitrile / butadiene / styrene copolymer, etc.), polyester resin (polybutylene, etc.) Terephthalate, polyethylene terephthalate, etc.), styrene / butadiene block copolymer, hydrogenated styrene / butadiene block copolymer, hydrogenated styrene / isoprene block copolymer, homopolyoxymethylene, copolymer polyoxymethylene, polyphenylene sulfonide, polyamide Resin (for example, polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 11, polyamide 12, polyamide 6,10, polyamide 6,12, polyamide 6 / 6,6, polyamide 6 / 6,12, polyamide MXD) (M-xylylenediamine), 6, polyamide 6, T, polyamide 9, T, polyamide 6, I, polyamide 6/6, T, polyamide 6/6, I, polyamide 6,6 / 6, T, polyamide 6 , 6/6, I, polyamide 6/6 T / 6, I, polyamide 6,6 / 6, T / 6, I, polyamide 6/12/6, T, polyamide 6,6 / 12/6, T, polyamide 6/12/6, I, polyamide 6 , 6/12/6, etc.), polyamideimide, polyarylate, polyarylsulfone, polyethersulfone, polyetherimide, polytetrafluoroethylene, polyetherketone, blend of polyphenylene ether and alkenyl resin, polyolefin resin, etc. Is mentioned. These may be used individually by 1 type and may use 2 or more types together.

(Other materials)
In the present invention, an additive can be arbitrarily used. Examples of such an additive include, but are not limited to, a powder filler dispersant (ethylene bisamide, calcium stearate, zinc stearate). , Stearic acid), functional group imparting agents (maleic acid, fumaric acid, itaconic acid, maleic anhydride, malic acid, citric acid), various colorants, coloring additives (such as titanium oxide), UV absorbers, antistatic agents , Stabilizers (zinc oxide, zinc sulfide, phosphorus stabilizers, sulfur stabilizers, hindered phenol stabilizers), flame retardants (phosphate ester flame retardants, halogen flame retardants), flame retardant aids (trioxides) Antimony), a monomer having an unsaturated bond with a peroxide (maleic acid, fumaric acid, itaconic acid, maleic anhydride, malic acid, citric acid, etc.) may be used alone. It may be used in combination of two or more. The additive may be added to the mixture or may be added when the mixture is melt-kneaded.

  In the present invention, an inorganic filler can be arbitrarily used. Examples of the inorganic filler include, but are not limited to, heavy calcium carbonate, colloidal calcium carbonate, soft calcium carbonate, silica, kaolin, Clay, barium sulfate, zinc oxide, alumina, magnesium hydroxide, talc, mica, glass flake, hydrotalcite, acicular filler (wollastonite, potassium titanate, basic magnesium sulfate, seplite, zonotlite, aluminum borate) , Glass beads, silica beads, alumina beads, carbon beads, glass balloons, carbon, magnetic fillers, piezoelectric / pyroelectric fillers, slidable fillers, fillers for sealing materials, UV absorbing fillers, damping fillers, conductive fillers (Ketjen Black, Acetile Black), glass fiber, carbon fiber, metal fiber and the like. These may be used individually by 1 type and may use 2 or more types together. The inorganic filler may be added to the mixture, or may be added when the mixture is melt-kneaded.

[Mixing method]
The mixing apparatus that can be used in the mixing method of the present invention uses any one of a mixing apparatus with a vertical stirring blade, a mixing apparatus with a horizontal stirring blade, a vertical tank rotation mixing apparatus, and a horizontal rotation mixing apparatus. Is preferred. The mixing device preferably has a stirring speed of 20 to 4000 rpm. Further, in order to increase the stirring efficiency, a baffle plate is preferably provided in addition to the stirring blade.

  As an example of a mixing apparatus, a mixing apparatus with a vertical stirring blade includes a super mixer (rotation number: 300 to 4000 rpm) manufactured by Kawata Corporation, whose outline is shown in FIG. Specifically, as shown in FIG. 1, the mixing device includes a mixing device body 1 with a vertical stirring blade (hereinafter also referred to as “device body portion 1”), an upper lid 2 of the device body portion 1, and a device. A power motor 3 attached to the main body 1, a discharge port 4 for discharging the mixture attached to the apparatus main body 1, and a stirring blade rotating by the power motor 3 in the apparatus main body 1 An upper blade 5 and a lower blade 6 as a stirring blade are provided, and a baffle plate 7 is optionally provided in the apparatus main body 1. The upper wing 5 and the lower wing 6 can perform strong mixing. Moreover, when the baffle plate 7 is provided, it is preferable that the amount of the raw material to be mixed exceeds the lower end of the baffle plate 7 in order to increase the stirring efficiency.

