JP2000212356A - Aromatic vinyl polymer resin composition, resin foaming sheet, production of resin foaming sheet and vessel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aromatic vinyl polymer resin composition excellent in heat resistance and oil resistance and further, excellent in balance of tensile elongation and stiffness and being expensive on production. SOLUTION: This aromatic vinyl polymer resin composition comprises (A) 30-95 pts.wt. aromatic vinyl polymer resin, (B) 70-5 pts.wt. polypropylene resin, (C) 1-10 pts.wt. copolymer of ethylene and 4-10C 1-alkene and (D) 1-15 pts.wt. block copolymer composed of a polymer block comprising a vinyl aromatic compound and a polymer block comprising a conjugated diene-based compound or its hydrogenated material based on 100 pts.wt. total amount of the components A, B and C. This vessel is obtained by molding the resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an aromatic material which is excellent in heat resistance and oil resistance, has an excellent balance of tensile properties and impact resistance, and is suitably used as a material for food containers and the like which is compatible with microwave cooking. The present invention relates to a vinyl polymer resin composition and a container formed by molding the aromatic vinyl polymer resin composition.

[0002]

2. Description of the Related Art Aromatic vinyl polymer resins represented by polystyrene and ABS resins are widely used in electronic equipment housings, food containers and the like by utilizing their excellent mechanical and electrical properties. Used.
However, the aromatic vinyl polymer resin has a problem that heat resistance and oil resistance are insufficient, and a container for a microwave oven or the like which is required to be excellent in both heat resistance and oil resistance as it is. There was a difficulty in using it.

As a method for improving the heat resistance of such an aromatic vinyl polymer resin, a method of copolymerizing methacrylic acid or maleic anhydride is known. However, this method can improve heat resistance, but cannot improve oil resistance.

Further, there is a polymer alloy obtained by adding a polyolefin resin such as a polypropylene resin and a compatibilizer such as a styrene-butadiene block copolymer to such an aromatic vinyl polymer resin. Since the vinyl polymer resin and the polyolefin resin are incompatible, even if a compatibilizing agent is added, the resulting polymer alloy has insufficient physical properties such as tensile elongation.

To improve tensile elongation and the like, it is effective to increase the amount of a compatibilizer. However, since the compatibilizer is expensive, there has been a problem of cost increase. Moreover, when the amount of the compatibilizer is increased,
There is also a problem that the tensile modulus of the obtained polymer alloy is reduced. Therefore, a method for improving the tensile elongation of the obtained polymer alloy without increasing the amount of the compatibilizer has been desired.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned conventional problems, and as a result, a polypropylene resin and a styrene-
To a polymer alloy obtained by adding a compatibilizer such as a diene block copolymer, ethylene and 1-C4-10
To provide an aromatic vinyl polymer resin composition which is excellent in heat resistance, oil resistance, excellent in balance between tensile elongation and rigidity, and inexpensive in production by blending a copolymer with an alkene in a specific ratio. And found that the present invention has been completed based on this finding.

That is, according to the present invention, there are provided (A) 30 to 94 parts by weight of an aromatic vinyl polymer resin, (B) 69 to 5 parts by weight of a polypropylene resin, (C) ethylene and 4 to 10 carbon atoms. 1 to 10 parts by weight of a copolymer with 1-alkene
And (D) a polymer composed of a polymer block composed of a vinyl aromatic compound and a polymer composed of a conjugated diene compound with respect to 100 parts by weight in total of the component (A), the component (B), and the component (C). An aromatic vinyl polymer resin composition comprising 1 to 15 parts by weight of a block copolymer comprising a block or a hydrogenated product thereof.

Next, the present invention according to claim 2 is characterized in that (A) 50 to 89 parts by weight of an aromatic vinyl polymer resin, (B) 49 to 10 parts by weight of a polypropylene resin, (C) ethylene and C 4 to C 4 10 to 1 to 8 parts by weight of a copolymer with 1-alkene
And (D) a polymer composed of a polymer block composed of a vinyl aromatic compound and a polymer composed of a conjugated diene compound with respect to 100 parts by weight in total of the component (A), the component (B), and the component (C). An aromatic vinyl polymer resin composition comprising 1 to 10 parts by weight of a block copolymer comprising a block or a hydrogenated product thereof.

The present invention according to claim 11 provides a resin foamed sheet comprising the resin composition according to any one of claims 1 to 10.

Further, the present invention according to claim 12 is a resin foamed sheet comprising the resin composition according to any one of claims 1 to 10 and having a density of 0.04 to 1.1 g / cc. Is provided.

The present invention according to claim 14 is characterized in that the resin composition according to any one of claims 1 to 10 is melt-kneaded together with a foaming agent in an extruder and then extruded from a mold. A method for producing a resin foam sheet is provided.

