JP2002121355A - Polystyrene resin composition and its molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polystyrene resin composition which remarkably improves printability and adherence of a molded article such as a film or a sheet, made of a styrenic block copolymer or a styrenic graft copolymer, and a molded article made therefrom. SOLUTION: The styrenic resin composition consists of (1) a styrene polymer having a syndiotactic structure, (2) a styrene/diene or styrene/olefin block or graft copolymer, and if necessary, (3) a styrene polymer having an atactic structure, wherein the content of the styrene polymer having a syndiotactic structure is 3-40 wt.%. The molded article is made from the composition and has a total haze of 5% or lower.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a styrenic resin composition and a molded article thereof, and more particularly, to a stin-based resin composition suitable as various packaging films, films, sheets or containers for packaging containers, and a molded article thereof. About.

[0002]

2. Description of the Related Art Styrene block copolymers such as SBS, SIS and SEBS and styrene graft copolymers are
It is used for various purposes as a modifier of another resin or a molded article containing the same as a main component (JP-A-2000-18617).
No. 9). However, in films and sheets containing or adding these styrene-based block copolymers or styrene-based graft copolymers as main components, there are many restrictions on the types of adhesives, inks, drying conditions, and the like during secondary processing. ,
Improvement is desired. In addition, a polystyrene having a syndiotactic structure (hereinafter, may be abbreviated as SPS) having crystallinity is mixed with polystyrene having an atactic structure (hereinafter sometimes abbreviated as aPS). It is known that a styrene-based polymer composition having improved solvent resistance can be obtained (see, for example, Japanese Patent Application No. Hei 11 (1999) -107).
-69454, Japanese Patent Application No. 11-69453, JP-A-12-79992, JP-A-11-27.
9347, JP-A-11-279348, JP-A-11-279349, JP-A-8-92385
JP-A-8-92444). However, this styrenic polymer composition has excellent solvent resistance, but is kneaded and molded at a temperature higher than the melting point of SPS (heat history at two high temperatures), and the oligomer content in the molded article increases. As a result, no reduction in the elution amount of the styrene oligomer was observed. This problem is particularly remarkable when an SPS homopolymer is used. In order to cope with this problem, a molding method using a dry blend material comprising aPS and a specific SPS has been proposed (Japanese Patent Application No. Hei 11 (1999) -107).
-284024). In this method, the molding temperature can be lowered by molding with dry blending and using SPS with a low melting point, so that an increase in the content of styrene oligomer in the molded article is suppressed and a reduction in the amount of styrene oligomer eluted is expected. Is done. As described above, various studies have been made on the modification of aPS, but studies on styrene-based block copolymers and styrene-based graft copolymers have not been sufficient.

[0003]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art and provides printability and adhesion of a molded article such as a film or sheet of a styrene-based block copolymer or a styrene-based graft copolymer. It is an object of the present invention to provide a styrenic resin composition and a molded article thereof which can significantly improve the properties.

[0004]

The inventor of the present invention has proposed that a styrene-based block copolymer or a styrene-based graft
It has been found that the above object can be achieved by blending PS or SPS with aPS. The present invention has been completed based on such findings. That is, the present invention provides a styrene-based polymer 3 having a syndiotactic structure.
Styrene-diene-based or styrene-olefin-based block or graft copolymer 9 to 40% by weight
A styrene-based resin composition comprising 7 to 60% by weight, a styrene-based polymer having a syndiotactic structure, 3 to 40% by weight, a styrene-diene-based or styrene-olefin-based block or graft copolymer 87 to 20%
% By weight and an atactic styrene polymer 10
The present invention provides a styrenic resin composition comprising the styrenic resin composition of up to 40% by weight, and a molded article comprising the styrenic resin composition and having a total haze of 5% or less.

[0005]

DETAILED DESCRIPTION OF THE INVENTION As described above, the styrenic resin composition of the present invention comprises a styrenic polymer having a syndiotactic structure and a styrene-diene or styrene-based polymer.
It contains an olefin-based block or graft copolymer, or a styrene-based polymer having a syndiotactic structure, a styrene-diene-based or styrene-olefin-based block or graft copolymer, and a styrene-based polymer having an atactic structure. It contains.

