JP2001240713A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition rich in resistances to heat and oil and excellent in tensile elongation properties by adding a partially hydrogenated block copolymer to a blend of a styrene resin and an olefin resin. SOLUTION: This resin composition contains (A) 95-5 pts.wt. styrene resin, 5-95 pts.wt. olefin resin, and, based on 100 pts.wt. sum of resins A and B, (C) 2-30 pts.wt. hydrogenated block copolymer which has a degree of hydrogenation of 35% or higher but lower than 70% and is obtained by partially hydrogenating a block copolymer containing at least one polymer block formed mainly from an aromatic vinylhydrocarbon and at least one polymer block formed mainly from a conjugated diene compound and having a content of units derived from the aromatic hydrocarbon of 30-80 wt.% and a vinyl bond content in the conjugated diene block of 20-90 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having excellent heat resistance, oil resistance and excellent tensile elongation characteristics. More specifically, the present invention relates to a resin composition suitable for food containers and the like comprising a styrene resin, an olefin resin, and a partially hydrogenated block copolymer having a specific structure.

[0002]

2. Description of the Related Art Styrene resins are widely used as injection molding materials and sheet molding materials because of their good workability and excellent mechanical properties. However, styrene resins have poor oil resistance, and when used in contact with oils such as margarine and sesame oil, their physical properties are sharply reduced, so that their use has been limited. Therefore, it has been attempted to mix an olefin resin to improve oil resistance. However, since the styrene-based resin and the olefin-based resin have poor compatibility, a peeling phenomenon occurs, resulting in a brittle composition.

[0003] In order to solve this problem, various compositions containing a block copolymer have been proposed. For example, JP-A-56-38338 discloses that a block copolymer having at least one vinyl aromatic compound polymer block A and at least one conjugated diene polymer block B is hydrogenated. A composition comprising a polyolefin-based resin and a polystyrene-based resin obtained by adding a hydrogenated block copolymer obtained by saturating at least 70% of a double bond of a block copolymer has been proposed. Discloses a hydrogenated block copolymer in which an AB block copolymer having a bound styrene content of 50% and a vinyl content before hydrogenation of 13% is hydrogenated by 92% of a double bond. . Also, Japanese Patent Application Laid-Open No.
No. 4550 also proposes a composition comprising a polyolefin-based resin and a polystyrene-based resin containing a similar hydrogenated block copolymer, specifically having a bound styrene content of 35% in isoprene before hydrogenation. Of an AB type block copolymer having a vinyl content of 8%
% Hydrogenated block copolymers and the like are disclosed. However, the hydrogenated block copolymers used in these compositions have high hydrogenation rates and have the disadvantage of low productivity. For example, the hydrogenation time required to obtain the hydrogenated block copolymer disclosed in JP-A-56-38338 is 6 hours, and the hydrogenated block copolymer disclosed in JP-A-1-174550 is required. The required hydrogenation time was 8 hours, a considerable time. Therefore, the appearance of a polymer which is a block copolymer which is easy to produce and has high productivity and which has excellent properties when added to a composition comprising a polyolefin resin and a polystyrene resin has been awaited. Further, in the composition disclosed herein, although the compatibility between the polyolefin resin and the polystyrene resin has been improved, the tensile elongation characteristics of the composition are not sufficient, and further improvement is desired.

[0004]

The object of the present invention is to provide a styrene-based resin and an olefin-based resin by adding a partially hydrogenated block copolymer having a specific structure to provide excellent heat resistance, oil resistance, and tensile elongation characteristics. An object is to provide an excellent resin composition.

[0005]

Means for Solving the Problems When the present inventors used a mixture of a styrene resin and an olefin resin,
As a result of a thorough study of a block copolymer having high heat resistance, oil resistance, excellent tensile elongation characteristics, and good productivity, a partially hydrogenated block copolymer having a specific structure was converted to styrene. It has been found that the object can be achieved by adding the compound to an olefin resin and an olefin resin, and the present invention has been completed.