Further, the present invention according to claim 15 provides:
(A) 30 to 94 parts by weight of an aromatic vinyl polymer resin,
(B) 69 to 5 parts by weight of a polypropylene resin, (C) copolymer 1 of ethylene and a 1-alkene having 4 to 10 carbon atoms
(D) a polymer block composed of a vinyl aromatic compound and a conjugated diene compound with respect to 10 parts by weight and 100 parts by weight of the total of the components (A), (B) and (C) The present invention provides a container formed by molding an aromatic vinyl polymer resin composition comprising 1 to 15 parts by weight of a block copolymer comprising a polymer block comprising: or a hydrogenated product thereof.

Finally, the present invention according to claim 16 provides a container formed by molding the resin foam sheet according to claims 11 to 13.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the present invention according to claim 1, as the component (A),
An aromatic vinyl polymer resin is used. Even if the aromatic vinyl polymer resin is a rubber-modified aromatic vinyl polymer resin,
It may be a non-rubber-modified aromatic vinyl polymer resin. As the aromatic vinyl polymer resin, as described in claim 3, a rubber-modified aromatic vinyl polymer resin containing 3 to 12% by weight of a rubbery polymer is preferable, and if necessary, a non-rubber-modified aromatic polymer resin is used. A vinyl polymer resin can be appropriately blended.

In the present invention, the rubber-modified aromatic vinyl polymer resin used as the component (A) is a styrene-based monomer or a styrene-based monomer and another comonomer in the presence of a rubber-like polymer. It is obtained by polymerization.

Examples of the styrene monomer include, in addition to the styrene monomer, styrene derivative monomers such as paramethylstyrene, α-methylstyrene, and para-t-butylstyrene. These styrene monomers are
Not only one type but also a combination of two or more types may be used.

Other comonomers include, for example,
Acrylonitrile, acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, methyl acrylate,
Ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate,
Examples thereof include butyl methacrylate, 2-ethylhexyl methacrylate, and divinylbenzene, and one or more of these can be used. These other comonomers can be used in combination with the above-mentioned styrene-based monomer at a ratio of 50% by weight or less. Among these, it is particularly preferable to use a styrene monomer.

On the other hand, examples of the rubber polymer include polybutadiene rubber, styrene-butadiene rubber, ethylene-propylene rubber (EPR, EPDM), acrylic rubber, nitrile rubber and the like. Among these, polybutadiene rubber is preferable.

In the present invention, the rubber-modified aromatic vinyl polymer resin used as the component (A) is a styrene monomer or a styrene monomer and another styrene monomer in the presence of a rubbery polymer as described above. It is obtained by polymerizing a comonomer by a known method. Specifically, for example, a rubber-modified aromatic vinyl polymer resin can be produced by dissolving a polybutadiene rubber in styrene and subjecting it to bulk polymerization or bulk-suspension polymerization.

As such a rubber-modified vinyl polymer resin, a polybutadiene rubber or a styrene-butadiene rubber-modified styrene polymer (high impact polystyrene) is preferable.

The amount of the rubbery polymer in the rubber-modified vinyl polymer resin is preferably 3 to 12% by weight, more preferably 5 to 11% by weight, and further preferably 7 to 10% by weight. If the amount of the rubbery polymer in the rubber-modified vinyl polymer resin is less than 3% by weight, the resulting polymer alloy may not be sufficiently improved in tensile elongation. On the other hand, when the amount of the rubber-like polymer in the rubber-modified vinyl polymer resin is more than 12% by weight, the rigidity decreases.

The rubber-modified aromatic vinyl polymer resin preferably has an area average particle size of the dispersed rubber particles of 0.1 to 1.5 μm, as described in claim 5. If the area average particle size of the dispersed rubber particles is smaller than 0.1 μm, the resulting polymer alloy has insufficient tensile elongation. On the other hand, if the area average particle size of the dispersed rubber particles is larger than 1.5 μm, gloss and rigidity are undesirably reduced. The dispersed rubber particles may be of a core-shell type or of a salami type.

The area average particle diameter Ds of the dispersed rubber particles is determined by first taking a transmission electron micrograph of an ultrathin section stained with osmic acid and examining 200 or more rubber particles in the transmission electron micrograph. , Is measured by substituting the major axis di into the following equation.

Ds = Σdi ³ / Σdi ²

In the present invention, as the aromatic vinyl polymer resin used as the component (A), the above-mentioned rubber-modified aromatic vinyl polymer resin is usually used, but if necessary, the non-rubber-modified aromatic vinyl resin may be used. As described above, the polymer resin can be appropriately compounded. In this case, as the aromatic vinyl polymer resin used as the component (A), as described in claim 2, a rubbery polymer is used.
Those which are rubber-modified aromatic vinyl polymer resins containing up to 12% by weight are preferred. As the aromatic vinyl polymer resin used as the component (A), those containing no rubber-modified aromatic vinyl polymer resin at all are not preferred because the resulting polymer alloy may not sufficiently improve the tensile elongation. By including the rubber-modified aromatic vinyl polymer resin, the tensile elongation of the obtained polymer alloy can be sufficiently improved.

