JP2000327849A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide thermoplastic resin compositions having a thermoplastic resin as the major component and improved in impact strength and chemical resistance without remarkably reducing the property balance of tensile strength, initial modulus, elongation and the like which the thermoplastic resin possesses, and their molded articles. SOLUTION: Thermoplastic resin compositions simultaneously meet the following (1) to (3) conditions, i.e., the thermoplastic resin composition comprise (1) (a) pts.wt. thermoplastic resin, (b) pts.wt. α-olefin/aromatic vinyl random copolymer, and (c) pts.wt. elastomer (2) at a weight composition ratio of (a) to [(b)+(c)] of 50:50 to 95:5 (3) with a weight composition ratio of (b) to (c) of 10:90 to 95:5. The thermoplastic resin compositions have such a morphology that the random copolymer is dispersed in particulate form in the continuous phase of the thermoplastic resin and furthermore, the particulate random copolymer is wrapped in the elastomer. Molded articles can be obtained by molding these thermoplastic resin compositions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermoplastic resin composition and a molded product thereof.

[0002]

2. Description of the Related Art It is well known in the art how to add a certain polymer to a thermoplastic resin to greatly improve the physical properties of the thermoplastic resin and increase its added value. Examples of the types of high performance include improvement in mechanical properties such as tensile strength, elastic modulus, impact strength, heat resistance, and chemical resistance. Improvements in moldability include improvements in fluidity and shrinkage. In addition, special functions include barrier properties, permanent antistatic properties, conductivity, flame retardancy, improved biodegradability, and the like.

[0003] As these polymer modifiers, for example, styrene-butadiene-styrene block copolymer, ethylene-propylene rubber and the like are added to polystyrene and polypropylene for the purpose of improving impact resistance. aside from that,
Styrene-butadiene-styrene copolymer, styrene-
Some styrene-based thermoplastic elastomers such as ethylene-butylene-styrene copolymer are used. However, unsaturated type block polymers such as styrene-butadiene-styrene copolymers lack chemical stability, so that deterioration of physical properties is unavoidable in the long term, and styrene-ethylene / butylene- The effect of adding saturated type block polymers such as styrene copolymers is not yet sufficient, and it is difficult to use them in terms of cost.

On the other hand, α-olefin-aromatic vinyl random copolymers are effective as a modifier for thermoplastic resins as described in JP-A-10-87918 and JP-A-10-87925. Some are known. However, it is still difficult to say that the modifying effect is sufficient for some applications.

[0005]

DISCLOSURE OF THE INVENTION The present invention improves the impact strength and chemical resistance of a thermoplastic resin without remarkably deteriorating the balance of physical properties such as tensile strength, initial elastic modulus and elongation. An object of the present invention is to provide a thermoplastic resin composition containing the thermoplastic resin as a main component and a molded product thereof.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have found that an α-olefin-aromatic vinyl random copolymer having a specific composition and structure in a thermoplastic resin. And a specific thermoplastic resin composition further combined with an elastomer, a known thermoplastic resin and an elastomer or a thermoplastic resin and an α-olefin-
The present inventors have found that they have a synergistic effect on the above-mentioned problems and are remarkably effective in solving the problems as compared with a thermoplastic resin composition comprising an aromatic vinyl random copolymer, and have completed the present invention.

That is, the present invention is a thermoplastic resin composition which satisfies the following conditions at the same time. It consists of a thermoplastic resin (a) part by weight, an α-olefin-aromatic vinyl random copolymer (b) part by weight, and an elastomer (c) part by weight, and (a): ((b) +
The weight composition ratio represented by (c)) is 50:50 to 95: 5.
And the weight composition ratio represented by (b) :( c) is 1
0:90 to 95: 5. Further, it is a molded product obtained by molding the thermoplastic resin composition.

[Thermoplastic resin] The thermoplastic resin used in the present invention is a known melt-moldable thermoplastic resin other than the α-olefin-aromatic vinyl random copolymer and the elastomer defined in the present invention. The thermoplastic resin is not particularly limited, but is preferably a styrene resin or an olefin resin. Examples of the styrene resin include polystyrene, rubber reinforced polystyrene (HIPS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer (AS resin), and methyl methacrylate-styrene copolymer ( MS resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), and the like. Examples of the olefin-based resin include polyethylene and polypropylene. Of these, polystyrene and polypropylene are particularly preferred. These can be used alone or in combination of two or more.

[Α-olefin-aromatic vinyl random copolymer] The α-olefin-aromatic vinyl random copolymer used in the present invention has an aromatic vinyl content of 1 to 9
It may be a random copolymer containing 9 mol% of an α-olefin and aromatic vinyl, and there is no particular limitation. Such a random copolymer is disclosed in, for example, JP-A-7-702.
An α-olefin-aromatic vinyl pseudo random copolymer described in JP-A No. 23 or WO98 / 09999 and an α-olefin-aromatic vinyl random copolymer described in JP-A-9-309925 are known. Among these random copolymers, α-olefin-aromatic vinyl random copolymer described in JP-A-9-309925 is
It is a more preferable random copolymer in view of the effects of the present invention.

