JP3334194B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having excellent transparency, heat sealability and impact resistance.

[0002]

2. Description of the Related Art Polyolefin resins such as polypropylene resin and polyethylene resin are inexpensive and excellent in moldability, mechanical strength, transparency, etc., and are used in a wide range of fields such as automobile interior and exterior parts, electric products, and food packaging. Are widely used as general-purpose resins. However, there is a disadvantage that the impact resistance is low and brittle especially at low temperatures. Also,
Transparency, heat sealability, etc. are not sufficient. In order to overcome this drawback, a method of mechanically mixing a polyolefin resin with an ethylene-propylene copolymer rubber, an ethylene-butene-1 copolymer rubber, or the like has been adopted as a general means.

[0003] Ethylene-propylene copolymer rubber is an effective material for improving impact resistance at low temperatures, and ethylene-butene-1 copolymer rubber is used for its transparency and heat-sealing properties. It is an effective material to improve. However, it is difficult to achieve these characteristics at the same time, and it is difficult to improve the transparency.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and a hydrogenated diene copolymer and an ethylene-α-olefin random copolymer specific to a polyolefin resin. The present invention provides a thermoplastic resin composition having low temperature impact resistance, transparency, and heat sealability.

[0005]

SUMMARY OF THE INVENTION The present invention provides (I) a high-density
Polyethylene, medium density polyethylene, low density polyethylene
, LLDPE (linear low density polyethylene), polyp
Propylene resin (however, ethylene-propylene block
Excluding copolymers), and poly-4-methyl-pentene
Selected from the group of -1 polyolefin-based resin (hereinafter
"(I) polyolefin resin") ,
(II) A hydrogenated diene-based copolymer obtained by hydrogenating a conjugated diene portion of an aromatic vinyl compound-conjugated diene block copolymer having a conjugated diene portion having a vinyl bond content of 60% or more by 90% or more (hereinafter referred to as “( II) a hydrogenated diene copolymer) and (III) an ethylene-α-olefin random copolymer (hereinafter sometimes referred to as “(III) random copolymer”) as main components. The composition ratio of each component is (I) / [(II) + (III)] (weight ratio) = 97/3.
-10/90, and (II) / (III) (weight ratio) = 10 /
The present invention provides a thermoplastic resin composition having a ratio of 90 to 90/10.

The polyolefin resin (I) used in the composition of the present invention includes high-density polyethylene, medium-density polyethylene, low-density polyethylene, LLDPE (linear low-density polyethylene), polypropylene resin, and poly-4-methyl. -Pentene-1 and the like. Preferably, it is a polypropylene resin, poly-4-methyl-pentene-1. The melt flow rate (MFR) of the polyolefin resin (I) used in the present invention (ASTM D
1238, 230 ° C, 2.16 kg load)
It is 100 g / 10 min, preferably 0.5 to 80 g / 10 min.

Next, (II) used in the composition of the present invention
The hydrogenated diene-based copolymer is obtained by hydrogenating a conjugated diene portion of an aromatic vinyl compound-conjugated diene copolymer having a vinyl bond content of 60% or more by 90% or more. This (II) hydrogenated diene copolymer comprises a vinyl aromatic compound polymer block (A) and a conjugated diene polymer or a random copolymer block (B) of a vinyl aromatic compound and a conjugated diene. (A)-(B) a block copolymer or, if necessary, a (A)-(B)-comprising a vinyl aromatic compound and a tapered block (C) in which a vinyl aromatic compound among conjugated dienes gradually increases. (C) a block copolymer or (A)-(B)-(A) block copolymer comprising a vinyl aromatic polymer block (A), wherein the ratio of vinyl aromatic compound / conjugated diene is weight The ratio of the vinyl aromatic compound in the component (A) and the optional component (C) is 3 to 30% by weight of the total monomer, and the vinyl in the conjugated diene portion is 0 to 30/100 to 70 in the ratio. A block copolymer having a bond content of 60% or more is hydrogenated to obtain a hydrogenated diene system in which at least 90% of the double bonds in the conjugated diene portion are saturated and the number average molecular weight is 50,000 to 600,000. Copolymers are preferred.