That is, the present invention relates to a method for producing a partially hydrogenated block (C) with respect to 100 parts by weight of a total of (A) 95 to 5% by weight of a styrene resin and (B) 5 to 95% by weight of an olefin resin. (C) containing 2 to 30 parts by weight of a polymer
Has at least one polymer block X mainly composed of a vinyl aromatic compound and at least one polymer block Y mainly composed of a conjugated diene compound, and has a bound vinyl aromatic compound content of 30 to 80% by weight. %, And the amount of vinyl bonds in the conjugated diene block before hydrogenation is 20 to 90% by weight. By hydrogenating the block copolymer, a double bond based on the conjugated diene compound in the block copolymer is obtained. A partially hydrogenated block copolymer obtained by saturating 35% or more and less than 70% of the resin composition.

Hereinafter, the present invention will be described in detail. The styrene resin used in the component (A) of the present invention may be a homopolymer or copolymer such as styrene, methylstyrene, ethylstyrene, isopropylstyrene, dimethylstyrene, paramethylstyrene, chlorostyrene, bromostyrene, and vinylxylene. Polymer, styrene-maleic anhydride copolymer, styrene-acrylic acid copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer Polymers. Further, an impact-resistant polystyrene resin obtained by mixing or graft-polymerizing a rubber such as butadiene rubber, styrene-butadiene rubber, or ethylene-propylene rubber with the above-mentioned styrene resin can be used. Particularly, polystyrene and rubber-modified impact-resistant polystyrene are preferable. Also, the melt flow of the styrenic resin of the present invention is used.
(MFR: 200 ° C., 5 kg load) is 0.5 to 20
g / 10 minutes is preferable, and 1 to 10 g / 10 minutes is more preferable.

The olefin resin used in the component (B) of the present invention includes α-olefins such as ethylene,
Propylene, 1-butene, isobutylene, 4-methyl-
The resin is not particularly limited as long as it is a resin obtained by polymerizing 1-pentene or the like. The copolymer may be a random copolymer or a block copolymer, and may be a copolymer rubber of two or three or more α-olefins, or a copolymer of α-olefin and another monomer. Olefin-based thermoplastic elastomer. These copolymer rubbers include ethylene-propylene copolymer rubber (EPR) and ethylene-butene copolymer rubber (EB
R), ethylene-propylene-diene copolymer rubber (E
PDM) and the like. Among them, homo- or block polypropylene is preferable. In particular, when a propylene-ethylene block resin having a crystal melting peak temperature of 155 ° C. or more by syndiotactic polypropylene homopolymer or DSC is used, the heat resistance of the obtained composition is high. The nature becomes high. The melt flow rate (MFR: 230 ° C., 2.16 Kg load) of the olefin resin of the present invention is preferably 0.5 to 60 g / 10 min, and 1 to 20 g / min.
g / 10 minutes is more preferred. Melt flow rate is 0.
If it is less than 5 g / 10 minutes, the moldability of the resulting composition will be poor, and if it exceeds 60 g / 10 minutes, the impact resistance will be reduced.

The partially hydrogenated block copolymer used in the component (C) of the present invention comprises at least one polymer block X mainly composed of a vinyl aromatic compound and at least one polymer block X.
A conjugated diene compound having a polymer block Y, a bound vinyl aromatic compound content of 30 to 80% by weight, and a vinyl bond amount in the conjugated diene block before hydrogenation of 20 to 90% by weight. % Of the block copolymer obtained by hydrogenating a block copolymer of 35% or more and less than 70% of the double bond based on the conjugated diene compound in the block copolymer. It is.

The polymer block X mainly composed of a vinyl aromatic compound has a weight ratio of the vinyl aromatic compound to the conjugated diene compound of 100/0 to 60/40, preferably 100/100.
/ 0 to 80/20. When a vinyl aromatic compound and a conjugated diene compound are copolymerized, the distribution of the conjugated diene compound in this block may be random, taper (a monomer component increases or decreases along the molecular chain), and some blocks. The shape or any combination thereof. As the vinyl aromatic compound used here, styrene, α-
One or more selected from alkylstyrenes such as methylstyrene, p-methylstyrene, p-tert-butylstyrene, paramethoxystyrene, vinylnaphthalene, 1,1-diphenylethylene, divinylbenzene, and the like, Among them, styrene is preferred.

