JPH09324084A - Block copolymer resin composition, molded item, and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a block copolymer resin compsn. excellent in clarity, impact resistance, and moldability by compounding a specific vinylarom. hydrocarbon block copolymer with a vinylarom. hydrocarbon polymer and by specifying the ratio of MFRS of these two polymers. SOLUTION: This compsn. comprises 10-90 pts.wt. vinylarom. hydrocarbon block copolymer which is formed a vinylarom. hydrocarbon (e.g. styrene) and a conjugated diene (e.g. 1,3-butadiene) in a wt. ratio of (60/40)-(90/10) and has a block ratio (%) defined by (W/W0 )×100 [wherein W is the wt. of vinylarom. hydrocarbon blocks in the block copolymer; and W0 is the total wt. of the vinylarom. hydrocarbon units] of 25-90% and a number-average mol.wt. of vinylarom. hydrocarbon blocks of pref. 5,000-35,000 and 40,000-200,000 and 90-10 pts.wt. vinylarom. hydrocarbon polymer (e.g. PS), and the ratio of MFRS of these two polymers is (1/5)-(5/1).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin comprising a vinyl aromatic hydrocarbon block copolymer comprising a vinyl aromatic hydrocarbon and a conjugated diene, which is excellent in transparency and impact resistance, and a vinyl aromatic hydrocarbon polymer. The present invention relates to a composition, a molded article and a method for producing the same.

[0002]

2. Description of the Prior Art When a vinyl aromatic hydrocarbon and a conjugated diene are block-copolymerized with an alkyllithium as an initiator in an organic solvent by living anionic polymerization, the weight ratio of the vinyl aromatic hydrocarbon and the conjugated diene and the copolymer. It is known that a vinyl aromatic hydrocarbon block copolymer having various physical properties can be obtained by the structure of. Vinyl aromatic hydrocarbon block copolymer is generally a polymer having excellent impact resistance and transparency, and when the content of conjugated diene in the vinyl aromatic hydrocarbon block copolymer is high, it becomes a thermoplastic elastomer. However, when the content of vinyl aromatic hydrocarbon increases, it shows the characteristics as a thermoplastic. Various manufacturing methods that take advantage of these excellent characteristics are disclosed in Japanese Patent Publication No.
6-19286, Japanese Patent Publication No. 48-4106, etc. Further, in addition to these excellent properties, the compatibility with various vinyl aromatic hydrocarbon polymers is also excellent, so that it is also used as a reinforcing agent. For example, JP-B-45-193.
88, Japanese Patent Publication No. 47-43618, Japanese Patent Publication No. 5
It is disclosed in Japanese Patent Publication No. 1-27701 and the like.

[0003]

However, although these vinyl aromatic hydrocarbon block copolymer resin compositions have relatively good transparency and impact resistance, they do not undergo a sufficient kneading operation. There are problems that desired transparency and impact resistance cannot be obtained, and that the kneading operation requires a great deal of cost.

[0004]

[Means for Solving Problems] Under these circumstances,
The inventors of the present invention have conducted extensive studies on easily obtaining a molded article having excellent transparency and impact resistance. As a result, the content of vinyl aromatic hydrocarbon in the vinyl aromatic hydrocarbon block copolymer and The object is achieved by mixing a vinyl aromatic hydrocarbon block copolymer having a specified block ratio and a vinyl aromatic hydrocarbon polymer such as various styrene resins at a specific MFR ratio and a specific ratio. It was found that the present invention has been completed.

That is, the present invention comprises (I) a vinyl aromatic hydrocarbon and a conjugated diene, and (1) the weight ratio of the vinyl aromatic hydrocarbon and the conjugated diene is 60/40 to 90/1.
0, (2) Block ratio (%) of vinyl aromatic hydrocarbon contained in the vinyl aromatic hydrocarbon block copolymer =
(W / W ₀ ) × 100 is 25 to 90% (where W = weight of vinyl aromatic hydrocarbon block in block copolymer, W ₀ = total weight of vinyl aromatic hydrocarbon in block copolymer) 10 to 90 parts by weight of the vinyl aromatic hydrocarbon block copolymer, and (II) 10 to 90 parts by weight of the vinyl aromatic hydrocarbon polymer, and the MFR of (I) and (II). Ratio is 1/5 to 5
/ 1 block copolymer resin composition [however, the total of (I) and (II) is 100 parts by weight], and a molded product obtained by molding the composition, particularly (I) and (II) above. ) Is simultaneously supplied to a molding machine and molded, and a manufacturing method thereof.