First, the ratio of vinyl aromatic compound / conjugated diene in all monomers is 0 to 30/100 to 7 by weight.
0, preferably 5 to 25/95 to 75. When the content of the vinyl aromatic compound exceeds 30% by weight, the resulting composition has insufficient balance of low-temperature impact resistance, transparency, and heat sealability. The vinyl aromatic compound binding content in the vinyl aromatic compound polymer block (A) and the taper block (C) formed as required is 0 to 30% by weight of all monomers, preferably 3 to 25% by weight. %. When the bond content of the vinyl aromatic compound of the component (A) or the components (A) and (C) exceeds 30% by weight of the total monomers, the resulting composition has low-temperature impact resistance, transparency, and heat sealability. Becomes insufficiently balanced.

Further, the vinyl bond content of the conjugated diene portion is at least 60%, preferably at least 70%, more preferably at least 80%. When the vinyl bond content is less than 60%, it is insufficient to ensure transparency. Here, the vinyl bond means that the conjugated diene is 1,2- or 3,4.
-Represents a monomer unit polymerized by a double bond at the bond position.

Further, the hydrogenated diene copolymer of the present invention requires that at least 90%, preferably 95% or more, of the double bond of the conjugated diene portion be hydrogenated and saturated. %, Heat resistance, weather resistance and ozone resistance are poor, and transparency is impaired.

Further, the hydrogenated diene copolymer of the present invention has a polystyrene equivalent number average molecular weight of 50,000 to 600,000,
Preferably it is 100,000 to 500,000. When the number average molecular weight is out of this range, the balance between impact resistance and transparency is lost.

[0012] The hydrogenated diene copolymer of the present invention comprises a block (A), a block (B) and, if necessary, a tapered block (C) or a block (A). Is used as an initiator to carry out living anionic polymerization to obtain a block copolymer, which is then obtained by hydrogenating the block copolymer.

As the vinyl aromatic compound, styrene,
t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene,
N, N-diethyl-p-aminoethylstyrene, vinylpyridine and the like can be mentioned, and styrene and α-methylstyrene are particularly preferred.

Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-diene.
Examples thereof include pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, and chloroprene, which can be industrially used and have excellent physical properties. In order to obtain a diene copolymer, 1,3-butadiene, isoprene, and 1,3-pentadiene are preferred, and 1,3-butadiene is more preferred.

As the organic solvent, pentane, hexane,
Hydrocarbon solvents such as heptane, octane, methylcyclopentane, cyclohexane, benzene, xylene and the like are used. As the organic alkali metal compound as a polymerization initiator, an organic lithium compound is preferable. As the organic lithium compound, an organic monolithium compound, an organic dilithium compound, and an organic polylithium compound are used.
Specific examples of these include ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, hexamethylene dilithium, butadienyl lithium, isoprenyl dilithium and the like. And used in an amount of 0.02 to 0.2 parts by weight per 100 parts by weight of monomer.

At this time, Lewis bases such as ethers and amines, such as diethyl ether, tetrahydrofuran, propyl ether, butyl ether, higher ethers, and the like, are used as regulators of the microstructure, that is, the vinyl bond content of the conjugated diene moiety. Ether derivatives of polyethylene glycol such as ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, and triethylene glycol dimethyl ether; examples of amines include tertiary amines such as tetramethylethylene diamine, pyridine and tributylamine; Used.

Further, the polymerization reaction is usually carried out at a temperature of -30.degree.
Performed at 50 ° C. Further, the polymerization may be carried out while controlling at a constant temperature, or may be carried out at an elevated temperature without removing heat.