The polymer block Y mainly composed of a conjugated diene compound has a weight ratio of the conjugated diene compound to the vinyl aromatic compound of from 100/0 to 60/40, preferably 1/100.
It is a polymer block having a composition range of 00/0 to 80/20. When a conjugated diene compound and a vinyl aromatic compound are copolymerized, the distribution of the vinyl aromatic compound in this block may be random, taper (the monomer component increases or decreases along the molecular chain), or partially. It may be block-shaped or any combination thereof. The conjugated diene compound used here is one of butadiene, isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene and the like. Alternatively, two or more types are selected, and among them, butadiene and / or isoprene are preferred.

The molecular structure of the block copolymer may be linear, branched, radial, or a combination thereof, but is preferably linear. Among them, a structure in which X is two or more is preferable, for example, XYX, XYX-
Y, Y-X-XY-X-Y structures are preferred, and especially X-
YX structures are particularly preferred. Each of the blocks X or Y may have the same structure, or may have different structures such as monomer component content, distribution in their molecular chains, molecular weight of the block, and microstructure. Is also good. For example, Xs at both ends may be XYX's having different molecular weights.

The content of the vinyl aromatic compound in the partially hydrogenated block copolymer (C) is 30 to 80% by weight, preferably 40 to 80% by weight, more preferably 45 to 75% by weight. If the content of the vinyl aromatic compound is less than 30% by weight, the affinity between the block copolymer and the styrene resin is insufficient, and the amount of the block copolymer present at the interface between the styrene resin phase and the olefin resin phase is not sufficient. Sufficient and lacks compatibilizing effect. On the other hand, if it exceeds 80% by weight, the affinity with the styrene resin becomes excessive, and the block copolymer is taken into the styrene resin phase, so that the compatibilizing effect is also insufficient.

The amount of vinyl bonds in the conjugated diene block before hydrogenation of the partially hydrogenated block copolymer (C) is from 20 to
It is 90% by weight, preferably 30-80% by weight, more preferably 40-75% by weight. Here, the amount of vinyl bonds in the conjugated diene block before hydrogenation refers to the conjugate incorporated in the block copolymer in the form of 1,2-bond, 3,4-bond and 1,4-bond. Of the diene compounds,
It is defined as a ratio of a 1,2-bond and a 3,4-bond incorporated. If the amount of vinyl bonds in the conjugated diene block before hydrogenation is less than 20% by weight, the affinity between the block copolymer and the olefin resin becomes insufficient, and the compatibilizing effect becomes insufficient. On the other hand, if the content exceeds 90% by weight, the affinity with the olefin resin becomes excessive and the block copolymer is taken into the olefin resin phase, so that the compatibilizing effect is also insufficient.

[0015] The partially hydrogenated block copolymer used in the present invention is obtained by hydrogenating the above block copolymer to obtain at least 35% of a double bond based on a conjugated diene compound in the block copolymer. % Is saturated. If the hydrogenation ratio is less than 35%, the affinity between the block copolymer and the olefin resin decreases, so that the block copolymer is incorporated into the styrene resin phase and the compatibilizing effect becomes insufficient. In addition, heat resistance during processing is reduced, and recyclability is poor. When the hydrogenation rate is 70% or more, the processability is poor, and the productivity is lower than when the hydrogenation rate is less than 70%. The amount of residual vinyl bonds in the partially hydrogenated block copolymer used in the present invention is as follows:
Preferably it is less than 10%, more preferably 5% or less, further preferably 3% or less. Here, the residual vinyl bond amount is the amount of the vinyl structure remaining without hydrogenation with respect to the first conjugated diene 100. When the residual vinyl bond content in the block copolymer is 10% or more, the compatibilizing effect becomes insufficient.

The weight average molecular weight of the polymer block X mainly composed of a vinyl aromatic compound of the partially hydrogenated block copolymer (C) is 5,000 to 50,000, and that of the polymer block Y mainly composed of a conjugated diene compound is 5,000. ~ 700
00 is preferred. The molecular weight of the polymer block X is 5000
If the molecular weight of the polymer block Y is less than 5,000, the affinity with the olefin resin is lowered and the compatibilizing effect is inferior.
Further, whether the molecular weight of the polymer block X is 50,000 or more,
When the molecular weight of the polymer block Y is 70,000 or more,
Since the molecular weight of the block copolymer becomes excessively large, the melt viscosity increases, the dispersion in the resin composition comprising the styrene resin and the olefin resin becomes insufficient, and the compatibilizing effect is poor.