Hereinafter, the present invention will be described in detail. The vinyl aromatic hydrocarbon block copolymer (I) used in the present invention is as follows. Examples of the vinyl aromatic hydrocarbon used in the vinyl aromatic hydrocarbon block copolymer (I) of the present invention include styrene, o-methylstyrene and p.
-Methyl styrene, p-tert-butyl styrene,
There are 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene and the like, but styrene is particularly common.

The conjugated diene used in the vinyl aromatic hydrocarbon block copolymer (I) of the present invention is 1,3-
Butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,
3-pentadiene, 1,3-hexadiene, etc.
Particularly common examples include 1,3-butadiene and isoprene.

The weight ratio derived from the vinyl aromatic hydrocarbon and the conjugated diene constituting the vinyl aromatic hydrocarbon block copolymer (I) of the present invention is 60/40 to 90/10, preferably 70/30. ~ 85/15. When the vinyl aromatic hydrocarbon and the conjugated diene are less than 60/40, the transparency and rigidity of the vinyl aromatic hydrocarbon block copolymer are
If it exceeds 90/10, the impact resistance is lowered, and the physical properties of the block copolymer resin composition are lowered, so that it cannot be put to practical use.

The number average molecular weight of the vinyl aromatic hydrocarbon block copolymer (I) of the present invention is preferably 60,000-5.
00000, more preferably 80,000 to 300
000. When it is less than 60,000, sufficient rigidity and impact resistance of the resin cannot be obtained, and when it is more than 500,000, workability is deteriorated and physical properties of the block copolymer resin composition are deteriorated. Absent.

The vinyl aromatic hydrocarbon polymer block is
It is obtained by polymerizing one or more of the above-mentioned vinyl aromatic hydrocarbons, and a polymer block composed of a single vinyl aromatic hydrocarbon or a copolymer block composed of a plurality of vinyl aromatic hydrocarbons. May be

The block ratio of the vinyl aromatic hydrocarbon contained in the vinyl aromatic hydrocarbon block copolymer of the present invention is 25 to 90% by weight, preferably 50 to 85% by weight. If it is less than 25% by weight, the transparency and rigidity will decrease, and if it exceeds 90% by weight, the impact resistance will decrease. Further, the block rate is required to be in this range in order to maintain good transparency when mixed with the vinyl aromatic hydrocarbon polymer (II) and molded. The block ratio of vinyl aromatic hydrocarbons is as follows: Block ratio (%) = (W / W ₀ ) × 100
(However, W = the weight of the vinyl aromatic hydrocarbon block in the vinyl aromatic hydrocarbon block copolymer, and W ₀ = the total weight of the vinyl aromatic hydrocarbon in the vinyl aromatic hydrocarbon block copolymer. ) Is required. Here, the total weight of vinyl aromatic hydrocarbons in the vinyl aromatic hydrocarbon block copolymer is the weight of all vinyl aromatic hydrocarbons subjected to polymerization, the weight of the vinyl aromatic hydrocarbon block,
The vinyl aromatic hydrocarbon block copolymer is subjected to ozonolysis [Y. TANAKA, et. al. , RUBBER
CHEMISTRY AND TECHNOLOGY,
58, 16 (1985)] In the GPC measurement of the obtained vinyl aromatic hydrocarbon polymer component (using an ultraviolet spectroscopic detector whose wavelength is set to 254 nm as a detector), the molecular weight corresponding to each peak is determined. Obtained from a calibration curve created using standard polystyrene and styrene oligomer,
Those having a number average molecular weight of more than 3000 were quantitatively determined from the peak area.

In the present invention, the number of vinyl aromatic hydrocarbon polymer blocks obtained by subjecting the above vinyl aromatic hydrocarbon block copolymer to ozonolysis is preferably two or more. The number average molecular weight of the vinyl aromatic hydrocarbon polymer block is 5,000 to 35,000.
And 40,000 to 200,000, more preferably 500.
0 to 30000 and 40000 to 150,000, particularly preferably 5000 to 20000 and 40000 to 700
It is desirable that each is included in the range of 00.