The block copolymer may be formed by any method. In general, the block (A) or the block (B) is first polymerized in the organic solvent using a polymerization initiator such as the alkali metal compound. Then, the block (B) or the block (A) is polymerized. It does not matter which of the block (A) or the block (B) is polymerized first. Further, the boundary between the block (A) and the block (B) does not necessarily need to be clearly distinguished. (A)-(B)-(C) block copolymer;
Alternatively, to obtain the (A)-(B)-(A) block copolymer, an aromatic vinyl compound is added using an organolithium initiator in an organic solvent to polymerize the block (A), and then to polymerize the block (A). A block (B) is prepared by adding a conjugated diene or a conjugated diene and an aromatic vinyl compound, and a taper block (C) or a block (A) is formed by adding a conjugated diene and an aromatic vinyl compound or an aromatic vinyl compound. May be polymerized. In this case, a method in which the taper block (C) or the block (A) is first polymerized, and then the block (B) and then the block (A) may be polymerized.

The (A)-(B) block copolymer, (A)-(B)-(C) block copolymer or (A)-(B)-(A) block thus obtained The copolymer may be a block copolymer having a polymer molecular chain extended or branched as represented by the following general formula by adding a coupling agent. [(A)-(B)] n-X, [(A)-(B)-(C)] n-X, or [(A)-(B)-(A)] n-X , (A), (B) and (C) are the same as above, and n is 2
X represents an integer of 4 to 4 and represents a coupling agent residue. ]

As the coupling agent at this time, for example, diethyl adipate, divinylbenzene, tetrachlorosilicon, butyltrichlorosilicon, tetrachlorotin,
Butyltrichlorotin, dimethylchlorosilicon, tetrachlorogermanium, 1,2-dibromoethane, 1,4
-Chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized linseed oil, tolylene diisocyanate, 1,2,4-benzenetriisocyanate and the like.

The bond content of the vinyl aromatic compound in the block copolymer is adjusted by the amount of the monomer supplied at the time of polymerization in each step, and the vinyl bond content of the conjugated diene portion is determined by varying the components of the micromodulator. It is adjusted by doing. Further, the number average molecular weight and the melt flow rate are adjusted by the addition amount of a polymerization initiator, for example, n-butyllithium.

The hydrogenated diene copolymer of the present invention is obtained by dissolving the block copolymer thus obtained in an inert solvent, at 20 to 150 ° C. and under a hydrogen pressure of 1 to 100 kg / cm ² . In the presence of a hydrogenation catalyst. Inert solvents used for hydrogenation include hydrocarbon solvents such as hexane, heptane, cyclohexane, benzene, toluene and ethylbenzene, and polar solvents such as methyl ethyl ketone, ethyl acetate, ethyl ether and tetrahydrofuran.

As the hydrogenation catalyst, dicyclopentadienyl titanium halide, nickel organic carboxylate,
Hydrogenation catalysts comprising an organic nickel carboxylate and an organometallic compound of Groups I to III of the Periodic Table; nickel, platinum, palladium, ruthenium, rhenium, rhodium metal catalysts supported on carbon, silica, diatomaceous earth, cobalt, Nickel, rhodium, ruthenium complex, or lithium aluminum hydride, p-toluenesulfonyl hydrazide, or Zr-Ti-Fe-V-Cr
Alloy, Zr-Ti-Nb-Fe-V-Cr alloy, LaN
such hydrogen storage alloy such as i ₅ alloys.

The hydrogenation rate of the double bond in the conjugated diene portion of the hydrogenated diene copolymer of the present invention can be determined by the amount of the hydrogenation catalyst, the amount of the hydrogenated compound, the hydrogen pressure during the hydrogenation reaction,
It is adjusted by changing the reaction time. The catalyst residue is removed from the hydrogenated block copolymer solution, a phenolic or amine-based antioxidant is added, and the (II) hydrogenated diene copolymer can be easily isolated from the polymer solution. Can be released. (II) Isolation of a hydrogenated diene copolymer is carried out, for example, by a method in which acetone or alcohol is added to the copolymer solution to cause precipitation, and the polymer solution is put into hot water with stirring to distill off the solvent. The method can be performed.