As the aromatic vinyl constituting the α-olefin-aromatic vinyl random copolymer used in the present invention, styrene and various substituted styrenes such as p
-Methylstyrene, m-methylstyrene, o-methylstyrene, ot-butylstyrene, mt-butylstyrene, pt-butylstyrene, p-chlorostyrene,
o-chlorostyrene, α-methylstyrene and the like. Further, divinylbenzene having a plurality of vinyl groups in one molecule and the like can also be mentioned. Of these aromatic vinyls, industrially preferred are styrene, α-methylstyrene and p-methylstyrene, and particularly preferred is styrene. Two or more of these aromatic vinyls may be used in combination.

The α-olefin constituting the α-olefin-aromatic vinyl random copolymer is an α-olefin having 2 to 20 carbon atoms, ie, ethylene, propylene, 1-butene, 1-hexene, 4- Methyl-1-
Penten, 1-octene and the like can be mentioned. Of these, ethylene and propylene are preferable as the α-olefin. Two or more olefins can be used in combination.

In the present invention, an ethylene-styrene random copolymer is a preferred example of an α-olefin-aromatic vinyl random copolymer. This will be further described.

The ethylene-styrene random copolymer suitably used in the present invention has a styrene content of 1 mol%.
~ 99%, preferably 5 ~ 98%, more preferably 10%
~ 97% ethylene-styrene random copolymer. Preferably, the stereoregularity of the phenyl group having an alternating structure of styrene and ethylene is 0.75 or more in isotactic dyad fraction m, more preferably m
Is 0.85 or more, particularly preferably 0.95 or more, and the alternating structure index λ of styrene and ethylene is 7 or more.
Ethylene-styrene random copolymers less than 0 and greater than 1, preferably less than 70 and greater than 5.

[0014] The ethylene-styrene random copolymer suitably used in the present invention has a chain structure composed of two or more styrene units linked by a head-tail, and the steric rule of the phenyl group in the chain structure. It is an isotactic ethylene-styrene random copolymer having an isotactic dyad fraction ms of greater than 0.5, preferably 0.7 or more, more preferably 0.8 or more. The isotactic dyad fractions m and ms and the alternating structure index λ shown here are those described in JP-A-9-30.
Details are described in Japanese Patent Application No. 9925.

In the thermoplastic resin composition of the present invention, the use of an ethylene-styrene random copolymer having a chain of styrene units linked by a head-tail and having a high stereoregularity can provide an initial elastic modulus, breaking strength, It is preferable in that a decrease in elongation and heat resistance can be minimized to obtain a thermoplastic resin composition having more excellent impact strength and chemical resistance.

The weight average molecular weight of the ethylene-styrene random copolymer suitably used in the present invention is preferably 60,000 or more when the styrene content is 1 mol% to less than 20 mol%.
It is more preferably 80,000 or more, and preferably 30,000 or more, more preferably 40,000 or more when the styrene content is 20 mol% to 99 mol%. The upper limit of the weight average molecular weight is not particularly limited, but is preferably 3,000,000 or less, more preferably 1,000,000 or less. When the molecular weight exceeds 3,000,000, the melt viscosity increases, and molding by a general molding method such as injection molding or extrusion molding tends to be difficult. Here, the weight average molecular weight (Mw) refers to a polystyrene-converted molecular weight determined by GPC using standard polystyrene.

The molecular weight distribution (Mw / Mn) is preferably 6 or less, more preferably 4 or less, particularly preferably 3 or less. Note that Mn represents a number average molecular weight, which can be similarly measured by a GPC method.

The ethylene-styrene random copolymer has been described as an example of the α-olefin-aromatic vinyl random copolymer used in the present invention. However, the above description applies to all α-olefin-aromatic vinyl random copolymers suitably used in the present invention.

The preferred α-olefins described above
The aromatic vinyl random copolymer is described in, for example,
It can be obtained by the production method described in JP-A-309925.

The α-olefin-aromatic vinyl random copolymer used in the present invention does not necessarily need to be a copolymer consisting only of aromatic vinyl and α-olefin, but may be any copolymer within the range specified in the present invention. Other monomers may be copolymerized as long as they are copolymerized. As other monomers to be copolymerized, aromatic vinyl constituting the α-olefin aromatic vinyl random copolymer and monomers other than those already described as the α-olefin, specifically propylene or the like having 3 to 20 carbon atoms. Α-olefin, butadiene, 1,4-hexadiene, 1,5-hexadiene,
Diene compounds such as ethylidene norbornene and vinylcyclohexene can be exemplified. These monomers may be used in combination of two or more. The amount of these other monomers is preferably kept within a range in which the preferred structure and stereoregularity of the present invention are maintained.