Further, the number average molecular weight of these vinyl aromatic hydrocarbon polymer blocks obtained by ozonolysis of the vinyl aromatic hydrocarbon block copolymers described above is 5,000 to 35.
Area (A1) and 40 in GPC in the range of 000
Area of GPC in the range of 000 to 200,000 (A
There is no particular limitation in 2), but A1 / A is preferable.
The area ratio of 2 is 75/25 to 9/91, particularly preferably 6
The range is 6/34 to 17/83. The number average molecular weight of these vinyl aromatic hydrocarbon polymer blocks is 5,000.
If it is not within the range of 35,000 and 40,000 to 200,000, the compatibility with the vinyl aromatic hydrocarbon polymer of the above (II) tends to deteriorate, and in particular, (I) and (II) are simultaneously supplied to the molding machine. There is a tendency for the transparency to be poor when molded by molding.

The structure of the vinyl aromatic hydrocarbon block copolymer (I) can take any form as long as the above requirements are met, but preferred examples include those having the following general formula. To be a. A ₁ -B-A ₂ b. A ₁ -C-B-A ₂ c. _{A 1 -B-A 2 -B-} A 1 d. _{A 2 -B-A 1 -B-} A 2 e. _{A 1 -B-A 1 -B-} A 2 f. _{A 1 -C-B-A 2} -B-A 1 g. _{A 1 -C-B-A 2} -C-B-A 1 h. _{(A 1 -B-A 2 -B} ) n -X i. _{(A 1 -C-B-A} 2 -B) n -X j. _{(A 1 -B-A 2 -B} ) n -X k. _{(A 1 -B-A 1 -B} -A 2 -B) n -X

A ₁ and A ₂ in the above structural formula are vinyl aromatic hydrocarbon polymer blocks, and their number average molecular weight is
And the area ratio thereof can be measured by the above-mentioned ozone decomposition and GPC measurement.

B in the above structural formula is a polymer block composed of a vinyl aromatic hydrocarbon and a conjugated diene. When there are two or more B in the structural formula, the structure (molecular weight, composition distribution, etc.) is It may be the same or different.

In the above structural formula, C is a conjugated diene polymer block, which can be obtained by polymerizing the above-mentioned conjugated diene. However, even if it is a polymer of a single conjugated diene, it is a copolymer of a plurality of conjugated dienes. May be Further, when there are two or more Cs in the structural formula, the molecular weights may be the same or different. When forming block C,
The amount of the conjugated diene added is not limited, but it is preferably 1 to 15% with respect to the total amount of the monomers.

Further, in the above structural formula, X is a residue of a polyfunctional coupling agent or a residue of a polyfunctional organolithium compound used as an initiator, and n is an integer of 2-4.
Examples of the polyfunctional coupling agent used in the present invention include silicon tetrachloride and epoxidized soybean oil.
Examples of the polyfunctional organic lithium compound include hexamethylene dilithium, butadienyl dilithium, and isoprenyl dilithium.

Next, the production of the vinyl aromatic hydrocarbon block copolymer (I) will be described. The vinyl aromatic hydrocarbon block copolymer (I) can be produced by polymerizing a vinyl aromatic hydrocarbon and a monomer of a conjugated diene with an organic lithium compound as an initiator in an organic solvent. As the organic solvent, butane, pentane, hexane, isopentane, heptane, octane, aliphatic hydrocarbons such as isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, alicyclic hydrocarbons such as ethylcyclohexane, or benzene, toluene Aromatic hydrocarbons such as ethylbenzene and xylene can be used.

The organic lithium compound is a compound in which one or more lithium atoms are bonded in the molecule, and examples thereof include ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium and t.
A monofunctional organolithium compound such as ert-butyllithium, the polyfunctional organolithium compound described above, and the like can be used.

As the vinyl aromatic hydrocarbon and the conjugated diene constituting the vinyl aromatic hydrocarbon block copolymer (I), those mentioned above can be used, and one kind or two or more kinds are selected for polymerization. Can be used.

The molecular weight of the vinyl aromatic hydrocarbon block copolymer (I) and the molecular weight of the vinyl aromatic hydrocarbon polymer block can be controlled by the addition amount of the initiator with respect to the addition amount of the monomer.

The block ratio of the vinyl aromatic hydrocarbon block copolymer (I) can be controlled by the addition amount of the randomizing agent when the vinyl aromatic hydrocarbon and the conjugated diene are copolymerized.

Tetrahydrofuran (THF) is mainly used as the randomizing agent, but other ethers, amines, thioethers, phosphoramides, alkylbenzene sulfonates, potassium or sodium alkoxides and the like can also be used. Suitable ethers include THF, dimethyl ether, diethyl ether,
Diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether and the like can be mentioned. As amines, tertiary amines such as trimethylamine, triethylamine, tetramethylethylenediamine, and cyclic amines can be used. In addition, triphenylphosphine, hexamethylphosphoramide, potassium or sodium alkylbenzene sulfonate, potassium or sodium butoxide and the like can be used as the randomizing agent.

