JP2002265690A - Impact resistant styrenic thermoplastic resin composition - Google Patents

Abstract

(57) [Problem] To provide an impact-resistant polystyrene resin having excellent weather resistance and chemical resistance. SOLUTION: (A) (1) 40 to 90% by weight of a partially or completely crosslinked saturated rubbery polymer, and (2) 10 to 60% by weight of a thermoplastic resin containing a polystyrene resin as an essential component. Thermoplastic elastomer consisting of 5 to 95 parts by weight, (B) polystyrene-based resin and / or polyolefin-based resin: 95 to 5 parts by weight and, if necessary, 100 parts by weight of components (A) and (B). (C) a compatibilizer: a composition comprising 0.1 to 50 parts by weight, wherein the composition contains 1 to 40% by weight of a saturated rubbery polymer in the composition; object.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a styrenic thermoplastic resin composition reinforced with a partially or completely crosslinked saturated rubbery polymer. More specifically, the present invention relates to a styrene-based thermoplastic resin composition reinforced with a partially or completely crosslinked saturated rubber-like polymer, having excellent weather resistance, chemical resistance and high impact resistance.

[0002]

2. Description of the Related Art Styrene resins are widely used in home electric appliance materials, food container / packaging materials, information equipment materials, and the like. When used in these applications, polystyrene itself is hard and brittle, so it is difficult to use high-impact polystyrene (HIP).
S) is also widely used. This high-impact polystyrene is generally prepared by dissolving polybutadiene in a styrene monomer and diluting this solution directly in the presence of a polymerization initiator by bulk polymerization or dilution with an organic solvent, or by dispersing this solution in water to form a polymerization initiator. It is produced by suspension polymerization in the presence. The rubber layer in the impact polystyrene must be crosslinked. The reason for this is that if not cross-linked, it is deformed in the flow direction during the molding process, resulting in a directionality in impact resistance, which is not preferable. In the method for producing impact-resistant polystyrene, rubber is crosslinked in one step when styrene is polymerized in the presence of an initiator.

[0003] The rubber which can be used at this time is a rubber capable of causing crosslinking at an initiator concentration at which a styrene monomer is polymerized at a constant rate, that is, a crosslinking having a double bond in a molecule like polybutadiene. It is limited to rubber that is easy to do. The reason for this is that, when a saturated rubber having no double bond is used, if the polymerization is carried out at an initiator concentration necessary for crosslinking the saturated rubber, a styrene monomer causes a runaway reaction and the polymerization cannot be controlled. On the other hand, a rubber having a double bond, as is generally well known, has poor mechanical strength due to a decrease in mechanical strength due to a decrease in molecular weight when used in a place with high light illuminance, for example, outdoors. Therefore, the impact-resistant polystyrene currently on the market has a serious problem that it cannot be used depending on the environment, and at present it cannot be used for a wide range of applications. There is a demand for the development of impact-resistant polystyrene using a saturated rubber having no double bond and having excellent weather resistance as a reinforcing agent.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an impact-resistant polystyrene resin excellent in weather resistance and chemical resistance in view of the above situation.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, unlike the usual method for producing high-impact polystyrene, for example, in an extruder or the like, Partial or complete cross-linking by kneading a saturated rubber-like polymer, polystyrene-based resin and a compatibilizer if necessary in the presence of a high concentration of a radical initiator and a cross-linking aid. By manufacturing a thermoplastic elastomer comprising a saturated rubber-like polymer and a matrix that is a fluid phase and a polystyrene resin, and then melt-mixing or pellet blending the obtained thermoplastic elastomer and the polystyrene resin, and the like. It has been found that an impact-resistant styrene-based thermoplastic resin having excellent weather resistance can be obtained. This impact-resistant styrene-based thermoplastic resin has better chemical resistance than ordinary impact-resistant polystyrene, but it is also possible to melt-mix this thermoplastic elastomer with a polyolefin-based resin or a polyolefin-based resin and a polystyrene-based resin. Alternatively, it has been found that by performing pellet blending or the like, an impact-resistant styrene-based thermoplastic resin having more excellent chemical resistance and excellent weather resistance can be obtained.

Another method is to knead a saturated rubbery polymer, a polystyrene resin, a polyolefin resin and a compatibilizer in the presence of a high concentration of a radical initiator and a crosslinking aid in an extruder. By manufacturing a partially or completely crosslinked saturated rubber-like polymer and a thermoplastic elastomer comprising a matrix comprising a polystyrene-based resin and a polyolefin-based resin, thereafter, the obtained thermoplastic elastomer and a polystyrene-based resin, or polyolefin It is also found that an impact-resistant styrene-based thermoplastic resin excellent in chemical resistance and weather resistance can be obtained by melt mixing or pellet blending of a polyolefin resin or a polyolefin resin with a polystyrene resin. Was completed.

That is, the present invention provides (A) (1) a partially or completely crosslinked saturated rubbery polymer (2) a thermoplastic resin containing a polystyrene resin as an essential component, preferably a polystyrene resin. A thermoplastic elastomer comprising a thermoplastic resin or a thermoplastic resin comprising a mixture of a polystyrene resin and a polyolefin resin: 5 to 95 parts by weight; (B) a polystyrene resin and / or a polyolefin resin: 95 to 5 parts by weight A styrene-based thermoplastic resin composition comprising 1 to 40% by weight of a saturated rubbery polymer in the composition. At this time, the ratio of (1) a partially or completely crosslinked saturated rubbery polymer and (2) a thermoplastic resin having a polystyrene resin as an essential component is (1) a partially or completely crosslinked saturated polymer. 40 to 90% by weight of rubbery polymer, (2) 10 to 60% by weight of thermoplastic resin containing polystyrene resin as an essential component
It is.

The composition of the present invention comprises a particulate cross-linked saturated rubber-like polymer and a polystyrene resin as a matrix or a mixture of a polystyrene resin and a polyolefin resin. In order to obtain a high-strength styrene-based thermoplastic resin composition, it is necessary that the interface strength (adhesion strength) between the particulate crosslinked saturated rubber-like polymer and the matrix resin is high. Further, when the matrix is composed of a mixture of a polystyrene resin and a polyolefin resin, the separation between the polystyrene resin and the polyolefin resin occurs due to lack of affinity, that is, compatibility, but it is necessary to prevent this. It is. The saturated rubbery polymer that is the component (A) of the composition of the present invention will be described in detail below, but preferred saturated rubbery polymers include olefin-based elastomers and styrene-based elastomers. When the saturated rubbery polymer is a styrene-based elastomer and the matrix is a polystyrene-based resin, there is an affinity, that is, compatibility between the styrene component in the styrene-based elastomer and the polystyrene-based resin. Accordingly, a high-strength styrene-based thermoplastic resin composition having a high interface strength between the crosslinked saturated rubber-like polymer and the matrix resin is obtained. However, other than this combination, it is necessary to use a compatibilizer which is the component (C). This amount is 0.1 to 50 parts by weight based on 100 parts by weight of the components (A) and (B).

Accordingly, the present invention relates to a method for preparing a polystyrene resin comprising: (A) 40 to 90% by weight of a partially or completely crosslinked saturated rubbery polymer; A thermoplastic resin containing, as an essential component, preferably a thermoplastic resin composed of a polystyrene resin or a thermoplastic resin composed of a mixture of a polystyrene resin and a polyolefin resin, a thermoplastic elastomer composed of 10 to 60% by weight: 95 parts by weight, (B) a polystyrene-based resin and / or a polyolefin-based resin: 95 to 5 parts by weight, and if necessary, 100 parts by weight of the components (A) and (B); A composition comprising 1 to 50 parts by weight, and wherein the saturated rubbery polymer in the composition is 1 to 40 parts by weight.
The present invention relates to an impact-resistant styrene-based thermoplastic resin composition in a weight percentage. Incidentally, the final composition of the composition of the present invention,
Partially or fully crosslinked saturated rubbery polymer,
A polystyrene resin or a mixture of a polystyrene resin and a polyolefin resin, and if necessary, a compatibilizer.

On the other hand, the composition of the present invention is basically obtained by dynamically crosslinking a mixture of a saturated rubbery polymer and a polystyrene resin or a mixture of a polystyrene resin and a polyolefin resin in the presence of a radical initiator and a crosslinking assistant. The thermoplastic elastomer as the component (A) and the mixture of the polystyrene-based resin or polyolefin-based resin as the component (B) or the mixture of the polystyrene-based resin and the polyolefin-based resin are melt-mixed or pellet-blended. In order to make the final composition of the composition of the present invention, the component (A) and the component (B) were melt-mixed or pellet-blended without co-existing a polystyrene resin or a polyolefin resin as the component (B). A method is also conceivable in which the styrene-based thermoplastic resin composition of the present invention is dynamically cross-linked in a single step to obtain the styrene-based thermoplastic resin composition of the present invention in one step.