For the purpose of improving the physical properties, two or more α-olefin-aromatic vinyl random copolymers having different styrene contents can be used in combination. In the present invention, the α-olefin-aromatic vinyl random copolymer may be partially modified by grafting, hydrogenation, functional group addition, or the like.

[Elastomer] The elastomer used in the present invention refers to a polymer substance exhibiting rubber elasticity at normal temperature. As an elastomer, it has the properties of rubber and plastic and has at least one constrained segment component (hard segment) for forming a constrained phase as a cross-linking point of a three-dimensional network and a soft segment for showing entropic elasticity as a network chain. Also included are thermoplastic elastomers. In the present invention, the elastomer used is not particularly limited and may be a known one, but the elastomer described below is preferably used.

The elastomer applicable to the present invention includes styrene elastomer, olefin elastomer, polyester elastomer, polyamide elastomer, urethane elastomer, isoprene rubber, butadiene rubber, 1,2-polybutadiene rubber, styrene-butadiene rubber. , Chloroprene rubber, nitrile rubber,
Examples include butyl rubber, methacrylate-butadiene-styrene rubber, ethylene-propylene rubber, chlorosulfonated polyethylene rubber, acrylic rubber, epichlorohydrin rubber, silicone rubber, fluorine rubber, urethane rubber, and the like. Of these, a styrene-based elastomer, an olefin-based elastomer, or an elastomer having a chemically crosslinked structure is preferred, and a styrene-based block copolymer is particularly preferred.

The above-mentioned block copolymer is included in the category of elastomers, and is, for example, a combination of a saturated rubber segment or an unsaturated rubber segment and a hard segment styrene-type polymer. The block copolymer suitably used in the present invention is not limited, and may be a linear or radial type, diblock or triblock, or any combination thereof. Further, the connecting portion connecting the soft segment and the hard segment may have a gradient with respect to the occupancy ratio of one monomer unit.

Examples of the block copolymer having an unsaturated rubber unit are represented by the following formulas (i) and (ii). S-D-R (-DS) n Formula (i) or Sx- (DS-) y-DS Formula (ii) where S is a styrene-based compound. A polymer block, preferably a polystyrene block, D is a diene-based polymer block in which a double bond is bonded with a single bond in between, preferably an isoprene or butadiene polymer block, R is a polyfunctional coupling reagent, n is an integer of 1 to 5, x is 0 or 1, and y is an integer of 0 to 4.

The block copolymer having an unsaturated rubber unit is produced using a catalyst such as alkyl lithium.
Further, a block copolymer having a saturated rubber unit can be formed by hydrogenation. For example, a linear (co) polymer is prepared by a method of continuously introducing a rubber monomer into a reaction vessel using a polymerization initiator such as alkyllithium or dilithiostilbene, or a bifunctional coupling reagent. It is obtained by coupling a block polymer of two segments. The branched structure can be obtained by using a suitable coupling reagent such as silicon halide, ester of monohydric alcohol of siloxane or carboxylic acid, dihaloalkane or alkene and divinylbenzene. Couplings can also be formed by other multifunctional coupling reagents.

Block copolymers having an unsaturated rubber unit include styrene-butadiene (SB), styrene-isoprene (SI), and styrene-butadiene-styrene (SB).
S), styrene-isoprene-styrene (SIS), α
-Methylstyrene-butadiene-α-methylstyrene,
α-methylstyrene-isoprene-α-methylstyrene block copolymer and the like can be exemplified. The styrene-based polymer block portion of the block copolymer is a homopolymer block such as styrene, α-methylstyrene or ring-substituted styrene, particularly styrene in which the ring is methylated,
Or a copolymer block of these and styrene.
Among these styrene units constituting the styrene polymer block portion, styrene and α-methylstyrene are preferred, and styrene is particularly desirable. The block copolymer having an unsaturated rubber unit is preferably a block copolymer containing butadiene or isoprene in a rubber block portion, or a block copolymer containing a copolymer block of both diene rubbers.

Desirable block copolymers having saturated rubber units are those containing at least one styrenic unit segment and at least one ethylene-butylene or ethylene-propylene copolymer block.
Examples of desirable block copolymers having such a saturated rubber unit include styrene-ethylene-butylene copolymer, styrene-ethylene-propylene copolymer, styrene-ethylene-butylene-styrene (SEBS) copolymer, and styrene. -Ethylene propylene-styrene (S
EPS) copolymer.

When a block copolymer having an unsaturated rubber unit is hydrogenated to obtain a block copolymer having a saturated rubber unit, the hydrogenation rate of the unsaturated rubber block copolymer is not particularly limited. A block copolymer in which 99% of the aliphatic double bonds are hydrogenated, while the hydrogenation ratio to the styrene aromatic double bonds is 5% or less is preferred.

The proportion of the styrenic polymer block portion is not particularly limited, but is generally preferably between 8 and 65% of the total weight of the block copolymer. Preferably, the block copolymer contains 10 to 35% by weight of the total weight of the block copolymer and a styrene-based block segment and 90 to 65% by weight of a rubber block segment.

