WO2001002487A1 - Polyester-polycarbonate composition with improved hot-plate weldability - Google Patents

Polyester-polycarbonate composition with improved hot-plate weldability Download PDF

Info

Publication number
WO2001002487A1
WO2001002487A1 PCT/US2000/018294 US0018294W WO0102487A1 WO 2001002487 A1 WO2001002487 A1 WO 2001002487A1 US 0018294 W US0018294 W US 0018294W WO 0102487 A1 WO0102487 A1 WO 0102487A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
core
rate
polytetrafluoroethylene
hot
Prior art date
Application number
PCT/US2000/018294
Other languages
French (fr)
Inventor
Akifumi Oshima
Terumasa Hirata
Original Assignee
General Electric Company
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 General Electric Company filed Critical General Electric Company
Priority to EP00946995A priority Critical patent/EP1115790A1/en
Priority to KR1020017002487A priority patent/KR20010073015A/en
Publication of WO2001002487A1 publication Critical patent/WO2001002487A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/18—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools
    • B29C65/20—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools with direct contact, e.g. using "mirror"
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • 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
    • B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/747—Lightning equipment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—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 a halogen; Compositions of derivatives of such polymers
    • C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers

Definitions

  • the present invention relates to a polyester resin composition that contains a polycarbonate resin, and more specifically relates to a resin composition that is optimal for use in the manufacture of automobile lamps, etc., by a hot-plate welding process.
  • Thermoplastic resins are widely used as automotive materials because of their advantages in terms of light weight, workability and economy, etc.
  • automobile rear combination housings, electrical circuit boxes and batteries, etc. are manufactured from thermoplastic resins, it is necessary to weld the resins.
  • Three main types of methods are used for such welding. Specifically, these are methods that use an adhesive agent, methods that depend on the heat of friction (vibration welding methods) and methods that use heating (hot-plate welding methods).
  • methods that use an adhesive agent use solvents, and are therefore undesirable from an environmental standpoint; furthermore, such methods suffer from the drawback of a long cycle time.
  • Hot-plate welding methods are most widely used; however, such methods suffer form the following drawbacks: first of all, when the resin is caused to contact the hot plate, a portion of the material remains on the hot plate, and the carbonized material thus produced lowers the strength of the weld, so that the product yield drops. As a result, an operation to remove the resin debris must be performed periodically. Secondly, when the resin is drawn from the hot plate, strings are drawn from the resin so that fine filament-form matter remains on the molded product. In particular, such problems are fatal in the case of optical products such as lamp lenses, etc.
  • the object of the present invention is to solve the abovementioned problems by improving the composition; more concretely, the object of the present invention is to provide a resin composition with improved hot-plate weldability in which no carbonized resin remains on the hot plate, and in which no fine filaments of the resin are drawn out.
  • the present invention comprises the following resin composition:
  • the present invention also comprises a resin composition which is characterized by the fact that the abovementioned core-shell polymer (C) is formed by polymerizing at least one type of shell-forming monomer selected from a set consisting of vinyl aromatic compounds, vinyl cyanide, alkyl acrylates, alkyl methacrylates, acrylic acid and methacrylic acid with a core consisting of an acrylate rubber or butadiene rubber.
  • a universally known resin can be used as the polyester resin (A) in the present invention.
  • resins include polycondensed polyesters obtained by a reaction between a dicarboxylic acid or derivative and a diol; polycondensed polyesters obtained by a reaction between a dicarboxylic acid or derivative and a cyclic ether compound; polycondensed polyesters obtained by a reaction between a metal salt of a dicarboxylic acid and a dihalogen compound; and polycondensed polyesters obtained by the ring- opening polymerization reaction of a cyclic ester compound.
  • Either aliphatic dicarboxylic acids or aromatic dicarboxylic acids may be used as the abovementioned dicarboxylic acid.
  • aliphatic dicarboxylic acids include aliphatic acids such as oxalic acid, succinic acid and adipic acid, etc.
  • alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, etc.
  • aromatic dicarboxylic acids which can be used include terephthalic acid, isophthalic acid, phthalic acid and chlorophthalic acid, etc. These acids may be used singly, or may be used in combinations consisting of two or more acids.