However, although this method is not to be denied, generally, when a mixture of a low-concentration saturated rubber-like polymer and a polystyrene-based resin or a mixture of a polystyrene-based resin and a polyolefin-based resin is dynamically crosslinked, a rubber-like polymer is used. Is difficult to crosslink. The reason for this is that the radical initiator and the crosslinking auxiliary, which are crosslinking agents, are also dispersed in the thermoplastic resin, so that they do not easily exist in the saturated rubbery polymer at a high concentration. Therefore, it becomes difficult to obtain a styrene-based thermoplastic resin composition in which a saturated rubber-like polymer is sufficiently crosslinked. For this reason, the composition of the present invention comprises (A) a thermoplastic elastomer comprising a partially or completely crosslinked saturated rubber-like polymer and a thermoplastic resin having a polystyrene-based resin as an essential component; (B) a polystyrene-based resin. And / or a polyolefin resin and, if necessary, a compatibilizer (C) as a basic component.

Hereinafter, the present invention will be described in detail. First, each component of the present invention will be described in detail. The partially or completely crosslinked saturated rubbery polymer in the component (A) of the thermoplastic resin composition of the present invention will be described. Examples of the saturated rubbery polymer of the present invention include olefin-based, styrene-based, ester-based, urethane-based, and vinyl chloride-based elastomers. Among them, olefin elastomer and styrene elastomer are characteristic
Preferred in terms of price.

Examples of the olefin elastomer include ethylene and α-olefin, acrylates such as vinyl acetate, methyl acrylate and butyl acrylate, and methacrylates such as methyl methacrylate, ethyl methacrylate and butyl methacrylate. Copolymers can be mentioned. Further, a hydrogenated conjugated diene polymer and the like can also be mentioned. In order to use these olefinic elastomers as the rubbery polymer in the component (A) of the impact-resistant styrenic thermoplastic resin composition of the present invention,
It must have rubber elasticity and has a JISA hardness of 9
It is preferably 0 or less. More preferably, it is 80 or less. Among these olefin-based elastomers, copolymers of ethylene and α-olefin and hydrogenated conjugated diene polymers are low-hardness and high rubber elasticity rubber-like polymers, resulting in styrene of high impact resistance. It is most preferable because it can be used as a thermoplastic resin composition.

The ethylene / α-olefin copolymer and the hydrogenated conjugated diene polymer which are preferably used ethylene / α-olefin copolymers will be described in detail. First, the ethylene / α-olefin copolymer will be described. This ethylene / α-olefin copolymer is
An ethylene / α-olefin-based copolymer mainly composed of ethylene and an α-olefin having 3 to 20 carbon atoms is preferable. Here, the meaning of "mainly" means that not only a binary copolymer of ethylene and an α-olefin but also a ternary or higher copolymer obtained by copolymerizing other monomers. Examples of the α-olefin having 3 to 20 carbon atoms include propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, heptene-1, octene-1, nonene-1, and decene-1. , Undecene-1, dodecene-1 and the like. These α-olefins may be used alone or in combination of two or more. Examples of the copolymerization component of the third component include conjugated dienes such as 1,3-butadiene and isoprene, and non-conjugated dienes such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, and ethylidene norbornene.

The ethylene / α-olefin copolymer (eg, EPDM) obtained by copolymerizing a conjugated diene and a non-conjugated diene as a third component is an ethylene / α-olefin-based copolymer which does not copolymerize a conjugated diene and a non-conjugated diene. It is inferior to copolymers in weather resistance and is not necessarily preferable, but it is excellent in weather resistance in comparison with polybutadiene because there are few diene components in the molecule. Therefore, the saturated rubbery polymer in the component (A) in the present invention also includes an ethylene / α-olefin-based copolymer obtained by copolymerizing a conjugated diene and / or a non-conjugated diene as the third component. In the case of an ethylene / α-olefin copolymer obtained by copolymerizing a conjugated diene and / or a non-conjugated diene as the third component, the content of the conjugated diene and / or the non-conjugated diene in the copolymer is as follows:
It is at most 50% by weight, preferably at most 30% by weight, more preferably at most 10% by weight. When the saturated rubbery polymer of the present invention is an ethylene / α-olefin copolymer obtained by copolymerizing a conjugated diene and / or a non-conjugated diene as the third component, the content in the copolymer is 50%. It is defined as a rubbery polymer of not more than% by weight.

The ethylene / α-olefin copolymer suitably used as the saturated rubbery polymer is preferably produced using a metallocene catalyst. In general, a metallocene-based catalyst is composed of a cyclopentadienyl derivative of a group IV metal such as titanium and zirconium and a co-catalyst, and is not only highly active as a polymerization catalyst but also has a higher polymer yield than a Ziegler-based catalyst. Has a narrow molecular weight distribution, and the distribution of α-olefin having 3 to 20 carbon atoms as a comonomer in the copolymer is uniform. Therefore, the polymer obtained with the metallocene-based catalyst has a more uniform cross-linking, exhibits excellent rubber elasticity, and results in a styrene-based thermoplastic resin having high impact resistance. The ethylene / α-olefin copolymer which is a rubbery polymer in the component (A) suitably used in the present invention has an α-olefin copolymerization ratio of 1 to 60% by weight.
Is more preferable, more preferably 10 to 50% by weight, and most preferably 20 to 45% by weight. If the copolymerization ratio of the α-olefin exceeds 60% by weight, the molded article obtained from the composition of the present invention is undesirably greatly reduced in tensile strength and the like. On the other hand, if it is less than 1% by weight, the effect of improving the impact resistance of the molded article obtained from the composition of the present invention is not obtained, which is not preferable.

The ethylene / α-olefin copolymer has a density of 0.800 to 0.900 g / cm ³ ,
It is preferably in the range of 0 to 0.900 g / cm ³ . By using a rubber-like polymer having a density in this range, a molded article having excellent impact resistance can be obtained.
The ethylene / α-olefin copolymer preferably has a long chain branch. The presence of the long-chain branch enables the density to be lower than the ratio (% by weight) of the copolymerized α-olefin without lowering the mechanical strength. Accordingly, a rubbery polymer having low density, low hardness and high strength can be obtained, and as a result, a molded article having excellent impact resistance can be obtained. When the saturated rubbery polymer in the component (A) of the present invention is an ethylene / α-olefin copolymer, the α-olefin in the copolymer preferably has 4 to 20 carbon atoms. More preferably, it is 6 to 20. Among them, ethylene-octene-1 copolymer in which α-olefin has 8 carbon atoms is most preferable because it can be easily crosslinked and can be made into a styrene-based thermoplastic resin having high impact resistance.

The ethylene / α-olefin copolymer preferably has a DSC melting point peak at room temperature or higher.
When it has a melting point peak, the form is stable in the temperature range below the melting point, the handleability is excellent, and the stickiness is small.
Further, the melt flow rate (MFR) of the ethylene / α-olefin copolymer is preferably in the range of 0.01 to 100 g / 10 minutes (measured at 190 ° C. under a load of 2.16 kg), and more preferably used. Is 0.2-20g
/ 10 minutes. Melt flow rate is 100g / 10
If the amount exceeds 0.01 minutes, the effect of imparting impact resistance is insufficient, and if it is less than 0.01 / 10 minutes, the fluidity at the time of dynamic crosslinking is poor, and the processability is undesirably reduced.

Next, the hydrogenated conjugated diene polymer will be described. This hydrogenated conjugated diene polymer is obtained by hydrogenating a conjugated diene such as polybutadiene and polyisoprene. Among them, hydrogenated polybutadiene is particularly preferable because of easy production. This hydrogenated conjugated diene polymer is
It has a 1,2 vinyl bond and a 1,4 vinyl bond. By having both 1,2 vinyl bond and 1,4 vinyl bond in the molecule, rubber elasticity is high, glass transition temperature (Tg) is lowered, and low temperature characteristics are improved. The 1,2-vinyl bond amount of the conjugated diene is preferably 5 to 95%. More preferably,
10 to 90%. When the amount of 1,2-vinyl bond is less than 5% or more than 95%, the performance as an elastomer is low and the effect of improving the impact resistance of the composition of the present invention is low.
Furthermore, low temperature characteristics are not preferable. In the hydrogenated conjugated diene polymer, the double bond based on the conjugated diene in the molecule does not necessarily need to be 100% hydrogenated. The hydrogenation rate is at least 50%, preferably at least 70%, more preferably at least 90%, particularly preferably at least 95%. By adding hydrogen, the weather resistance is greatly improved even if it is not 100%. When the saturated rubbery polymer of the present invention is a hydrogenated diene polymer, its double bond is 50%
The above is defined as a hydrogenated rubbery polymer.