The syndiotactic structure in the styrenic polymer (SPS) having a syndiotactic structure is a syndiotactic structure in which the stereochemical structure is a side chain with respect to a main chain formed from carbon-carbon bonds. Has a steric structure in which phenyl groups are alternately located in opposite directions, and its tacticity is quantified by nuclear magnetic resonance ( ¹³ C-NMR) using isotope carbon. ¹³ C
-Tacticity measured by the NMR method can be represented by an existing ratio of a plurality of continuous structural units, for example, a dyad for two, a triad for three, a pentad for five, S in the present invention
PS is usually 75% or more, preferably 85% or more in racemic diad, or 30% in racemic pentad
Polystyrene, poly (alkylstyrene) having a syndiotacticity of 50% or more, preferably 50% or more,
Poly (halogenated styrene), poly (halogenated alkylstyrene), poly (alkoxystyrene), poly (vinyl benzoate), hydrogenated polymers thereof and mixtures thereof, or copolymers containing these as main components Is referred to. Here, poly (alkylstyrene) includes poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene), poly (tertiary butylstyrene), poly (phenylstyrene), poly (vinylnaphthalene), Examples include poly (vinyl styrene), and examples of poly (halogenated styrene) include poly (chlorostyrene), poly (bromostyrene), and poly (fluorostyrene). Examples of poly (halogenated alkylstyrene) include poly (chloromethylstyrene), and examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene).

[0007] Of these, particularly preferred styrene polymers include polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (ethylstyrene), poly (divinylbenzene) and poly (p-methylstyrene). -Tert-butylstyrene), poly (p-chlorostyrene), poly (m-chlorostyrene), poly (p-fluorostyrene), hydrogenated polystyrene and copolymers containing these structural units.

[0008] Such SPS can be prepared, for example, using a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst in an inert hydrocarbon solvent or in the absence of a solvent. (A monomer corresponding to the union) can be produced (JP-A-62-187708). For poly (halogenated alkylstyrene), see JP-A-1-46.
No. 912, these hydrogenated polymers are disclosed in
It can be obtained by the method described in JP-A-8505.

The comonomer in the styrenic copolymer includes, in addition to the above-mentioned styrenic polymer monomers, olefin monomers such as ethylene, propylene, butene, hexene and octene; diene monomers such as butadiene and isoprene; Examples include diene monomers and polar vinyl monomers such as methyl methacrylate, maleic anhydride, and acrylonitrile. In particular, a styrene-based polymer having 70 to 97 mol% of styrene repeating units and 3 to 30 mol% of alkylstyrene repeating units is preferably used.

In the present invention, the molecular weight of SPS is not particularly limited, but the melt flow index (MI) measured at 300 ° C. under a load of 1.2 kg is 1 to 60, preferably 3 to 60, more preferably 10 to 60. belongs to. Here, if the MI is less than 1, the dispersibility in preparing the composition may be insufficient. Furthermore, when MI exceeds 60, the mechanical properties may not be sufficient. Also, SP
The melting point (Tm) of S is preferably 255 ° C. or less, and 250 ° C.
The following are more preferred. When the melting point exceeds 255 ° C., the resin temperature during kneading and molding becomes high, and the styrene-diene-based or styrene-olefin-based block or graft copolymer suffers from thermal deterioration, causing problems such as bumps and discoloration in the molded product. There are cases. Further, the crystallization temperature (Tc) of the SPS is preferably 200 ° C. or lower, more preferably 195 ° C. or lower. If the crystallization temperature exceeds 200 ° C., the dispersion in the resin to be modified may be insufficient. The crystallization temperature was determined by a differential scanning calorimeter (DSC) to be 300.
It refers to the peak temperature of crystallization that appears when the temperature is lowered from 5 ° C. to 50 ° C. at a rate of 5 to 20 ° C./min.

[0011] In the composition of the present invention, SPS is 3-4.
0% by weight, preferably 3 to 30% by weight, more preferably 5 to 30% by weight. This content is 3
If the amount is less than 40% by weight, the effect of improving the secondary workability is insufficient, and if it exceeds 40% by weight, the toughness of the molded article may be insufficient.

Next, the styrene-diene-based or styrene-olefin-based block copolymer is, for example,
It is obtained by copolymerizing vinyl aromatic hydrocarbon and conjugated diene in an organic solvent using an organic lithium compound as an initiator. Here, as the vinyl aromatic hydrocarbon,
Styrene, o-methylstyrene, p-methylstyrene,
Examples thereof include p-tert-butylstyrene, 1,3-butylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, and 1,1-diphenylethylene, and styrene is particularly common. These may be used alone or in combination of two or more. The conjugated diene is not particularly limited as long as it is a diolefin having a pair of conjugated double bonds.
Examples thereof include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. Or two or more kinds can be used in combination. Examples of the styrene-olefin block copolymer include hydrogenated products of the styrene-diene block copolymer described above.