The melt flow rate (MFR: 230 ° C., 2.16 kg load) of the partially hydrogenated block copolymer (C) is preferably from 0.1 to 50 g / 10 min, more preferably from 0.5 to 50 g / 10 min. 20 g / 10 min, more preferably 1 to
10 g / 10 min. 0.1g of melt flow rate
If it is less than / 10 minutes, the melt viscosity is too high to obtain a sufficient compatibilizing effect, and if it exceeds 50 g / 10 minutes, the effect of reinforcing the interface between the styrene resin and the olefin resin decreases.

The method for producing the partially hydrogenated block copolymer (C) is not particularly limited, and a known method is employed. For example, a vinyl aromatic compound and a conjugated diene compound are polymerized in an inert solvent using the technique of living anion polymerization using an organolithium catalyst described in Japanese Patent Publication No. 36-19286, whereby the block copolymer is formed. Polymers can be produced. A method in which a monolithium compound such as n-butyllithium, sec-butyllithium, tert-butyllithium, etc. is used as an organic lithium catalyst, and is sequentially polymerized in the order of X, Y, X to form a block, and in the order of XY After forming an XY type living block copolymer, a method of forming a triblock copolymer having an XYX structure with a bifunctional coupling agent, and polymerizing in the order of X and Y using a dilithium compound. ,
There is a method of forming a triblock copolymer having an XYX structure. The content of the vinyl aromatic compound is controlled by controlling the feed monomer of the vinyl aromatic compound and the conjugated diene compound.
It is done by composition. Adjustment of the vinyl bond amount of the conjugated diene compound is performed by using a vinylating agent. Examples of the vinylating agent include amines such as N, N, N ', N'-tetramethylethylenediamine, trimethylamine, triethylamine, diazobicyclo [2,2,2] octane, tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol dibutyl ether. −
Ethers such as ter, thioethers, phosphines,
Examples thereof include phosphoramides, alkylbenzene sulfonates, potassium and sodium alkoxides, and the like.

A partially hydrogenated block copolymer can be obtained by subjecting the block copolymer obtained above to a hydrogenation reaction (hereinafter referred to as hydrogenation reaction) by a known method. As the catalyst used for the hydrogenation reaction, (1) a supported heterogeneous catalyst and (2) a Ziegler-type catalyst or a homogeneous catalyst using a titanocene compound are known. Specific methods are described in JP-B-42-8704 and JP-B-43-66.
No. 36, preferably JP-B-63-4
No. 841 or JP-B-63-5401 to obtain a solution of a partially hydrogenated block copolymer by adding a target amount of hydrogen in an inert solvent in the presence of a hydrogenation catalyst. Can be.

The partially hydrogenated block copolymer can be obtained by removing the solvent from the thus obtained solution of the partially hydrogenated block copolymer by an ordinary method. If necessary, a step of demineralizing metals can be adopted. If necessary, a reaction terminator, an antioxidant, a neutralizing agent, a surfactant and the like may be used. In particular, in the composition of the present invention, at least 40%, preferably at least 50%, of the partially hydrogenated block copolymer (C) is present at the interface between the styrene resin (A) and the olefin resin (B). Is preferred. When the abundance is 40% or more, the adhesive strength at the interface between the styrene-based resin and the olefin-based resin is excellent, so that excellent performance in tensile elongation properties is exhibited.

As the compounding ratio of each component of the present invention, the compounding ratio of the styrene resin (A) and the olefin resin (B) is 95: 5 to 5:95 by weight. To increase the rigidity, increase the mixing ratio of the styrenic resin (A),
When importance is placed on oil resistance, it is possible to adjust to increase the compounding ratio of the olefin resin (B). However, a styrene resin (A) and an olefin resin (B) are preferable from the viewpoint of a balance between rigidity, heat resistance, and oil resistance. Is 80:20 to 40:60
Is the weight ratio. Partially hydrogenated block copolymer (C)
Is 2 to 30 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight of the total of the styrene resin (A) and the olefin resin (B). If it is less than 2 parts by weight, the compatibilizing effect becomes insufficient. On the other hand, if it exceeds 30 parts by weight, the rigidity is reduced and it is not economical.