Next, the styrene elastomer will be described. Examples of the styrene-based elastomer include a hydrogenated aromatic vinyl / conjugated diene block and a random copolymer. Further, there may also be mentioned those containing a block component of aromatic vinyl or a block component of hydrogenated conjugated diene in a part of the hydrogenated aromatic vinyl / conjugated diene random copolymer. Further, an ethylene / aromatic vinyl random copolymer may be used. The hydrogenated aromatic vinyl / conjugated diene block copolymer will be described in detail. This block copolymer has at least one polymer block (S) mainly composed of an aromatic vinyl compound and at least one hydrogenated polymer block (S). It is a block copolymer composed of a polymer block (B) mainly composed of a conjugated diene. Its structure is, for example, S-
B, S-B-S, B-S-B-S, (S-B-) nSi
And so on. Examples of the conjugated diene include butadiene and isoprene. The amount of aromatic vinyl in the hydrogenated aromatic vinyl / conjugated diene block or random copolymer is preferably 1 to 70% by weight, more preferably 5 to 60% by weight, and still more preferably 10 to 5% by weight.
0% by weight.

When the saturated rubber-like polymer contains an aromatic vinyl component and the thermoplastic resin as the matrix is a polystyrene resin, the strength becomes higher when the compatibilizer as the component (C) is used. However, even if not used, it becomes a high-strength styrene-based thermoplastic resin and is not usually used. When the compatibilizer is not used and the amount of the aromatic vinyl in the hydrogenated aromatic vinyl / conjugated diene block or the random copolymer is less than 1% by weight, the styrenic thermoplastic resin composition of the present invention is molded. The strength of the obtained molded product is low.
If it exceeds 70% by weight, the rubbery properties are reduced, the performance as an elastomer is low, and the effect of improving the impact resistance of the styrenic thermoplastic resin composition of the present invention is low. The conjugated diene in the hydrogenated aromatic vinyl / conjugated diene block or random copolymer has a 1,2 vinyl bond and a 1,4 vinyl bond. By having both 1,2 vinyl bond and 1,4 vinyl bond in the molecule, rubber elasticity is high, glass transition temperature (Tg) is lowered, and low temperature characteristics are improved. The 1,2-vinyl bond amount of the conjugated diene is preferably 5 to 95%.
More preferably, it is 10 to 90%. When the 1,2-vinyl bond content is less than 5% or more than 95%, the performance as an elastomer is low, and the effect of improving the impact resistance of the styrene-based thermoplastic resin composition of the present invention is low. Furthermore, low temperature characteristics are not preferable.

The hydrogenated aromatic vinyl / conjugated diene block or random copolymer, which is a saturated rubbery polymer in the component (A) of the composition of the present invention, has a double bond based on a conjugated diene in the molecule. It need not be 100% hydrogenated. The hydrogenation rate is 50% or more, preferably 7%.
It is 0% or more, more preferably 90% or more, and particularly preferably 95% or more. 100% by hydrogenation
Even if not, the weather resistance is greatly improved. When the saturated rubbery polymer of the present invention is a hydrogenated aromatic vinyl / conjugated diene block or a random copolymer, it is defined as a rubbery polymer in which the double bond thereof is hydrogenated by 50% or more. As described above, the styrene-based elastomer which is the saturated rubbery polymer as the component (A) of the present invention preferably includes a hydrogenated aromatic vinyl / conjugated diene block or a random copolymer. Among them, the hydrogenated aromatic vinyl / conjugated diene random copolymer has high rubber elasticity, and the molded article molded from the styrene-based thermoplastic resin composition of the present invention using this as a saturated rubber-like polymer has high Shows impact resistance. Therefore, a hydrogenated aromatic vinyl / conjugated diene random copolymer is more preferable as the styrene-based elastomer.

Furthermore, the ethylene / aromatic vinyl random copolymer, which is one of the styrene elastomers, is preferably an ethylene / styrene random copolymer, but this ethylene / styrene random copolymer has some disadvantages. I have. That is, the impact resistance at low temperatures is not sufficient as compared with the hydrogenated aromatic vinyl / conjugated diene random copolymer. The reason is that the hydrogenated conjugated diene component in the hydrogenated aromatic vinyl / conjugated diene random copolymer has 1,2-vinyl bonds and 1,4-vinyl bonds, and this portion (olefin component) is branched. This is because the ethylene / styrene random copolymer has a structure, but does not have a branched structure. The styrene-based thermoplastic resin composition of the present invention using this ethylene / styrene random copolymer as a saturated rubbery polymer can be used for applications where low-temperature impact resistance is not required.

The styrene elastomer used in the present invention has a melt flow rate (MFR) of 0.01 to 20.
g / 10 minutes (measured at 230 ° C. under a load of 2.16 kg) is preferably used, and more preferably 0.1 g / min.
1 to 10 g / 10 minutes. Melt flow rate is 20
If it exceeds g / 10 minutes, the effect of imparting impact resistance is insufficient, and if it is less than 0.01 / 10 minutes, the fluidity at the time of dynamic crosslinking is poor, and the processability is undesirably reduced. The saturated rubbery polymer in the component (A) of the composition of the present invention may be used as a mixture of a plurality of types. In such a case, it is possible to further improve the workability. The saturated rubbery polymer in the component (A) needs to be partially or completely crosslinked. The molded product obtained from the styrene-based thermoplastic resin composition of the present invention has a high impact resistance when cross-linked when compared with a case where the cross-linking is not performed.
Heat resistance and the like are greatly improved. When the ratio of the crosslinked rubbery polymer (rubbery polymer that does not dissolve in the solvent) in the total saturated rubbery polymer in the styrene-based thermoplastic resin composition of the present invention is defined by the degree of crosslinking, the degree of crosslinking is , 30% or more, and 5
It is preferably 0% or more.

Next, the polystyrene resin which is an essential component of the thermoplastic resin in the component (A) and the polystyrene resin which is the component (B) in the styrene thermoplastic resin composition of the present invention will be described. The polystyrene resin is basically a polymer of a styrene monomer, that is, a copolymer of polystyrene or a styrene monomer and another monomer. Examples of the copolymerizable monomer include α-methylstyrene, p-chlorostyrene, p-bromostyrene,
Styrene monomers such as 4,5-tribromostyrene, acrylonitrile, unsaturated nitrile monomers such as methacrylonitrile, methyl acrylate, acrylate monomers such as butyl acrylate, methyl methacrylate, Methacrylic acid ester monomers such as ethyl methacrylate, maleic anhydride, acid anhydride monomers such as itaconic anhydride, maleimide, N-methylmaleimide, maleimide monomers such as N-phenylmaleimide, acrylic acid, Organic acid monomers such as methacrylic acid can be exemplified. Of these, polystyrene is inexpensive and most preferred. Further, a polystyrene-based resin composed of a copolymer of a styrene monomer, an acrylate monomer and a methacrylate monomer was used as the thermoplastic resin in the component (A) or the component (B). A molded article obtained from the styrene-based thermoplastic resin composition has excellent weather resistance and is preferable.

The melt flow rate (MFR) of the polystyrene resin used is 0.1 to 50 g / 10 minutes (20 minutes).
0 ° C., measured under a load of 5 kg). Further, the range is more preferably 0.5 to 30 g / 10 minutes. If it is less than 0.1 g / 10 minutes, the flowability of the styrene-based thermoplastic resin composition of the present invention is low, and the processability is poor. On the other hand, if it exceeds 50 g / 10 minutes, the strength of a molded article molded from the styrene-based thermoplastic resin composition of the present invention is not sufficient. In addition, this polystyrene resin is (A)
The polystyrene resin in the component and the polystyrene resin in the component (B) may be the same or different. Further, in the component (A) or the component (B),
More than one type of polystyrene resin may be used.

Next, the polyolefin resin used in combination with the polystyrene resin in the component (A) of the styrene thermoplastic resin composition of the present invention and the polyolefin resin used in the component (B) will be described. The polyolefin resin can be roughly classified into a polyethylene resin, a polypropylene resin, or a mixture of a polyethylene resin and a polypropylene resin. High-density polyethylene (HDP)
E), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), a copolymer of an acrylic vinyl monomer and ethylene (EEA, EMMA, etc.) or a copolymer of a vinyl acetate monomer and ethylene (EV
A) and the like. However, among these, high density polyethylene (HDPE), low density polyethylene (LDPE) and linear low density polyethylene (L
LDPE) is particularly preferred because it can be obtained at low cost. These polyethylene resins may be used alone,
Further, two or more kinds may be used in combination.