The mixing method of the present invention will be described below with reference to FIG.
1st Embodiment which concerns on the mixing method of this invention supplies and mixes said (A) component, said (B) component, and said (C) component in order to a mixing apparatus, respectively.
Specifically, when a mixing device with a vertical stirring blade is used as the mixing device, first, the power motor 3 is stopped, the discharge port 4 is closed, the upper lid 2 of the device main body 1 is opened, and the above ( The component A), the component (B), and the component (C) are sequentially supplied, then the upper lid 2 is closed, the power motor 3 is started, and mixed at a predetermined rotational speed. After a predetermined mixing time has elapsed, the discharge port 4 is opened, and the mixture is discharged with the power motor 3 activated.

In the second embodiment according to the mixing method of the present invention, the component (A) and the component (B) are sequentially supplied to the mixing device and mixed, and then the mixing device (C) is mixed. Feed ingredients and mix further.
Specifically, when a mixing device with a vertical stirring blade is used as the mixing device, first, the power motor 3 is stopped, the discharge port 4 is closed, the upper lid 2 of the device main body 1 is opened, and the above ( The component A) and the component (B) are sequentially supplied, then the upper lid 2 is closed, the power motor 3 is started, and mixed at a predetermined rotational speed. After a predetermined mixing time has elapsed, the power motor 3 is temporarily stopped and the upper cover 2 is opened, then the above (C) is supplied, the upper cover 2 is closed, the power motor 3 is started, and a predetermined rotational speed Mix with. After a predetermined mixing time has elapsed, the discharge port 4 is opened, and the mixture is discharged with the power motor 3 activated.

3rd Embodiment which concerns on the mixing method of this invention is 60-80 mass parts among 100 mass parts of said (A) component, the said (B) component, and the remainder of the said (A) component to a mixing apparatus. Each is supplied and mixed in order, and then the component (C) is supplied to the mixing device and further mixed.
Specifically, when a mixing device with a vertical stirring blade is used as the mixing device, first, the power motor 3 is stopped, the discharge port 4 is closed, the upper lid 2 of the device main body 1 is opened, and the above ( A) 60 to 80 parts by mass out of 100 parts by mass of the component, the component (B), and the remaining part of the component (A) are sequentially supplied, then the upper lid 2 is closed and the power motor 3 is started. And mixing at a predetermined rotational speed. After a predetermined mixing time has elapsed, the power motor 3 is temporarily stopped and the upper cover 2 is opened, then the above (C) is supplied, the upper cover 2 is closed, the power motor 3 is started, and a predetermined rotational speed Mix with. After a predetermined mixing time has elapsed, the discharge port 4 is opened, and the mixture is discharged with the power motor 3 activated.

In the fourth embodiment according to the mixing method of the present invention, the component (A) is supplied to a mixing device, and the component (B) is supplied and mixed while stirring the component (A). The component (C) is supplied and further mixed.
Specifically, when a mixing device with a vertical stirring blade is used as the mixing device, first, the power motor 3 is stopped, the discharge port 4 is closed, the upper lid 2 of the device main body 1 is opened, and the above ( A) The component is supplied, and then the upper lid 2 is closed, the power motor 3 is started, and stirring is performed at a predetermined rotational speed. Then, while stirring the component (A), the component (B) is supplied from the opening (not shown) of the upper lid 2 of the mixing device 1 and mixed. After the supply of the component (B) is completed, the opening is closed, and after a predetermined mixing time has elapsed, the power motor 3 is temporarily stopped and the upper lid 2 is opened, and then the (C) is supplied, 2 is closed, the power motor 3 is started, and mixing is performed at a predetermined rotational speed. After a predetermined mixing time has elapsed, the discharge port 4 is opened, and the mixture is discharged with the power motor 3 activated.

In the fifth embodiment of the mixing method of the present invention, the oil of the component (B) is supplied while being dispersed by a disperser attached to the mixing device in the first to fourth embodiments.
Specifically, when a mixing device with a vertical stirring blade is used as the mixing device, first, the power motor 3 is stopped, the discharge port 4 is closed, the upper lid 2 of the device main body 1 is opened, and the above ( A) The component is supplied, and then the upper lid 2 is closed, the power motor 3 is started, and stirring is performed at a predetermined rotational speed. Then, while stirring the component (A), the component (B) is supplied and mixed while being dispersed by a disperser (not shown) attached to a mixing device. After the supply of the component (B) is completed, the opening is closed, and after a predetermined mixing time has elapsed, the power motor 3 is temporarily stopped and the upper lid 2 is opened, and then the (C) is supplied, 2 is closed, the power motor 3 is started, and mixing is performed at a predetermined rotational speed. After a predetermined mixing time has elapsed, the discharge port 4 is opened, and the mixture is discharged with the power motor 3 activated.