  • dicarboxylic acid derivatives that can be used include anhydrides, ester compounds, hydrochlorides and salts with alkali metals such as potassium and sodium, etc.
  • Diols that can be used include both aliphatic diols and aromatic diols.
  • aliphatic diols include dihydric alcohols such as ethylene glycol, propylene glycol, butane-l,4-diol and hexamethylene glycol, etc.; ethylene glycol and butane-l,4-diol are especially desirable.
  • aromatic diols examples include bisphenol A and resorcinol, etc. These diols may be used singly, or may be used in combinations consisting of two or more diols.
  • Examples of cyclic ether compounds that can be used include ethylene oxide and propylene oxide, etc.
  • Examples of dihalogen compounds that can be used include compounds obtained by substituting the two hydroxy groups of the abovementioned diols with halogen atoms, e. g., chlorine or bromine.
  • Cyclic ester compounds that can be used include ⁇ -caprolactone, etc.
  • Polyester resins (A) that are especially desirable for use in the present invention are polyethylene terephthalate resins obtained aromatic dicarboxylic acids, especially terephthalic acid, isophthalic acid or ortho- phthalic acid, and ethylene glycol or butylene glycol, and polybutylene terephthalates obtained from the aforementioned terephthalic acid, etc., and 1,4-butanediol.
  • the amount of this polyester resin (A) that is contained in the composition is 98 to 1 wt % of the resin composition; this content is preferably 80 to 5 wt %, and is even more preferably 60 to 15 wt %. If the aforementioned upper-limit value is exceeded, the impact resistance deteriorates; on the other hand, if the content is less than the aforementioned lower-limit value, the chemical resistance of the composition deteriorates.
  • Aromatic polycarbonates obtained by the universally known phosgene process or fusion process can be used is the abovementioned polycarbonate resin (B) in the present invention.
  • Polycarbonate resins consist of a carbonate component and a diphenol component. Examples of precursor substances that can be used to derive the carbonate component include phosgene and diphenyl carbonate, etc.
  • diphenol components examples include 2,2-bis(4-hydroxyphenyl)propane (so-called bisphenol A), 2,2-bis(3,5- dibromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4- hydroxyphenyl)propane, l,l-bis(4-hydroxyphenyl)cyclohexane, l,l-bis(3,5- dimethyl-4-hydroxyphenyl)cyclohexane, l,l-bis(4-hydroxyphenyl)decane, l,4bis(4-hydroxyphenyl)propane, l,l-bis(4-hydroxyphenyl)cyclododecane, l,l-bis(3,5-dimethyl-4-hydroxyphenyl)cyclododecane, 4,4-dihydroxydiphenyl ether, 4,4-oxyphenol, 4,4-dihydroxy-3,3-dichlorodiphenyl ether and 4,4- dihydroxydiphenyl
  • Polycarbonate resins (B) that are desirable for use in the present invention include (for example) LEX AN (registered trademark) 101 and LEXAN (registered trademark) 121, etc., which are bisphenol A polycarbonate resins commercially marketed by General Electric Co.
  • the content of the polycarbonate resin (B) in the resin composition is 1 to 98 wt %, preferably 15 to 90 wt %, and even more preferably 30 to 80 wt %.
  • component (B) may be an aromatic copolyester carbonate.
  • component (B) may be an aromatic copolyester carbonate.
  • such a component also has ester units originating in an aromatic diol and an aliphatic dicarboxylic acid with 6 to 18 carbon atoms.
  • the phosgene method or fusion method which are already universally known as methods for manufacturing aromatic polycarbonates, can be used to manufacture such aromatic copolyester carbonates. (See U.S. Patent No. 4,238,596, U.S. Patent No. 4,238,597 and U.S. Patent No. 3,169,121.)
  • the core-shell copolymer constituting component (C) of the present invention is a copolymer formed by graft-polymerizing one or more shell- forming monomers on a rubber-form core.
  • copolymers include copolymers formed by grafting a polystyrene or polymethacrylate, etc., as a shell on a core consisting of an acrylate type rubber, butadiene type rubber, polyorganosiloxane or compound rubber consisting of these rubbers.