When high density polyethylene (HDPE) is used, its density generally ranges from 0.930 to 0.970.
g / cm ³ and the melt flow rate (MF
R) is 0.05 to 100 g / 10 min (190 ° C, 2.
(Measured under a load of 16 kg). When low-density polyethylene (LDPE) or linear low-density polyethylene (LLDPE) is used, its density is generally in the range of 0.900 to 0.930 g / m ² and the melt flow rate (MFR) is 0.05-1
00g / 10 min (measured at 190 ° C under a load of 2.16 kg)
Is preferably within the range. Melt flow rate is 1
When it exceeds 00 g / 10 minutes, the mechanical strength and heat resistance of the molded article obtained from the composition of the present invention are insufficient, and when it is less than 0.05 g / 10 minutes, the molding of the composition of the present invention may fail. However, the fluidity is poor and the molding processability is undesirably reduced.

Examples of the polypropylene resin include homopolypropylene, copolymer resins (including block and random) of propylene with other α-olefins such as ethylene, butene-1, pentene-1, and hexene-1. be able to. The melt flow rate (MFR) of the polypropylene resin is 0.1 to 100 g / 10 min (230
C., measured under a load of 2.16 kg). When the melt flow rate exceeds 100 g / 10 minutes, the mechanical strength of a molded article obtained from the composition of the present invention,
If the heat resistance is insufficient, and if the heat resistance is less than 0.1 g / 10 minutes, the composition of the present invention will have poor flowability when molding, and the molding processability will decrease, which is not desirable.

The polyolefin resin used in the present invention comprises a polyethylene resin and / or a polypropylene resin as described above, and the polypropylene resin is preferably higher in heat resistance than the polyethylene resin. Among them, homopolypropylene resins have the highest heat resistance and are more preferable. However, homopolypropylene generally tends to be oxidatively decomposed and has a tendency to decrease in mechanical strength due to a decrease in molecular weight during long-term use. On the other hand, polyethylene resins generally have a tendency to crosslink without being oxidatively decomposed and maintain or improve mechanical strength. Therefore, when using a polypropylene resin, especially when used for applications requiring durability, use a homopolypropylene and a polyethylene resin together or use a random or block polymer of propylene and ethylene. There is also. In addition,
This polyolefin-based resin may be the same as or different from the polyolefin-based resin used in combination with the polystyrene-based resin as the component (A) and the polyolefin-based resin in the component (B). Further, two or more kinds of polyolefin resins may be used in the component (A) or the component (B).

Next, the compatibilizer which is the component (C) in the styrenic thermoplastic resin composition of the present invention will be described. When a styrene elastomer is used as the saturated rubbery polymer in the component (A) of the composition of the present invention, the styrene component is contained in the molecule of the elastomer,
(A) is compatible with the polystyrene resin as the component,
The component (A) and the component (B) have high interfacial adhesion, and a composition excellent in impact resistance can be obtained by using only these two components without using a compatibilizer. However, when an olefin-based elastomer is used as the saturated rubbery polymer in the component (A), it is incompatible with the polystyrene-based resin which is an essential component of the thermoplastic resin in the component (A). Or when using a polyolefin resin in combination,
There is no compatibility between the polyolefin resin and the polystyrene resin. Therefore, due to the low interfacial adhesion between the particulate crosslinked olefin elastomer and the polystyrene resin and the phase separation between the polyolefin resin and the polystyrene resin, as a result, compared to the styrene thermoplastic resin composition of the present invention. The mechanical strength of the molded product is low.
Therefore, it is necessary to impart an interfacial adhesion function between the particulate crosslinked olefin elastomer and the polystyrene resin, and to impart an affinity between the polyolefin resin and the polystyrene resin, and the styrene thermoplastic resin composition of the present invention. In some cases, a compatibilizer as the component (C) is required depending on the combination.

As the compatibilizer as the component (C),
The component (A) is not particularly limited as long as it has a function of compatibilizing the saturated rubbery polymer and the polystyrene-based resin and the polystyrene-based resin and the polyolefin-based resin in the component. Components having a component or a component compatible with polystyrene and a component having a polyolefin-based component or a component compatible with polyolefin can be used. For example, A is polystyrene or a copolymer of polystyrene, preferably polystyrene, B is polyethylene, polypropylene, an ethylene / α-olefin copolymer containing ethylene and an α-olefin having 3 to 20 carbon atoms, and hydrogenated polybutadiene. , An A-B type block copolymer composed of hydrogenated polyisoprene, etc., an A-grafted B copolymer, a B-grafted A copolymer, and the like. Further, a copolymer in which A is randomly introduced into the B polymer component, a copolymer in which B is randomly introduced into the A polymer component, specifically, for example, an ethylene-styrene random polymer described below. Similarly, a copolymer in which an A monomer component, that is, a styrene monomer is randomly introduced into a B polymer component made of polyethylene can also be mentioned. Where B or A
May be single or a combination of two or more.

Specific examples thereof include polystyrene-grafted polypropylene, styrene-butadiene block or random copolymer, hydrogenated styrene-isoprene block or random copolymer, and ethylene-styrene random copolymer. it can.
Among these, in particular, styrene-butadiene block or random copolymer, hydrogenated styrene-isoprene block or random copolymer, ethylene-styrene random copolymer, when it plays a role as a high compatibilizer itself. At the same time, it has the effect of increasing the impact resistance in a supplementary manner and is also excellent in weather resistance, so that it is most preferable. When the compatibilizer as the component (C) is a hydrogenated styrene-butadiene or isoprene block or a random copolymer or an ethylene-styrene random copolymer, this is also the component (A),
The component (A) is distinguished by being crosslinked while the component (C) is not crosslinked.

The compatibilizer as the component (C) in the styrenic thermoplastic resin composition of the present invention is present in the thermoplastic elastomer as the component (A), that is, a saturated rubbery polymer and a polystyrene resin. May be added when dynamically cross-linking a thermoplastic resin containing as an essential component, or the thermoplastic elastomer (A) and the polystyrene resin and / or polyolefin resin (B) may be melted. It may be accompanied during mixing or pellet blending. The compatibilizer as the component (C) may be a single type or a combination of a plurality of types. The composition of the present invention which does not require the compatibilizer as the component (C), for example, a rubbery polymer having a styrene component in the molecule in the final composition and a composition in which the matrix component is a polystyrene resin, Particularly preferred. Because, when a molded article comprising the styrene-based thermoplastic resin composition of the present invention and a general polystyrene are mixed and recycled, if the combination requiring a compatibilizer is used, the styrene-based thermoplastic resin composition of the present invention is used. It is necessary to add a new compatibilizer when mixing a molded article made of a product with general polystyrene. In the case of this combination, it is not necessary to add a new compatibilizer.

Next, the composition of the styrene-based thermoplastic resin composition of the present invention will be described. First, the composition of a partially or completely crosslinked saturated rubbery polymer which is the component (A) and a thermoplastic elastomer containing a polystyrene resin as essential components will be described. Preferably, the component ratio of the thermoplastic elastomer is 40 to 90% by weight of the saturated rubbery polymer and 10 to 60% by weight of the thermoplastic resin. More preferably, 50 to 75% by weight of a saturated rubbery polymer and 25 to 50% by weight of a thermoplastic resin, and particularly preferably 55 to 70% by weight of a saturated rubbery polymer and 30 to 45% by weight of a thermoplastic resin. is there. When the content of the saturated rubber-like polymer is less than 40% by weight, a crosslinking reaction of the saturated rubber-like polymer hardly occurs during the production of the thermoplastic elastomer, and the thermoplastic elastomer has a low degree of crosslinking. Therefore, in the styrene-based thermoplastic resin composition of the present invention comprising the thermoplastic elastomer and the polystyrene-based resin and / or the polyolefin-based resin, the saturated rubber-like polymer is deformed in the flow direction at the time of molding and the performance is stabilized. The molded product does not. 90 saturated rubbery polymer
If the amount is more than 10% by weight, the fluidity of the thermoplastic elastomer is lacking, which causes problems such as inability to process the styrene-based thermoplastic resin composition. The thermoplastic elastomer may be added with a third component as described below, but this amount is an external number.