  The mixing device having the disperser used in the fifth embodiment is not limited to the following, but examples include a spiral pin mixer and a pro shear mixer manufactured by Taiheiyo Kiko Co., Ltd. The pro-shear mixer is a mixing device with a horizontal stirring blade, and can continuously supply the component (B) by the disperser, and the components (A) and (B) can be mixed in a small size. It is an apparatus capable of mixing at a high speed (1500 to 4000 rpm) with a blade or mixing at a low speed (10 to 100 rpm) with a large stirring blade. When the component (B) is continuously supplied while being dispersed by the disperser, for example, it is preferable to use this mixing apparatus.

  In the mixing method of the present invention, the stirring rotation speed and mixing time for mixing the components (A) to (C) are determined after the oil of the component (B) has sufficiently penetrated into the component (A) and mixed. It is possible to adjust so that the oil of component (B) does not bleed out from the mixture. In the above mixing method, when the rotation speed is constant, the mixing time that does not bleed out can be set to a short mixing time from the mixing method of the first embodiment to the mixing method of the fourth embodiment. Furthermore, mixing time can be further shortened by supplying (B) component, disperse | distributing with a disperser like 5th Embodiment.

  In addition, in the mixing method of 2nd Embodiment-5th Embodiment, it is preferable to perform mixing with (A) component and the said (B) component until it does not ooze out substantially by an oil bleed-out test. “The oil bleed-out test does not substantially ooze” means that, in the oil bleed-out test, a mixture of 15 g of the component (A) and the component (B) is placed on a white water-absorbing paper and pressed. It means that pressing is performed for 1 minute under conditions of room temperature (5 to 40 ° C.) and pressure of 5 MPa using a molding machine, and oil does not soak into the water-absorbing paper after pressurization. When the temperature at the time of pressing is increased to about 70 ° C., the oil of component (B) attached to the surface of the hydrogenated product of the vinyl aromatic compound-conjugated diene compound copolymer of component (A) is added to the hydrogenated product. Since it is absorbed into the object, room temperature conditions are required.

[Method for producing thermoplastic resin]
Examples of the melt kneader that melts and kneads the mixture that can be used in the method for producing the thermoplastic resin of the present invention include, for example, a batch mixer, a continuous mixer, and an extruder, and in particular, a single screw extruder and a twin screw. An extruder is preferred. In the case of a single screw extruder, it is preferable to use a supply device for the mixture and a supply device for supplying other resins and additives.

  As a single screw extruder that can be used in the method for producing the thermoplastic resin of the present invention, a screwer having a screw that drives back and forth while a Bush screw rotates, a kneading screw (unimelt screw, DSM screw, And an extruder provided with a dull image screw and a pin-type screw).

  Examples of the twin screw extruder that can be used in the method for producing the thermoplastic resin of the present invention include a non-meshing type counter-rotating extruder, a meshing type counter-rotating extruder, and a meshing type co-rotating twin-screw extruder. It is done. Here, the mesh type co-rotating twin screw extruder is Coperion's ASK Megacon series, Megaplus series, MC18 series, Toshiba Machine's TEM BS series, SS series, SX series, Nippon Steel Works' TEX α Series, α2 series, α3 series. In particular, the ZSK MC18 series with high torque, the TEM SX series from Toshiba Machine, and the TEX α3 series from Nippon Steel Works are particularly preferable because the screw rotation speed can be set low and the resin temperature is low and the productivity is high.

A twin-screw extruder that can be used in the method for producing a thermoplastic resin of the present invention will be described with reference to FIG.
This twin-screw extruder can use, for example, Coperion ZSK-40Mc, but as shown in the figure, 12 barrels (extruder length L = 48 × screw diameter) from the first barrel 8a to the twelfth barrel 8l. ), And a drive motor 10 such as an inverter motor or a DC motor that drives the extruder 9, and a speed reducer 11 that reduces the rotational speed of the drive motor 10. A first supply port 12 is connected to the first barrel 8a of the twin-screw extruder 9, a second supply port 13 is connected to the fifth barrel 8e, and a vacuum vent 14 is connected to the eleventh barrel 8k. A first weight type feeder 15 and a second weight type feeder 16 are connected to the first supply port 12, and a third weight type feeder 17 is connected to the second supply port 13. The extruder 9 is provided with a die head 18 connected to the twelfth barrel 8 l on the downstream side and a die plate 19 connected to the downstream side of the die head 18. Although not shown, the die head 18 is provided with a breaker plate for filtering the molten resin and a metal screen. Five to 200 orifices having a diameter D = 1 to 6 mm and a length L = 1 to 30 mm are attached to the die plate 19 on the downstream side of the die head 18. The number of orifices is determined by the amount of extrusion, and can be set to 5 to 50 kg / hr per orifice. In addition, the screw rotation speed of this extruder 9 can be used in the range of 100-1500 rpm.