  • Core-shell copolymers, methods for manufacturing such copolymers, and the use of core-shell copolymers in combination with polycarbonate resins and polyester resins as impact resistance improving agents, are described in (for example) U.S. Patent No.
  • thermoplastic composition which is superior in terms of weather resistance, and which is formed by mixing a polycarbonate resin and/ or polyester resin, a polyolefin rubber graft copolymer and a core-shell copolymer is disclosed in Japanese Patent Application Kokai No. Hei 9-302206.
  • these references do not mention the thermal fusibility of the resin compositions; furthermore, there is no suggestion of the mixing of core-shell copolymers and poly tetrafluor oethy lenes .
  • the core consists of an acrylate rubber or a butadiene rubber.
  • Acrylate rubbers are rubbers derived from acrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate and butyl methacrylate, etc.
  • such rubbers are obtained from methyl methacrylate, ethyl methacrylate, propyl methacrylate or mixtures of these.
  • Desirable monomers for forming the shell by graft polymerization onto such a core consist of at least one monomer selected from a set consisting of vinyl aromatic compounds, vinyl cyanide, alkyl acrylates, alkyl methacrylates, acrylic acid and methacrylic acid. It is desirable that the monomers forming the aforementioned core and/ or shell contain multifunctional compounds which can act as cross-linking agents and/ or grafting agents, such as butylene diacrylate or divinylbenzene. Especially desirable for use in the present invention is a methyl methacrylate-butadiene- styrene polymer (MBS) obtained by polymerizing methyl methacrylate and styrene with a butadiene rubber.
  • MBS methyl methacrylate-butadiene- styrene polymer
  • the amount of this core-shell copolymer (C) that is contained in the resin composition is 0.5 to 18 wt %, preferably 1 to 15 wt %, and even more preferably 3 to 13 wt %. If the content is less than the aforementioned lower-limit value, the effect in improving the hot-plate weldability is insufficient; on the other hand, if the content exceeds the aforementioned upper-limit value, the moldability and mechanical strength of the composition may drop.
  • the polytetrafluoroethylene constituting component (D) of the present invention is in itself universally known. Furthermore, a composition including a polyester carbonate resin, a polycarbonate resin, a phosphoric acid ester and a polytetrafluoroethylene is disclosed in Japanese Patent Application Kokai No. Hei 9-183893; here, the polytetrafluoroethylene is added together with the phosphoric acid ester in order to improve the flame retarding properties. There is no mention of thermal weldability in this reference, and there is no suggestion of the mixing of a core-shell copolymer and polytetrafluoroethylene.
  • the polytetrafluoroethylene constituting component (D) used in the present invention can be manufactured by any universally known manufacturing method.
  • this polytetrafluoroethylene is obtained by a suspension polymerization process or emulsion polymerization process.
  • the polytetrafluoroethylene used in the present invention have a number average molecular weight of 30,000 or greater. In cases where the molecular weight is less than this value, the effect in improving the hot-plate weldability is insufficient. The inferred reason for this will be described below without limiting the present invention.
  • a polytetrafluoroethylene with long molecular chains extends across the molten portions and non-molten portions of the resin, so that portions of the molecular chains are fixed in the non-molten portions, while other portions extend into the molten portions of the resin.
  • the content of this polytetrafluoroethylene (D) in the resin composition is 0.01 to 4 wt %, preferably 0.1 to 2 wt %, and even more preferably 0.1 to 1 wt %. If this content is less than the abovementioned lower-limit value, the effect in improving the hot-plate weldability is insufficient. On the other hand, if this content exceeds the abovementioned upper-limit value, die wells are formed, so that there is a drop in productivity when the resin is extruded.
  • hot-plate weldability is conspicuously improved as a result of the combined use of the abovementioned core-shell copolymer (C) and polytetrafluoroethylene (D).
  • the effect of the present invention may be inferred as follows without limiting the present invention: specifically, as was described above, the polytetrafluoroethylene constituting component (D) carries the molten thermoplastic resin away from the hot plate; furthermore, the core-shell copolymer constituting component (C) strengthens the melt tension of the resin composition so that the resin that is carried away is prevented from being pulled into fine filaments.