As the non-rubber-modified aromatic vinyl polymer resin, the styrene-based monomer described in the description of the rubber-modified aromatic vinyl-polymer resin, or the styrene-based monomer and another comonomer are polymerized. Things. Specifically, for example, general-purpose polystyrene (GPPS) or the like can be suitably used.

Next, in the present invention, a polypropylene resin is used as the component (B). Here, examples of the polypropylene resin include, in addition to a propylene homopolymer, a copolymer of propylene and another α-olefin (such as a propylene-ethylene copolymer). Among these, it is preferable to use a propylene-ethylene copolymer as described in claim 6 from the viewpoint of improving the tensile elongation of the obtained polymer alloy.

Further, in the propylene-ethylene copolymer, as described in claim 7, the amorphous portion obtained by crystallization fractionation of the polypropylene resin is 13 to 20% by weight, and the amorphous portion is Ethylene content of 20 to
Most preferred is a 40% by weight propylene-ethylene copolymer. Here, when the amorphous portion is less than 13% by weight, the tensile elongation of the obtained polymer alloy is low. On the other hand, when the amorphous portion exceeds 20% by weight, the rigidity is reduced, and thus both are not preferable. Further, the ethylene content in the amorphous part is 20%.
When the amount is less than 40% by weight or more than 40% by weight, the tensile elongation of the obtained polymer alloy is reduced.

The crystallization fractionation for measuring the amount of amorphous part can be performed by the following method. (1) 5 ± 0.05 g of a sample was precisely weighed and placed in a 1000 mL eggplant-shaped flask, and BHT (antioxidant) 1 ±
After adding 0.05 g, the rotor and para-xylene 70 were added.
Add 0 ± 10 mL. (2) Next, a condenser is attached to the eggplant-shaped flask, and the flask is heated in an oil bath at 140 ± 5 ° C. for 120 ± 30 minutes while the rotor is operated to dissolve the sample in para-xylene. (3) Next, after pouring the contents of the flask into a 1000 mL beaker, while stirring the solution in the beaker with a stirrer, allow the solution to cool to room temperature (25 ° C.) (8 hours or more).
Thereafter, the precipitate is collected by filtration with a wire mesh. (4) The filtrate was further filtered through a filter paper, and the filtrate was filtered using methanol 2000 in a 3000 mL beaker.
Pour into ± 100 mL, and stir the liquid at room temperature (25 ° C.) with a stirrer for 2 hours or more. (5) Next, the precipitate is collected by filtration with a wire mesh, air-dried for 5 hours or more, and 240 to 27 at 100 ± 5 ° C in a vacuum dryer.
After drying for 0 minutes, a xylene-soluble component is recovered at 25 ° C. (6) On the other hand, the precipitate collected by a wire mesh in the above (3) is dissolved again in para-xylene according to the above methods (1) and (2), and then dissolved in 2000 ± 100 mL of methanol contained in a 3000 mL beaker. Quickly, and stir with a stirrer for 2 hours or more.
℃). (7) Next, the precipitate is filtered through a wire mesh, air-dried for 5 hours or more, and then 240 to 270 at 100 ± 5 ° C in a vacuum dryer.
After drying for 25 minutes, xylene insolubles are collected at 25 ° C. 25 ° C
The content (w) of the soluble component with respect to xylene is represented by w (% by weight) = 100 × C / A, where Ag is the sample weight and Cg is the weight of the soluble component recovered in (5). , The content of the insoluble component is (100-w)
It is expressed in% by weight. Among these, the content of the xylene-soluble component corresponds to the amount of the amorphous part.

The ethylene content in the amorphous part can be measured by the following method. A 220 mg sample was collected in an NMR sample tube and mixed with a 1,2,4-trichlorobenzene / deuterated benzene mixed solvent (volume 90/10) 3.
After adding mL, cap it and dissolve uniformly at 130 ° C., and measure ¹³ C-NMR under the following conditions.

Apparatus: JNM-EX400, manufactured by JEOL Ltd. Pulse width: 9 μs (45 °) Pulse repetition time: 4 seconds Spectrum width: 20000 Hz Measurement temperature: 130 ° C. Number of integrations: 1000 to 10000 times

The ethylene unit content in the amorphous part is a value determined by the following method.

That is, the ¹³ C-NMR of the sample was measured, and based on the seven peak intensities in the 35 to 21 ppm [tetramethylsilane (TMS) chemical shift standard] region in the spectrum, ethylene (E), propylene (P ) Tr
The iad chain fraction (mol%) is calculated by the following equation.