The addition amount of the randomizing agent is preferably 0.001 to 10 parts by weight based on 100 parts by weight of all charged monomers. The time of addition may be before the start of the polymerization reaction or before the polymerization of block B in the general structural formula of the vinyl aromatic hydrocarbon block copolymer. In addition, it is possible to add additionally if necessary.

In addition, the block ratio can also be obtained by mechanically continuously feeding the vinyl aromatic hydrocarbon and the conjugated diene to the polymerization vessel, or by alternately adding the vinyl aromatic hydrocarbon and the conjugated diene to the polymerization vessel little by little. You can control.

The vinyl aromatic hydrocarbon polymer (II) used in the present invention includes i) a vinyl aromatic hydrocarbon polymer, ii) a vinyl aromatic hydrocarbon and a (meth) acrylic ester. Polymers may be mentioned.

As the vinyl aromatic hydrocarbon polymer of i), a homopolymer of the above-mentioned vinyl aromatic hydrocarbon or a copolymer of two or more kinds of vinyl aromatic hydrocarbon is used. Particularly common is polystyrene.

Ii) A copolymer of vinyl aromatic hydrocarbon and (meth) acrylic acid ester can be obtained by polymerizing the above vinyl aromatic hydrocarbon and (meth) acrylic acid ester.

Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, (2-ethyl) hexyl acrylate, methyl methacrylate, ethyl methacrylate. , Butyl methacrylate, (2-hydroxy) ethyl methacrylate and the like.

The above-mentioned copolymer of vinyl aromatic hydrocarbon and (meth) acrylic ester has a weight ratio of vinyl aromatic hydrocarbon / (meth) acrylic ester of 5/95.
Or more, preferably 40/60 or more, and more preferably 70/30 or more, obtained by polymerizing a monomer mixture.

The MFR defined by the block copolymer resin composition of the present invention is JIS K-6871 (200 ° C., 5 k
(g load), which can be adjusted by the molecular weight of components (I) and (II) or the amount of plasticizer added. Specifically, with respect to the molecular weight, (I) can be adjusted by the addition amount of the initiator as described above, and (II) can be adjusted by the molecular weight modifier such as mercaptans. Examples of the plasticizer used include butyl stearate and white mineral oil.

In the block copolymer resin composition of the present invention, the ratio of MFR of the components (I) and (II) is from 1/5 to
It should be 5/1, more preferably 1/4 to 4/1. If it deviates from this range, the compatibility of the both becomes poor, the transparency of the molded article is deteriorated, and molding defects such as flow marks occur, which is not preferable. In particular (I)
This defect tends to occur when (II) and (II) are simultaneously supplied to a molding machine for molding.

In the block copolymer resin composition of the present invention, the mixing ratio of the components (I) and (II) is 10 / 90-9.
It must be 0/10. If it is less than 10/90, the impact resistance is inferior, and if it exceeds 90/10, the rigidity is inferior and it cannot be put to practical use.

In the present invention, a rubber-modified styrenic polymer such as high impact polystyrene (HIPS) can be added for the purpose of preventing blocking of the sheet or film as long as the transparency thereof is not impaired.
The specific amount added is 1 with respect to the composition of the present invention.
It is preferably 0 parts by weight or less.

In order to effectively utilize the block copolymer composition shown in the present invention in various fields, it is desirable to add various additives as necessary. Examples of the additives include various stabilizers, lubricants, processing aids, antiblocking agents, antistatic agents, antifogging agents, light resistance improvers, softeners, plasticizers, pigments and inorganic fillers.

As the stabilizer, 2,6-di-t-butyl-
Examples thereof include phenolic antioxidants such as 4-methylphenol and phosphorus antioxidants such as trisnonylphenyl phosphite. Antiblocking agent, antistatic agent,
Examples of the lubricant include fatty acid amide, ethylene bis stearamide, sorbitan monostearate, saturated fatty acid ester of aliphatic alcohol, pentaerythritol fatty acid ester and the like. Examples of the inorganic filler include silica, talc, titanium oxide, calcium carbonate, alumina, aluminum hydroxide, kaolin, glass beads and the like. These additives are preferably used in the range of 5 parts by weight or less based on the block copolymer composition.

The composition of the present invention comprises the components (I) and (I)
It can be obtained by mixing I), and the mixing method may be any known method. For example, it may be dry blended with a Henschel mixer, a tumbler mixer, a V blender, a ribbon blender, or the like, and may be melted with an extruder and pelletized. Alternatively, a method of removing the solvent after mixing the polymer solutions can be used.