In addition, when supplying the said mixture using the twin-screw extruder 9, it is provided with the 1st supply port 12 of the uppermost stream of the extruder 9, the 2nd supply port 13, or additional using a single supply machine. It is possible to supply from a third supply port (not shown) on the downstream side of the second supply port 13, or it may be divided and supplied.
When the thermoplastic resin is supplied, it may be supplied from the first supply port 12, the second supply port 13, or the third supply port of the extruder 9, using a single supply device. . Further, it may be divided and supplied.
When the reinforcing agent is supplied, it is supplied from the uppermost first supply port 12 of the extruder 9, the second supply port 13, or the third supply port (not shown) using a single supply machine. It doesn't matter. Further, it may be divided and supplied.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited at all by the following Examples.

  Evaluation methods and raw materials used in each example and comparative example are shown below.

〔Evaluation method〕
(Oil bleed out test)
Using a press molding machine with a room temperature of 25 ° C. and a maximum pressure of 10 MPa, a 0.5 mm thick aluminum sheet, a white absorbent paper with a diameter of 15 cm, and a sample (mixture) 15 g are placed in this order on a 3 mm thick iron plate. An aluminum sheet having a thickness of 0.5 mm and an iron plate having a thickness of 3 mm were placed thereon. Then, the pressure of the press molding machine was set to 5 MPa, and pressing was performed for 1 minute. After the pressing was completed, the pressure was released, the sample was taken out, and the area of the oil soaked in the water-absorbing paper was measured. In the measurement, black paper was placed on the back of the water-absorbing paper, and visual judgment and measurement of the maximum diameter were performed.
The results of the bleed-out test were evaluated as follows.
1: The bleed-out oil is hardly visible.
2: Maximum diameter of bleed-out oil point is 0.5 mm or less 3: Maximum diameter of bleed-out oil point is 1.0 mm or less 4: Maximum diameter of bleed-out oil point is 2.0 mm or less 5: The maximum diameter of the bleed-out oil point is 4.0 mm or less 6: The maximum diameter of the bleed-out oil point is 8.0 mm or less 7: The maximum diameter of the bleed-out oil point is 16.0 mm or less 8: The bleed-out The maximum diameter of the obtained oil is 16 mm or more. The sticky feeling whether the mixture is sticky or not is good with the above evaluation results of 1 to 3, and the evaluation result is 4 or more, and the sticky feeling is strong.
Further, in the present specification, “substantially does not bleed” means that the evaluation result of the oil bleed out test is 3 or less, that is, the maximum diameter of the bleed out oil point is 1.0 mm or less. means.

(Just after mixing and long-term storage stability test)
13 kg of sample (mixture) is put in a 25 kg paper bag, a 50 kg load is added on it, and immediately after mixing (within 10 minutes) and after 48 hours, the paper bag is opened to generate a lump of sample (mixture) The situation was evaluated. Furthermore, when a lump was generated, the upper side of the paper bag was held, and then the paper bag was lifted and dropped to the floor 10 times to observe the lump state. Next, this sample (mixture) was put into a CE-W4 hopper manufactured by Kubota, Ltd., a weight-type feeder, and a weight-type feeder discharge port under the condition of an extrusion rate of 50 kg / h while turning the agitator inside the hopper at 200 rpm. The stability of the polymer and the appearance of lumps remaining in the hopper were visually evaluated.
The results of the mixing and long-term storage test were evaluated as follows.
1: There is no lump of mixture in the paper bag. Supply stability at the outlet of the heavy feeder is good, and there is no lump inside the hopper.
2: There is a lump of the mixture in the paper bag, but the lump breaks and becomes smaller by dropping the paper bag to the floor 10 times. Supply stability at the outlet of the heavy feeder is good, and there is no lump inside the hopper.
3: There is a lump of the mixture in the paper bag, but the lump becomes small by dropping the paper bag to the floor 10 times. The supply stability at the outlet of the heavy feeder is good, but there is a small lump inside the hopper.
4: There is a lump of mixture in the paper bag, but the lump is broken by dropping the paper bag to the floor 10 times. The supply stability at the outlet of the heavy feeder is good, but there is a large lump inside the hopper.
5. There is a lump of mixture in the paper bag, and even if the paper bag is dropped 10 times on the floor, the lump will crack. At the beginning, the mixture comes out from the outlet of the heavy-weight feeder, but it will not come out. There is a big lump inside the hopper.
6). There is a lump of mixture in the paper bag, and even if the paper bag is dropped 10 times on the floor, the lump does not break. No mixture comes out of the weight feeder outlet. There is a big lump in the hopper.
7). Other: Pellet and powder were classified inside the hopper.
In addition, since the above evaluation results are 1 to 3 and the storage stability is good, the supply stability when the mixture is supplied from the feeder to the extruder is good, and no large lump remains in the hopper. Production is possible. When a mixture having the above-described storage stability of 4 to 7 is used, a supply trouble may occur, and thus production is impossible.