F _EPE = [K (Tδδ) / T] × 100 f _PPE = [K (Tβδ) / T] × 100 f _EEE = [K (Sγδ) / 4T + K (Sδδ) / 2T]
× 100 f _PPP = [K (Tββ) / T] × 100 f _PEE = [K (Sβδ) / T] × 100 f _PEP = [K (Sββ) / T] × 100

Where T = K (Tδδ) + K (Tβδ) +
K (Sγδ) / 4 + K (Sδδ) / 2 + K (Tββ) +
K (Sβδ) + K (Sββ).

Here, for example, f _EPE is EPTria
The d-chain fraction (mol%) is shown, and K (Tδδ) is Tδδ
The integrated intensity of the peak attributed to carbon is shown.

Next, the ethylene unit content (% by weight)
Using the above triad chain fraction, it is calculated by the following equation.

Ethylene unit content (% by weight) = 28 ｛3
f _EEE +2 (f _PEE + f _EPE ) + f _PPE + f _PEP ｝ × 100
/ [28 ｛3f _EEE +2 (f _PEE + f _EPE ) + f _PPE + f
_PEP ｝ +42 ｛3f _PPP +2 (f _PPE + f) + f _EPE + f
_PEE ｝]

The propylene-ethylene copolymer as described above has a melt flow rate (MI) of 0.1 to 3
Those at 0 g / min are preferred. If the MI is smaller than 0.1 g / min, molding becomes difficult, while if the MI is larger than 30 g / min, the tensile elongation of the obtained polymer alloy is reduced. MI is a value measured at 230 ° C. and a load of 2.16 kg.

The method for producing the propylene-ethylene copolymer used in the present invention is not particularly limited as long as a propylene-ethylene copolymer having the above properties can be obtained. Any method can be selected and adopted.

In the present invention, a copolymer of ethylene and a 1-alkene having 4 to 10 carbon atoms is used as the component (C). Here, as the 1-alkene having 4 to 10 carbon atoms, for example, 1-butene, 1-hexene, 1-octene, 2-ethyl-1-hexene and the like can be mentioned.

As the copolymer of ethylene and a 1-alkene having 4 to 10 carbon atoms, as described in claim 10,
Preferably having density of 0.87~0.93g / cm ^3, especially a density of those more preferably 0.89~0.92g / cm ^3. When the density is less than 0.87 g / cm ^3, the rigidity of the obtained polymer alloy is slightly reduced. On the other hand, when the density exceeds 0.93 g / cm ³ , the degree of improvement in tensile elongation of the obtained polymer alloy is increased. Becomes smaller.

Further, in the present invention, as the component (D),
A block copolymer composed of a polymer block composed of a vinyl aromatic compound and a polymer block composed of a conjugated diene compound or a hydrogenated product thereof is used.

The block copolymer comprising a polymer block comprising a vinyl aromatic compound and a polymer block comprising a conjugated diene compound or a hydrogenated product thereof includes, for example, a styrene-butadiene block copolymer,
Styrene-butadiene block copolymer hydrogenated product (SEB
S), styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer (SEPS), and the like.

The block copolymer comprising a polymer block composed of a vinyl aromatic compound and a polymer block composed of a conjugated diene compound or a hydrogenated product thereof is preferably selected from the group consisting of: In particular, one or more polymers selected from the group consisting of styrene-butadiene block copolymers, styrene-isoprene block copolymers, and hydrogenated products thereof are preferred.

Further, as described in claim 9, styrene is used as a block copolymer composed of a polymer block composed of a vinyl aromatic compound and a polymer block composed of a conjugated diene compound or a hydrogenated product thereof. It is more preferable to use a hydrogenated product of a styrene-isoprene block copolymer or a hydrogenated product of a styrene-butadiene block copolymer containing 50% by weight or more, since the resulting polymer alloy has excellent surface impact strength.

In the present invention, the proportions of the components (A) to (D) are 30 to 94 parts by weight of the component (A), 69 to 5 parts by weight of the component (B), and 1 to 10 parts by weight of the component (C). Is a ratio of 1 to 15 parts by weight of the component (D) with respect to 100 parts by weight of the total amount, and preferably, as in the present invention according to claim 2,
Ratio of 1 to 10 parts by weight of component (D) based on 100 to 100 parts by weight of 50 to 89 parts by weight of component (A), 49 to 10 parts by weight of component (B), and 1 to 8 parts by weight of component (C). And more preferably 60 to 78 parts by weight of component (A) and component 3
8 to 20 parts by weight, total amount of 2 to 8 parts by weight of component (C) 10
The ratio of the component (D) is 2 to 8 parts by weight with respect to 0 parts by weight.

If the proportion of the aromatic vinyl polymer resin as the component (A) is less than 30 parts by weight, the rigidity of the obtained resin composition is reduced. It is not preferable because the effect of improvement is not sufficient.

Next, when the blending ratio of the polypropylene resin (B) is less than 5 parts by weight, the effect of improving the heat and oil resistance is not sufficient, while when it exceeds 69 parts by weight, the obtained resin composition Is not preferred because the rigidity of the rubber is reduced.