  • the core-shell copolymer (C) also acts to increase the viscosity of the resin composition, and it appears that this also inhibits the pulling of the resin into filaments.
  • the hot-plate weldability is conspicuously improved by the addition of components (C) and (D).
  • Customary additives such as coloring agents (pigments or dies), thermal stabilizers, anti-oxidants, weather resistance improving agents, slip agents, mold release agents, crystal nucleus forming agents, plasticizers, flame retarding agents, fluidity improving agents, impact resistance improving agents, anti-static agents and ester interchange preventing agents, etc., may be appropriately added to the resin composition of the present invention during mixing or molding of the resin, as long as there is no loss of the object of the present invention.
  • molding method there are no particular restrictions on the molding method used, either; various types of methods may be used. Examples include injection molding, gas-assisted molding, cold-hot cycle molding, blow molding, extrusion molding, and thermo-forming molding, etc. Injection molding is especially desirable for use.
  • PET MA-580, manufactured by Mitsubishi Rayon K.K.
  • MBS KANEACE B-56 (trademark), manufactured by Kanegafuchi Kagaku Kogyo K.K.
  • SEBS KRATON G1651, manufactured by Shell Kagaku K.K.
  • the hot-plate weldability was evaluated in terms of the level of filament drawing and the amount of resin adhering to the plate (hot plate) as shown below. Details of the evaluation methods are shown below along with details of other evaluation methods used.
  • MI Melt Flow Index
  • a Teflon sheet was placed on a hot plate heated to 300°C or 370°C, and a sample piece was light pressed against this.
  • the sample piece used in each case was l A bar, and a Vi x Vi inch cross section was subjected to testing. After heating for 15 seconds, the sample piece was pulled away, and the cross section was examined. The length of the filament-form resin that was extended when the pressed cross section was stripped away was measured. This test was performed three times, and the maximum value obtained was recorded.
  • a Teflon sheet was placed on a hot plate heated to 300°C or 370°C, and a sample piece was light pressed against this.
  • the sample piece used in each case was Vi bar, and a Vi x Vi inch cross section was subjected to testing. After heating for 15 seconds, the sample piece was pulled away, and the extent of filament drawing was observed. The weight of the sample piece was measured before and after this welding test, and the difference between the two values obtained was taken as the amount of resin adhering to the plate. This test was performed three times, and the mean value obtained was recorded.
  • the respective components used were mixed in the proportions shown in Table 1, and pellets were manufactured by extruding the respective mixtures at a set temperature of 280 to 300°C and an rpm of 300 to 400 rpm using a two-shaft extruding machine.
  • Various evaluation sample pieces (described below) were injection-molded from these pellets, and were used in testing. The evaluation results are shown in Table 1.
  • the level of filament drawing is reduced as the amount of core-shell copolymer increases, in the order of Comparative Example 1 (containing no MBS), Comparative Example 2 (5 wt % MBS), Comparative Example 5 (10 wt % MBS) and Comparative Example 6 (20 wt %).
  • Comparative Example 5 the heat resistance of the resin composition drops, and problems appear in the mechanical strength (IZOD), when the MBS content exceeds a certain level.
  • thermoplastic resin composition of the present invention the hot-plate weldability is conspicuously improved as a result of the presence of a core-shell copolymer (C) and polytetrafluoroethylene (D) with a specified molecular weight in the composition.

Abstract

The object of the present invention is to provide a resin composition with improved hot-plate weldability, in which no carbonized resin remains on the hot plate, and in which there is no drawing out of fine filaments of the resin. The present invention provides a resin composition which contains (A) a polyester resin at the rate of 98 to 1 wt %; (B) a polycarbonate resin at the rate of 1 to 98 wt %; (C) a core-shell copolymer at the rate of 0.5 to 18 wt %, and (D) a polytetrafluoroethylene with a number average molecular weight of 30,000 or greater at the rate of 0.01 to 4 wt % (with the total of (A) through (D) being 100 wt %).

Description

POLYESTER-POLYCARBONATE COMPOSITION WITH IMPROVED HOT-PLATE WELDAB ILITY
BACKGROUND OF THE INVENTION
The present invention relates to a polyester resin composition that contains a polycarbonate resin, and more specifically relates to a resin composition that is optimal for use in the manufacture of automobile lamps, etc., by a hot-plate welding process.