Next, (III) used in the composition of the present invention
The ethylene-α-olefin random copolymer is obtained, for example, by copolymerizing ethylene with an α-olefin and / or a non-conjugated diene using a Ziegler catalyst. The α-olefin used as a comonomer of the (III) random copolymer is an α-olefin having 3 to 12 carbon atoms, and specifically, propylene, butene-1, pentene-1, 4- Methylpentene
1, hexene-1, heptene-1, octene-1 and the like, preferably propylene and butene-1.
These α-olefins can be used alone or in combination of two or more.

Specific examples of the (III) non-conjugated diene copolymerized with the random copolymer include dicyclopentadiene, tricyclopentadiene, 5-methyl-2,5-
Norbornadiene, 5-methylene-2-norbornene,
5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-isopropylidene-2-norbornene, cyclooctadiene, vinylcyclohexene, 1,5,9-cyclododecatriene, 1,4-hexadiene, , 6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 3,6
-Dimethyl-1,7-octadiene; and the like, preferably 5-ethylidene-2-norbornene and dicyclopentadiene.

(III) The random copolymer can be produced in a hydrocarbon solvent by using a catalyst comprising a combination of a vanadium compound and / or a titanium compound and an organic metal compound belonging to Groups I to IV of the periodic table. it can.

Among these, as the vanadium compound, a trivalent to pentavalent vanadium compound soluble in an inert organic solvent is preferably used, and vanadium halides, oxyhalides, chelate complexes with oxygen-containing compounds, vanadate esters Are preferred. More specifically, vanadium tetrachloride, vanadium oxytrichloride, vanadium trisacetyl acetate, tris ethoxide vanadate, tri-n-butoxide vanadate, di-n-butoxy monochloride vanadate, vanadium tetrachloride and / or Examples include a reaction composition of vanadium oxytrichloride and alcohol. These are used alone or as a mixture of two or more.

As the titanium compound, a titanium trichloride catalyst dissolved in a solid or a solvent, a titanium trichloride or a titanium tetrachloride compound supported on magnesium chloride or the like is used. These compounds can be used in combination with a third component such as an electron donor.

Examples of the organometallic compounds of Groups I to IV of the periodic table include organolithium compounds, organozinc compounds, organomagnesium compounds and organoaluminum compounds. More specific examples include triethylaluminum, tri-i-butylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride and the like.

The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the random copolymer (III) used in the present invention is 3
~ 120, preferably 5-90. If the Mooney viscosity is less than 3, the impact resistance of the resulting composition will be insufficient, while if it exceeds 120, the transparency will be impaired.

The weight average molecular weight (Mw) and the number average molecular weight (Mw) of the random copolymer (III) used in the present invention
The molecular weight distribution (Mw / Mn) represented by the ratio of n) is 1.
It is 3 to 10, preferably 1.3 to 6, and more preferably 1.5 to 4. When Mw / Mn is less than 1.3, it is difficult to produce (III) a random copolymer using a Ziegler catalyst, while when it exceeds 10, transparency of the resulting composition is impaired. It is.

Furthermore, the (III) random copolymer used in the present invention has a ratio of ethylene / α-olefin / non-conjugated diene of 30 to 90/10 to 70/0 by weight.
8, preferably 35 to 85/15 to 65/0 to 5, and when ethylene is smaller than this range, the balance of transparency, heat sealability and impact resistance is impaired.