Further, ethylene of component (C) and carbon number 4 to
If the blending ratio of the copolymer of 10 with the 1-alkene is less than 1 part by weight, the effect of the addition of the compound will not be observed. On the other hand, when the compounding ratio of the component (C) exceeds 10 parts by weight, the tensile elongation modulus is reduced although the tensile elongation and the impact resistance are improved.

Further, the blending ratio of the block copolymer composed of the polymer block composed of the vinyl aromatic compound of the component (D) and the polymer block composed of the conjugated diene compound or a hydrogenated product thereof is less than 1 part by weight. If it is, the tensile elongation and impact resistance of the obtained resin composition cannot be improved. On the other hand, when the compounding ratio of the component (D) exceeds 15 parts by weight, although there is an effect of improving tensile elongation and impact resistance, it causes a decrease in tensile modulus and a problem in cost.

The present invention basically has the contents as described above. However, if necessary, various additives such as a phenol or phosphorus antioxidant, a plasticizer such as liquid paraffin, stearic acid, etc. , A release agent such as zinc stearate and calcium stearate, an external lubricant such as ethylenebisstearylamide, various pigments, a flame retardant, and a silicone oil.

In producing the resin composition of the present invention, there is no particular limitation, and a known method can be employed. For example, a known method using a known kneader such as a single-screw extruder, a twin-screw extruder, or a Banbury mixer can be employed. The kneading temperature is preferably from 160 to 280C. The resin composition of the present invention is molded by a known molding method such as injection molding, extrusion molding, thermoforming, hollow molding, foam molding, and the like. Sheets, foams, films, injection molded products of various shapes, hollow molded products, It can be formed into various molded products such as compressed air molded products, and can be used for food containers and the like. In this case, extrusion molding, thermoforming and foam molding are particularly preferable as the molding method. The molded article obtained from the resin composition of the present invention obtained as described above can be subjected to antistatic treatment, coloring, painting and plating as required. Among these uses, in the present invention, a resin foam sheet which has conventionally been difficult to form stably and favorably (claim 1)
1, which can correspond to the molding of claim 12).

That is, as described in claim 12, the resin composition according to any one of claims 1 to 10 comprises:
In addition, by forming a resin foam sheet having a density of 0.04 to 1.1 g / cc, good molding can be stably performed. The thickness of the resin foam sheet is preferably 0.1 to 20 mm, as described in claim 13.

In order to obtain such a resin foamed sheet comprising the resin composition of the present invention according to any one of claims 1 to 10, the method according to claim 14 can be employed. That is, the present invention according to claim 14 is characterized in that the resin composition according to any one of claims 1 to 10 is melt-kneaded together with a foaming agent in an extruder and then extruded from a mold. Is provided.

Specifically, by mixing a foaming agent in an extruder or the like with a resin component containing the above-mentioned components (A) to (D) as essential components and further containing components that can be blended as required, the purpose is as follows. Can be obtained.

That is, after mixing the resin composition of the present invention according to any one of claims 1 to 10 with a nucleating agent, the mixture is supplied to the first extruder of a tandem type foam extruder, and
The resin composition and the low-boiling substance were uniformly mixed with the low-boiling substance after being injected with heat at a temperature of 0 to 250 ° C., and immediately and continuously supplied to the second-stage extruder. ~ 18
By cooling the mixture to 0 ° C. and discharging it into the atmosphere from a mold attached to the tip of the extruder, a desired resin foam sheet can be obtained. Further, after mixing the resin composition of the present invention according to any one of claims 1 to 10 with a chemical foaming agent,
By mixing the gas generated by the reaction between the heat-melted resin composition and the chemical foaming agent by introducing the resin into the extruder, and discharging the mixed gas from the die at the tip of the extruder, a desired resin foam sheet is obtained. Can also.

As the foaming agent used here, any one which is generally used as a foaming agent for a thermoplastic resin can be used. Specifically, for example,
Hydrocarbon compounds such as propane, butane, pentane and hexane; halogenated hydrocarbon compounds such as CFC-12, CFC-11, CFC-22, CFC-123, CFC-134, methyl chloride and methylene chloride; A chemical foaming agent that generates a gas by an exothermic or endothermic reaction can be used.

The expansion ratio varies depending on the intended use, but can be 1.1 to 20 times. When it is 1.1 times or more, it is preferable in terms of weight reduction and the like, and when it is 20 times or less, it is preferable in terms of the state of forming foam cells. When obtaining a resin foam sheet, talc,
Inorganic substances such as silica gel and calcium carbonate and chemical foaming agents can be added. Further, calcium stearate, zinc stearate, magnesium stearate and the like can be used as a lubricant.

The foamed resin sheet thus obtained can be used as a single layer, but can also be used as a laminated sheet using heat fusion or an adhesive. The raw material of the sheets to be laminated is not particularly limited.