The composition of the thermoplastic elastomer as the component (A) of the present invention is as described above, and the composition in the styrene-based thermoplastic resin composition of the present invention may be partially or completely as the component (A). A thermoplastic elastomer of the above composition comprising a saturated rubber-like polymer cross-linked to a thermoplastic resin having a polystyrene resin as an essential component: 5 to 95 parts by weight,
Component (B): polystyrene resin and / or polyolefin resin: 95 to 5 parts by weight, and when adding a compatibilizer, the phase (C) is added to the component (A) and 100 parts by weight of the component (B). Solubilizer: consists of 0.1 to 50 parts by weight, and the content of the saturated rubbery polymer in the composition is 1 to 40% by weight.
Preferably, a thermoplastic elastomer of the above composition comprising a partially or completely crosslinked saturated rubbery polymer as the component (A) and a thermoplastic resin containing a polystyrene resin as an essential component: Parts by weight, 92.5 to 25 parts by weight of a polystyrene resin and / or a polyolefin resin as the component (B) and 100 parts by weight of the components (A) and (B) when the compatibilizer is added. (C) compatibilizer: 0.1 to 25 parts by weight, and the saturated rubbery polymer in the composition is 5 to 35% by weight. In particular,
A thermoplastic elastomer of the above composition comprising a partially or completely crosslinked saturated rubbery polymer which is preferably the component (A) and a thermoplastic resin having a polystyrene resin as an essential component: 10 to 50 parts by weight, (B) Polystyrene resin and / or polyolefin resin as component: 9
When adding 0 to 50 parts by weight and a compatibilizer, (A)
(C) Compatibilizer: 0.1 to 10 parts by weight with respect to 100 parts by weight of the component and the component (B), and the composition contains 10 to 30% by weight of a saturated rubbery polymer.

When the amount of the component (A) is less than 5 parts by weight, the amount of the saturated rubbery polymer in the styrene-based thermoplastic resin composition is small, and the impact resistance of a molded product obtained by molding the same is small. Inferior. When the amount of the component (A) exceeds 95 parts by weight, the amount of the saturated rubber polymer of the styrene-based thermoplastic resin composition increases, and the molded product obtained by molding the same becomes elastomeric, and has a high mechanical strength and In particular, it has a low flexural modulus and impairs the performance as a resin. When the component (B) exceeds 95 parts by weight and less than 5 parts by weight,
The same applies to the case where the component (A) is less than 5 parts by weight and more than 95 parts by weight, respectively. Use as needed (C)
The ingredients, if used, exceed 50 parts by weight,
In general, the compatibilizer is expensive, is inferior in economical efficiency, and sometimes causes a decrease in physical properties of a molded article obtained by molding the styrene-based thermoplastic resin composition of the present invention. When the content of the saturated rubbery polymer in the composition is less than 1% by weight, the impact resistance of a molded article obtained by molding the styrene-based thermoplastic resin composition of the present invention is low. If it exceeds 40% by weight, the molded article obtained by molding the styrene-based thermoplastic resin composition becomes elastomeric, and has low mechanical strength, particularly low flexural modulus, and impairs the performance as a resin.

The final composition of the styrenic thermoplastic resin composition of the present invention may be a partially or completely crosslinked saturated rubbery polymer, a polystyrene resin or a polystyrene resin and a polyolefin resin, if necessary. The final composition is 1-40% by weight of partially or completely crosslinked saturated rubbery polymer, and 99-60% by weight of polystyrene resin or polystyrene resin and polyolefin resin. %, When a compatibilizer is used, the compatibilizer is 0.1 to 50 parts by weight based on 100 parts by weight of the total of the saturated rubbery polymer and the polystyrene resin or the total of the polystyrene resin and the polyolefin resin. . When a polyolefin resin is used in combination, the ratio between the polystyrene resin and the polyolefin resin is preferably 100 to 50% by weight of the polystyrene resin and 0 to 50% by weight of the polyolefin resin. The reason for this is that the thermoplastic resin composition of the present invention is a composition that takes advantage of the characteristics of polystyrene resins, for example, rigidity and moldability.

As described above, the styrenic thermoplastic resin composition of the present invention basically comprises a partially or completely cross-linked saturated rubbery polymer as component (A) and a polystyrene resin as essential components. A partially or completely crosslinked saturated rubber-like polymer resin as the component (B) and, if necessary, a compatibilizer as the component (C). As other components, for example, polystyrene resins, resins other than polyolefin resins, softeners, glass fibers, organic or inorganic fibers such as polyacrylonitrile fibers or carbon fibers, metal fibers such as copper or brass, potassium titanate , Whisker such as magnesium oxysulfate, aluminum borate, calcium carbonate, magnesium carbonate, silica, carbon bra Click, titanium oxide, clay,
In addition to powdered inorganic fillers such as mica, talc, magnesium hydroxide, and aluminum hydroxide, plasticizers such as polyethylene glycol and dioctyl phthalate (DOP),
Additives such as organic / inorganic pigments, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, flame retardants, silicone oils, antiblocking agents, foaming agents, antistatic agents, antibacterial agents, etc. can also be used in combination. it can. Among these, the softener has an effect of further improving the impact resistance of a molded article obtained by molding the styrene-based thermoplastic resin composition of the present invention, and is a very effective component. As this softening agent, paraffin type,
Process oils such as naphthenic are particularly preferred. These softeners are usually added to the thermoplastic elastomer which is the component (A). When the softener is added, the amount of the softener is 0.1 to 100 parts by weight of the saturated rubbery polymer.
5 to 200 parts by weight, preferably 1 to 100 parts by weight, more preferably 1 to 50 parts by weight, particularly preferably 1 to 20 parts by weight. If the amount is less than 0.5 part by weight, the effect is low when a softener is added. If the amount exceeds 200 parts by weight, bleed out of the softener becomes remarkable, which is not preferable.

Further, as the resin other than the polystyrene resin and the polyolefin resin, for example, resins such as polyphenylene ether resin, polyvinyl chloride resin, polyamide resin, polyester resin, polyphenylene sulfide resin, polycarbonate resin, polymethacrylate resin, etc. 2
A mixture of more than one species can be used in combination. Among these, polyphenylene ether-based resins are particularly preferred because they have good compatibility with polystyrene-based resins. When a polyphenylene ether-based resin is present, heat resistance or flame retardancy can be imparted. When a resin other than the polyphenylene ether-based resin is allowed to coexist, it is preferable to newly coexist a compatibilizer other than the above-described compatibilizer.

Next, a method for producing the styrenic thermoplastic resin composition of the present invention will be described. Although not limited to this manufacturing method, it can be usually manufactured by the following method. That is, first, a thermoplastic resin having a saturated rubber-like polymer and a polystyrene resin as essential components, preferably a mixture of a polystyrene resin or a polystyrene resin and a polyolefin resin, a radical initiator, a crosslinking aid and Accordingly, the compatibilizer as the component (C) is twin-screw extruder,
The saturated rubbery polymer is partially or completely subjected to dynamic crosslinking by heat treatment with a Banbury mixer or the like to produce a thermoplastic elastomer as the component (A) of the composition of the present invention. Then, the obtained thermoplastic elastomer as the component (A) and the mixture of the polystyrene resin or the polyolefin resin or the mixture of the polystyrene resin and the polyolefin resin as the component (B) are subjected to a single screw extruder, a twin screw extruder, or the like. Can be produced by melt mixing or pellet blending. In general, it is preferable to add the compatibilizer when producing a thermoplastic elastomer by dynamic crosslinking, but it is also possible to produce the compatibilizer by the following addition method. For example,

(1) A method of producing a thermoplastic elastomer by first crosslinking without adding a compatibilizer and then adding a compatibilizer after crosslinking a saturated rubbery polymer. For example, adding from the middle of the twin-screw extruder. (2) A method in which a thermoplastic elastomer as the component (A), a polystyrene resin and / or a polyolefin resin as the component (B) are melt-mixed with a compatibilizer. (3) thermoplastic elastomer pellets as component (A)
(B) A method of mixing a polystyrene resin pellet and / or a polyolefin resin pellet, which is a component, with a compatibilizer pellet. Etc.

Further, there is the following manufacturing method. That is, as described above, when performing dynamic crosslinking, when the concentration of the saturated rubber-like polymer is low, the crosslinking efficiency is low and it is difficult to produce the styrene-based thermoplastic resin composition of the present invention in one step. The saturated rubbery polymer and the polystyrene resin are heat-treated in a twin-screw extruder, a Banbury mixer or the like in the presence of a radical initiator and a crosslinking aid to partially or completely crosslink the saturated rubbery polymer (B This is a method of producing a styrene-based thermoplastic resin composition of the present invention by adding a polystyrene-based resin and / or a polyolefin-based resin as a component. When a twin-screw extruder is used, a method of adding a polystyrene resin and / or a polyolefin resin, which is the component (B), in the middle of the extruder is used. This method is
It is more economical than melt blending or pellet blending of component (A) and component (B).