The average molecular weight of the block portion is not limited, but the styrene-based block segment has a number average molecular weight of 5,000 to 125,000, preferably 7,000 to 6
And the rubber segment is 10,000.
0 to 300,000, desirably 30,000 to 15
It is in the range of 0000. The overall average molecular weight of the block copolymer generally ranges from 25,000 to 250,000, preferably from 35,000 to 200,000.

The block copolymer can be further modified with a functional group such as maleic anhydride.

As the block copolymer described above,
For example, “KRATON” manufactured by Shell Japan, “Septon” and “Hibler” manufactured by Kuraray, “Toughtec” manufactured by Asahi Kasei, “JSR TR” manufactured by Nippon Synthetic Rubber Co., and Decks
o "VECTORTM" manufactured by Polymers is commercially available, and these can be used as an elastomer.

The present invention relates to a thermoplastic resin, α-olefin-
It is a thermoplastic resin composition comprising an aromatic vinyl random copolymer and an elastomer. The mixing ratio of each component is as follows: (a) parts by weight of the thermoplastic resin composition;
When (b) parts by weight of the aromatic vinyl random copolymer and (c) parts by weight of the elastomer, (a): ((b) +
(C)) = 50: 50-95: 5, and (b):
(C) = 10: 90 to 95: 5, preferably
(B) :( c) = 15: 85 to 90:10, more preferably (b) :( c) = 25: 75 to 75:25. The thermoplastic resin composition of the present invention contains a thermoplastic resin as a main component in an amount of 50% by weight or more, and further improves impact strength, chemical resistance, etc. without reducing the physical properties of the thermoplastic resin as much as possible. It is to let. (A): ((b) +
(C)) = 50: 50-95: 5, and (b) :( c)
If the ratio is out of the range of 10:90 to 95: 5, the characteristics of the respective components are not obtained, and the modifying effect is not sufficiently exhibited, which is not preferable. In particular, when the compounding ratio (c) of the elastomer exceeds 45% by weight of the whole, long-term deterioration of physical properties is likely to become apparent.

When the morphology of the thermoplastic resin composition of the present invention is observed using a transmission electron microscope (TEM), it is found that the α-olefin-aromatic vinyl random copolymer is granular in the thermoplastic resin forming a continuous phase. Has been found by the present inventors to be a morphology of a form in which the elastomer is wrapped around the polymer. The elastomer appears to be the binder. For example, 85% by weight of a polystyrene-based polymer (manufactured by Denki Kagaku Kogyo KK, Denka TX Polymer TX-100), 10% by weight of a styrene-ethylene random copolymer having a styrene / ethylene content of 15/85 mol%, and Hydrogenated styrene-butadiene-styrene copolymer (SEB
S) (KRATON G-1652, manufactured by Shell Co., Ltd.) 5% by weight, and then kneaded with a twin-screw extruder at a temperature of 230 ° C. (described later as Example 4)
Into a thin section, and a transmission electron microscope (2000, manufactured by JEOL Ltd.)
Fig. 1 shows a photograph of the morphology observed using CX type).
As shown. For comparison, a polystyrene-based polymer (T
X-100) of a thermoplastic resin composition (to be described later as Comparative Example 6) in which 85% by weight and 15% by weight of an ethylene-styrene random copolymer (described above) were similarly kneaded by an extruder; Combined (same TX-10
0) A thermoplastic resin composition (described later as Comparative Example 7) in which 85% by weight and 15% by weight of a hydrogenated styrene-butadiene-styrene copolymer (G-1652) were similarly kneaded by an extruder was similarly used. Photographs of the morphology observed with a transmission electron microscope are shown in FIGS. 2 and 3, respectively.

FIG. 2 shows an ethylene-styrene random copolymer island (dispersed phase) in the sea (continuous phase) of a polystyrene polymer as a thermoplastic resin, and FIG. 3 shows a hydrogenated styrene sea in a polystyrene polymer sea. -Morphology in which islands of butadiene-styrene copolymer exist. On the other hand, in the case of the thermoplastic resin composition of the present invention, as shown in FIG. 1, islands of the ethylene-styrene random copolymer exist in the sea of the polystyrene-based polymer, and around the islands, hydrogenated styrene-butadiene- It can be seen that the morphology is such that the styrene copolymer is wrapped around. We have:
It is believed that the thermoplastic resin composition of the present invention exhibits a synergistic effect in improving impact resistance and chemical resistance due to such morphology.

Next, a method for producing the thermoplastic resin composition of the present invention will be described. The method used for obtaining the thermoplastic resin composition of the present invention is not particularly limited as long as it enables effective dispersion and mixing, and a known method can be used. For example, a single screw extruder, 2
Melt mixing can be performed with a screw extruder, Banbury mixer, plast mill, co-kneader, heated roll, or the like.
It is also a preferable method to uniformly mix the respective raw materials using a Henschel mixer, a ribbon blender, a super mixer, a tumbler or the like before performing the melt kneading. Further, a method of mixing a raw material with a polymer in a solution state and then removing a solvent is also applicable. The order of addition is not particularly limited. For example, a thermoplastic resin may be added to an α-olefin-aromatic vinyl random copolymer / elastomer mixture, or an α-olefin-aromatic vinyl random copolymer may be added. It may be added to the thermoplastic / elastomer mixture.

