WO2015130240A1 - Polymer composition for rotomolding - Google Patents

Polymer composition for rotomolding Download PDF

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Publication number
WO2015130240A1
WO2015130240A1 PCT/TH2015/000013 TH2015000013W WO2015130240A1 WO 2015130240 A1 WO2015130240 A1 WO 2015130240A1 TH 2015000013 W TH2015000013 W TH 2015000013W WO 2015130240 A1 WO2015130240 A1 WO 2015130240A1
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Prior art keywords
polymer
polymer composition
particle size
mixtures
composition
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Application number
PCT/TH2015/000013
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French (fr)
Inventor
Pornthip TANGCHAREETSAKUL
Alongkorn KANOKBORIBOON
Chumphol CHIENGSIRISUPAWONG
Original Assignee
Scg Chemicals Co., Ltd
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Priority claimed from TH1401001061A external-priority patent/TH153601A/en
Application filed by Scg Chemicals Co., Ltd filed Critical Scg Chemicals Co., Ltd
Publication of WO2015130240A1 publication Critical patent/WO2015130240A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013Fillers, pigments or reinforcing additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/346Clay

Definitions

  • This invention relates to a polymer composition for rotomolding.
  • plastic process technologies can be employed conditional on application's purpose and shape of articles. Hence, a proper process should be selected.
  • the plastic processing techniques can be divided into six categories, which are
  • Thermoforming - thermoforming is a process of heating plastic sheet to its softening point, stretching it over the mold using vacuum pressure, air pressure or mechanical force, and holding it in place until it cools and solidifies into the desired shape.
  • Thermoplastic plastic sheets or films are typically used for this technique.
  • Extrusion - this technique is a continuous process, which is applied a principle of melting the plastic in the barrel, forcing a .molten plastic through a die that shapes it into a specified cross-section.
  • plasties transform from solid to liquid and back to a desired solid shape in accordance with the die shape.
  • Injection Molding it is one of principal plastic processing, simply by injecting molten plastic into a mold.
  • Various materials can be applied such as thermoplastic polymers, thermosetting polymers, and elastomers.
  • a simple procedure comprises feeding .materials into the heated barrel, mixing, and forcing the molten material, into a mold cavity. Generally, this technique is employed for manufacturing the articles having 5 to 90 kg weight.
  • molding materials Prior to molding materials, a mixing/compounding step is required to enhance a good mixing of all components.
  • molding materials generally preheated
  • the preheated process can be conducted with numerous approaches, for example, using a hoi metallic plate, using an infrared radiation, using a microwave oven, using a high frequency oven, and using a hot mold.
  • Blow maiding ⁇ blow molding is a continuous manufacturing process, usually employed to produce .narrow and hollow containers, e.g. bottles, etc.
  • Four types of blow molding are commonly used in the industry - extrusion blow trio I ding, injection blow molding, stretch injection blow molding and indirect blow molding.
  • Roto oidmg ⁇ it is predominantly used to manufacture large hollow articles, such as water tanks with a capacity ranging from 10 liters up to 1.0 cubic meters comprising four main steps - filling plastic powder into the desire mold; heating the plastic powder and rotating the mold into two dimensions simultaneously to coat the molten plastic on the moid; then cooling and rotating simultaneously; and finally removing the articles off the moid.
  • U.S. Pat No 5,530,055 discloses a polymer composition for rotational molding comprising 5-25 percent by weight, of a linear low density polyethylene having a density of 0,915-0.925 g/cm*, a melt index of at most. 12 g/10 min,; at least 75 percent by weight of a polyethylene having a density of 0.93-0.945 g/cm ' ⁇ a melt index of at. most 3-8 g/10 min.; 5-25 percent by weight of a relatively high density polyethylene having a density of 0.95-0.965 g/cm ' , a melt index of at. least 1 g/ 10 min,; and sufficient amount of crystallizing agents to enhance greater impact strength.
  • U.S. Pat No 5,532,282 discloses a rotomoiding composition
  • a rotomoiding composition comprising a first thermoplastic polymer of ethylene, a foaming agent, which comprises a carbon dioxide-releasing inorganic salt, and a nucleating agent/foaming coagent selected from a mixture of stearic acid and zinc stearate, and a mixture of calcium stearate and stearamide; and a second thermoplastic polymer of ethylene as particulate matter of a sixe significantly smaller than said first size; wherein said first thermoplastic polymer and said second thermoplastic polymer may he the same or different.
  • the first and second thermoplastic polymer has melt index about. 30g /i0 min.