(Izod test and tensile elongation test)
Pellets produced by an extruder from the mixture produced in each example and comparative example were molded into test pieces with an injection molding machine (IS-80AM injection molding machine manufactured by Toshiba Machine). The cylinder temperature at that time was 240 to 290 ° C., and the mold temperature was 60 to 90 ° C. About the obtained molded object, Izod impact strength and tensile elongation were measured. Izod impact strength was evaluated according to ASTM D256 as a 1/8 inch notched short rail. Tensile elongation was evaluated with a 1/8 inch dumbbell according to ASTM D658.

〔material〕
(Hydrogenated product of vinyl aromatic compound-conjugated diene compound copolymer (A))
A1: SEBS (G1651 manufactured by Kraton Polymer Japan Company) having a particle size of 250 μm, a weight average molecular weight of 200,000, a styrene part content of 30% by mass, and a conjugated diene compound hydrogenation content of 70% by mass was used.
A2: SEBS (H1387 manufactured by Asahi Kasei Chemicals Corporation) having an average particle diameter of 270 μm, a weight average molecular weight of 280,000, a styrene part content of 30% by mass, and a hydrogenation content of a conjugated diene compound of 70% by mass was used. .
A3: SEBS (6150, manufactured by TSRC Corporation of China) having an average particle size of 260 μm, a weight average molecular weight of 280,000, a styrene part content of 30% by mass, and a hydrogenation content of a conjugated diene compound of 70% by mass was used. .
A4: SEBS (H-1051 manufactured by Asahi Kasei Chemicals Corporation) having a particle size (diameter) of 3 mm (pellet) was used.
A5: SEBS (H1272 from Asahi Kasei Chemicals Corporation oil exhibition) containing oil and having a particle diameter (diameter) of 3 mm (pellet) was used.

(Oil (B))
B1: A paraffinic oil having a weight average molecular weight of 600 (Kaneda High Coal K-350) was used.
B2: A mixture of paraffinic oil and naphthenic oil having a weight average molecular weight of 1000 (PW380 manufactured by Idemitsu Kosan Co., Ltd.) was used.
B3: Paraffinic oil having a weight average molecular weight of 450 (PW90 manufactured by Idemitsu Kosan Co., Ltd.) was used.

(Resin incompatible with oil (C))
C1: Polyphenylene ether having a reduced viscosity of 0.51 and an average particle size of 600 μm was used.
C2: A pellet having a length of 3 mm and a diameter of 3 mm of 80 parts by mass of polyphenylene ether and 20 parts by mass of polystyrene was used.
C3: 80 parts by mass of polyphenylene ether having a reduced viscosity of 0.51 and an average particle size of 600 μm and 20 parts by mass of pellets having a length of 3 mm and a diameter of 3 mm (PS6, polystyrene 685) were mixed (dry blend) Used).
C4: 80 kg by weight of polyphenylene ether and 20 parts by weight of polystyrene (polystyrene 685 manufactured by PS Japan) 3 kg long and 3 kg in diameter 60 kg pellets (5000 parts by weight), and 3 mm in length and 3 mm in diameter HIPS (CT60 manufactured by Petrochemical Co., Ltd., Malaysia) 38 kg (5000 parts by mass) was used.
C5: Polyphenylene ether having a reduced viscosity of 0.41 and an average particle size of 520 μm was used.

(Other materials)
D1: Petroleum resin (Imabe P-140 manufactured by Idemitsu Petrochemical Co., Ltd.) was used.

[Examples and Comparative Examples]
Example 1
Using the mixing device with a vertical stirring blade shown in FIG. 1 (Super mixer SMG-100 manufactured by Kawata Co., Ltd., volume 100 L, with baffle plate, lower wing: BL type standard, upper wing: SI type), the conditions were changed. The components (A) to (C) were mixed to prepare a mixture. Supply 12 kg (100 parts by mass) of (A1) to the mixing device with vertical stirring blades, then supply 6.0 kg (50 parts by mass) of (B1), and set the rotation speed of the super mixer (mixing device). Mix at 485 rpm for 4 minutes. Then, 15 g of the sample was taken from the mixer, and after performing an oil bleed out test, the sample was returned, 9 kg (75 parts by mass) of (C1) was supplied, and mixed for 1 minute. This mixture was extracted from the outlet and packed in 13 kg in a 25 kg paper bag.
The evaluation results for the above mixture were as follows.
・ Bleed out test: 1
・ Storability immediately after mixing: 1
・ Long-term storage: 2
Next, the above mixture was melt-kneaded. 2 is a twin screw extruder as shown in FIG. 2 (ZSK-40Mc manufactured by Coperion, barrel number 12, first supply port for the first barrel, second supply port for the fifth barrel, and vacuum vent for the eleventh barrel. ), 225 parts by mass of the mixture (supplied while turning the agitator) charged into the raw material hopper of the first weight feeder (CE-W-2 manufactured by Kubota Corporation), and the second weight feeder (manufactured by Kubota Corporation) The melt-kneaded material 4906 parts by mass of 80 parts by mass of polyphenylene ether having a reduced viscosity of 0.51, an average particle size of 600 μm and 20 parts by mass of polystyrene (polystyrene 685 manufactured by PS Japan) charged into a raw material hopper of CE-W4) It supplied from 1 supply port. And after blending 19 parts by mass of polystyrene (polystyrene 685 manufactured by PS Japan) and 5000 parts by mass of HIPS (CT60 manufactured by Petrochemical Co. of Malaysia), a third weight feeder (CE-W4 manufactured by Kubota Corporation) Was supplied to the raw material hopper, and supplied to the extruder from the second supply port. The barrel temperature was set at 280 ° C., and the operation was performed at a screw rotation speed of 400 rpm and an extrusion rate of 200 kg / hr.
As a result of the melt kneading of the above mixture, the extrusion stability was good, and the physical properties of the obtained composition were good.

