WO2008032556A1 - Article en résine thermoplastique moulé par extrusion-soufflage - Google Patents

Article en résine thermoplastique moulé par extrusion-soufflage Download PDF

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Publication number
WO2008032556A1
WO2008032556A1 PCT/JP2007/066610 JP2007066610W WO2008032556A1 WO 2008032556 A1 WO2008032556 A1 WO 2008032556A1 JP 2007066610 W JP2007066610 W JP 2007066610W WO 2008032556 A1 WO2008032556 A1 WO 2008032556A1
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WO
WIPO (PCT)
Prior art keywords
weight
thermoplastic resin
parts
hollow molded
polystyrene
Prior art date
Application number
PCT/JP2007/066610
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English (en)
Japanese (ja)
Inventor
Sachiko Kondo
Junichi Nishino
Akio Nakajima
Original Assignee
Konami Digital Entertainment Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konami Digital Entertainment Co., Ltd. filed Critical Konami Digital Entertainment Co., Ltd.
Publication of WO2008032556A1 publication Critical patent/WO2008032556A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00—Indexing scheme relating to blow-moulding
    • B29C2949/07—Preforms or parisons characterised by their configuration
    • B29C2949/0715—Preforms or parisons characterised by their configuration the preform having one end closed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/06—Injection blow-moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2009/00—Use of rubber derived from conjugated dienes, as moulding material
    • B29K2009/06—SB polymers, i.e. butadiene-styrene polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2025/00—Use of polymers of vinyl-aromatic compounds or derivatives thereof as moulding material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene

Definitions

  • the present invention relates to a thermoplastic resin hollow molded article formed by blow molding using a thermoplastic resin composition as a raw material.
  • Patent Document 1 discloses a hollow molded article molded using polychlorinated butyl (PVC) as a raw material.
  • PVC polychlorinated butyl
  • Patent Document 1 Japanese Patent Laid-Open No. 2003-251747
  • An object of the present invention is to provide a thermoplastic resin hollow molded article excellent in resilience, flexibility and impact resistance without using a chlorine-based material.
  • Still another object of the present invention is to provide a thermoplastic resin hollow molded article excellent in printability.
  • the thermoplastic resin hollow molded article to be improved by the present invention is a thermoplastic resin hollow molded article formed by blow molding (hollow molding) using a thermoplastic resin composition as a raw material.
  • Blow molding is a general method for forming a hollow molded product by expanding a tubular thermoplastic resin material (parison) toward the inner surface of a mold by fluid pressure.
  • the thermoplastic resin hollow molded article of the present invention includes 60 to 80 parts by weight of styrene butadiene elastomer (SB elastomer) and 40 to 20 parts by weight of polystyrene, and the total of styrene butadiene elastomer and polystyrene is 100 parts by weight.
  • SB elastomer styrene butadiene elastomer
  • thermoplastic resin composition is used.
  • the molded thermoplastic resin hollow molded product has a density of 985 to 1023 kg / m 3 . Under these conditions, when a thermoplastic hollow resin molded article is molded, a thermoplastic hollow resin molded article having good resilience, flexibility and impact resistance without using a chlorine-based material such as PVC can be obtained. .
  • the weight part of the styrene butadiene elastomer is less than 60 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition, the flexibility and reducibility of the thermoplastic resin hollow molded article deteriorates, and styrene
  • the part by weight of the butadiene elastomer exceeds 80 parts by weight, the moldability and impact resistance of the hollow molded product are lowered.
  • the polystyrene part exceeds 40 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition, the flexibility and restorability of the hollow molded article decreases, and the polystyrene part becomes less than 20 parts by weight.
  • the moldability and impact resistance of the hollow molded product are lowered. Also, if the density of the thermoplastic resin hollow molded product is lower than 983 kg / m 3 , the impact resistance of the hollow molded product will be reduced, and if the density is higher than 1005 kg / m 3 , the flexibility and resilience of the hollow molded product will be reduced. And molding processability decreases
  • HIPS high-impact polystyrene
  • GP general-purpose polyethylene
  • the thermoplastic resin hollow molded article is preferably molded so that the polydispersity of the thermoplastic resin hollow molded article is 1.5 to 2.0.
  • the polydispersity is a value obtained by dividing the weight average molecular weight Mw by the number average molecular weight Mn, and can be represented by Mw / Mn.