  • US 2002/0120051 A discloses a plastic part molded by injection molding comprising (a) lustrous pigments comprising metallic pigment particles or platelets which have a predominantly two-dimensional shape, and (b) hollow or solid filler particles which have a substantially isometric body shape and have a diameter of 10 to 200
  • the lustrous pigments are pearfescent pigments based on mica or metal pigments coated with metal oxides.
  • the particle of the lustrous pigments has a diameter of 2 to 80 pra.
  • PCT Patent Publication WO 2013/096696 A I discloses a rotomolding composition comprising ai least 95 percent by weight of a thermoplastic polymer; and from O. ' l to 3 percent by weight of metal oxide lamellae; wherein the rotomolding composition is characterized by at least one of the following properties: (a) having a retention ai elongation at. break of at least 85 percent after 4000 hours of accelerated aging; or (b) having a ductility improvement of at least 50 percent relative to a similar composition free of said metal oxide lamellae.
  • Said thermoplastic polymer is an ethylene based polymer or a propylene based polymer.
  • this invention attempts to address the above mentioned problem, i.e. a metal powder rotomolding composition providing glittering surface articles. This is performed by improving said composition using an appropriate amount and size of lustrous materials: and an appropriate amount and size of polymer powders.
  • This invention relates to a polymer composition for rotomolding comprising polymer; lustrous material with particle size of 1 urn to 2 mm not more than 1 5 percent by weight of polymer; and optionally, an effective amount of additives for rotational molding technique, not more than 5 percent by wei ght of polymer.
  • the purpose of this invention is to provide a rotomolding plastic composition for manufacturing plastic articles with pronounced surface effect, particularly providing articles with glittering or sparkling surface.
  • Figure i shows an article produced by rotomolding composition according to example i
  • Figure 2 shows an article produced by inventive rotomolding composition according to example 2
  • a polymer composition for rotomolding according to this in ention comprising
  • an effective amount of additives for rotational molding technique not more than 5 percent by weight of polymer.
  • said polymer has a particle size of 300 - 1.500 urn, preferably 300 - 1200 ⁇ . ⁇ , and more preferably 500-1000 ⁇ .
  • said polymer is selected from polyethylene, polypropylene, polyvinyl chloride, or mixtures of thereof.
  • said polyethylene is selected from linear low density polyethylene, low density polyethylene, .medium density polyethylene, high density polyethylene or mixtures of thereof, which has melt index of 2- 15 g/IO min.
  • said lustrous material has particle size of 5 urn to 1.6 mm, more preferably 5 to 1000 ⁇ , and most preferably 100 to 600 am.
  • said lustrous material is selected from metallic particles, metallic pigment platelets, high retractive pigment, or mixtures of thereof.
  • said high refractive pigment is mica-based pearlescem pigment, metal pigment coated with metal oxide, or mixtures of thereof.
  • said additive is selected from antioxidants, UV stabilizer, light stabilizer, antimicrobial agent, flame retardant, or mixtures of thereof
  • said polypropylene is selected from homopoiymer or copolymer polypropylene with melt index of 2- 1 5 g/ 10 min.
  • Molded plastic centrifuge processes produce large and hollow inside, such as water tanks with a capacity ranging from 10 liters up to 10 cubic meters of four main steps.
  • the rotomolding is applied to manufacture large hollow articles, such as water tanks with a capacity ranging from 10 liters up to 10 cubic meters comprising tour main steps as follows:
  • a composition was prepared by mixing polyethylene having a melt index of 3-10 g/10 min and particle size of 200-300 pm, lustrous material (i.e, metallic particles) having particle size not over 200 pm in the amount of 1-3 percent by weight of polyethylene, and an additive in an amount of not over 5 percent by weight of polyethylene at an elevated temperature. Then reduce the average particle size of the mixture to 400 ⁇ , and finaiiy .fabricate the final sample product by rotomolding technique.
  • the prepared sample does not show glittering surface (i.e. matte surface) as shown in Figure I ,
  • a composition was prepared by mixing polyethylene having a melt index of 3-10 g/10 mtn and particle size of 500- 1000 ⁇ , lustrous material (i.e. pearleseent pigment) having particle size not over 200 un in the amount of 1 -3 percent, by weight of polyethylene, and an additive in an amount of not over 5 percent by weight of polyethylene at an elevated temperature. Then reduce the average particle size of the mixture to 400 ⁇ and finally fabricate the final sample, product by rotomolding technique.
  • the prepared sample does not show glittering surface (i.e. matte surface) as shown in Figure 2.