[0013] The block copolymer used in the present invention is small.
At least one vinyl aromatic hydrocarbon block
Both have one conjugated diene or its hydrogenated block,
For example, those represented by the following general formula can be mentioned. A
-B, A- (BA)_n, A- (BA)_n-B or B
-(AB)_{n + 1}A linear block copolymer represented by
[(AB)_k]_{m + 2}−X, [(AB)_k-A]_{m + 2}
−X, [(BA)_k] _{m + 2}-X or [(BA)_k−
B]_{m + 2}-X, a radial block copolymer represented by the formula
Wherein A represents a vinyl aromatic hydrocarbon polymer block,
B represents a conjugated diene polymer or a hydrogenated block thereof,
X is a residue of a coupling agent or a polyfunctional organic lithium compound.
And n, k and m are integers of 1 to 5
Is shown. ]

Among them, for example, styrene-butadiene block copolymer (SBR), hydrogenated styrene-
Butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene-butylene-styrene block copolymer (SBBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS) ), Styrene-isoprene block copolymer (SIR), hydrogenated styrene
Isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), hydrogenated styrene-butadiene-isoprene-styrene block copolymer (SEEPS) and the like are preferable.

In the styrene-diene-based or styrene-olefin-based graft copolymer, a styrene-based resin is included in a styrene-based resin continuous phase, and the styrene-based resin is grafted onto a rubber component such as polybutadiene. It is a polymer based on a structure in which particles made of a rubbery polymer are dispersed.

The content of the styrene structure in the styrene-diene-based or styrene-olefin-based block or graft copolymer used in the present invention is as follows.
There is no particular limitation, but it is preferably at least 25 mol%. Here, when the styrene structure is less than 25 mol%, S
In some cases, the dispersibility with PS deteriorates, and the desired effect of improving the secondary workability cannot be exhibited. The molecular weight of the styrene-diene-based or styrene-olefin-based block or graft copolymer is not particularly limited, but generally, the number average molecular weight is 50,000 to 500,000.
0, preferably 70,000 to 300,000.
Here, if the number average molecular weight is less than 50,000, the mechanical properties of the obtained molded product are not sufficient. The number average molecular weight is determined by gel permeation chromatography (G
PC).

The styrenic resin composition of the present invention may contain a styrene-based polymer (aPS) having an atactic structure as a component in an amount of up to 40% by weight, if necessary. Here, the compounding amount of aPS is 40% by weight.
If it exceeds 300, the toughness and the thermal processing characteristics will be reduced. The aPS used in the present invention is a styrene polymer industrially obtained by radical polymerization by a method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization. The polystyrene obtained by such radical polymerization usually has an atactic structure and does not have stereoregularity. In addition, polystyrene having an atactic structure referred to herein is a polymer composed of one or more aromatic vinyl compounds or a copolymer of one or more other vinyl monomers copolymerizable with one or more aromatic vinyl compounds. Polymers, hydrogenated polymers of these polymers and mixtures thereof may be used, such as aPS, HIPS, AS,
ABS and the like are included.

Here, the aromatic vinyl compound includes styrene, α-methylstyrene, methylstyrene, ethylstyrene, isopropylstyrene, tertiary butylstyrene, phenylstyrene, vinylstyrene, chlorostyrene, bromostyrene, fluorostyrene, chloromethyl. There are styrene, methoxystyrene, ethoxystyrene and the like, and these are used alone or in combination of two or more. Among them, preferred aromatic vinyl compounds include styrene, p-methylstyrene, m-methylstyrene, ethylstyrene and p-tert-butylstyrene.

Other copolymerizable vinyl monomers include:
Vinyl compounds such as ethylene, propylene, butadiene, isoprene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate,
Cyclohexyl acrylate, dodecyl acrylate,
Alkyl acrylates such as octadecyl acrylate, phenyl acrylate, and benzyl acrylate;
Methyl methacrylate, ethyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate,
Alkyl methacrylates such as dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate, maleimide, N-
Methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (p-
And maleimide compounds such as (bromophenyl) maleimide.