  • molded products with a relatively high polydispersity Mw / Mn tend to have a relatively low impact resistance, and molded products with a relatively low polydispersity Mw / Mn have a relatively low impact resistance. Tend to be higher.
  • Polydispersity of hollow molded product Mw / Mn is 1.5 to 2.0 When out of the range, that is, when the polydispersity Mw / Mn of the hollow molded product is smaller than 1.5, the flexibility and the restorability of the hollow molded product are reduced, and the polydispersity Mw / Mn of the hollow molded product is reduced. When the value is larger than 2.0, the impact resistance of the hollow molded article is lowered. On the other hand, when the thermoplastic resin hollow molded product is molded so that the polydispersity Mw / Mn is in the range of 1.5 to 2.0 as in the present invention, the restorability and flexibility are reduced. A hollow molded product with good impact resistance can be obtained.
  • thermoplastic resin hollow molded article excellent in flexibility, resilience and impact resistance can be obtained even using a thermoplastic resin for blow molding generally used in blow molding.
  • a resin coating is applied to the surface of a molded thermoplastic resin hollow molded product and printing is performed on the hollow molded product, if the thermoplastic resin for blow molding is used as it is, the thermoplastic hollow molded product can be used.
  • the coating property of the resin coating is weak. Therefore, in the present invention, it is preferable to use a thermoplastic resin for injection molding (injection molding) instead of the thermoplastic resin for professional molding as the thermoplastic resin!
  • injection molding injection molding
  • thermoplastic resin which is a molding material
  • the thermoplastic resin is a mixed material of styrene butadiene elastomer (SB elastomer), impact-resistant polystyrene (no-impact polystyrene) (HIPS), and a stabilizer (manufactured by Polych ems, Taiwan). Model No. PSR. H8530) was used.
  • this mixed material has 60 to 80 parts by weight of styrene butadiene elastomer, 40 to 20 parts by weight of polystyrene, and a total of styrene butadiene elastomer and polystyrene. It mix
  • blends suitably so that it may become 100 weight part.
  • a thermoplastic resin material for injection is used in consideration of printability after molding.
  • the stabilizer contained in the thermoplastic resin is a general stabilizer used for imparting the moldability of the hollow molded product.
  • the stabilizer contained in the thermoplastic resin is Regardless of the examples and comparative examples, the amount is uniformly 2 parts by weight.
  • a generally used blow molding machine is used as the molding apparatus. Using this molding machine, the above mixed material is softened at a molding temperature of 150 to 180 ° C. and poured into a mold, which is cooled and dried to produce a hollow molded product.
  • These hollow molded products are Examples 1 to 3 described later. Change the weight part of styrene butadiene elastomer and silicone or i-patate polystyrene, or use other materials instead of styrene butadiene elastomer and silicone or impact polystyrene. ) Etc.] can be used to create the following comparative example
  • the dimensions of the molded hollow molded article can be appropriately changed according to the shape and dimensions of the mold.
  • the performance evaluation described later especially flexibility, resilience, impact resistance
  • a hollow molded product having a substantially oval shape is formed so that performance evaluation such as flexibility evaluation described later can be performed.
  • the thickness of the molded hollow molded product is about 2 mm.
  • coloring a hollow molded article it may be molded using a thermoplastic resin material mixed with a pigment in advance.
  • a pigment for general styrene butadiene elastomer.
  • thermoplastic resin paint an inexpensive and general polypropylene resin paint can be used.
  • a blow molding material is used as the thermoplastic resin paint
  • a hollow molded article with good printability and poor coating adhesion of the resin paint cannot be obtained. It was. Therefore, in the present embodiment, the above-described thermoplastic resin for injection is used in place of the thermoplastic resin material for blow molding.
  • the resin coating was applied using a commonly used tambo printer (a type of intaglio offset printing).
  • the hollow molded product can be crushed and the hollow molded product can be restored to its original size after being crushed, that is, air can be taken in and out of the hollow molded product.
  • a through-hole with a diameter of about 4 mm is provided to communicate the inside and outside of the hollow molded product.
  • the hollow molded product of this embodiment having such a through hole can be used as a water gun for a toy by handling it in water (for example, by squeezing it in water and returning it to its original state). Monkey.