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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)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

This invention relates to a polymer composition for rotomolding comprising polymer; lustrous material with particle size of 1 μm to 2 mm not more than 15 percent by weight of polymer; and optionally, an effective amount of additives for rotational molding technique, not more than 5 percent by weight of polymer. This composition is used to manufacture plastic articles with pronounced surface effect, particularly providing articles with glittering or sparkling surface.

Description

POLYMER COMPOSITION FOR ROTOMOIJMNG
FIELD OF THE INVENTION
This invention relates to a polymer composition for rotomolding. BACKGROUND OF THE INVENTION
in the present, most of daily life's devices are made from polymer, for example, household goods, office appliances, auto parts, medical devices, etc. This is because polymers are widely available, inexpensive, and easy to process or moid.
A variety of plastic process technologies can be employed conditional on application's purpose and shape of articles. Hence, a proper process should be selected. The plastic processing techniques can be divided into six categories, which are
1. Thermoforming - thermoforming is a process of heating plastic sheet to its softening point, stretching it over the mold using vacuum pressure, air pressure or mechanical force, and holding it in place until it cools and solidifies into the desired shape. Thermoplastic plastic sheets or films are typically used for this technique.
2. Extrusion - this technique is a continuous process, which is applied a principle of melting the plastic in the barrel, forcing a .molten plastic through a die that shapes it into a specified cross-section. During extrusion, plasties transform from solid to liquid and back to a desired solid shape in accordance with the die shape.
3. Injection Molding■■■■ it is one of principal plastic processing, simply by injecting molten plastic into a mold. Various materials can be applied such as thermoplastic polymers, thermosetting polymers, and elastomers. A simple procedure comprises feeding .materials into the heated barrel, mixing, and forcing the molten material, into a mold cavity. Generally, this technique is employed for manufacturing the articles having 5 to 90 kg weight.
4. Compression molding■■■■ this technique has been applied for a long time, however; it is still widely used, especially for rubber and thermosetting polymers. Prior to molding materials, a mixing/compounding step is required to enhance a good mixing of all components. Typically, molding materials (generally preheated) are placed in a mold cavity, then applied a pressure for a certain period of time, and finally cooled. The preheated process can be conducted with numerous approaches, for example, using a hoi metallic plate, using an infrared radiation, using a microwave oven, using a high frequency oven, and using a hot mold.
5, Blow maiding ~ blow molding is a continuous manufacturing process, usually employed to produce .narrow and hollow containers, e.g. bottles, etc. Four types of blow molding are commonly used in the industry - extrusion blow trio I ding, injection blow molding, stretch injection blow molding and indirect blow molding.
6. Roto oidmg■■■■ it is predominantly used to manufacture large hollow articles, such as water tanks with a capacity ranging from 10 liters up to 1.0 cubic meters comprising four main steps - filling plastic powder into the desire mold; heating the plastic powder and rotating the mold into two dimensions simultaneously to coat the molten plastic on the moid; then cooling and rotating simultaneously; and finally removing the articles off the moid.
Several prior art documents disclosed a polymer composition for rotational molding with numerous compositions and quantities are shown as follows.