When the thermoplastic elastomer which is the component (A) of the composition of the present invention is produced by dynamic crosslinking, the radical initiator which is a crosslinking agent to be used is a radical initiator such as an organic peroxide or an organic azo compound. Is mentioned. As a specific example, 1,1-bis (t-butylperoxy)-
3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (T-butylperoxy) cyclododecane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-
Peroxyketals such as butylperoxy) butane and n-butyl-4,4-bis (t-butylperoxy) valerate; di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide; α,
α′-bis (t-butylperoxy-m-isopropyl) benzene, α, α′-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,
5-bis (t-butylperoxy) hexane and 2,
5-dimethyl-2,5-bis (t-butylperoxy)
Dialkyl peroxides such as hexine-3; acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide;
Diacyl peroxides such as lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and m-trioyl peroxide; t-butylperoxyacetate, t -Butyl peroxyisobutyrate, t-butyl peroxy-2
-Ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, di-t-
Butyl peroxyisophthalate, 2,5-dimethyl-
Peroxyesters such as 2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, and cumylperoxyoctate; and t-butyl hydroperoxide; Cumene hydroperoxide, diisopropylbenzene hydroperoxide,
Hydroperoxides such as 2,5-dimethylhexane-2,5-dihydroperoxide and 1,1,3,3-tetramethylbutyl peroxide can be exemplified.

Among these compounds, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl -2,5-bis (t-butylperoxy) hexane and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 are preferred. When the saturated rubbery polymer is crosslinked by the above method, these radical initiators are used in an amount of 0.02 to 3 parts by weight, preferably 0.05 to 1 part by weight, based on 100 parts by weight of the saturated rubbery polymer. Used in The level of crosslinking is mainly determined by this amount. If the amount is less than 0.02 parts by weight, the crosslinking is insufficient, and if the amount exceeds 3 parts by weight, the crosslinking rate is not greatly improved, so that it is not a preferable direction.

As a crosslinking aid, divinylbenzene, triallyl isocyanurate, triallyl cyanurate,
Diacetone diacrylamide, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate,
Trimethylolpropane triacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diisopropenylbenzene, P-quinone dioxime, P, P5'-dibenzoylquinone dioxime, phenylmaleimide, allyl methacrylate, N , N5'-
m-phenylene bismaleimide, diallyl phthalate,
Tetraallyloxyethane, 1,2-polybutadiene and the like are preferably used. These crosslinking aids may be used in combination of two or more. The crosslinking aid is used in an amount of 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the saturated rubbery polymer. If the amount is less than 0.1 part by weight, the crosslinking rate is low, which is not preferable. If the amount exceeds 5 parts by weight, the crosslinking rate is not greatly improved, and an excessive amount of the crosslinking aid remains, which is not a preferable direction. As a method for crosslinking, it is preferable to use a radical initiator and a crosslinking aid as described above, but in addition, a phenol resin or bismaleimide may be used as a crosslinking agent.

As the equipment for producing the thermoplastic elastomer as the component (A) of the composition of the present invention by dynamic crosslinking, the above-described twin screw extruder, kneader other than the Banbury mixer, and a single screw extruder can also be used. . Among these facilities, a twin-screw extruder is preferably used in order to achieve particularly efficient crosslinking. The twin-screw extruder uniformly and finely disperses a saturated rubber-like polymer and a thermoplastic resin containing a polystyrene-based resin as an essential component, and can also preferably carry out a crosslinking reaction with a crosslinking agent to continuously produce a crosslinked product. Suitable to do. A specific manufacturing method can be manufactured through the following processing steps. That is, a saturated rubber-like polymer and a polystyrene resin or a mixture of a polystyrene resin and a polyolefin resin are charged into a hopper of an extruder. A radical initiator and a crosslinking aid, which are crosslinking agents,
It may be added together with the rubbery polymer and the thermoplastic resin from the beginning, or may be added in the middle of the extruder.
When adding oil as a softening agent, it may be added from the middle of the extruder, or may be added separately at the beginning and during the middle. A part of the saturated rubbery polymer and the thermoplastic resin may be added in the middle of the extruder. When heated and melted and kneaded in the extruder, the saturated rubber-like polymer and the radical initiator and the crosslinking auxiliary undergo a crosslinking reaction, and furthermore, if necessary, add an oil or the like and melt-knead to form a crosslinking reaction. After sufficient kneading and dispersion, the mixture is taken out of the extruder. The thermoplastic elastomer which is the component (A) of the composition of the present invention can be obtained by pelletizing.

The styrenic thermoplastic resin composition of the present invention is obtained by melt-mixing or pellet blending the thermoplastic elastomer (A) and the polystyrene resin and / or polyolefin resin (B). As the composition, the styrene-based thermoplastic resin composition can be used to produce various molded articles by any molding method. As the molding method, injection molding, extrusion molding, compression molding, blow molding, calender molding, foam molding and the like are preferably used.

[0049]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In these examples and comparative examples, the test methods used for evaluating various physical properties, and the production methods of the thermoplastic elastomer used for the raw materials and the blending are as follows. 1. Test method (1) Tensile strength Measured at 23 ° C. in accordance with JIS K6251. (2) Tensile elongation Measured at 23 ° C. by a method according to JIS K6251. (3) Flexural modulus Measured at 23 ° C. by a method according to JIS K6758.

(4) Izod impact strength Measured at 23 ° C. by a method according to JIS K6758. (V notch, 1/4 inch test) (5) Heat resistance (HDT) Measured according to JIS K7207. (6) Weather resistance Evaluation was made using a sunshine weather meter (65 ° C., with rain). Evaluation was made based on the retention of Izod impact strength after 1000 hours. X, 80 to 90% for retention rate of less than 80%
Less than is indicated by 、, and 90% or more is indicated by ◎. The samples subjected to the weather resistance evaluation were those having a very general weather resistance formulation (with an ultraviolet inhibitor and an antioxidant added).

(7) Chemical Resistance (Oil Resistance) A container having a width of 65 mm × 65 mm and a height of 45 mm was formed. Put 10 cc of coconut oil in this container,
After heating for 0 minutes, the deformation of the container was evaluated. Large deformation is indicated by ×, small deformation is indicated by 、, and no deformation is indicated by ◎. (8) Degree of Crosslinking 0.5 g of a sample is dissolved in a solvent that dissolves both the non-crosslinked rubbery polymer and the polystyrene resin, for example, 200 m of xylene
Reflux for 4 hours in l. The solution is filtered through a filter paper for quantification, the residue on the filter paper is vacuum-dried and quantified, and the ratio of the weight of the residue to the weight of the rubbery polymer in the sample (%)
It was calculated as

2. Raw materials (1) Saturated rubbery polymer (a) Ethylene / octene-1 copolymer Produced by a method using a metallocene catalyst described in JP-A-3-1630088. The ethylene / octene-1 composition ratio of the copolymer was 72/28 (weight ratio) (referred to as TPE-1). (B) Ethylene / propylene / dicyclopentadiene copolymer-1 It was produced by a method using a metallocene catalyst described in Japanese Patent No. 163088. The composition ratio of ethylene / propylene / dicyclopentadiene in the copolymer is 50/4
It was 1/9 (weight ratio). (Referred to as TPE-2)

(C) Ethylene / propylene / dicyclopentadiene copolymer-2 Produced by a general method using a Tigler catalyst.
The composition ratio of ethylene / propylene / dicyclopentadiene in the copolymer was 47.5 / 43 / 9.5 (weight ratio). (Referred to as TPE-3) (d) Hydrogenated polybutadiene Produced by the method described in JP-A-60-220147. Before the hydrogenation, the 1,2-vinyl bond amount of the polybutadiene portion was 30% by weight, and the hydrogenation rate was 99%. (Referred to as TPE-4) (e) Hydrogenated styrene-butadiene random copolymer Produced by a known method. The styrene / butadiene ratio before hydrogenation was 10/90 (weight ratio), the 1,2-vinyl bond amount was 21% by weight, and the hydrogenation rate was 95%. (T
(Referred to as PE-5)

(F) Hydrogenated styrene-butadiene block copolymer It was produced by a known method. The styrene / butadiene ratio before hydrogenation was 20/80 (weight ratio), the 1,2 vinyl bond amount was 35% by weight, and the hydrogenation rate was 90%. (T
(G) Hydrogenated styrene-isoprene block copolymer Septon (trade name: 2023, styrene content: 13%) manufactured by Kuraray Co., Ltd. (referred to as TPE-7) (h) Ethylene-styrene random copolymer Coalescence was produced by the method described in JP-A-7-70223. The ethylene / styrene composition ratio of the copolymer is 30 /
70 (weight ratio) (referred to as TPE-8)

(2) Polystyrene resin (a) Polystyrene (trade name: GP68, manufactured by Asahi Kasei Corporation)
5) (referred to as PS) (b) Prototype of Asahi Kasei Corporation Styrene / methyl methacrylate copolymer (methyl methacrylate 20% by weight) (M
(C) Prototype of Asahi Kasei Corporation Styrene / n-butyl acrylate copolymer (n-butyl acrylate 5% by weight)
(Referred to as BS) (d) Impact-resistant polystyrene (trade name, manufactured by Asahi Kasei Corporation)
HIPS492R) (referred to as HIPS) (e) Poly (styrene-acrylonitrile) (trade name 769) manufactured by Asahi Kasei Corporation (referred to as AS)