Examples of the form of the thermoplastic resin composition of the present invention include a film, a block, a pellet, a sheet, and a strand.

When the thermoplastic resin composition of the present invention is obtained by melt-mixing, the melt-kneading temperature is not particularly limited as long as the thermoplastic resin is sufficiently melted, but is preferably from 100 to 350 ° C, more preferably from 150 to 300 ° C. Is particularly preferred.

[0040] The thermoplastic resin composition of the present invention can be crosslinked as required. Examples of the crosslinking method include a chemical method by adding a crosslinking agent such as a peroxide and sulfur and, if necessary, a co-crosslinking agent and the like, radiation crosslinking, and the like. Examples of the crosslinking process include a static method, a dynamic vulcanization method, and the like.

Examples of the crosslinking agent include organic peroxides, sulfur, phenols, isocyanates, thiurams, morpholine disulfides and the like. These include stearic acid, oleic acid, zinc stearate, zinc oxide and the like. A crosslinking aid, a co-crosslinking agent, a vulcanization accelerator and the like can be used in combination. Examples of the organic peroxide crosslinking agent include hydroperoxide, dialkyl peroxide, diallyl peroxide, diacyl peroxide, peroxyester, ketone peroxide and the like.
Examples of the radiation crosslinking include a crosslinking method using an electron beam, radiation, or the like.

The thermoplastic resin composition of the present invention may contain a filler, a stabilizer, an antioxidant, a light resistance improver, an ultraviolet absorber, a plasticizer, a softener, a lubricant, a processing aid, a coloring agent, depending on the purpose. Agents, pigments, antistatic agents, flame retardants, anti-fogging agents, anti-blocking agents, nucleating agents, foaming agents and the like can be added.
These can be used alone or in combination of two or more.

Among the above, there are no particular restrictions on the amounts of stabilizers, antiaging agents, lightfastness improvers, ultraviolet absorbers, lubricants, coloring agents, pigments, antiblocking agents, crystal nucleating agents, etc.
From the balance between physical properties and economy, 5% by weight or less is practical as an addition amount.

Examples of usable fillers include mica, talc, clay, calcium carbonate, magnesium carbonate, aluminum hydroxide, hydrotalcite, glass fiber, glass beads, glass balloon, glass flake, silica, carbon black, graphite, Titanium oxide, magnesium hydroxide, potassium titanate whisker, carbon fiber, alumina, kaolin clay, silicic acid,
Examples thereof include calcium silicate, quartz, zirconia, potassium titanate, alumina, and metal particles. These shapes may be any of flakes, spheres, granules, powders, irregular shapes, and the like, and are not particularly limited.

Examples of usable stabilizers include phenol-based, benzophenone-based, sulfylate-based, benzotriazole-based, hydrazine-based, sulfur-based, phosphorus-based, amine-based, and epoxy-based compounds. More specifically, phenolic antioxidants such as 2,6-di-t-butyl-4-methylphenol and phosphorus-based antioxidants such as trisnonylphenylphosphite can be exemplified.

Examples of usable plasticizers include phthalic acid ester compounds, pyromellitic acid ester compounds, trimellitic acid ester compounds, trimesic acid ester compounds,
Benzoic acid ester compounds, adipic acid ester compounds,
Azelaic acid ester compound, sebacic acid ester compound, polyester compound, terpene resin, rosin resin, coumarone / indene resin, petroleum resin, paraffin, process oil, low molecular weight polyolefin, low molecular weight polystyrene, aromatic carboxylic acid ester, phosphoric acid Examples include esters, chlorinated paraffins, and epoxy compounds.

Examples of usable lubricants include hydrocarbons, fatty acids, fatty acid metal salts, fatty acid esters, fatty acid amides, polyethylene glycol, polyglycerol, silicone compounds and the like. More specifically, ethylene bis stearamide, sorbitan monostearate, pentaerythritol fatty acid ester and the like can be mentioned.

Usable antistatic agents are classified into low-molecular compound kneading type, permanent antistatic type comprising a polymer having a specific structure, and the like. Cationic, anionic, nonionic, amphoteric, etc. Activators and the like. Examples of the cationic surfactant include primary alkylamine salts, tertiary alkylamine salts, quaternary alkylammonium salts, and alkylpyridinium salts.