The thermoplastic resin composition of the present invention may contain optional additives as required. The type of the additive is not particularly limited as long as it is generally used for compounding the resin. For example, silica, calcium carbonate,
Inorganic fillers such as magnesium carbonate, calcium sulfate, talc, etc., organic fibers, pigments such as titanium oxide, carbon black, iron oxide, stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bistea Lubricants such as loamide, mold release agents,
Plasticizers such as organic polysiloxanes and mineral oils, hindered phenol and phosphorus antioxidants, flame retardants, ultraviolet absorbers, antistatic agents, reinforcing agents such as glass fibers, carbon fibers, metal whiskers, etc. Additives or mixtures thereof are mentioned.

The method for producing the resin composition of the present invention is not particularly limited, and a known method can be used. For example, a melt kneading method using a general kneader such as a Banbury mixer, a single screw extruder, a twin screw extruder, a coneder, a multi-screw extruder, and a method of dissolving or dissolving each component. After the dispersion and mixing, a method of heating and removing the solvent is used. Preferably, the styrene resin (A), the olefin resin (B) and the partially hydrogenated block copolymer (C) are sufficiently dissolved and mixed, and the partially hydrogenated block copolymer (C) is 180 ° C. or higher, preferably 200 ° C. or higher, which is a condition for moving to the interface between the phase A) and the olefin-based resin (B), and a shear rate of 100 seconds
It is preferable to knead under the condition of ^-1 . Preferably, a method using a twin screw extruder is used. Further, it is preferred that the master pellets are once kneaded by these methods to produce a master pellet, and molded using the master pellet, and if necessary, foamed.

[0024]

EXAMPLES The present invention will be described more specifically and in detail with reference to the following Examples, but it should not be construed that the present invention is limited to these Examples. (1) Components used and preparation thereof (a) Styrene resin Commercially available high impact polystyrene resin: 475D (manufactured by A & M Styrene Co.) (b) Olefin resin (b-1) Propylene resin Commercial homopolypropylene resin: PL500A (manufactured by Montelusd-K Sunrise Co., Ltd.) (b-2) Ethylene resin Commercially available high-density polyethylene resin: Suntech J301 (manufactured by Asahi Chemical Industry Co., Ltd.)

(C) A block copolymer having a stirrer and a jacket having an inner volume of 100 l
The reactor was washed, dried and purged with nitrogen, and a cyclohexane solution containing 33 parts by weight of styrene purified in advance was charged. Next, n-butyllithium and tetramethylethylenediamine were added, and polymerization was carried out at 70 ° C. for 1 hour. Then, a cyclohexane solution containing 34 parts by weight of butadiene purified in advance was added, and a cyclohexane solution containing 33 parts by weight was further added for 1 hour. Polymerized for 1 hour.

A part of the obtained block copolymer solution was sampled, and octadecyl-3- (3,5-di-t-butyl-4
0.3 parts by weight of (hydroxyphenyl) propionate was added to 100 parts by weight of the block copolymer, and then the solvent was removed by heating (the obtained copolymer is referred to as polymer I). Polymer I had a styrene content of 66% by weight, a 1,2-vinyl bond amount in the polybutadiene portion of 50% by weight, and a number average molecular weight of 56,000. In addition, the styrene content was measured using infrared spectroscopy (IR). The amount of vinyl bonds was measured by infrared analysis (IR) and calculated by the Hampton method. The number average molecular weight was measured by using gel permeation chromatography (GPC).