BRIEF DESCRIPTION OF THE RELATED ART
Thermoplastic resins are widely used as automotive materials because of their advantages in terms of light weight, workability and economy, etc. When automobile rear combination housings, electrical circuit boxes and batteries, etc., are manufactured from thermoplastic resins, it is necessary to weld the resins. Three main types of methods are used for such welding. Specifically, these are methods that use an adhesive agent, methods that depend on the heat of friction (vibration welding methods) and methods that use heating (hot-plate welding methods). Among these methods, methods that use an adhesive agent use solvents, and are therefore undesirable from an environmental standpoint; furthermore, such methods suffer from the drawback of a long cycle time. In the case of vibration welding methods, particles of the powdered resin are scattered, so that the working environment is poor; moreover, there are restrictions in terms of design, and problems such as contamination of the welded parts, etc. Accordingly, such methods are used only in limited applications. Hot-plate welding methods are most widely used; however, such methods suffer form the following drawbacks: first of all, when the resin is caused to contact the hot plate, a portion of the material remains on the hot plate, and the carbonized material thus produced lowers the strength of the weld, so that the product yield drops. As a result, an operation to remove the resin debris must be performed periodically. Secondly, when the resin is drawn from the hot plate, strings are drawn from the resin so that fine filament-form matter remains on the molded product. In particular, such problems are fatal in the case of optical products such as lamp lenses, etc.
In order to solve the abovementioned problems, methods in which a special sheet is used in the hot-plate welding machine, or in which welding is performed without contact with the welding machine, have been employed. However, such methods require a considerable expenditure on equipment, and do not provide an essential solution to the abovementioned problems.
PROBLEMS TO BE SOLVED BY THE INVENTION
Accordingly, the object of the present invention is to solve the abovementioned problems by improving the composition; more concretely, the object of the present invention is to provide a resin composition with improved hot-plate weldability in which no carbonized resin remains on the hot plate, and in which no fine filaments of the resin are drawn out.
Specifically, the present invention comprises the following resin composition:
A resin composition which contains
(A) a polyester resin at the rate of 98 to 1 wt %,
(B) a polycarbonate resin at the rate of 1 to 98 wt %,
(C) a core-shell copolymer at the rate of 0.5 to 18 wt %, and
(D) a polytetrafluoroethylene with a number average molecular weight of 30,000 or greater at the rate of 0.01 to 4 wt % (with the total of A through D being 100 wt %). Furthermore, the present invention also comprises a resin composition which is characterized by the fact that the abovementioned core-shell polymer (C) is formed by polymerizing at least one type of shell-forming monomer selected from a set consisting of vinyl aromatic compounds, vinyl cyanide, alkyl acrylates, alkyl methacrylates, acrylic acid and methacrylic acid with a core consisting of an acrylate rubber or butadiene rubber.
A universally known resin can be used as the polyester resin (A) in the present invention. Examples of such resins include polycondensed polyesters obtained by a reaction between a dicarboxylic acid or derivative and a diol; polycondensed polyesters obtained by a reaction between a dicarboxylic acid or derivative and a cyclic ether compound; polycondensed polyesters obtained by a reaction between a metal salt of a dicarboxylic acid and a dihalogen compound; and polycondensed polyesters obtained by the ring- opening polymerization reaction of a cyclic ester compound.
Either aliphatic dicarboxylic acids or aromatic dicarboxylic acids may be used as the abovementioned dicarboxylic acid. Examples of aliphatic dicarboxylic acids include aliphatic acids such as oxalic acid, succinic acid and adipic acid, etc. Furthermore, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, etc., may also be cited as examples. Examples of aromatic dicarboxylic acids which can be used include terephthalic acid, isophthalic acid, phthalic acid and chlorophthalic acid, etc. These acids may be used singly, or may be used in combinations consisting of two or more acids. Furthermore, examples of dicarboxylic acid derivatives that can be used include anhydrides, ester compounds, hydrochlorides and salts with alkali metals such as potassium and sodium, etc.