The thermoplastic resin composition of the present invention contains the above components (I) to (III) as main components, and the mixing ratio thereof is (I) / [(II) + (III)] (weight Ratio) = 97/3
-10/90, preferably 95 / 5-20 / 80, and (II) / (III) (weight ratio) = 10 / 90-90 / 10,
Preferably it is 20 / 80-70 / 30. When the component (I) exceeds 97% by weight in the composition, the effects of the present invention, that is, the effects of improving the balance of impact resistance at low temperatures, transparency, and heat sealing properties are poor, while if less than 10% by weight, The amount of the component (I) is too small, so that the molded product becomes too soft, and the mechanical strength inherent to the component (I) is greatly reduced. When the ratio of the component (II) to the component (III) is less than 10% by weight, the effect of improving transparency and heat sealability is poor, while when it exceeds 90% by weight, the impact strength is poor. .

The composition of the present invention can be obtained by mixing by a commonly used method. For example,
(II) A kneader blender, a Banbury mixer, a hot roll, or an extruder is used so that the hydrogenated diene copolymer and the (III) random copolymer have a composition ratio of 10/90 to 90/10 by weight. Melting and mixing using or mixing a solution in which (II) a hydrogenated diene copolymer and (III) a random copolymer are each dissolved in an organic solvent, and then removing the solvent Removing the mixture, or (II) hydrogenated diene copolymer or (III)
When producing a random copolymer, there is a method of producing a copolymer in the presence of a copolymer solution of the other party. In this way, after the (II) hydrogenated diene-based copolymer and (III) random copolymer have been previously mixed, this is added to the (I) polyolefin-based resin, and finally the composition of the present invention (I) polyolefin resin, (II) hydrogenated diene copolymer and (III) random copolymer are blended so as to obtain the following composition, and mixed by the above-mentioned various mixing means. Thus, the method of mixing the composition of the present invention is not particularly limited,
It is important to mix each component so as to finally obtain the composition of the present invention.

The composition of the present invention contains polystyrene resin , acrylonitrile-butadiene-styrene copolymer, ethylene-vinyl acetate copolymer, hydrogenated styrene-butadiene-styrene. Block copolymer, hydrogenated styrene-isoprene-styrene
Triblock copolymers, polybutadienes and the like can be blended.

The composition of the present invention may contain conventional auxiliary additives such as antioxidants, heat stabilizers, ultraviolet absorbers, inorganic or organic fillers, reinforcing agents, slip agents, coloring agents and the like. You can also.

The composition of the present invention can be obtained by subjecting molding methods such as injection molding, blow molding, T-die molding and inflation, and further to secondary processing such as stretching and stamping molding to produce interior and exterior parts for automobiles and electric products. It can be used for various parts, various packaging materials such as food storage, stationery, and other general industrial materials.

[0039]

The thermoplastic resin composition of the present invention has excellent low-temperature impact resistance, transparency and heat sealability. Although such a modification effect is not clear, it is assumed that the dispersing effect of the specific (II) hydrogenated diene-based copolymer and (III) random copolymer in the composition is appropriately balanced. Conceivable.

[0040]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples unless it exceeds the gist of the invention. In the examples, parts and% are by weight unless otherwise specified. Various measurements in the examples were based on the following methods.

(II) Analytical Method of Hydrogenated Diene Copolymer The styrene content was analyzed by infrared analysis based on the absorption of a phenyl group at 679 cm ⁻¹ . Vinyl bond content of the conjugated diene portion; calculated by the Hampton method using infrared analysis. Hydrogenation rate: determined by ¹ H-NMR analysis. Molecular weight: 135 ° C. using trichlorobenzene as a solvent
Gel permeation chromatography (G
PC) in terms of polystyrene.

(III) Analytical method composition ratio of random copolymer : It was determined by ¹ H-NMR analysis. Mw / Mn: 13 using trichlorobenzene as a solvent
It was determined and calculated in terms of polystyrene using gel permeation chromatography (GPC) at 5 ° C. Mooney viscosity: measured according to JIS K6300. Melt flow rate (MFR); JIS K7210
It measured according to. The measurement conditions were 230 ° C. and a load of 2.1.
6 kg was adopted.

Measurement of physical properties of composition Total haze: Measured according to JIS K6782. Heat sealability (peel strength): Measured according to JIS Z1707. Film impact test: Measured according to JIS Z1707.