The method for obtaining the molded article of the present invention will be described below. The method for obtaining the molded article of the present invention from the thermoplastic resin composition of the present invention is not particularly limited, and a known method can be used. Specifically, the shape can be given by injection molding, T-die method, tubular method, inflation method, extrusion molding such as profile extrusion, blow molding, hollow molding, vacuum molding, air pressure molding, compression / transfer molding, powder molding, etc. It is possible. Stretch orientation can be carried out if necessary. In addition, these molded products can be further secondary molded. Examples of such an example include obtaining various trays from a sheet by air pressure molding.

Uses of the thermoplastic resin composition of the present invention include foods, machines, containers for electric parts, stationery, OA equipment, home appliances, automobile parts, packaging containers, tubes, hoses,
Examples include films and sheets.

The molded article made of the thermoplastic resin composition of the present invention can be subjected to a surface treatment for the purpose of improving printability and the like. The method of the surface treatment is not particularly limited, and a physical method, a chemical method, and the like can be used. Examples thereof include a corona discharge treatment, an ozone treatment, a plasma treatment, a flame treatment, and an acid / alkali treatment. it can. Of these, corona discharge treatment is preferred in terms of ease of implementation, cost, continuous treatment, and the like.

[0052]

EXAMPLES The present invention will be further described with reference to examples below, but the present invention is not limited to these examples.

First, a method for analyzing the ethylene-styrene random copolymer obtained in each of the following Reference Examples will be described.

¹³ C-NMR spectrum Instrument; α-500 solvent manufactured by JEOL Ltd .; Deuterated chloroform or deuterated 1,1,2,2-tetrachloroethane Reference sample; TMS method; First, tetrachloroethane triplet based on TMS The shift value of the center peak of the ¹³ C-NMR peak was determined, and then each peak shift value of the copolymer was calculated based on the triplet center peak of tetrachloroethane. The shift value of the triplet center peak of tetrachloroethane is 7
3.89 ppm. Quantify peak area ¹³ C
-NMR spectrum measurement is performed by NOE (Nuclear
A pulse width of 45 was obtained by a proton gate decoupling method in which Overhauser Effect was eliminated.
° pulse and a repetition time of 5 seconds as a standard.

Styrene content in ethylene-styrene random copolymer ( ¹ H-NMR method) Equipment: α-500 manufactured by JEOL Ltd. and AC-250 manufactured by BRUCKER Solvent: heavy chloroform or heavy 1,1,2,2 2-tetrachloroethane reference sample; TMS method; peak derived from phenyl group proton (6.5 to 6.5)
7.5 ppm) and a proton peak (0.8 to 3 ppm) derived from an alkyl group.

Molecular weight of ethylene-styrene random copolymer in Reference Example Equipment: Gel Permeation Chromatograph (GP
C), HLC-8020 manufactured by Tosoh Corporation (however, TH at room temperature)
The copolymer insoluble in F is GPC-7 manufactured by Senshu Kagaku Co., Ltd.
100) Solvent; tetrahydrofuran (THF) (However, 1,2,4-trichlorobenzene is used as a copolymer insoluble in THF at room temperature) Reference sample; standard polystyrene Method; standard polystyrene conversion by GPC It was determined as a weight average molecular weight.

DSC (differential scanning calorimetry) measurement [The melting point is shown as a reference value. Equipment: DSC200 manufactured by Seiko Denshi Co., Ltd. Method: Measured at a heating rate of 10 ° C./min under a stream of N ₂ .

The physical properties of the resin composition were evaluated by the following methods. The flexural modulus is 1/4 inch bar, JIS
It was determined according to K-7113 "Plastic tensile test method".

The tensile elongation at break was determined using a No. 2 dumbbell having a thickness of 1 mm according to JIS K-7113 "Plastic tensile test method".

The impact resistance was determined by molding a notched 1/4 inch bar at 23 ° C. according to JIS K-7110 “Hard plastic Izod impact test method”.

The surface hardness is of type D according to JIS K-7215 "Durometer hardness test method for plastics".
Durometer hardness was determined.

The MFR was measured according to JIS K-7210 “Testing method for flow of thermoplastics”. The measurement was performed at a measurement temperature of 230 ° C. and a test load of 5 kgf.

The chemical resistance was evaluated by the following method. The dumbbell used in the tensile test was immersed in acetone and hexane for 24 hours, and the weight change rate was determined. Weight change rate is 50% or more
··· ×, less than 30 to 50% ··· △, 10 to 30%
Less than ... ○, less than 0-10% ・ ・ ・ ・ ◎

Next, as reference examples, synthesis examples (production examples) of various compounds, catalysts and cocatalysts used in the examples will be described. Reference Example-1 [Synthesis of transition metal compound rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride] Organometallics, 13 , 964 (19)
According to 94), synthesis was performed in the following order (1) to (3).

(1) Synthesis of precursor compound 1,1-isopropylidene-4,5-benzoindene Can. J. Chem. 62 , 1751 (1984), referring to the synthesis of 6,6-diphenylfulvene. However, the starting materials were acetone instead of benzophenone and 4,5 instead of cyclopentadiene.
-Benzoindene was used.