(Comparative Example 1)
The same operation as in Example 1 was carried out except that (C1) in Example 1 was not used. The evaluation results were as follows.
・ Bleed out test: 1
・ Short storage immediately after mixing: 6
・ Long-term storage: 6
Moreover, the said mixture blocked with the raw material hopper of CE-W2, and the supply to the extruder was impossible.

(Comparative Example 2)
The same operation as in Example 1 was performed except that (A1) in Example 1 was changed to (A4). The evaluation results were as follows.
・ Bleed out test: 8
・ Storability immediately after mixing: 6
・ Long-term storage: 6
The extrusion stability was the same as that of Comparative Example 1.

(Comparative Example 3)
(A1) in Example 1 was changed to (A5), and the same procedure as in Example 1 was performed except that no oil was used. The evaluation results were as follows.
・ Bleed out test: 1
・ Storability immediately after mixing: 7
・ Long-term storage: 7
Although the extrusion stability was good, the Charpy value increased with the passage of time, the DTUL (deflection temperature under load) decreased, and the MFR (melt flow rate) increased.

(Comparative Example 4)
The same operation as in Example 1 was performed except that (A1) in Example 1 was changed to (A5). The evaluation results were as follows.
・ Bleed out test: 8
・ Storability immediately after mixing: 6
・ Long-term storage: 6
Moreover, the said mixture blocked with the raw material hopper of CE-W2, and the supply to the extruder was impossible.

(Comparative Example 5)
The same procedure as in Example 1 was performed except that (C1) in Example 1 was changed to (D1).
When petroleum resin was used, oil entered the petroleum resin and the mixture of SEBS and oil was in close contact, causing blocking.
The evaluation results for the mixture of Comparative Example 5 were as follows.
・ Bleed out test: 1
・ Storability immediately after mixing: 6
・ Long-term storage: 6
Moreover, the said mixture blocked with the raw material hopper of CE-W2, and the supply to the extruder was impossible.

(Example 2)
The same procedure as in Example 1 was performed except that (C1) in Example 1 was (C2). The evaluation results were as follows.
・ Bleed out test: 1
・ Storability immediately after mixing: 1
・ Long-term storage: 1
Also, the extrusion stability was good, and the physical properties of the obtained composition were good.

(Example 3)
The same procedure as in Example 1 was performed except that (C1) in Example 1 was changed to (C3). The evaluation results were as follows.
・ Bleed out test: 1
・ Storability immediately after mixing: 1
・ Long-term storage: 1
Also, the extrusion stability was good, and the physical properties of the obtained composition were good.

Example 4
(A1) of Example 1 is 1.3 kg (100 parts by mass), (B1) is 0.7 kg (50 parts by mass), (C1) of Example 1 is (C4), and mixing is performed by a tumbler. (Plattec Co., Ltd. SKD-200) was used in the same manner as in Example 1 except that the rotation was performed at 22 rpm for 30 minutes. The evaluation results were as follows.
・ Bleed-out test: 3
・ Storability immediately after mixing: 1
・ Long-term storage: 1
Moreover, it was the same except having supplied the said mixture to the 2nd weight type feeder. As a result of the melt kneading of the mixture, the extrusion stability was good, and the physical properties of the obtained composition were good.

(Example 5)
The same procedure as in Example 1 was performed except that (C1) in Example 1 was changed to (C5). The evaluation results were as follows.
・ Bleed out test: 1
・ Storability immediately after mixing: 1
・ Long-term storage: 2
Also, the extrusion stability was good, and the physical properties of the obtained composition were good.

(Example 6)
The same procedure as in Example 1 was performed except that the amount of (B1) in Example 1 was changed to 20 parts by mass. The evaluation results were as follows.
・ Bleed out test: 1
・ Storability immediately after mixing: 1
・ Long-term storage: 1
Also, the extrusion stability was good, and the physical properties of the obtained composition were good.