U.S. Pat No 5,530,055 discloses a polymer composition for rotational molding comprising 5-25 percent by weight, of a linear low density polyethylene having a density of 0,915-0.925 g/cm*, a melt index of at most. 12 g/10 min,; at least 75 percent by weight of a polyethylene having a density of 0.93-0.945 g/cm'\ a melt index of at. most 3-8 g/10 min.; 5-25 percent by weight of a relatively high density polyethylene having a density of 0.95-0.965 g/cm ', a melt index of at. least 1 g/ 10 min,; and sufficient amount of crystallizing agents to enhance greater impact strength.
U.S. Pat No 5,532,282 discloses a rotomoiding composition comprising a first thermoplastic polymer of ethylene, a foaming agent, which comprises a carbon dioxide-releasing inorganic salt, and a nucleating agent/foaming coagent selected from a mixture of stearic acid and zinc stearate, and a mixture of calcium stearate and stearamide; and a second thermoplastic polymer of ethylene as particulate matter of a sixe significantly smaller than said first size; wherein said first thermoplastic polymer and said second thermoplastic polymer may he the same or different. The first and second thermoplastic polymer has melt index about. 30g /i0 min. U.S. Patent Publication No. US 2002/0120051 A i discloses a plastic part molded by injection molding comprising (a) lustrous pigments comprising metallic pigment particles or platelets which have a predominantly two-dimensional shape, and (b) hollow or solid filler particles which have a substantially isometric body shape and have a diameter of 10 to 200
Figure imgf000004_0001
The lustrous pigments are pearfescent pigments based on mica or metal pigments coated with metal oxides. The particle of the lustrous pigments has a diameter of 2 to 80 pra.
PCT Patent Publication WO 2013/096696 A I discloses a rotomolding composition comprising ai least 95 percent by weight of a thermoplastic polymer; and from O.'l to 3 percent by weight of metal oxide lamellae; wherein the rotomolding composition is characterized by at least one of the following properties: (a) having a retention ai elongation at. break of at least 85 percent after 4000 hours of accelerated aging; or (b) having a ductility improvement of at least 50 percent relative to a similar composition free of said metal oxide lamellae. Said thermoplastic polymer is an ethylene based polymer or a propylene based polymer.
However, no prior arts disclose a metal powder rotomolding composition, which provides glittering surface articles. Existing flittering surface articles (e.g. auto pans or up to 2 liters packaging, etc.) are produced by either blow molding or injection molding techniques. Several studies revealed an effort to develop the metal povvder rotomolding composition. None of them are able to achieve glittering surface articles.
Consequently, this invention attempts to address the above mentioned problem, i.e. a metal powder rotomolding composition providing glittering surface articles. This is performed by improving said composition using an appropriate amount and size of lustrous materials: and an appropriate amount and size of polymer powders.
SUMMARY OF THE INVENTION
This invention relates to a polymer composition for rotomolding comprising polymer; lustrous material with particle size of 1 urn to 2 mm not more than 1 5 percent by weight of polymer; and optionally, an effective amount of additives for rotational molding technique, not more than 5 percent by wei ght of polymer. The purpose of this invention is to provide a rotomolding plastic composition for manufacturing plastic articles with pronounced surface effect, particularly providing articles with glittering or sparkling surface.
BRI EF DESCRIPTION OF THE DRAWINGS
Figure i shows an article produced by rotomolding composition according to example i Figure 2 shows an article produced by inventive rotomolding composition according to example 2
DETAILED DESCRIPTION OF TOE EMBODIMENTS
The following is a more detailed description of the composition for rotomolding according to this invention.
A polymer composition for rotomolding according to this in ention comprising
- polymer;
- lustrous material with particle size of 1 μ·π to 2 mm .not more than 15 percent by weight of polymer; and
- optionally, an effective amount of additives for rotational molding technique, not more than 5 percent by weight of polymer.