The molded article of the present invention is obtained by supplying the above composition to a molding machine such as an injection molding machine, a blow molding machine, a sheet molding machine, an injection-blow molding machine or an inflation molding machine, and molding the composition. be able to. Further, as a method of simultaneously supplying components (I) and (II) to the molding machine without mixing and melting the components (I) and (II) before feeding them to the molding machine, the above-described dry blending method can be used. It is also possible to employ a method of supplying the resin and a method of quantitatively supplying both resins separately to the hopper of the molding machine. It is not particular about the supply method.

As the screw of the molding machine, a full flight screw having the highest versatility can be used, but a dullage type having a higher kneading property can also be used.

The heat-shrinkable film which is one of the molded products of the present invention is a uniaxial, biaxial or extruded sheet or film extruded by the known T-die method or tubular method using the above block copolymer resin composition. It can be obtained by multiaxial stretching. Examples of uniaxial stretching include a method of stretching an extruded sheet with a tenter in a direction orthogonal to the extrusion direction, a method of stretching an extruded tubular film in the circumferential direction, and the like. As an example of biaxial stretching, after the extruded sheet is stretched in the extrusion direction with a roll, and then stretched in a direction orthogonal to the extrusion direction with a tenter, the extruded tubular film is simultaneously extruded in the extrusion direction and the circumferential direction. Alternatively, a method of stretching separately may be used.

The stretching temperature during film formation is not particularly limited, but is preferably 60 to 120 ° C. If the temperature is less than 60 ° C, the sheet or film is easily broken during stretching, and
If the temperature exceeds 0 ° C, it is difficult to obtain good shrinkage properties, which is not preferable. The stretch ratio during film formation is not particularly limited, but is preferably 1.5 to 8 times. If it is less than 1.5 times, the heat shrinkage tends to be insufficient, and if it exceeds 8 times, stretching is difficult, which is not preferable. When these films are used as heat-shrinkable labels or packaging materials, the heat shrinkage rate is preferably 10% or more at 80 ° C. 10
If it is less than%, a high temperature is required at the time of shrinkage, which is not preferable because it tends to adversely affect the article to be coated. The thickness of the film is preferably 10 to 300 μm.

As the use of the heat-shrinkable film, a heat-shrinkable label, a heat-shrinkable cap seal and the like are particularly suitable, but they can also be appropriately used for a packaging film and the like.

[0044]

EXAMPLES The present invention will be described in detail below with reference to examples. However, the present invention is not limited to the following examples.

Production of Block Copolymers A, B, DG A structural feature as shown in Table 1 by polymerizing styrene and butadiene in cyclohexane using n-butyllithium as an initiator and tetrahydrofuran as a randomizing agent. A block copolymer having The number average molecular weight of the polystyrene blocks A ₁ and A ₂ was adjusted by the amount of n-butyllithium and styrene added, and the block ratio was adjusted by the amount of tetrahydrofuran added.

Production Method of Block Copolymer C The structure of the block copolymer is (A ₁ -B-A ₂ -B) ₄ -X
A block copolymer represented by the following general formula was produced, and its structural characteristics are also shown in Table 1. Specifically, A ₁ −
After completion of the polymerization to B-A ₂ -B, it was prepared by the addition of 1/4 mole of silicon tetrachloride with respect to n- butyl lithium using to the coupling reaction.

Examples 1 to 8 and Comparative Examples 1 to 5 The polymers shown in Table 2 were used as the component (II), and the components shown in Tables 3 and 4 were dry blended in a tumbler mixer,
Using FS-55 (2oz injection molding machine) manufactured by Nissei Plastic Industry Co., Ltd., at 220 ° C. length × width × thickness = 100 mm × 1
A 00 mm × 2 mm plate was injection-molded and used for the physical property test. The results are also shown in Tables 3 and 4.
From the physical properties shown in the table, it can be seen that the block copolymer resin composition of the present invention is excellent in transparency and impact resistance.

The physical properties shown in Tables 3 and 4 were measured by the following methods. (1) Drop weight strength: In the atmosphere of the above-mentioned plate at 20 ° C., a weight having a tip R of 10 m / mφ was dropped by changing the weight and the height, and the maximum height at which breakage did not occur was found. Displayed in height. (2) Haze: The above-mentioned plate was ASTM-D-1003.
Was measured according to the method described above. The condition of the plate used for measurement was adjusted at 23 ° C. × 50% × 24 hours after injection molding.