(Example 7)
The same procedure as in Example 1 was performed except that the amount of (B1) in Example 1 was changed to 200 parts by mass. The evaluation results were as follows.
・ Bleedout test: 2
・ Storability immediately after mixing: 1
・ Long-term storage: 3
Also, the extrusion stability was good, and the physical properties of the obtained composition were good.

(Comparative Example 6)
The same operation as in Example 1 was performed except that the amount of (B1) in Example 1 was changed to 350 parts by mass. The evaluation results were as follows.
・ Bleed out test: 8
・ Storability immediately after mixing: 6
・ Long-term storage: 6
Moreover, the supply stability of the mixture was poor, and extrusion was not possible.

(Example 8)
The same procedure as in Example 1 was performed except that the amount of (C1) in Example 1 was changed to 20 parts by mass. The evaluation results were as follows.
・ Bleed out test: 1
・ Storability immediately after mixing: 2
・ Long-term storage: 3
Also, the extrusion stability was good, and the physical properties of the obtained composition were good.

Example 9
The same procedure as in Example 1 was performed except that the mixing time in Example 1 was changed from 4 minutes to 2 minutes. The evaluation results were as follows.
・ Bleedout test: 2
・ Storability immediately after mixing: 2
・ Long-term storage: 3
Also, the extrusion stability was good, and the physical properties of the obtained composition were good.

(Example 10)
The same operation as in Example 1 was performed except that the mixing time of Example 1 was changed from 4 minutes to 1 minute. The evaluation results were as follows.
・ Bleed-out test: 3
・ Storability immediately after mixing: 3
・ Long-term storage: 4
Also, the extrusion stability was good, and the physical properties of the obtained composition were good.

(Example 11)
The same procedure as in Example 1 was performed except that (A1) in Example 1 was changed to (A2). The evaluation results were as follows.
・ Bleed out test: 1
・ Storability immediately after mixing: 1
・ Long-term storage: 2
Also, the extrusion stability was good, and the physical properties of the obtained composition were good.

(Example 12)
The same procedure as in Example 1 was performed except that (A1) in Example 1 was changed to (A3). The evaluation results were as follows.
・ Bleed out test: 1
・ Storability immediately after mixing: 1
・ Long-term storage: 2
Also, the extrusion stability was good, and the physical properties of the obtained composition were good.

(Example 13)
The same procedure as in Example 1 was performed except that (B1) in Example 1 was changed to (B2). The evaluation results were as follows.
・ Bleed out test: 1
・ Storability immediately after mixing: 1
・ Long-term storage: 2
Also, the extrusion stability was good, and the physical properties of the obtained composition were good.

(Example 14)
The same operation as in Example 1 was performed except that (B1) in Example 1 was changed to (B3). The evaluation results were as follows.
・ Bleed out test: 1
・ Storability immediately after mixing: 1
・ Long-term storage: 2
Also, the extrusion stability was good, and the physical properties of the obtained composition were good.

(Example 15)
In the supply to the mixing apparatus of (A1) and (B1) of Example 1, 70 parts by mass of (A1) is supplied first, then (B1) is supplied, and the remaining of (A1) It implemented similarly to Example 1 except having changed into the method of supplying 30 mass parts. The evaluation results were as follows.
・ Bleed out test: 1
・ Storability immediately after mixing: 1
・ Long-term storage: 2
Also, the extrusion stability was good, and the physical properties of the obtained composition were good.

(Example 16)
The supply of (B1) in Example 1 was changed to the method of supplying (A1) with stirring, and the same procedure as in Example 1 was carried out except that the mixing time was changed from 4 minutes to 2 minutes. Specifically, place the tank containing (B1) on the lid of the supermixer, attach a pipe to the barrel at the bottom of the tank, and enter the supermixer from the top of the pipe, stirring (A1). While (B1) was opened, (B1) was supplied.
The evaluation results for the mixture of Example 16 were as follows.
・ Bleed out test: 1
・ Storability immediately after mixing: 1
・ Long-term storage: 2
Also, the extrusion stability was good, and the physical properties of the obtained composition were good.

(Example 17)
The same operation as in Example 16 was performed except that a distributor having six 1 mm holes was attached to the tip of the oil pipe of Example 16. The evaluation results were as follows.
・ Bleed out test: 1
・ Storability immediately after mixing: 1
・ Long-term storage: 2
Also, the extrusion stability was good, and the physical properties of the obtained composition were good.

  Tables 1 and 2 show the compositions of the mixtures of the above Examples and Comparative Examples, the mixing methods, and the evaluation results thereof.

  If the mixture of the present invention, the mixing method thereof, and the melt kneading method of the thermoplastic resin composition for melting and kneading the mixture are employed, the mixture has no stickiness and excellent long-term storage, and the melt kneading operation of the mixture is It can be carried out stably, and it can be seen that the obtained resin composition has various physical properties.

The mixture of the present invention, the mixing method thereof, and the resin composition obtained from the melt-kneading method using the mixture are OA materials (printers, copying machines, etc.), electronic materials, optical materials, battery case materials, battery cell materials. It is suitable for application fields such as film and sheet.