  • Comparative Example 1 is a conventional technique of the present invention, which is a blend of a thermoplastic resin hollow molded product using a chlorine-based material.
  • EVA ethylene acetate butyl resin
  • Comparative Example 2 ethylene vinyl acetate resin was used as an alternative material for polychlorinated bule compared to Comparative Example 1.
  • Comparative Example 3 As compared with Comparative Example 1, ethylene butane elastomer was used as an alternative material for polychlorinated bur.
  • Comparative Example 4 30 parts by weight of ethylene butadiene elastomer was reduced compared to Comparative Example 3, and 30 parts by weight of ethylene acetate butyl resin was newly added.
  • Comparative Example 5 10 parts by weight of ethylene butadiene elastomer was reduced compared to Comparative Example 3, and 10 parts by weight of high impact polystyrene was newly added.
  • Comparative Example 6 50 parts by weight of ethylene butadiene elastomer was reduced with respect to Comparative Example 3, and 50 parts by weight of high impact polystyrene was newly added.
  • Comparative Example 7 is used only as a comparison target of Example 4 described later for printability evaluation.
  • Example 1 compared to Comparative Example 1, ethylene butadiene elastomer was used as an alternative material for PVC. Ma, No, and high impact polystyrene compounded materials were used. In Example 1, 20 parts by weight of high-impact polystyrene is added to the total amount of styrene butadiene elastomer and no-impact polystyrene!
  • Example 2 10 parts by weight of ethylene butadiene elastomer was reduced compared to Example 1, and 10 parts by weight of high impact polystyrene was increased. In other words, in Example 2, 30 parts by weight of high-inert polystyrene is blended with respect to the total of styrene butadiene elastomer and no-impact polystyrene.
  • This Example 2 can also be used for a printability evaluation performed as a secondary effect, and is also used as Example 4 described later using a thermoplastic resin for injection.
  • Example 3 the amount of ethylenebutadiene elastomer was reduced by 20 parts by weight and that of high impact polystyrene was increased by 20 parts by weight. In other words, in Example 3, 40 parts by weight of high impact polystyrene is blended with respect to the total of styrene butadiene elastomer and no-impact polystyrene!
  • Table 1 shows a summary of the blending ratios (parts by weight) of the above-described Examples and Comparative Examples.
  • the overall evaluation is ⁇ If all evaluation items except for are ⁇ , the overall evaluation is ⁇ ). If there is no X but there is at least one ⁇ , the overall evaluation is ⁇ . If there was any X, the overall evaluation was X regardless of the presence or absence of ⁇ , ⁇ , ⁇ .
  • Table 2 shows the results of each performance evaluation (excluding printability evaluation).
  • Comparative Example 1 is a conventional thermoplastic resin hollow molded product, and the molding processability, flexibility, resilience, and impact resistance are all ⁇ . However, since the non-chlorinated type is X, the overall evaluation of Comparative Example 1 was X. [0039] Comparative Example 2 was non-chlorinated, molding processability, and flexibility. However, since the resilience was X, the overall evaluation of Comparative Example 2 was X. In Comparative Example 2, the resilience was X, so the impact resistance was confirmed! /, Not (one).
  • Comparative Example 3 was non-chlorinated and reversible, and the flexibility was A. However, since the moldability was X, the overall evaluation of Comparative Example 3 was X. In Comparative Example 3, since the moldability was X, impact resistance was confirmed! /, Not (1).
  • Comparative Example 4 was non-chlorinated, had good processability and flexibility, and had a resilience of ⁇ and an impact resistance of X. Therefore, the overall evaluation of Comparative Example 4 was X.
  • Comparative Example 5 was non-chlorinated and flexible. However, since the molding processability, resilience and impact resistance were ⁇ , the overall evaluation of Comparative Example 5 was ⁇ .
  • Comparative Example 6 dechlorination and molding processability were ⁇ , and impact resistance was ⁇ . However, since the flexibility and resilience were X, the overall evaluation of Comparative Example 6 was X.
  • Example 1 non-chlorinated and molding processability was ⁇ , and flexibility, restorability and impact resistance were ⁇ .
  • the overall evaluation of Example 1 was ⁇ .
  • Example 2 the non-chlorinated type was ⁇ , and the molding processability, flexibility, resilience and impact resistance were ⁇ .
  • the overall evaluation of Example 2 was “ ⁇ ”.