Diols that can be used include both aliphatic diols and aromatic diols. Examples of aliphatic diols include dihydric alcohols such as ethylene glycol, propylene glycol, butane-l,4-diol and hexamethylene glycol, etc.; ethylene glycol and butane-l,4-diol are especially desirable. Furthermore, examples of aromatic diols that can be used include bisphenol A and resorcinol, etc. These diols may be used singly, or may be used in combinations consisting of two or more diols.
Examples of cyclic ether compounds that can be used include ethylene oxide and propylene oxide, etc. Examples of dihalogen compounds that can be used include compounds obtained by substituting the two hydroxy groups of the abovementioned diols with halogen atoms, e. g., chlorine or bromine. Cyclic ester compounds that can be used include ε-caprolactone, etc.
Polyester resins (A) that are especially desirable for use in the present invention are polyethylene terephthalate resins obtained aromatic dicarboxylic acids, especially terephthalic acid, isophthalic acid or ortho- phthalic acid, and ethylene glycol or butylene glycol, and polybutylene terephthalates obtained from the aforementioned terephthalic acid, etc., and 1,4-butanediol. The amount of this polyester resin (A) that is contained in the composition is 98 to 1 wt % of the resin composition; this content is preferably 80 to 5 wt %, and is even more preferably 60 to 15 wt %. If the aforementioned upper-limit value is exceeded, the impact resistance deteriorates; on the other hand, if the content is less than the aforementioned lower-limit value, the chemical resistance of the composition deteriorates.
Aromatic polycarbonates obtained by the universally known phosgene process or fusion process (for example, see Japanese Patent Application Kokai No. Sho 63-215763 and Japanese Patent Application Kokai No. Hei 2-124934) can be used is the abovementioned polycarbonate resin (B) in the present invention. Polycarbonate resins consist of a carbonate component and a diphenol component. Examples of precursor substances that can be used to derive the carbonate component include phosgene and diphenyl carbonate, etc. Furthermore, examples of diphenol components that can be used include 2,2-bis(4-hydroxyphenyl)propane (so-called bisphenol A), 2,2-bis(3,5- dibromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4- hydroxyphenyl)propane, l,l-bis(4-hydroxyphenyl)cyclohexane, l,l-bis(3,5- dimethyl-4-hydroxyphenyl)cyclohexane, l,l-bis(4-hydroxyphenyl)decane, l,4bis(4-hydroxyphenyl)propane, l,l-bis(4-hydroxyphenyl)cyclododecane, l,l-bis(3,5-dimethyl-4-hydroxyphenyl)cyclododecane, 4,4-dihydroxydiphenyl ether, 4,4-oxyphenol, 4,4-dihydroxy-3,3-dichlorodiphenyl ether and 4,4- dihydroxy-2,5-dihydroxydiphenyl ether, etc. These diphenol components may be used singly or in combination. In addition, compounds that have three or more phenolic hydroxy groups may also be used.
Polycarbonate resins (B) that are desirable for use in the present invention include (for example) LEX AN (registered trademark) 101 and LEXAN (registered trademark) 121, etc., which are bisphenol A polycarbonate resins commercially marketed by General Electric Co. The content of the polycarbonate resin (B) in the resin composition is 1 to 98 wt %, preferably 15 to 90 wt %, and even more preferably 30 to 80 wt %.
Alternatively, component (B) may be an aromatic copolyester carbonate. In addition to carbonate units originating in a universally known aromatic diol, such a component also has ester units originating in an aromatic diol and an aliphatic dicarboxylic acid with 6 to 18 carbon atoms. The phosgene method or fusion method, which are already universally known as methods for manufacturing aromatic polycarbonates, can be used to manufacture such aromatic copolyester carbonates. (See U.S. Patent No. 4,238,596, U.S. Patent No. 4,238,597 and U.S. Patent No. 3,169,121.)