1: Mixer body with vertical stirring blades 2: Upper lid 3: Power motor 4: Discharge port 5: Upper blade 6: Lower blade 7: Baffle plates 8a to 8l: 1st barrel to 12th barrel 9: Twin screw extruder 10: drive motor 11: speed reducer 12: first supply port 13: second supply port 14: vacuum vent 15: first weight feeder 16: second weight feeder 17: third weight feeder 18: die head 19: Die plate

Claims (23)

A hydrogenated vinyl aromatic compound-conjugated diene compound copolymer (A) having an average particle size of less than 1 mm;
30 to 300 parts by mass of oil (B) with respect to 100 parts by mass of the component (A),
A mixture obtained by mixing 1.0 part by mass or more of the oil and the incompatible resin (C) with respect to 100 parts by mass of the component (A).   The mixture according to claim 1, wherein the resin that is incompatible with the oil as the component (C) is a polyphenylene ether resin.   The mixture according to claim 1 or 2, wherein the vinyl aromatic compound in the component (A) is styrene.   The mixture according to any one of claims 1 to 3, wherein the conjugated diene compound in the component (A) is butadiene.   The mixture according to any one of claims 1 to 3, wherein the conjugated diene compound in the component (A) is isoprene.   The mixture according to any one of claims 1 to 5, wherein the vinyl aromatic compound-conjugated diene compound copolymer is a block copolymer.   The vinyl aromatic compound-conjugated diene compound copolymer of the component (A) contains 5 to 95% by mass of the vinyl aromatic compound and 95 to 5% by mass of the conjugated diene compound. A mixture according to claim 1.   The structure of a hydrogenated product of the vinyl aromatic compound-conjugated diene compound copolymer is a hydrogenated product of a vinyl aromatic compound-conjugated diene compound copolymer, according to any one of claims 1 to 7. Mixture of.   The structure of the hydrogenated product of the vinyl aromatic compound-conjugated diene compound copolymer is a hydrogenated product of vinyl aromatic compound-conjugated diene compound copolymer-vinyl aromatic compound. A mixture according to claim 1.   The mixture according to any one of claims 1 to 9, wherein a weight average molecular weight of the hydrogenated product of the vinyl aromatic compound-conjugated diene compound copolymer is 50,000 to 400,000.   The mixture according to any one of claims 1 to 10, wherein the oil is paraffinic oil and / or naphthenic oil.   The mixture according to any one of claims 1 to 11, wherein the oil has a weight average molecular weight of 400 to 3,000.   13. The resin according to claim 1, wherein the resin that is incompatible with the oil as the component (C) is a polyphenylene ether resin having an average particle size in the range of 0.05 to 1.0 mm. blend. The resin that is incompatible with the oil of the component (C) is a polyphenylene ether resin having an average particle size of 0.1 to 6.0 mm,
The mixture according to any one of claims 1 to 12, wherein the polyphenylene ether resin of the component (C) contains 10 to 90% by mass of a polyphenylene ether resin and 90 to 10% by mass of a polystyrene resin. .   The method for mixing a mixture according to any one of claims 1 to 14, wherein the component (A), the component (B), and the component (C) are sequentially supplied to and mixed with a mixing device. .   The component (A) and the component (B) are sequentially supplied to a mixing device and mixed, and then the component (C) is supplied to the mixing device and further mixed. 15. The method for mixing a mixture according to any one of 14 above.   60 to 80 parts by mass of 100 parts by mass of the component (A), the component (B), and the remainder of the component (A) are sequentially supplied to the mixing device and mixed, and then the mixing device The method for mixing a mixture according to any one of claims 1 to 14, wherein the component (C) is supplied to the mixture and further mixed.   The component (A) is supplied to a mixing device, while the component (A) is stirred, the component (B) is supplied and mixed, and then the component (C) is supplied and further mixed. The mixing method of the mixture of any one of Claims 1-14.   The mixing method according to any one of claims 16 to 18, wherein the mixing of the component (A) and the component (B) is performed until substantially no leaching occurs in an oil bleed out test.   The mixing method according to any one of claims 15 to 19, wherein the oil of the component (B) is supplied while being dispersed by a disperser attached to the mixing device.   The said mixing apparatus consists of any one of the mixing apparatus with a vertical stirring blade, the mixing apparatus with a horizontal stirring blade, a vertical tank rotation type mixing apparatus, and a horizontal rotation type mixing apparatus. The mixing method according to item.   The manufacturing method of a thermoplastic resin composition which melt-kneads the mixture mixed using the mixing method of any one of Claims 15-21 using a melt-kneader with a thermoplastic resin.   The method for producing a thermoplastic resin composition according to claim 22, wherein the melt kneader is one of a single screw extruder and a twin screw extruder.

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