The styrenic resin composition of the present invention may contain other thermoplastic resins, thermoplastic elastomers and various additives in addition to the above-mentioned components (1) and (2), as long as the object of the present invention is not impaired. (1-1) Thermoplastic resin other than SPS Examples of the thermoplastic resin other than SPS that may be used in the present invention include linear high-density polyethylene, linear low-density polyethylene, high-pressure low-density polyethylene, and isotactic. Polyolefin resins represented by polypropylene, syndiotactic polypropylene, block polypropylene, random polypropylene, polybutene, 1,2-polybutadiene, poly4-methylpentene, cyclic polyolefins and copolymers thereof, isotactic polystyrene, polycarbonate, Polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins such as polyamide 6 and polyamide 6,6, polyphenylene ether,
Any known material such as PPS can be used. These thermoplastic resins can be used alone or in combination of two or more.

(1-2) Thermoplastic Elastomer Specific examples of the thermoplastic elastomer that may be used in the present invention include, for example, butadiene-acrylonitrile-styrene-core-shell rubber (ABS), methyl methacrylate-butadiene-styrene-core-shell rubber. (MB
S), methyl methacrylate-butyl acrylate-styrene-core-shell rubber (MAS), octyl acrylate-butadiene-styrene-core-shell rubber (MAB)
S), core-shell type elastomers such as alkyl acrylate-butadiene-acrylonitrile-styrene-core-shell rubber (ABS), butadiene-styrene-core-shell rubber (SBR), natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiocol rubber Olefin rubber such as acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM), linear low density polyethylene elastomer, and methyl methacrylate-butyl Core-shell type particle-like elastic bodies such as siloxane-containing core-shell rubbers such as acrylate-siloxane, or rubbers obtained by modifying these. These can be used alone or in combination of two or more.

(1-3) Various additives (a) Antioxidant The antioxidant can be arbitrarily selected from phosphorus, phenol, sulfur and other known ones.
In addition, these antioxidants can be used alone or in combination of two or more. Furthermore, 2
-[1-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] is also preferably used.

(B) Plasticizer The plasticizer may be selected from known materials such as polyethylene glycol, polyamide oligomer, ethylene bisstearamide, phthalic acid ester, polystyrene oligomer, polyethylene wax and silicone oil. it can. These plasticizers can be used alone or in combination of two or more.

(C) Ultraviolet absorber The ultraviolet absorber is not particularly limited, and a known one can be used. For example, 2,2-hydroxy-5
-Methylphenylbenzotriazole, 2,2-hydroxy-3-t-butyl-5-methylphenyl-5-chlorobenzotriazole, 2,2-hydroxy-3 ′,
Benzotriazole-based ultraviolet absorbers such as 5′-di-t-butylphenyl-5-chlorobenzotriazole;
Benzophenone UV absorbers such as hydroxy-4-methylbenzophenone, hydroxybenzoate UV absorbers such as 2,4-di-t-butylphenyl-3,5-dibutyl-4-hydroxybenzoate, and titanium oxide Inorganic fine particles. Of these, benzotriazole-based ultraviolet absorbers are preferred. These can be used alone or in combination of two or more. These ultraviolet absorbers are composed of the resin component 10
It can be added at a ratio of 0.05 to 2 parts by weight with respect to 0 parts by weight.

The styrenic resin composition of the present invention can be produced by melt-kneading the above components. The melting temperature at this time is 230 to 280 ° C, preferably 240 to 280 ° C. Here, when the temperature is lower than 230 ° C., the dispersion of SPS and aPS in the composition is reduced, and the effect of improving the secondary workability may not be sufficient. Also, 2
If the temperature exceeds 80 ° C., problems such as bumps and coloring may occur due to decomposition of the styrene-diene-based or styrene-olefin-based block or graft copolymer.

The molded article of the present invention comprises the styrene resin composition as described above, and has a total haze of 5% or less. Here, when the total haze exceeds 5%, the film or sheet cannot be used for applications requiring transparency. The molded article of the present invention can be produced by various methods. For example, (a) a method of dry-blending the components, melt-kneading to prepare a molding material, and then molding (b) S
After melt-kneading PS and other components to prepare a masterbatch material, dry blending with other components and molding.
(C) It can be manufactured by a method of dry-blending the materials of the constituent components and directly molding. The styrenic resin composition of the present invention can be molded by the same processing means as ordinary thermoplastic resins. For example, injection molding,
It can be formed by blow molding, extrusion casting, inflation molding, stretch molding, thermoforming, or the like. In the case of stretch molding, either uniaxial stretching or biaxial stretching may be used. According to the present invention, various molded articles can be produced by the above method. In particular, cast films, inflation films, stretched films, sheets, and molded articles thereof require secondary processing such as printing and bonding. Yes, the styrenic resin composition of the present invention is useful.