In the present invention, in addition to the above-mentioned resin foam sheet, the resin composition of the present invention according to claim 1 can be formed into a container as in the present invention according to claim 15. As described above, the molding means is injection molding, extrusion molding, or the like. Further, as described in claim 16, a container can be formed by molding the resin foam sheet according to claims 11 to 13. This container is heat resistant,
Since it is excellent in oil resistance, has an excellent balance between tensile elongation and rigidity, and is inexpensive in production, it can be suitably used as a material for various food containers, particularly for microwave-compatible food containers.

[0062]

Next, the present invention will be described in detail with reference to examples.

Example 1 As the component (A), HIPS (manufactured by Idemitsu Petrochemical, trade name: HT53, area average particle size of dispersed rubber particles = 0.8 μm)
m) 40 parts by weight and GPPS (manufactured by Idemitsu Petrochemical, trade name:
HH32) 30 parts by weight, block polypropylene (Block PP-A) (Idemitsu Petrochemical, M
I = 8 g / 10 min, amorphous part content 16%, amorphous part ethylene content 35%) 27 parts by weight, copolymer (C) of ethylene and 1-alkene (trade name, manufactured by Idemitsu Petrochemical Co., Ltd.) :
Moretec 0138N, density 0.92 g / cm ³ ) 3 parts by weight, and based on the total 100 parts by weight,
A twin-screw kneading extruder (manufactured by Toshiba Machine Co., Ltd.) using 4 parts by weight of SEBS (trade name: Tuftec H1041, styrene content 30% by weight) as a component (D)
The mixture was kneaded at 220 ° C using TEM-35) to produce pellets.

The produced pellets were extruded at 220 ° C.
A sheet having a thickness of 0.4 mm was formed and evaluated for tensile properties, DuPont impact strength and heat and oil resistance. JIS for tensile properties
According to K 7127, it was measured using a No. 2 dumbbell on the basis of the gripper. DuPont impact strength is JIS K7
211. The evaluation of heat resistance and oil resistance was performed by the following method. That is, the sheet was cut into a test piece of 50 × 50 mm, and MC was colored red with a small amount of oil red or the like.
Immediately after applying T oil (manufactured by RIKEN Vitamin, actor), it was put into a constant temperature bath at 80 ° C., and evaluated by observing the surface state after 3 minutes. When the surface was not eroded and there was no portion colored in red, it was evaluated as ○, and when the surface was eroded and there was a portion colored in red, it was evaluated as x. Table 1 shows the results.

Examples 2 to 9 and Comparative Examples 1 to 5 Pellets were produced in the same manner as in Example 1 except that the types and mixing ratios of the components (A) to (D) were changed as shown in Table 1. , Tensile properties, DuPont impact strength and heat and oil resistance were evaluated. Table 1 shows the conditions and results.

[0066]

[Table 1] Table 1 (Part 1)

[0067]

[Table 2] Table 1 (Part 2)

[0068]

[Table 3] Table 1 (Part 3)

[Footnotes to Table 1] 1) HIPS (manufactured by Idemitsu Petrochemical, trade name: HT53, area average rubber particle size of dispersed rubber particles = 0.8 μm) 2) GPPS (manufactured by Idemitsu Petrochemical, trade name: HH32) 3) Block PP-A (manufactured by Idemitsu Petrochemical, MI = 8 g /
10 minutes, amorphous part content 16%, amorphous part ethylene content 35
%) 4) Block PP-B (manufactured by Idemitsu Petrochemical, MI = 8 g /
10 minutes, amorphous part amount 11%, amorphous part ethylene amount 35%) 5) Block PP-C (manufactured by Idemitsu Petrochemical, MI = 8 g /
6) Copolymer of ethylene and 1-alkene (manufactured by Idemitsu Petrochemical, trade name: Mooretec 0138N, density: 0.92 g) 10 minutes, amorphous part amount 15%, amorphous part ethylene amount 45%)
/ Cm ³ ) 7) Copolymer of ethylene and 1-alkene (manufactured by Dow Chemical, trade name: Engage EG8100, density 0.87)
g / cm ³ ) 8) SEBS (made by Asahi Kasei Corporation, trade name: Tuftec H104)
1, styrene content 30% by weight) 9) SEPS (manufactured by Kuraray, trade name: Septon 2104,
(Styrene content: 65% by weight) 10) MI of the entire composition is shown at 200 ° C. and 5 k
It is a measured value of g load. 11) Conforms to JIS K 7127 12) Conforms to JIS K 7127 13) Conforms to JIS K 7211

Table 1 shows the following. Example 3 uses SEPS having a higher styrene content than SEBS used in other examples as the component (D) (compatibilizer). Compared with the corresponding Example 1, the tensile modulus is slightly inferior to Example 1 (SEBS) but within an acceptable range. On the other hand, tensile elongation, particularly TD, was determined in Example 3 (SEP
S) is much better, and the Dupont impact strength is also very good at 2.1J. From this fact, when a component having a particularly high styrene content is used as the component (D) in the composition of the present invention, the tensile strength (particularly,
It can be seen that TD) and a remarkable improvement in impact strength can be realized.