  • Example 3 the chlorine-free, flexibility, resilience and impact resistance were ⁇ , and the molding processability was ⁇ . The overall evaluation of Example 3 was ⁇ .
  • Comparative Example 7 is a hollow molded article using the same blow molding thermoplastic resin as in Example 2 at the same blending ratio as in Example 2 (see Table 1).
  • Example 4 is the same as Example 2, but differs from Example 2 in that it is a hollow molded body using a thermoplastic resin for injection molding (see Table 1).
  • the printability evaluation of Comparative Example 7 was X
  • the printability evaluation of Example 4 was ⁇ . This result shows that, despite being molded by blow molding, printability is better when the thermoplastic resin material for injection molding is used as the molding material than the thermoplastic resin material for blow molding. Show.
  • the density of the hollow molded article was measured for some comparative examples and examples (only styrene butadiene elastomer and no-impact polystyrene blends) for which the above performance evaluation was completed. Specifically, samples obtained by cutting out a portion of the hollow molded products of Comparative Examples 3, 5, 6 and Examples;! ⁇ 3 with a razor were used as density measurement samples, and these samples were used as density gradient tubes (constant temperature). (With water tank) (RMB-6 by Ikeda Rika Co., Ltd.), and the density of each sample was measured from the position after 15 minutes. The density measurement results are shown in Table 4.
  • the polydispersity M w / Mn of the hollow molded product was measured for some of the comparative examples and examples for which the above performance evaluation was completed (only blending of styrene butadiene elastomer and no-impact polystyrene). Specifically, first, as in the measurement of density, a part of the hollow molded product of Comparative Examples 3, 5, 6 and Examples;! 30 mg was weighed. The weighed presample was dissolved in 20 ml of o-dichlorobenzene at 145 ° C. to prepare a presample solution. This pre-sample solution became slightly cloudy.
  • this pre-sample solution was filtered through a sintered filter having a pore size of 0.45 m, and the filtrate was used as a sample for measuring the polydispersity Mw / Mn. At this time, the filtrate was transparent.
  • chromatography using a cross-fractionation chromatography (CFC) apparatus (Mitsubishi Yuka T-150A type) was performed, the average molecular weight was measured, and a molecular weight curve was prepared. The molecular weight was calibrated in terms of polystyrene.
  • This chromatography was performed in a GPC mode (GPC-IR mode) using a GPC column (3 Shodex AT-806MS X manufactured by Showa Denko KK).
  • the column temperature was 140 ° C.
  • monodisperse polystyrene manufactured by Tosoh Corporation
  • ODCB o-dichlorobenzene
  • the flow rate is 1 ⁇ Oml / min
  • the sample concentration is 30 mg / 20 ml
  • the injection volume is 500 ⁇ 1
  • the sampling interval is 0.5 s. did.
  • a 0.05% dibutylhydroxytoluene (BHT) solution was used as an external standard substance for flow rate calibration.
  • BHT dibutylhydroxytoluene
  • the polarities of the styrene component and the butadiene component are opposite.
  • detection was performed with an infrared spectrophotometer (IR) (1ACVF type, manufactured by Miran) with a small change in detection response depending on the composition.
  • IR infrared spectrophotometer
  • Table 5 shows the measurement results of the calculated weight average molecular weight, number average molecular weight, and polydispersity Mw / Mn.
  • a hollow molded article using a conventional PVC material that does not use a chlorine-based material such as polychlorinated bur and does not reduce molding processability can be obtained.
  • the ability to obtain a hollow thermoplastic resin molded product having the same flexibility, resilience and impact resistance is obtained with S.
  • thermoplastic resin containing 60 to 80 parts by weight of styrene butadiene elastomer and 40 to 20 parts by weight of polystyrene, and a total of 100 parts by weight of the styrene butadiene elastomer and polystyrene, There 983 ⁇ ; If 1005kg / m 3 and so as to molding the thermoplastic resin hollow molded article, Nag resilient using a chlorine-based material such as PVC, excellent flexibility and impact resistance thermoplastic resin hollow molded Goods can be obtained.
  • thermoplastic resin for injection molding
  • the adhesion of the coating film of the resin coating to the hollow molded article is improved, and the thermoplastic resin hollow having excellent printability is obtained.