[0027]

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. In addition, the test method and raw material used in the following Examples and Comparative Examples are as follows. [Adhesive Resistance] Dick Dry AS-102A (polyether urethane type) manufactured by Dainippon Ink and Chemicals, Inc. as the main ingredient, and Dick Dry AS-102B (epoxy type)
Was applied at 5 g / m ² with an adhesive active ingredient, and dried at 50 ° C. The haze of the molded article before and after applying the adhesive and the shrinkage ratio (10 cm □) before and after applying the adhesive were measured. The haze was measured according to JIS K7105. [Print resistance] Apply ULTIMA 507 primary color indigo ink,
After printing, appearance and Nichiban cellophane tape (18mm width)
Was evaluated. ：: No wrinkles, shrinkage, uneven printing, etc., no peeling of ink on cellophane tape ×: Wrinkles, shrinkage, uneven printing

[Raw Materials] SPS1: Syndiotactic (styrene-p-methylstyrene) copolymer manufactured by Idemitsu Petrochemical Co., Ltd., 15 mol% of p-methylstyrene, Tm = 238 ° C., MI (300)
° C, 1.2 kgf) = 20, Tc = 190 ° C SPS2: Syndiotactic (styrene-p-methylstyrene) copolymer manufactured by Idemitsu Petrochemical Co., Ltd., 7 mol% of p-methylstyrene, Tm = 247 ° C MI (300 ° C,
1.2 kgf) = 4, Tc = 180 ° C. SPS3: Syndiotactic (styrene-p-methylstyrene) copolymer manufactured by Idemitsu Petrochemical Co., Ltd., 7 mol% of p-methylstyrene, Tm = 244 ° C. MI ( 300 ° C,
1.2 kgf) = 4, Tc = 198 ° C. SPS4: Syndiotactic styrene homopolymer manufactured by Idemitsu Petrochemical Co., Ltd., Tm = 271 ° C., MI (300)
° C, 1.2 kgf) = 4, Tc = 233 ° C ・ PS1: SEBS manufactured by Kuraray (Septon 810)
4. Styrene content 60%) ・ PS2: KURARAY SEPS (Septon 210, trade name)
4. PS3: Asahi Kasei SBS (trade name: Asaflex 83)
0) ・ PS4: Asahi Kasei SBS (trade name: Asaflex 81)
0) ・ PS5: Asahi Kasei SBS (trade name: Asaflex 81)
5) PS6: Atactic polystyrene (trade name: HH32) manufactured by Idemitsu Petrochemical Co., Ltd. Antioxidant: pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] (manufactured by Ciba Specialty Chemical, trade name: IRGANOX1010) UV absorber: 2,2-hydroxy-3-t-butyl-5-methylphenyl-5-chlorobenzotoazole

Example 1 SPS1 / PS1 / Antioxidant / UV absorber 20 /
After blending at a ratio (weight) of 80 / 0.1 / 0.3, 3
The mixture was melt-kneaded at 250 ° C. with a 0 mmφ twin-screw extruder to obtain pellets. Using the obtained pellets, a sheet forming machine with a coat hanger die attached to a 30 mmφ single screw extruder
The sheet was extruded at 50 ° C. and cooled with a roll at 25 ° C. to prepare an unstretched sheet. Subsequently, the film was stretched twice at 90 ° C. in the longitudinal direction and 4.5 times at 110 ° C. in the transverse direction to obtain a stretched film having a thickness of 50 μ. The adhesive resistance and print resistance of this film were evaluated, and the results are shown in Table 1.

Examples 2-6 and Comparative Examples 1-2 Except that the composition of the resin composition was changed as shown in Table 1,
A stretched film was prepared in the same manner as in Example 1, and its adhesive resistance and print resistance were evaluated. The results are shown in Table 1.

Example 7 PS6 / antioxidant / ultraviolet absorber 100 / 0.5 /
After blending at a ratio (weight) of 1.5, the mixture was melt-kneaded at 230 ° C. with a 30 mmφ twin screw extruder to obtain pellets. SPS
After blending 1 / PS4 / the pellets in a ratio (weight) of 20/60/20, a 50 mmφ single screw (Dalmage type screw) extruder was fitted with an annular die having a diameter of 50 mmφ and a gap of 1 mm, and an output of 20 kg / hr At 250 ° C. to adjust the blow ratio to 2.5 and the draw ratio to 13, thereby obtaining an inflation film having a thickness of 30 μm. At the time of inflation molding, an air ring was used, and a heat insulator was attached to the stabilizer to stabilize the bubbles. Table 1 shows the evaluation results of the obtained films.