Examples 4 and 5 are examples in which the proportion of the component (C) (copolymer of ethylene and 1-alkene) is low and high, respectively, as compared with the corresponding Example 1. is there. From Table 1, it is needless to say that the physical property balance of each example is good, but when each is compared with Example 1, in Example 4, a slight improvement in the tensile modulus is obtained. The improvement in the tensile elongation indicates that the tensile properties can be adjusted by adjusting the mixing ratio of the component (C).

The sixth embodiment is different from the first embodiment in that (D)
It can be seen that even when the mixing ratio of the component (compatibilizer) is further reduced by 1 part by weight to 3 parts by weight, an acceptable range of tensile elongation and the like can be achieved.

In the seventh embodiment, (D) is twice as large as that of the first embodiment.
Component, but the tensile elongation (M
D and TD) and Dupont impact strength are improved.
Other physical properties, which did not reach Example 1, were acceptable. This indicates that in the present invention, an excellent composition can be obtained even when the component (D) is added in a relatively large amount of 8 parts by weight.

In Comparative Example 1, the component (C) (ethylene and 1-
In the case where the (copolymer with alkene) and the component (D) (compatibilizer) are not blended, the tensile elongation (both MD and TD)
And the DuPont impact strength was 0.1 J or less, and the impact resistance was extremely low. Furthermore, it turns out that heat resistance and oil resistance are also inferior. Comparative Example 2 was a case where the component (C) was not blended, and although the Dupont impact strength and tensile elongation were improved to some extent as compared with Comparative Example 1, it can be seen that the tensile elongation was still insufficient.

In Comparative Example 3, a large amount of the component (D) (compatibilizer) was added.
Although the tensile elongation (TD, MD) and Dupont impact strength were improved, the tensile modulus (TD, MD) was low, and the physical property balance was lacking. From this, expensive (D)
It is clear that even when a large amount of the component is added, the effect of the combination reaches a plateau.

In Comparative Example 4, a large amount of the component (C) (copolymer of ethylene and 1-alkene) was blended. Compared with Example 1, tensile elongation (TD, MD),
Although the DuPont impact strength improves, the tensile modulus (T
D, MD) were low and lacked physical property balance. From this, it is clear that a sufficient effect cannot be obtained even when the component (C) is added in a large amount. Comparative Example 5 is a high impact polystyrene alone, but it is found that heat resistance and oil resistance are inferior.

Example 10 and Comparative Example 6 Pellets were produced in the same manner as in Example 1 except that the types and mixing ratios of the components (A) to (D) were changed as shown in Table 2. 100 parts by weight of the produced pellets, 1 part by weight of a foaming agent (manufactured by Eiwa Chemical Industry Co., Ltd., trade name: Cerbon SC-K) and 0.05 parts by weight of a lubricant (manufactured by NOF Corporation, trade name: calcium stearate) After blending with a tumbler, melt kneading at a temperature of 210 ° C. in a single screw extruder,
By opening to the atmosphere, a foamed sheet having a thickness of 1 mm was obtained. Table 2 shows the density, expansion ratio, and evaluation results of tensile properties, Dupont impact strength, and heat and oil resistance of the obtained foamed sheet in the same manner as in Example 1.

[0078]

[Table 4] Table 2

[Footnotes in Table 2] 1) to 13) are the same as in Table 1.

From Table 2, it can be seen that (C) of the resin composition of the present invention
In Example 10, which is a resin foam sheet produced from the resin composition of the present invention, as compared with Comparative Example 6 having no component,
It is clear that the tensile elongation is excellent in both the machine direction and the transverse direction.

[0081]

The aromatic vinyl polymer resin composition according to the present invention according to any one of claims 1 to 10 has excellent heat resistance and oil resistance, and also has an excellent balance between tensile elongation and rigidity. In addition, the aromatic vinyl polymer resin composition of the present invention according to any one of claims 1 to 10 can improve tensile elongation and the like without increasing the amount of the expensive component (D), and therefore, is economical. The above is also advantageous. Various molded articles can be obtained from the aromatic vinyl polymer resin composition according to the present invention. For example, as described in claims 11, 12, and 13, it is possible to form a resin foam sheet, which has conventionally been difficult to form stably and favorably,
A resin foam sheet having excellent heat resistance and oil resistance and an excellent balance between tensile elongation and rigidity can be obtained. Further, the resin composition according to any one of claims 1 to 10 and the resin foam sheet according to claim 11 can be formed into a container as in the invention according to claim 15 or the invention according to claim 16. It has excellent heat resistance, oil resistance, excellent balance between tensile elongation and rigidity, and is inexpensive to manufacture.
Particularly, it can be suitably used as a material for a microwave-compatible food container.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 53/02 C08L 53/02 // B29C 47/00 B29C 47/00 B29K 25:00 B29L 22:00 ( 72) Inventor Koji Kato 1-1, Anesaki Beach, Ichihara City, Chiba Prefecture Idemitsu Petrochemical Co., Ltd. (72) Inventor Hiroyuki Yamazaki 631 Sakado, Sakura City, Chiba Prefecture Dainippon Ink & Chemicals, Inc. 631 Sakado, Sakura-shi, Chiba F-term (reference) in Dainippon Ink and Chemicals, Inc. KF14 4J002 AC03W AC07W AC08W BB053 BB12X BB15W BB15X BC03W BC04W BG04W BN14W BP014 FD010 FD170 GG01