According to the invention, said polymer has a particle size of 300 - 1.500 urn, preferably 300 - 1200 μ.πι, and more preferably 500-1000 μνη.
According to the invention, said polymer is selected from polyethylene, polypropylene, polyvinyl chloride, or mixtures of thereof.
According to the invention, said polyethylene is selected from linear low density polyethylene, low density polyethylene, .medium density polyethylene, high density polyethylene or mixtures of thereof, which has melt index of 2- 15 g/IO min.
According to the invention, said lustrous material has particle size of 5 urn to 1.6 mm, more preferably 5 to 1000 μηι, and most preferably 100 to 600 am. According to the invention, said lustrous material is selected from metallic particles, metallic pigment platelets, high retractive pigment, or mixtures of thereof.
According to the invention, said high refractive pigment is mica-based pearlescem pigment, metal pigment coated with metal oxide, or mixtures of thereof.
According to the invention, said additive is selected from antioxidants, UV stabilizer, light stabilizer, antimicrobial agent, flame retardant, or mixtures of thereof
According to the invention, said polypropylene is selected from homopoiymer or copolymer polypropylene with melt index of 2- 1 5 g/ 10 min.
The following is a further detailed description of the rotomokfing according to this invention.
Molded plastic centrifuge processes produce large and hollow inside, such as water tanks with a capacity ranging from 10 liters up to 10 cubic meters of four main steps.
The rotomolding is applied to manufacture large hollow articles, such as water tanks with a capacity ranging from 10 liters up to 10 cubic meters comprising tour main steps as follows:
- filling plastic powder into the desire moid;
- heating the plastic powder through a mold temperature of 1 70 - 230°C to melt plastic powder and rotating the mold into two dimensions simultaneously to coat the molten plastic on the mold;
- cooling and rotating simultaneously; and
- removing the articles off the moid.
The inventors conducted experiments using the rotomolding composition according to this invention by varying particle size of lustrous materials. The following examples are shown a comparative result- Example 1
A composition was prepared by mixing polyethylene having a melt index of 3-10 g/10 min and particle size of 200-300 pm, lustrous material (i.e, metallic particles) having particle size not over 200 pm in the amount of 1-3 percent by weight of polyethylene, and an additive in an amount of not over 5 percent by weight of polyethylene at an elevated temperature. Then reduce the average particle size of the mixture to 400 μτη, and finaiiy .fabricate the final sample product by rotomolding technique. The prepared sample does not show glittering surface (i.e. matte surface) as shown in Figure I ,
Example 2
A composition was prepared by mixing polyethylene having a melt index of 3-10 g/10 mtn and particle size of 500- 1000 μηι, lustrous material (i.e. pearleseent pigment) having particle size not over 200 un in the amount of 1 -3 percent, by weight of polyethylene, and an additive in an amount of not over 5 percent by weight of polyethylene at an elevated temperature. Then reduce the average particle size of the mixture to 400 μπ and finally fabricate the final sample, product by rotomolding technique. The prepared sample does not show glittering surface (i.e. matte surface) as shown in Figure 2.
From Examples 1 and 2, it reveals that the particle size of polymer and lustrous materials affects obviously product appearance.
It will be clear to those skilled in the art tha the present invention was described above with reference to a few preferred embodiments. The Invention, however, is by no means limited to these embodiments. Equivalent and/or alternative embodiments and modifications, which may or may not be apparent to the average skilled person, are conceivable. Such modifications and embodiments may very well fail within the scope of protection, applied for as defined in the appended claims.