Example 8 SPS1 / PS5 / Antioxidant / 50% UV absorber
After blending at a ratio (weight) of 50 / 0.2 / 0.5, 3
23mm with a 0mmφ twin screw extruder (LABOTEX manufactured by JSW)
The mixture was melt-kneaded at 0 ° C. to form pellets. The pellet / PS
5 in a ratio (weight) of 60/40, 50 mm
Attach a coat hanger die to a φ single-screw (Dalmage type screw) extruder.
It was melt-extruded at 0 ° C. and cooled at 25 ° C. to produce a 500 μ thick sheet. Table 1 shows the evaluation results of the obtained sheets.

Comparative Example 1 A stretched film was prepared in the same manner as in Example 1 except that SPS1 was not used, and the evaluation results of the adhesive resistance and print resistance are shown in Table 1. Example 9 Example 1 was repeated except that SPS4 was used instead of SPS1.
A stretched film was prepared in the same manner as described above, and the evaluation results of the adhesive resistance and print resistance are shown in Table 1. Separately, a stretched film was prepared using the material having this composition at an extrusion temperature of 290 ° C. In addition, gels and lumps were scattered on the film.

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

The styrenic resin composition of the present invention is effective for producing molded articles such as sheets and films having remarkably excellent printability and adhesiveness, and is particularly useful for cast films, inflation films, stretched films and sheets. Or, it is useful for manufacturing a molded article such as a molded article that requires secondary processing such as printing and bonding. Therefore, the present invention is particularly useful for OA equipment parts, miscellaneous goods, light electric parts, daily necessities, food packaging, laminating films, and heat shrink films.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 25:00) C08L 25:00) F-term (Reference) 4F071 AA12 AA12X AA22 AA22X AA75 AA77 AA84 AA88 AH04 BA01 BB05 BB06 BB07 BB08 BB09 BC01 4J002 BC032 BC033 BC042 BC043 BC082 BC083 BC092 BC093 BC112 BC113 BC122 BC123 BN141 BP011 FD020 FD050 FD070 GG02 4J026 AA68 BA05 HA06 HB15 HB16 HC06 HD02 HD06 HD15 HD16 HE01

Claims (7)

[Claims] 1. A styrene resin composition comprising 3 to 40% by weight of a styrene polymer having a syndiotactic structure and 97 to 60% by weight of a styrene-diene or styrene-olefin block or graft copolymer. 2 to 40% by weight of a styrene polymer having a syndiotactic structure, 87 to 20% by weight of a block or graft copolymer of a styrene-diene system or a styrene-olefin system, and 10 to a styrene polymer having an atactic structure. A styrenic resin composition consisting of about 40% by weight. 3. The styrene polymer having a syndiotactic structure has a melting point (Tm) of 255 ° C. or less and a crystallization temperature (Tm).
3. The styrenic resin composition according to claim 1, wherein c) is 200 ° C. or less and the melt index is 1 to 60. 4. Styrene-diene or styrene-
The olefin block copolymer is represented by the formula AB, A- (B
-A) _n , A- (BA) _n -B or B- (AB)
linear block copolymer represented by _{n + 1} , [(A-
B) _k ] _{m + 2} −X, [(AB) _k −A] _{m + 2} −X,
[(BA) _k ] _{m + 2} -X or [(BA) _k -B]
The styrene resin composition according to any one of claims 1 to 3, which is a radial block copolymer represented by _{m + 2-} X. Wherein A represents a vinyl aromatic hydrocarbon polymer block, B represents a conjugated diene polymer or a hydrogenated block thereof, and X represents a residue of a coupling agent or an initiator such as a polyfunctional organic lithium compound. Represents a residue, and n, k and m are 1 to
Indicates an integer of 5. ] 5. Styrene-diene or styrene-
The olefin block copolymer is SBR, SBS, S
The styrenic resin composition according to any one of claims 1 to 4, which is at least one of BBS, SI, SIS, SEBS, and SEPS. 6. A molded article comprising the styrenic resin composition according to any one of claims 1 to 5, wherein the total haze is 5% or less. 7. A cast film, an inflation film,
7. A stretched film, sheet or thermoformed product thereof.
The molded article according to the above.