(3) Polyolefin resin Isotactic homopolypropylene (trade name: PM900A) manufactured by Japan Polyolefin Co., Ltd. (referred to as PP) (4) Radical initiator: 2,5-dimethyl-2, manufactured by NOF Corporation 5-bis (t-
Butylperoxy) hexane (trade name Perhexa 25)
B) (referred to as POX) (5) Crosslinking aid Triallyl isocyanurate (TA) manufactured by Nippon Kasei Co., Ltd.
(6) Softener (paraffin oil) Diana Process Oil (trade name PW-) manufactured by Idemitsu Kosan
380)

(7) Compatibilizing agent (a) Hydrogenated styrene-butadiene block copolymer Tuftec (styrene content 60%) manufactured by Asahi Kasei Corporation
(Referred to as HTR) (b) Styrene-grafted polypropylene Modiper (styrene content 30) manufactured by NOF Corporation
%) (Trade name: A3100) (referred to as SGP) (c) Ethylene-styrene random copolymer Produced by the method described in JP-A-7-70223. The ethylene / styrene composition ratio of the copolymer is 40 /
(D) Epoxy styrene / hydrogenated conjugated diene copolymer manufactured by Daicel Corporation, Epofriend (trade name: A102)
0) (referred to as E-HTR)

[0058]

Examples 1 to 4 Twin screw extruder (40 mmφ, L / D = 4
7) using TPE-1 / PS / HTR / POX / T
AIC = 65.0 / 35.0 / 5.9 / 0.50 / 1.
0 (weight ratio) and melt extrusion was performed at a cylinder temperature of 220 ° C. TPE- from the injection port at the center of the extruder
1, 39 parts by weight of a softening agent (paraffin oil) were injected with respect to 100 parts by weight of the total amount of PS to obtain thermoplastic elastomer pellets (referred to as TPV-1). 1 / PS / HTR /
Softening agent = 44.9 / 24.1 / 14.1 / 26.9 (weight ratio), and the degree of crosslinking of the rubbery polymer was 82%. The obtained pellets were mixed with PS and PP so as to have the composition shown in Table 1, and were melt-extruded with a twin-screw extruder. The pellet was molded by an injection molding machine (Toshiba IS45PNV) to obtain a molded product. Table 1 shows the characteristics of the molded product.

[0059]

[Comparative Example 1] TPE-1 / PS / HTR / POX / TA
The composition and ratio of the IC were determined by TPE-1 / PS / POX / TA
A pellet of a thermoplastic elastomer was obtained in the same manner as in Example 1 except that IC = 65.0 / 35.0 / 0.50 / 1.0 (weight ratio) (referred to as TPV-2). The composition of this thermoplastic elastomer is TPE-1
/PS/softener=46.8/25.2/28.1 (weight ratio), and the degree of crosslinking of the rubbery polymer was 81%. The obtained pellets and PS were mixed so as to have the composition shown in Table 1, and were extruded by a twin-screw extruder. The pellet was molded by an injection molding machine (Toshiba IS45PNV) to obtain a molded product. Table 1 shows the characteristics of the molded product.

[0060]

Example 5 TPV-1 pellets, PS and HTR pellets were pellet-blended with the same composition as in Example 2 without being melted and extruded, and the mixed pellets were molded by an injection molding machine (Toshiba IS45PNV) to obtain molded products. Was. Table 1 shows the characteristics of the molded product.

Embodiments 6 and 7: TPE-1 / PS / HTR / POX /
The composition and ratio of TAIC were TPE-1 / PS / PP / H
TR / POX / TAIC = 65.0 / 17.5 / 17.
A pellet of a thermoplastic elastomer was obtained in the same manner as in Example 1 except that the weight ratio was 5 / 5.9 / 0.50 / 1.0 (referred to as TPV-3). The composition of this thermoplastic elastomer is TPE-1 / PS / PP / HTR
/Softener=44.9/12.12/12.1/4.1/2
6.9 (weight ratio), the degree of crosslinking of the rubbery polymer was 72%. The obtained pellets were mixed with PS and PP so as to have the composition shown in Table 1, and were melt-extruded with a twin-screw extruder. The pellet was molded by an injection molding machine (Toshiba IS45PNV) to obtain a molded product. Table 1 shows the characteristics of the molded product.

[0061]

[Comparative Example 2] An HIPS injection molding machine (Toshiba IS45PN)
V) to obtain a molded product. Table 1 shows the characteristics of the molded product.

Embodiment 8 TPE-1 / PS / HTR / POX / TA
The composition of the IC was changed to TPE-2 / PS / HTR / POX / TA
A pellet of a thermoplastic elastomer was obtained in the same manner as in Example 1 except for using an IC (referred to as TPV-4). The composition of this thermoplastic elastomer is TPE-2
/PS/HTR/softener=44.9/24.1/4.1
/26.9 (weight ratio), the degree of crosslinking of the rubbery polymer is 87
%Met. The obtained pellets and PS were mixed so as to have the composition shown in Table 2 and melt-extruded with a twin-screw extruder. The pellet was molded by an injection molding machine (Toshiba IS45PNV) to obtain a molded product. Table 2 shows the characteristics of the molded product.

[0062]

Embodiment 9 TPE-1 / PS / HTR / POX / TA
The composition of the IC was changed to TPE-3 / PS / HTR / POX / TA
A pellet of a thermoplastic elastomer was obtained in the same manner as in Example 1 except for using an IC (referred to as TPV-5). The composition of this thermoplastic elastomer is TPE-3
/PS/HTR/softener=44.9/24.1/4.1
/26.9 (weight ratio), the degree of crosslinking of the rubbery polymer is 89
%Met. The obtained pellets and PS were mixed so as to have the composition shown in Table 2 and melt-extruded with a twin-screw extruder. The pellet was molded by an injection molding machine (Toshiba IS45PNV) to obtain a molded product. Table 2 shows the characteristics of the molded product.

[0063]

Embodiment 10 TPE-1 / PS / HTR / POX / T
The composition of AIC was TPE-4 / PS / HTR / POX / T
Except for using AIC, a thermoplastic elastomer pellet was obtained in the same manner as in Example 1 (referred to as TPV-6). The composition of this thermoplastic elastomer is TPE-4
/PS/HTR/softener=44.9/24.1/4.1
/26.9 (weight ratio), the degree of crosslinking of the rubbery polymer is 62
%Met. The obtained pellets and PS were mixed so as to have the composition shown in Table 2 and melt-extruded with a twin-screw extruder. The pellet was molded by an injection molding machine (Toshiba IS45PNV) to obtain a molded product. Table 2 shows the characteristics of the molded product.

[0064]

Embodiment 11 TPE-1 / PS / HTR / POX / T
The composition and ratio of AIC were determined as TPE-5 / PS / POX / T
Pellets of a thermoplastic elastomer were obtained in the same manner as in Example 1 except that AIC = 65.0 / 35.0 / 0.50 / 1.0 (weight ratio) (referred to as TPV-7). The composition of this thermoplastic elastomer is TPE-5
/PS/softener=46.8/25.2/28.1 (weight ratio), and the degree of crosslinking of the rubbery polymer was 69%. The obtained pellets and PS were mixed so as to have the composition shown in Table 2 and melt-extruded with a twin-screw extruder. The pellet was molded by an injection molding machine (Toshiba IS45PNV) to obtain a molded product. Table 2 shows the characteristics of the molded product.

[0065]

Example 12 The thermoplastic elastomer pellets (TPV-7) obtained in Example 11 were mixed with PS and HTR so as to have the composition shown in Table 2, and were melt-extruded with a twin-screw extruder.
The pellet was molded by an injection molding machine (Toshiba IS45PNV) to obtain a molded product. Table 2 shows the characteristics of the molded product.

Embodiment 13 TPE-1 / PS / HTR / POX / T
The composition and ratio of AIC were determined as TPE-6 / PS / POX / T
Pellets of a thermoplastic elastomer were obtained in the same manner as in Example 1 except that AIC = 65.0 / 35.0 / 0.50 / 1.0 (weight ratio) (referred to as TPV-8). The composition of this thermoplastic elastomer is TPE-6
/PS/softener=46.8/25.2/28.1 (weight ratio), and the degree of crosslinking of the rubbery polymer was 73%. The obtained pellets and PS were mixed so as to have the composition shown in Table 2 and melt-extruded with a twin-screw extruder. The pellet was molded by an injection molding machine (Toshiba IS45PNV) to obtain a molded product. Table 2 shows the characteristics of the molded product.