(2) Synthesis of Precursor Compound Isopropylidenebis4,5-benzo-1-indene Under an Ar atmosphere, 21 mmol of 4,5-benzoindene was dissolved in 70 ml of THF, and an equivalent amount of BuLi was added at 0 ° C.
Was added and stirred for 3 hours. THF in which 21 mmol of 1,1-isopropylidene-4,5-benzoindene was dissolved was added, and the mixture was stirred at room temperature overnight. 100 ml of water and 150 ml of diethyl ether were added and the mixture was shaken. The organic layer was separated, washed with saturated saline, dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained yellow solid was washed with hexane and dried, and isopropylidenebis 4,5-benzo-1-
3.6 g of indene was obtained. The yield was 46%. ¹ H
7.2 to 8.0 ppm by NMR spectrum measurement
(M, 12H), 6.65 ppm (2H), 3.75 p
pm (4H) and a peak at 1.84 ppm (6H). The measurement was performed using CDCl ₃ as a solvent based on TMS.

(3) Synthesis of transition metal compound rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride 7.6 mmol of the above isopropylidenebis4,5-benzo-1-indene under an Ar atmosphere And 7.2 mmol of zirconium tetrakisdimethylamide in toluene 50
Then, the mixture was stirred at 130 ° C. for 10 hours. Under reduced pressure, toluene was distilled off, 100 ml of methylene chloride was added, and the mixture was cooled to -78 ° C. 13. dimethylamine hydrochloride
4 mmol was slowly added, the temperature was slowly raised to room temperature, and the mixture was stirred for 2 hours. After evaporating the solvent, the obtained solid was
Subsequently, the resultant was washed with a small amount of THF to obtain 0.84 g of rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride of yellow lantern. 21% yield
Met.

According to ¹ H-NMR spectrum measurement, 8.
01 ppm (m, 2H), 7.75 ppm (m, 2H)
H), 7.69 ppm (d, 2H), 7.48-7.5.
8 ppm (m, 4H), 7.38 ppm (d, 2H),
7.19 ppm (d, 2H), 6.26 ppm (d, 2H)
H) had a peak at 2.42 ppm (s, 6H). ^{The 1} H-NMR spectrum was measured using CDCl ₃ as a solvent based on TMS. In addition, elemental analysis was performed using an elemental analyzer 1108 (manufactured by Fisons, Italy), and C63.86% and H3.98% were obtained. (Theoretical values are C 65.39%, H 4.16%
It is. )

Reference Example 2 [Synthesis of Ethylene-Styrene Random Copolymer] Reference Example-2-; Synthesis of P-1 Polymerization was carried out as follows using a polymerization vessel having a capacity of 150 L, a stirrer and a jacket for heating and cooling. went. Charge 60 L of dehydrated cyclohexane and 12 L of styrene,
The mixture was heated and stirred at 0 ° C. Triisobutyl aluminum 84
mmol, methylalumoxane (Tosoh Akzo, P
MAO-s) was added in an amount of 84 mmol based on Al, ethylene was immediately introduced, and the mixture was stabilized at a pressure of 1.0 MPa. After that, the catalyst obtained in the above synthesis example, rac-dimethylmethylenebis ( 4,5-benzo-
84 μm of 1-indenyl) zirconium dichloride
ol, about 100 mL of a toluene solution of 1 mmol of triisobutylaluminum was added to the polymerization vessel. Polymerization was carried out for 3 hours while maintaining the ethylene pressure at 1.0 MPa. After completion of the polymerization, the obtained polymerization solution was degassed, and then treated by the crumb forming method as described below to recover the polymer. 150 L of the polymerization solution containing a vigorously stirred dispersant
Into 85 ° C. heated water for 1 hour. Then 9
After heating to 7 ° C. and stirring for 1 hour, hot water containing crumb was poured into cold water to collect crumb. The crumb is air-dried at 50 ° C. and then vacuum degassed at 60 ° C. to obtain a crumb-shaped polymer (P-1) 13k having a size of about several mm.
g was obtained. The analysis values of the obtained ethylene-styrene random copolymer P-1 are shown in Table 2.

Reference Example-2- Synthesis of P-2 Polymerization was carried out in the same manner as in Reference Example-2- under the conditions shown in Table 1, and then post-treatment was carried out in the same manner as in Reference Example-2- to obtain polymer (P
-2) 10 kg was obtained. The analytical values of the obtained ethylene-styrene random copolymer P-2 are shown in Table 2.

[0071]

[Table 1]

[0072]

[Table 2]

Example 1 Commercially available polypropylene (F-1 manufactured by Grand Polymer Co., Ltd.)
03) 8.5 kg, 1 kg of the ethylene-styrene random copolymer P-1 described in Reference Example 2, and styrene-
Hydrogenated compound of butadiene-styrene block copolymer (KRATON G-1652, manufactured by Shell) 0.5 k
g was mixed with a 20 L Henschel mixer, and then melt-kneaded at a temperature of 230 ° C. with a 30 mmφ twin screw extruder. The physical properties of the obtained resin composition were evaluated by the methods described above, and the results are shown in Table 3.