Then, using the remaining block copolymer solution, di-p-trisbis (1-cyclopentagenenyl)
Hydrogenation was performed at a temperature of 70 ° C. using titanium and n-butyllithium as a hydrogenation catalyst, and a part of the polymer solution was sampled to obtain Polymer II. Polymer II had a hydrogenation rate of 26%. In addition, the hydrogenation rate was measured using a nuclear magnetic resonance apparatus (NMR). The hydrogenation rate is measured by measuring the amount of hydrogen gas to be supplied with a flow meter and stopping the gas supply when the target hydrogenation rate is achieved.
I did. The remaining polymer solution was hydrogenated again to obtain a copolymer solution of polymers III and IV. Polymer I
II had a hydrogenation rate of 44%, but the required time from the start of hydrogenation was 30 minutes. In addition, polymer IV
The hydrogenation rate was 65%, but the time required from the start of hydrogenation was 45 minutes. In each of the copolymer solutions, the solvent was removed by heating after the addition of the stabilizer in the same manner as in Polymer I to prepare various polymers (II to IV). Table 1 shows the polymer structure of each sample.

A block copolymer was obtained in the same manner as in Example 1 except that the amounts of styrene and the amounts of n-butyllithium and tetramethylethylenediamine were changed. The obtained polymer had a styrene content of 60% by weight, a 1,2-vinyl bond content of the polybutadiene portion of 25% by weight, and a number average molecular weight of 76,000 (referred to as polymer V). Further, using a block copolymer solution, hydrogenation was carried out in the same manner as in Example 1 to prepare a polymer VI. Table 1 shows the polymer structure of each sample. Thus, a block copolymer was similarly obtained except that tetramethylethylenediamine was not added. The obtained polymer had a styrene content of 60% by weight, a 1,2-vinyl bond amount in the polybutadiene portion of 12% by weight, and a number average molecular weight of 74,000.

Further, using a block copolymer solution,
Hydrogenation was performed in the same manner as described above to prepare Polymers VII and VIII. Table 1 shows the polymer structure of each sample. A block copolymer was obtained in the same manner as in Example 1 except that the amount of styrene charged and the amounts of n-butyllithium and tetramethylethylenediamine were changed. The obtained polymer had a styrene content of 50% by weight, a 1,2-vinyl bond amount in the polybutadiene portion of 40% by weight, and a number average molecular weight of 62,000 (referred to as polymer IX).

Further, using a block copolymer solution,
Hydrogenation was carried out in the same manner as described above to prepare Polymers X and XI. Table 1 shows the polymer structure of each sample. The amount of styrene initially charged is 37 parts by weight.
A block copolymer was obtained in the same manner except that the amount of styrene charged after butadiene polymerization was changed to 29 parts by weight. The obtained polymer had a styrene content of 66% by weight, a 1,2-vinyl bond amount in the polybutadiene portion of 48% by weight, and a number average molecular weight of 54,000.

Further, using a block copolymer solution,
Hydrogenation was carried out in the same manner as described above to prepare Polymer XII.
The polymer structure is shown in Table 1. 100 liter capacity with stirrer and jacket
The reactor was washed, dried and purged with nitrogen, and a cyclohexane solution containing 30 parts by weight of styrene purified in advance was charged. Next, n-butyllithium and tetramethylethylenediamine were added, and the mixture was polymerized at 70 ° C. for 1 hour. Then, a cyclohexane solution containing 40 parts by weight of previously purified isoprene was added, and for 1 hour, a cyclohexane solution containing 30 parts by weight was further added. Polymerized for 1 hour.

A part of the obtained block copolymer solution was sampled, and octadecyl-3- (3,5-di-t-butyl-4) was sampled.
0.3 parts by weight of (hydroxyphenyl) propionate was added to 100 parts by weight of the block copolymer, and then the solvent was removed by heating (the obtained copolymer was polymer XI).
II). Polymer XIII has a styrene content of 6
0% by weight, the total amount of vinyl bonds in the polyisoprene portion was 40% by weight, and the number average molecular weight was 52,000.

Then, using the remaining block copolymer solution, di-p-trisbis (1-cyclopentagenenyl)
Using titanium and dibutylmagnesium as hydrogenation catalysts,
Hydrogenation was performed at a temperature of 70 ° C. to obtain polymer XIV.
Polymer XIV had a hydrogenation rate of 52%. The remaining polymer solution was re-hydrogenated to obtain a polymer-XV copolymer solution. Polymer XV has a hydrogenation rate of 92%.
%Met. Table 1 shows the polymer structure of each sample.