[0066]

Embodiment 14 TPE-1 / PS / HTR / POX / T
The composition and ratio of AIC were determined as TPE-7 / PS / POX / T
Pellets of a thermoplastic elastomer were obtained in the same manner as in Example 1 except that AIC = 65.0 / 35.0 / 0.50 / 1.0 (weight ratio) (referred to as TPV-9). The composition of this thermoplastic elastomer is TPE-7
/PS/softener=46.8/25.2/28.1 (weight ratio), and the degree of crosslinking of the rubbery polymer was 75%. The obtained pellets and PS were mixed so as to have the composition shown in Table 2 and melt-extruded with a twin-screw extruder. The pellet was molded by an injection molding machine (Toshiba IS45PNV) to obtain a molded product. Table 2 shows the characteristics of the molded product.

[0067]

Embodiment 15 TPE-1 / PS / HTR / POX / T
The composition and ratio of AIC were determined as TPE-8 / PS / POX / T
Pellets of a thermoplastic elastomer were obtained in the same manner as in Example 1 except that AIC = 65.0 / 35.0 / 0.50 / 1.0 (weight ratio) (referred to as TPV-10). The composition of this thermoplastic elastomer is TPE-8
/PS/softener=46.8/25.2/28.1 (weight ratio), and the degree of crosslinking of the rubbery polymer was 48%. The obtained pellets and PS were mixed so as to have the composition shown in Table 2 and melt-extruded with a twin-screw extruder. The pellet was molded by an injection molding machine (Toshiba IS45PNV) to obtain a molded product. Table 2 shows the characteristics of the molded product.

[0068]

Embodiment 16 TPE-1 / PS / HTR / POX / T
The composition of AIC was changed to TPE-1 / PS / SGP / POX / T
Except for using AIC, a thermoplastic elastomer pellet was obtained in the same manner as in Example 1 (referred to as TPV-11). The composition of this thermoplastic elastomer is TPE-1
/PS/SGP/softener=44.9/24.1/4.1.
/26.9 (weight ratio), the degree of crosslinking of the rubbery polymer is 82
%Met. The obtained pellets and PS were mixed so as to have the composition shown in Table 3, and were melt-extruded with a twin-screw extruder. The pellet was molded by an injection molding machine (Toshiba IS45PNV) to obtain a molded product. Table 3 shows the properties of the molded product.

[0069]

Embodiment 17 TPE-1 / PS / HTR / POX / T
The composition of the AIC was TPE-1 / PS / ESP / POX / T
Except for using AIC, a thermoplastic elastomer pellet was obtained in the same manner as in Example 1 (referred to as TPV-12). The composition of this thermoplastic elastomer is TPE-1
/ PS / ESP / softener = 44.9 / 24.1 / 4.1.
/26.9 (weight ratio), the degree of crosslinking of the rubbery polymer is 83
%Met. The obtained pellets and PS were mixed so as to have the composition shown in Table 3, and were melt-extruded with a twin-screw extruder. The pellet was molded by an injection molding machine (Toshiba IS45PNV) to obtain a molded product. Table 3 shows the properties of the molded product.

[0070]

Examples 18 and 19 Table 3 shows the thermoplastic elastomer pellets (TPV-1) obtained in Example 1 and MS and BS.
And melt-extruded with a twin-screw extruder. This pellet is injected into a molding machine (Toshiba IS45PNV).
To obtain a molded product. Table 3 shows the properties of the molded product. As a result of the weather resistance test, the sample of Example 2 was slightly yellowed, but Examples 18 and 19 were not yellowed at all and were extremely excellent in weather resistance.

[0071]

Embodiment 20 TPE-1 / PS / HTR / POX / T
The composition and ratio of AIC were determined as TPE-1 / AS / HTR / P
OX / DVB = 55.0 / 45.0 / 10.0 / 0.5
A pellet of a thermoplastic elastomer was obtained in the same manner as in Example 1 except that the ratio was set to 0 / 1.0 (weight ratio) (TP
V-13). The composition of this thermoplastic elastomer is TPE-1 / AS / HTR / softener = 36.9 / 3
0.2 / 6.7 / 26.2 (weight ratio), the degree of crosslinking of the rubbery polymer was 78%. The obtained pellet and AS,
E-HTR was mixed so as to have the composition shown in Table 3 and melt-extruded with a twin-screw extruder. These pellets are injected into an injection molding machine (Toshiba I
(S45PNV) to obtain a molded product. Table 3 shows the properties of the molded product.

[0072]

[Table 1]

[0073]

[Table 2]

[0074]

[Table 3]

[0075]

The styrenic thermoplastic resin composition of the present invention is a material having excellent weather resistance and impact resistance. Further, when a polyolefin-based resin is contained as a component, the material is extremely excellent in chemical resistance. This material is used for applications such as packaging materials, housing-related materials, automotive materials, OA equipment materials, tools, daily necessities, etc., especially impact-resistant polystyrene (HI).
PS) can be used in applications where it is difficult to use due to problems such as weather resistance and chemical resistance, and plays a major role in the industrial world.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C08L 23/16 C08L 23/16 25/04 25/04 25/10 25/10 51/06 51/06 53 / 00 53/00 53/02 53/02 F-term (reference) 4J002 AC034 AC04W AC05W AC06W AC064 AC08X AC08Y BB03Y BB034 BB05W BB054 BB06W BB06Y BB08W BB12Y BB124 BB14Y BB15W BB15Y BB154 BC04X04 BC04Y04

Claims (12)

[Claims] 1. (A) (1) 40 to 90% by weight of a partially or completely crosslinked saturated rubbery polymer, and (2) 10 to 60% by weight of a thermoplastic resin containing a polystyrene resin as an essential component. And a thermoplastic elastomer comprising: 5 to 95 parts by weight; (B) a polystyrene resin and / or a polyolefin resin: 95 to 5 parts by weight;
An impact-resistant styrenic thermoplastic resin composition wherein the composition contains 1 to 40% by weight of a saturated rubbery polymer. 2. The impact-resistant styrenic heat according to claim 1, further comprising 0.1 to 50 parts by weight of a compatibilizer (C) based on 100 parts by weight of the components (A) and (B). Plastic resin composition. 3. The thermoplastic elastomer of the component (A) may further contain a softening agent based on 100 parts by weight of the saturated rubbery polymer.
The impact-resistant styrene-based thermoplastic resin composition according to claim 1, which contains 0.5 to 200 parts by weight. 4. The thermoplastic resin according to claim 1, wherein (A) (2) the thermoplastic resin containing a polystyrene resin as an essential component is a polystyrene resin or a mixture of a polystyrene resin and a polyolefin resin. Impact-resistant styrenic thermoplastic resin composition. 5. The thermoplastic elastomer (A) is a thermoplastic resin comprising a saturated rubber-like polymer and a polystyrene resin or a thermoplastic resin comprising a mixture of a saturated rubber-like polymer, a polystyrene resin and a polyolefin resin. The impact-resistant styrene-based thermoplastic resin composition according to any one of claims 1 to 4, wherein styrene is dynamically crosslinked in the presence of a crosslinking agent. 6. The impact-resistant styrene-based thermoplastic resin composition according to claim 1, wherein the saturated rubbery polymer is an olefin-based elastomer and / or a styrene-based elastomer. 7. The impact-resistant styrene-based thermoplastic resin according to claim 6, wherein the olefin-based elastomer is an ethylene / α-olefin-based copolymer mainly composed of ethylene and an α-olefin having 3 to 20 carbon atoms. Composition. 8. The olefin-based elastomer comprises ethylene polymerized by a metallocene-based catalyst and C3-C20.
The impact-resistant styrene-based thermoplastic resin composition according to claim 6 or 7, which is an ethylene / α-olefin-based copolymer mainly composed of α-olefin. 9. The impact-resistant styrene-based thermoplastic resin according to claim 7, wherein the olefin-based elastomer is an ethylene / α-olefin-based copolymer mainly composed of ethylene and an α-olefin having 6 to 20 carbon atoms. Composition. 10. The impact-resistant styrene-based thermoplastic resin composition according to claim 6, wherein the styrene-based elastomer is a hydrogenated aromatic vinyl / conjugated diene random or block copolymer. 11. The impact-resistant styrene-based thermoplastic resin composition according to claim 1, wherein the polyolefin-based resin is mainly composed of a polypropylene-based resin. 12. The compatibilizer comprises an AB block copolymer, an A-grafted B copolymer, a B-grafted A copolymer, and a monomer component of B in the A polymer component. One or two or more copolymers selected from copolymers in which a monomer component of A is randomly introduced into a polymer component [here,
A is mainly polystyrene or a polymer compatible with polystyrene. B is one or more types selected from the group consisting of polyethylene, polypropylene, ethylene / α-olefin copolymer mainly composed of ethylene and α-olefin having 3 to 20 carbon atoms, hydrogenated polybutadiene, and hydrogenated polyisoprene. United. ] The impact-resistant styrene-based thermoplastic resin composition according to any one of claims 1 to 11.