Claims (16)

[Claims] (A) Aromatic vinyl polymer resin 30 to 9
4 parts by weight, (B) 69 to 5 parts by weight of a polypropylene resin,
(C) 1 to 10 parts by weight of a copolymer of ethylene and a 1-alkene having 4 to 10 carbon atoms, and 100 parts by weight of the total amount of the components (A), (B) and (C) On the other hand, (D) a block copolymer comprising a polymer block comprising a vinyl aromatic compound and a polymer block comprising a conjugated diene compound or 1 to 15 parts by weight of a hydrogenated product thereof. Aromatic vinyl polymer resin composition. 2. (A) Aromatic vinyl polymer resin 50 to 8
9 parts by weight, (B) 49 to 10 parts by weight of a polypropylene resin, (C) 1 to 8 parts by weight of a copolymer of ethylene and a 1-alkene having 4 to 10 carbon atoms, and components (A) and ( A block copolymer comprising (D) a polymer block composed of a vinyl aromatic compound and a polymer block composed of a conjugated diene compound, or a block copolymer thereof, based on 100 parts by weight of the total amount of the component (B) and the component (C). An aromatic vinyl polymer resin composition comprising 1 to 10 parts by weight of a hydrogenated product. 3. The resin composition according to claim 1, wherein (A) the aromatic vinyl polymer resin is a rubber-modified aromatic vinyl polymer resin containing 3 to 12% by weight of a rubbery polymer. 4. The resin composition according to claim 3, wherein the rubber-modified aromatic vinyl polymer resin is a polybutadiene rubber or a styrene-butadiene rubber-modified styrene polymer. 5. The resin composition according to claim 3, wherein the rubber-modified aromatic vinyl polymer resin has an area average particle size of dispersed rubber particles of 0.1 to 1.5 μm. 6. The resin composition according to claim 1, wherein (B) the polypropylene resin is a propylene-ethylene copolymer. 7. (B) The polypropylene resin has 13 amorphous portions obtained by crystallization fractionation of the polypropylene resin.
The resin composition according to claim 6, which is a propylene-ethylene copolymer in which the content of ethylene in the amorphous portion is 20 to 40% by weight. 8. A block copolymer comprising (D) a polymer block composed of a vinyl aromatic compound and a polymer block composed of a conjugated diene compound or a hydrogenated product thereof is a styrene-butadiene block copolymer, The resin composition according to any one of claims 1 to 7, wherein the resin composition is at least one polymer selected from the group consisting of a styrene-isoprene block copolymer and a hydrogenated product thereof. 9. A block copolymer comprising (D) a polymer block comprising a vinyl aromatic compound and a polymer block comprising a conjugated diene compound or a hydrogenated product thereof contains styrene in an amount of 50% by weight or more. The resin composition according to claim 8, wherein: 10. (C) Ethylene and 1 to 4 carbon atoms
The copolymer with the alkene has a density of 0.87 to 0.93 g;
The resin composition according to any one of claims 1 to 9, wherein the resin composition has a density of / cm ³ . 11. A resin foam sheet comprising the resin composition according to claim 1. 12. A resin composition comprising the resin composition according to claim 1 and having a density of 0.04 or more.
1.1 g / cc resin foam sheet. 13. The resin foam sheet according to claim 11, wherein the sheet thickness is 0.1 to 20 mm. 14. After kneading the resin composition according to claim 1 together with a foaming agent in an extruder,
A method for producing a resin foam sheet, which is extruded from a mold. 15. An aromatic vinyl polymer resin (A)
94 parts by weight, (B) 69 to 5 parts by weight of a polypropylene resin, (C) 1 to 10 parts by weight of a copolymer of ethylene and a 1-alkene having 4 to 10 carbon atoms, and components (A) and ( A block copolymer comprising (D) a polymer block composed of a vinyl aromatic compound and a polymer block composed of a conjugated diene compound, or a block copolymer thereof, based on 100 parts by weight of the total amount of the component (B) and the component (C). A container formed by molding an aromatic vinyl polymer resin composition comprising 1 to 15 parts by weight of a hydrogenated product. 16. A container formed by molding the resin foam sheet according to claim 11.