Claims

Claims
1. A polymer composition for rotomolding comprising
- polymer;
- lustrous material with particle size of 1 pm to 2 mm not more than 15 percent by weigh t of polymer; and
- optionally, an effective amount of additives for rotational molding technique, not more than 5 percent by weight of polymer.
2. The polymer composition of claim L wherein said polymer has particle size of 300 - I 500 μηι.
3. The polymer composition of claim 1 or 2, wherein said polymer particle size is preferably 300 - 1200 um, and more preferably 500·· 1000 turn
4. The polymer composition as claimed in any one of claims I to 3, wherein said polymer is selected from polyethylene, polypropylene, polyvinyl chloride, or mixtures of thereof.
5. The polymer composition of claim 4, wherein said polyethylene is selected from linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene or mixtures of thereof.
6. The polymer composition of claim 4 or 5, wherein said polyethylene has melt index of2- l 5 g/10 rain,
7. The polymer composition of claim 4, wherein said propylene is selected from homopolymer or copolymer,
8. The polymer composition of claim 7, wherein said homopoiymer or copolymer polypropylene has melt index of 2» 15 g/ 10 min..
9. The polymer composition of claim i, wherein said lustrous material has particle size of 5 pm to 1.6 mm, more preferably 5 to 1000 um, and most preferably .100 to 600 u .
.
10. The polymer composition of claim 1 or 9, wherein said lustrous material is selected from metallic particles, metallic pigment platelets, high refractive pigment, or mixtures of thereof.
1 1 , The polymer composition of claim 10, wherein said high refractive pigment is mic * based pearlescent pigment, racial pigment coated with metal oxide, or mixtures of thereof
12. The polymer composition of claim 1 , wherein said additive is selected from antioxidants, UV stabilizer, light stabilizer, antimicrobial agent, flame retardant, or mixtures of thereof.
1/1
Figure imgf000010_0001
Figure imgf000010_0002
PCT/TH2015/000013 2014-02-28 2015-02-27 Polymer composition for rotomolding WO2015130240A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TH1401001061A TH153601A (en) 2014-02-28 Polymer compositions for plastic molding by centrifugation technique.
TH1401001061 2014-02-28

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12134213B2 (en) 2018-03-22 2024-11-05 Dow Global Technologies Llc Process for forming a rotational molded article

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1694006A1 (en) * 1968-01-31 1971-03-11 Dynamit Nobel Ag Process for the production of profiles with a copper-colored metallic effect from plasticized polyvinyl chloride
JPS54138048A (en) * 1978-04-19 1979-10-26 Toyo Alum Kk Chorine-containing thremoplastic resin composition having metallic luster and molded article therof
EP0145363A2 (en) * 1983-11-21 1985-06-19 Shin-Etsu Chemical Co., Ltd. A formable vinyl chloride-based resin composition
US4599376A (en) * 1984-03-28 1986-07-08 Toyoda Gosei Kabushiki Kaisha Polyvinyl chloride composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1694006A1 (en) * 1968-01-31 1971-03-11 Dynamit Nobel Ag Process for the production of profiles with a copper-colored metallic effect from plasticized polyvinyl chloride
JPS54138048A (en) * 1978-04-19 1979-10-26 Toyo Alum Kk Chorine-containing thremoplastic resin composition having metallic luster and molded article therof
EP0145363A2 (en) * 1983-11-21 1985-06-19 Shin-Etsu Chemical Co., Ltd. A formable vinyl chloride-based resin composition
US4599376A (en) * 1984-03-28 1986-07-08 Toyoda Gosei Kabushiki Kaisha Polyvinyl chloride composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12134213B2 (en) 2018-03-22 2024-11-05 Dow Global Technologies Llc Process for forming a rotational molded article

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