Examples 2 to 4 and Comparative Examples 1 to 7 Commercially available polypropylene (F-1 manufactured by Grand Polymer Co., Ltd.)
03), polystyrene (Denka Styrol GP-1 manufactured by Denki Kagaku Kogyo Co., Ltd.), polystyrene-based polymer (Denka TX Polymer TX-100 manufactured by Denki Kagaku Kogyo Co., Ltd.), and the ethylene-styrene random copolymer obtained in Reference Example 2. Hydrogenated compounds of the combined P-1, P-2, and / or styrene-butadiene-styrene block copolymer (KRATON G-1652, manufactured by Shell), hydrogenated compounds of styrene-isoprene-styrene block copolymer (Septon 2104, manufactured by Kuraray Co., Ltd.) at a compounding ratio of Table 3 in Example 1.
By operating in the same manner as in, resin compositions of Examples 2 to 4 and Comparative Examples 1 to 7 were obtained. Table 3 shows the physical property evaluation results.

[0075]

[Table 3]

[0076]

The thermoplastic resin composition of the present invention and a molded article obtained by molding the same are a thermoplastic resin composition comprising a known thermoplastic resin and an elastomer or a thermoplastic resin and an α-olefin-aromatic. Compared with the thermoplastic resin composition comprising a vinyl random copolymer and these molded articles, the impact strength and chemical resistance are improved without significantly lowering the balance of physical properties such as tensile strength, initial elastic modulus and elongation. You.

[Brief description of the drawings]

FIG. 1 is a transmission electron micrograph (100,000 times magnification) showing the morphology of a thermoplastic resin composition of the present invention (Example 4).

FIG. 2 is a transmission electron micrograph (100,000 times magnification) showing the morphology of a thermoplastic resin-α-olefin-aromatic vinyl random copolymer composition of a comparative example (Comparative Example 6).

FIG. 3 is a transmission electron micrograph (100,000 times magnification) showing a morphology of a thermoplastic resin-elastomer composition of a comparative example (Comparative Example 7).

Front page of the continued F-term (reference) 4J002 AA01W AC03Y AC06Y AC07Y AC08Y AC09Y BB03W BB10X BB12W BB14X BB15Y BB16Y BB17X BB18Y BB27Y BC01X BC03W BC04X BC06W BC07W BC08X BC10X BC11X BD13Y BG04Y BG06W BG10W BN14W BN15W BN16W BP01Y BP03Y CF00Y CK02Y CL00Y CP03Y FD010 FD020 FD030 FD070 FD100 FD140 FD150 FD170

Claims (8)

[Claims] 1. A thermoplastic resin (a) part by weight, an α-olefin-aromatic vinyl random copolymer (b) part by weight,
And a thermoplastic resin composition comprising parts by weight of an elastomer (c), wherein the weight composition ratio represented by (a): ((b) + (c)) is 50:50 to 95: 5, and
(B): The weight composition ratio represented by (c) is 10:90 to 9
The thermoplastic resin composition, wherein the ratio is 5: 5. 2. A thermoplastic resin (a) part by weight, an α-olefin-aromatic vinyl random copolymer (b) part by weight,
A thermoplastic resin composition consisting of parts by weight of an elastomer (c) and an elastomer (c), wherein a weight composition ratio represented by (a): ((b) + (c)) is 50:50 to 95: 5,
(B): The weight composition ratio represented by (c) is 10:90 to 9
5: 5, and the α-olefin-aromatic vinyl random copolymer is almost uniformly dispersed in a granular form in a continuous phase composed of a thermoplastic resin, and an elastomer further surrounds the granular form. The thermoplastic resin composition having an elliptical morphology. 3. The thermoplastic resin composition according to claim 1, wherein the α-olefin-aromatic vinyl random copolymer is an ethylene-styrene random copolymer. 4. The α-olefin-aromatic vinyl random copolymer has a stereoregularity of a phenyl group having an alternating structure composed of an ethylene unit and a styrene unit of 0.75 or more in terms of isotactic dyad fraction m. Ethylene having an alternating structure index λ smaller than 70 and larger than 1
3. The thermoplastic resin composition according to claim 1, which is a styrene random copolymer. 5. The α-olefin-aromatic vinyl random copolymer has a chain structure composed of two or more styrene units linked by a head-tail, and a phenyl group of the chain structure has an isotactic steric structure. 3. The thermoplastic resin composition according to claim 1, which is an ethylene-styrene random copolymer having regularity. 6. The method according to claim 1, wherein the elastomer is a styrenic block copolymer.
Item 12. The thermoplastic resin composition according to Item 1. 7. The method according to claim 1, wherein the thermoplastic resin is a styrene resin and / or an olefin resin.
7. The thermoplastic resin composition according to any one of 6. 8. A molded article obtained by molding the thermoplastic resin composition according to any one of claims 1 to 7.