Example 1 Production of hydrogenated diene copolymer (II) -1 In a 10 liter autoclave, 5,000 g of degassed and dehydrated cyclohexane, 1,3-butadiene 9
50 g were charged, 200 g of tetrahydrofuran and 0.3 g of n-butyllithium were added, and adiabatic polymerization from 10 ° C. was performed. 45 minutes later, 50 g of styrene was added, and polymerization was further performed. Then, the reaction solution was heated to 70 ° C., 1.5 g of n-butyllithium and 1.5 g of 2,6-di-t-butyl-p-cresol were added, and 0.5 g of bis (cyclopentadienyl) titanium dichloride was further added. 2 g of diethylaluminum chloride was added, and hydrogen pressure was 10 kg / cm ²
For 1 hour.

The solvent was removed from the reaction solution to obtain a solid.
The resulting solid had a number average molecular weight of 295,000, M
The FR was 2.0 g / 10 minutes, the vinyl bond content in the butadiene portion before hydrogenation was 80%, and the hydrogenation rate was 99%.

Production of random copolymer (III) -1 EP01SP manufactured by Nippon Synthetic Rubber Co., Ltd. was used. α-
The olefin type is propylene, the ethylene content is 78%, the Mooney viscosity ((ML _{1 + 4} , 100 ° C.) is 19, Mw / M
n was 2.0.

Preparation of a blend comprising the components (II) to (III)
Using a 55 mmφ full flight type single screw extruder, a random copolymer (III) -1 with a hydrogenated diene copolymer (II) -1 at a head temperature of 220 ° C. in a weight ratio of (II) )-1 / (III) -1 = 30/70.

20 parts of the blend obtained in the preparation of the composition were mixed with 80 parts of a polypropylene resin (F8277, manufactured by Nihon Petrochemical Co., Ltd.)
The mixture was melt-mixed with a 4-liter Banbury mixer. After kneading, after sheet forming, square pellet, 400mm
Using a 40 mmφ extruder with a T-die, a film having a thickness of 40 μm was obtained. Table 1 shows the physical properties of the obtained film.

Example 2 In the preparation of the formulation of Example 1, (II) -1 / (III) -1
(Weight ratio) = 60/40, except that it was carried out in the same manner as in Example 1. Table 1 shows the results. Comparative Examples 1 and 2 The same procedures as in Example 1 were carried out except that (II) -1 or (III) -1 used in preparing the composition of Example 1 was used alone for preparing the composition. Table 1 shows the results. Comparative Examples 1 to
2 shows that the transparency is inferior and the balance of heat sealability-impact-transparency is inferior to Examples 1 and 2.

Example 3 In place of (III) -1 used in the preparation of the compound of Example 1, EBM2041P (manufactured by Nippon Synthetic Rubber Co., Ltd.) (ethylene content = 80%, Mooney viscosity (ML _{1 + 4} , 100 ℃)
= 15, and an ethylene-butene copolymer rubber having Mw / Mn = 1.9 (hereinafter referred to as "(III) -2")). Table 1 shows the results.

Example 4 The procedure of Example 3 was repeated except that (III) -2 and (II) -1 used in Example 3 were used and the composition was changed. Table 1 shows the results.

Comparative Example 3 The same procedure as in Comparative Examples 1 and 2 was carried out except that the random copolymer (III) -2 used in Example 3 was used alone. Table 1 shows the results. It can be seen that Comparative Example 3 is inferior in transparency and inferior in heat-sealing-impact-transparency balance as compared with Example 3 or Example 4. Comparative Examples 4 and 5 In the preparation of the blend of Example 1, (II) -1 / (II
I) -1 (weight ratio) = 95/5 or 5/95, except that it was carried out in the same manner as in Example 1. Table 1 shows the results.