  • a molded product is obtained.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un article en résine thermoplastique moulé par extrusion-soufflage lequel présente d'excellentes capacité de recouvrance élastique, flexibilité et résistance aux chocs sans utiliser de matière contenant du chlore. L'invention concerne précisément un article en résine thermoplastique moulé par extrusion-soufflage ayant une densité de 983-1005 kg/m3, lequel est produit par moulage par extrusion-soufflage en utilisant, en tant que matière première, une composition de résine thermoplastique contenant 60-80 parties en poids d'un élastomère de styrène-butadiène et 40-20 parties en poids d'un polystyrène, le total de l'élastomère de styrène-butadiène et du polystyrène étant de 100 parties en poids.
PCT/JP2007/066610 2006-09-12 2007-08-28 Article en résine thermoplastique moulé par extrusion-soufflage WO2008032556A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006246351A JP2008069189A (ja) 2006-09-12 2006-09-12 熱可塑性樹脂中空成形品
JP2006-246351 2006-09-12

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WO2008032556A1 true WO2008032556A1 (fr) 2008-03-20

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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50121351A (fr) * 1974-03-09 1975-09-23
JPH0525360A (ja) * 1991-10-17 1993-02-02 Asahi Chem Ind Co Ltd ブロツク共重合体樹脂組成物
JPH0673252A (ja) * 1992-08-27 1994-03-15 Showa Denko Kk 積層体用樹脂組成物
JPH07216186A (ja) * 1994-01-31 1995-08-15 Denki Kagaku Kogyo Kk ブロック共重合体組成物及び熱収縮性フィルム
JPH07216187A (ja) * 1994-01-31 1995-08-15 Denki Kagaku Kogyo Kk 透明高強度樹脂組成物
JPH0967486A (ja) * 1995-08-31 1997-03-11 Daicel Chem Ind Ltd 耐衝撃性スチレン系樹脂組成物
JPH09324084A (ja) * 1996-06-05 1997-12-16 Denki Kagaku Kogyo Kk ブロック共重合体樹脂組成物、成形体及びその製造方法
JPH10130443A (ja) * 1996-10-31 1998-05-19 Sumitomo Chem Co Ltd ブロー成形品
JPH11255851A (ja) * 1998-03-09 1999-09-21 Asahi Chem Ind Co Ltd 線状ブロック共重合体及び樹脂組成物
JP2001220489A (ja) * 2000-02-08 2001-08-14 Jsr Corp 射出成型用組成物及び玩具
JP2001224868A (ja) * 2000-02-17 2001-08-21 Toytec:Kk 玩具用樹脂素材
JP2003113285A (ja) * 2001-10-04 2003-04-18 Asahi Kasei Corp 射出成形組成物

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50121351A (fr) * 1974-03-09 1975-09-23
JPH0525360A (ja) * 1991-10-17 1993-02-02 Asahi Chem Ind Co Ltd ブロツク共重合体樹脂組成物
JPH0673252A (ja) * 1992-08-27 1994-03-15 Showa Denko Kk 積層体用樹脂組成物
JPH07216186A (ja) * 1994-01-31 1995-08-15 Denki Kagaku Kogyo Kk ブロック共重合体組成物及び熱収縮性フィルム
JPH07216187A (ja) * 1994-01-31 1995-08-15 Denki Kagaku Kogyo Kk 透明高強度樹脂組成物
JPH0967486A (ja) * 1995-08-31 1997-03-11 Daicel Chem Ind Ltd 耐衝撃性スチレン系樹脂組成物
JPH09324084A (ja) * 1996-06-05 1997-12-16 Denki Kagaku Kogyo Kk ブロック共重合体樹脂組成物、成形体及びその製造方法
JPH10130443A (ja) * 1996-10-31 1998-05-19 Sumitomo Chem Co Ltd ブロー成形品
JPH11255851A (ja) * 1998-03-09 1999-09-21 Asahi Chem Ind Co Ltd 線状ブロック共重合体及び樹脂組成物
JP2001220489A (ja) * 2000-02-08 2001-08-14 Jsr Corp 射出成型用組成物及び玩具
JP2001224868A (ja) * 2000-02-17 2001-08-21 Toytec:Kk 玩具用樹脂素材
JP2003113285A (ja) * 2001-10-04 2003-04-18 Asahi Kasei Corp 射出成形組成物

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