[0034]

[Table 1]

(2) Preparation of resin composition and measurement of physical properties Each of the components (a), (b) and (c) was blended in the proportions shown in Tables 2 and 3 and a 30 mm twin screw extruder was used. Using 2
Melt kneading was performed at a temperature of 20 ° C. to form pellets. still,
The measurement standards and test methods of the physical properties shown in Examples and Comparative Examples are as follows. The obtained pellet was injection molded at 220 ° C., and the following various properties 1 to 7 were measured. 1. Tensile elongation property: In accordance with ASTM D638, the tensile elongation at break of an injection molded test piece was measured. The pulling speed was 5 mm / min. 2. Heat resistance: In accordance with ASTM D1525, the Vicat softening point of the injection molded test piece at a load of 1 kgf was measured.
The index was used.

3. Rigidity: In accordance with ASTM D790, a bending test was performed on an injection-molded test specimen to measure a flexural modulus. 4. Block copolymer interface abundance: The ratio to the total blended amount in the block copolymer existing at the interface between the styrene-based resin phase and the olefin-based resin phase was measured and calculated by the following method. An ultra-thin section of a plane parallel to the flow direction of the resin at the time of molding is cut out from an injection molded article of the resin composition with an ultramicrotome, stained with ruthenium tetroxide, and photographed with a transmission electron microscope at a magnification of 10,000. Take. By analyzing the image of this photograph, the area of the block copolymer present in the styrene resin phase or the olefin resin phase is measured, and the ratio (a) to the total area subjected to the image analysis is calculated.
Further, assuming that the weight ratio of the block copolymer calculated from the compounding ratio of the resin composition is (b), the ratio (c) of the block copolymer present at the interface between the styrene resin phase and the olefin resin phase is as follows: ((B)-(a)) / (b) × 10
0%. This value was used as an index.

5. Oil resistance: Using a sheet extruder, the resin composition was made into a sheet having a thickness of 1 mm, formed into a container having a height of 2 cm, a length of 10 cm and a width of 10 cm, and applied with synthetic coconut oil on the inner surface. The heating temperature at which the rate of change in the inner volume of the container when heated for 1 hour was 10% was determined. It was determined that the higher the temperature, the better the oil resistance. 6. Heat aging resistance: When the resin composition was injection-molded, the resin composition was kept in a molding machine at a temperature of 240 ° C. for 10 minutes, then the plate was injection-molded, and the surface condition was visually judged. Evaluation was made in three stages according to the flash output. ○ (none) <△ (slightly present) <× (present) Processability: MFR of pellets of resin composition (200 ° C.
/ 5 Kg load) and used as an index. Table 2 shows the results of Examples 1 to 7 below.

Examples 1 to 3 70% by weight of impact-resistant polystyrene as the component (a)
This is an example of the resin composition of the present invention in which 30% by weight of (b-1) no-homo polypropylene is blended as the component (b), and a partially hydrogenated block copolymer is blended with the component (c). It can be seen that the resin composition is excellent in heat resistance, oil resistance and heat aging resistance in addition to high tensile elongation characteristics and rigidity. Examples 4 and 5 45% by weight of impact-resistant polystyrene as component (a)
This is an example of the resin composition of the present invention wherein the homopolypropylene of (b-1) is 55% by weight as the component (b) and the partially hydrogenated block copolymer is mixed with the component (c). In addition to high tensile elongation characteristics and rigidity, this resin composition has excellent heat resistance, oil resistance, and heat aging resistance.

Examples 6 and 7 Examples are the same as in Examples 1 to 3, except that Example 6 uses a partially hydrogenated block copolymer having different amounts of styrene at both ends. This is an example in which isoprene is used as a conjugated diene compound. Both resin compositions are compositions having heat resistance, oil resistance, and heat aging resistance in addition to high tensile elongation characteristics and rigidity as in the other examples. When the MFR of Example 7 was measured, it was 5.5 g / 1.
It was 0 minutes. In contrast, the polymer XIV of Example 7
The MFR of the resin composition using polymer-XV having a high degree of hydrogenation in place of was 4.9 g / 10 minutes. It can be seen that the resin composition of the present invention is excellent in processability.
The excellent properties of the resin composition of the present invention will become more apparent by comparison with the following comparative examples. Table 3 shows the results of Comparative Examples 1 to 8 below.