Comparative Examples 6-7 In the preparation of the formulation of Example 3, (II) -1 / (II
I) -2 (weight ratio) = 95/5 or 5/95, except that it was carried out in the same manner as in Example 3. Table 1 shows the results. Comparative Examples 4 to 7 are cases in which a composition out of the range of the composition of the present invention was used, and Examples 1 to 2 or Examples 3 to 4 were used.
In comparison with the above, it can be seen that sufficient heat sealing properties, impact properties and transparency were not balanced.

Examples 5 to 8 A catalyst comprising a combination of vanadium oxychloride trichloride and ethylaluminum sesquichloride was used in place of the random copolymer (III) -1 used in the preparation of the blend of Example 1. The procedure was performed in the same manner as in Example 1 except that the random copolymers (III) -3 to 6 shown in Table 2 were trial-produced in an n-hexane solvent. Table 2 shows the results.

Examples 9 to 11 In the same manner as in the preparation of the hydrogenated diene copolymer of Example 1, the hydrogenated diene copolymer (II) -2 to (I) shown in Table 2 was used.
I) -4 was prepared, and instead of the hydrogenated diene copolymer (II) -1 used in the preparation of the blend of Example 1, (II) -2 to (II) -4 shown in Table 2 The procedure was performed in the same manner as in Example 1, except that was used. Table 2 shows the results.

Comparative Example 8 A hydrogenated diene copolymer (II) -5 shown in Table 2 was produced in the same manner as in the production of the hydrogenated diene copolymer of Example 1, and the blending of Example 1 was carried out. Example 1 was repeated except that (II) -5 shown in Table 2 was used instead of (II) -1 used in the preparation of the product. Table 2 shows the results. In Comparative Example 11, a hydrogenated diene copolymer having a vinyl bond content of less than 60% and outside the range of the present invention was used. In this case, it can be seen that a sufficient balance between the heat sealing property, the impact property, and the transparency was not obtained.

Comparative Example 9 A hydrogenated diene copolymer (II) -6 shown in Table 2 was produced in the same manner as in the production of the hydrogenated diene copolymer of Example 1, and the blending of Example 1 was carried out. Example 2 was carried out in the same manner as in Example 1 except that (II) -6 shown in Table 2 was used instead of (II) -1 used in the preparation of the product. Table 2 shows the results. Comparative Example 12 also uses a hydrogenated diene copolymer having a vinyl bond content of less than 60%. In this case, it can be seen that a sufficient balance between the heat sealing property, the impact property, and the transparency was not obtained.

Comparative Example 10 In Example 1, (I) / [(II) + (III)] = 10
The procedure was performed in the same manner as in Example 1 except that the condition was changed to 0/0. Table 2 shows the results.

[0059]

[Table 1]

[0060]

[Table 2]

[0061]

The thermoplastic resin composition of the present invention has an excellent balance of transparency, heat sealing properties and impact properties, and various packaging materials such as interior and exterior parts for automobiles, various parts for electric products, food wrapping and the like. It is useful for stationery and other general industrial materials.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-4-57848 (JP, A) JP-A-3-172339 (JP, A) JP-A-1-256557 (JP, A) JP-A-3-25639 72512 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 23/02-23/22 C08L 53/00-53/02

Claims (1)

(57) [Claims] (1) High density polyethylene, medium density poly
Ethylene, low density polyethylene, LLDPE (linear low
Density polyethylene), polypropylene resin (however,
Excluding Tylene-propylene block copolymer), and
A polyolefin-based resin selected from the group of poly-4-methyl-pentene-1 , (II) an aromatic vinyl compound-conjugated diene block copolymer having a conjugated diene moiety having a vinyl bond content of 60% or more; A hydrogenated diene-based copolymer obtained by hydrogenating a conjugated diene portion of at least 90%, and (III) an ethylene-α-olefin-based random copolymer as main components,
The composition ratio of each component is (I) / [(II) + (III)] (weight ratio) = 97/3 to 10/90, and (II) / (III) (weight ratio) = 10/90 to 90 / 10.