Example 9 The composition dry-blended with the composition of Example 2 was sheeted to a thickness of 0.3 mm at 210 ° C. using a VE-40-50 (sheet molding machine) manufactured by Tanabe Plastic Machinery Co., Ltd. It was molded and its physical properties were measured. Table 5 shows the results. It has good transparency and impact resistance and can be used as a sheet.

Example 10 A sheet having a thickness of 0.3 mm was formed in the same manner as in Example 9 using the composition dry-blended with the composition of Example 1. Then, using a biaxial stretching device manufactured by Toyo Seiki Co., Ltd., 1
The film was horizontally uniaxially stretched 5 times at 00 ° C. to prepare a heat-shrinkable film. The physical properties are shown in Table 5. It has good transparency, impact resistance and heat shrinkage, and can be used as a heat shrinkable film.

Comparative Example 6 The composition dry-blended with the composition of Comparative Example 3 was sheeted to a thickness of 0.3 mm at 210 ° C. using VE-40-50 (sheet forming machine) manufactured by Tanabe Plastic Machinery Co., Ltd. It was molded and its physical properties were measured. Table 5 shows the results.

Comparative Example 7 A sheet having a thickness of 0.3 mm was formed in the same manner as in Example 9 using the composition dry-blended with the composition of Comparative Example 4. Then, using a biaxial stretching device manufactured by Toyo Seiki Co., Ltd., 1
The film was horizontally uniaxially stretched 5 times at 00 ° C. to prepare a heat shrinkable film. The physical properties are shown in Table 5.

The physical properties in Table 5 were measured by the following methods. (1) Tensile strength: Measured according to JIS K-6732. (2) Impact strength: A film impact tester manufactured by Tester Sangyo Co., Ltd. was used, and in Example 9, the tip R was 10 m /
The weight of mΦ was measured, and in Example 10, the weight of R at the tip was 25 m / mΦ. (3) Haze: The above-mentioned sheet and film are ASTM-D
It was measured by the method of -1003. (4) Thermal shrinkage: The film of Example 10 was immersed in warm water of 80 ° C. for 30 seconds, and calculated by the following formula. Thermal shrinkage (%) = {(L ₁ −L ₂ ) / L ₁ } × 100 L ₁ : Length before shrinking L ₂ : Length after shrinking

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

[Table 3]

[0057]

[Table 4]

[0058]

[Table 5]

[0059]

The block copolymer resin composition of the present invention has excellent transparency and impact resistance, and can be injection-molded, blow-molded, sheet-molded, inflation-molded, etc., so that various molded articles, sheets, films, It can be used as a heat-shrinkable film. Furthermore, the sheet once formed can be used as various secondary processed products by subjecting it to vacuum forming or the like. Further, since the present composition has excellent moldability, it can be applied to an economical process in which each component in the composition is simultaneously supplied to a molding machine for molding.

Claims (5)

[Claims] 1. A composition comprising (I) a vinyl aromatic hydrocarbon and a conjugated diene, (1) a vinyl aromatic hydrocarbon and a conjugated diene in a weight ratio of 60/40 to 90/10, and (2) a vinyl aromatic. Block ratio (%) of vinyl aromatic hydrocarbon contained in the hydrocarbon block copolymer = (W / W ₀ ) × 10
0 is 25 to 90% (where W is the weight of the vinyl aromatic hydrocarbon block in the block copolymer, W _{0 is} the total weight of the vinyl aromatic hydrocarbon in the block copolymer). Aromatic hydrocarbon block copolymer 10-90
And (II) vinyl aromatic hydrocarbon polymer 10 to 90 parts by weight, and the ratio of MFR of (I) and (II) is 1/5 to 5
The block copolymer resin composition is characterized in that the total amount of (I) and (II) is 100 parts by weight. 2. The number average molecular weight of the vinyl aromatic hydrocarbon polymer block of (I) according to claim 1 is 5,000 to 3.
The block copolymer resin composition, which is 5,000 and 40,000 to 200,000. 3. A molded product comprising the block copolymer resin composition according to claim 1. 4. (I) and (II) according to claim 1 or 2.
[However, the ratio of MFR of (I) and (II) is 1/5 to 5 /
[1] is simultaneously supplied to a molding machine and molded. 5. (I) and (II) according to claim 1 or 2.
[However, the ratio of MFR of (I) and (II) is 1/5 to 5 /
1] is simultaneously supplied to a molding machine to perform molding.