Comparative Example 1 This is an example of a resin composition containing 70% by weight of high-impact polystyrene and 30% by weight of homopolypropylene, but not containing a styrene block copolymer. The compatibility is poor, and the oil resistance as well as the tensile elongation properties are extremely poor. Comparative Examples 2 to 6,8 This is a composition in which 70% by weight of impact-resistant polystyrene and 30% by weight of homopolypropylene are blended with a styrene-based block copolymer, and the block copolymer has a structure specified in the present invention. As a result, the resin composition has a remarkably poor tensile elongation property and a reduced balance of properties.

Comparative Example 7 This is an example of the same composition as in Examples 4 and 5, except that the block copolymer does not have the structure specified in the present invention. Has become. Example 8 The component (b) of Example 1 was changed from (b-1) to (b-2).
A similar resin composition was obtained. As in Example 1, a resin composition having good compatibility was obtained.

[0042]

[Table 2]

[0043]

[Table 3]

[0044]

【The invention's effect】 [Brief description of the drawings]

FIG. 1 is an example of a transmission electron micrograph of a thermoplastic resin composition of Example 1 of the present invention. Most of the hydrogenated block copolymer (black streak layer) is present at the boundary between the propylene resin phase (undyed, light phase) and the styrene resin phase (dyed, dark phase).

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08L 53/02 C08L 53/02 55/02 55/02 (72) Inventor Masahiro Sasagawa 1-chome, Yakko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture. No. 3-1 Asahi Kasei Kogyo Co., Ltd. F-term (reference) 4J002 BB03X BB05X BB12X BB14X BB15X BB17X BB18X BC03W BC04W BC06W BC07W BC08W BC11W BG01W BG04W BH01W BN06W BN14W 01001 FD01 BP01 010 HA15 HA16 HA26 HA39 HB05 HB06 HB07 HB08 HB14 HB15 HB16 HB26 HB39 HC05 HC06 HC07 HC08 HC14 HC15 HC16 HC26 HC39 HE02 HE06

Claims (6)

[Claims] (A) 95 to 5% by weight of a styrene resin,
(B) Total amount 100 of 5-95% by weight of olefin resin 100
(C) 2 to 30 parts by weight of a partially hydrogenated block copolymer, and (C) contains at least one polymer block X mainly composed of a vinyl aromatic compound and at least one Having a polymer block Y mainly composed of a conjugated diene compound having a bound vinyl aromatic compound content of 30 to
By hydrogenating a block copolymer which is 80% by weight and has a vinyl bond content of 20 to 90% by weight in the conjugated diene block before hydrogenation, a diene based on the conjugated diene compound in the block copolymer is obtained. 35% or more of heavy bonds 7
A resin composition characterized by being a partially hydrogenated block copolymer obtained by saturating less than 0%. (C) having at least one polymer block X mainly composed of a vinyl aromatic compound and at least one polymer block Y mainly composed of a conjugated diene compound; Compound content of 40-80% by weight
By hydrogenating a block copolymer in which the amount of vinyl bonds in the conjugated diene block before hydrogenation is 30 to 80% by weight, double bonds based on the conjugated diene compound in the block copolymer are formed. The resin composition according to claim 1, which is a partially hydrogenated block copolymer obtained by saturating 40% or more and less than 70%. 3. The resin composition according to claim 1, wherein the residual vinyl bond amount in the (C) partially hydrogenated block copolymer is less than 10%. 4. The (C) partially hydrogenated block copolymer has an XYX structure.
4. The resin composition according to any one of items 1 to 3. 5. The method according to claim 1, wherein (C) the vinyl aromatic compound in the partially hydrogenated block copolymer is styrene, and the conjugated diene compound is butadiene.
The resin composition according to any one of the above. 6. The resin composition according to claim 1, wherein the olefin resin (B) is a propylene resin.