The core-shell copolymer constituting component (C) of the present invention is a copolymer formed by graft-polymerizing one or more shell- forming monomers on a rubber-form core. Examples of such copolymers include copolymers formed by grafting a polystyrene or polymethacrylate, etc., as a shell on a core consisting of an acrylate type rubber, butadiene type rubber, polyorganosiloxane or compound rubber consisting of these rubbers. Core-shell copolymers, methods for manufacturing such copolymers, and the use of core-shell copolymers in combination with polycarbonate resins and polyester resins as impact resistance improving agents, are described in (for example) U.S. Patent No. 3864428, U.S. Patent No. 4180434, U.S. Patent No. 4257937 and U.S. Patent No. 4264487. Furthermore, a thermoplastic composition which is superior in terms of weather resistance, and which is formed by mixing a polycarbonate resin and/ or polyester resin, a polyolefin rubber graft copolymer and a core-shell copolymer is disclosed in Japanese Patent Application Kokai No. Hei 9-302206. However, these references do not mention the thermal fusibility of the resin compositions; furthermore, there is no suggestion of the mixing of core-shell copolymers and poly tetrafluor oethy lenes .
In core-shell copolymers that are desirable for use in the present invention, the core consists of an acrylate rubber or a butadiene rubber. Acrylate rubbers are rubbers derived from acrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate and butyl methacrylate, etc. Preferably, such rubbers are obtained from methyl methacrylate, ethyl methacrylate, propyl methacrylate or mixtures of these. Desirable monomers for forming the shell by graft polymerization onto such a core consist of at least one monomer selected from a set consisting of vinyl aromatic compounds, vinyl cyanide, alkyl acrylates, alkyl methacrylates, acrylic acid and methacrylic acid. It is desirable that the monomers forming the aforementioned core and/ or shell contain multifunctional compounds which can act as cross-linking agents and/ or grafting agents, such as butylene diacrylate or divinylbenzene. Especially desirable for use in the present invention is a methyl methacrylate-butadiene- styrene polymer (MBS) obtained by polymerizing methyl methacrylate and styrene with a butadiene rubber. The amount of this core-shell copolymer (C) that is contained in the resin composition is 0.5 to 18 wt %, preferably 1 to 15 wt %, and even more preferably 3 to 13 wt %. If the content is less than the aforementioned lower-limit value, the effect in improving the hot-plate weldability is insufficient; on the other hand, if the content exceeds the aforementioned upper-limit value, the moldability and mechanical strength of the composition may drop.
The polytetrafluoroethylene constituting component (D) of the present invention is in itself universally known. Furthermore, a composition including a polyester carbonate resin, a polycarbonate resin, a phosphoric acid ester and a polytetrafluoroethylene is disclosed in Japanese Patent Application Kokai No. Hei 9-183893; here, the polytetrafluoroethylene is added together with the phosphoric acid ester in order to improve the flame retarding properties. There is no mention of thermal weldability in this reference, and there is no suggestion of the mixing of a core-shell copolymer and polytetrafluoroethylene.
The polytetrafluoroethylene constituting component (D) used in the present invention can be manufactured by any universally known manufacturing method. Preferably, this polytetrafluoroethylene is obtained by a suspension polymerization process or emulsion polymerization process.
It is necessary that the polytetrafluoroethylene used in the present invention have a number average molecular weight of 30,000 or greater. In cases where the molecular weight is less than this value, the effect in improving the hot-plate weldability is insufficient. The inferred reason for this will be described below without limiting the present invention. During hotplate welding, the resin in the vicinity of the hot plate is melted, but the portions of the resin that are distant from the hot plate are not melted. A polytetrafluoroethylene with long molecular chains extends across the molten portions and non-molten portions of the resin, so that portions of the molecular chains are fixed in the non-molten portions, while other portions extend into the molten portions of the resin. When the resin is pulled away from the hot plate, the molten resin entangled with the polytetrafluoroethylene chains extending into the molten portions of the resin is pulled by the non-molten portions so that this molten resin is carried away from the hot plate. However, if a polytetrafluoroethylene with short molecular chains is used, it is hardly possible for this polytetrafluoroethylene to extend across the molten portions and non-molten portions of the resin. As a result, when the resin is pulled away from the hot plate, the polytetrafluoroethylene remains on the hot plate together with the molten resin. Accordingly, in order to improve the hot-plate weldability, it appears that it is necessary to use a polytetrafluoroethylene whose molecular weight exceeds a certain value.
The content of this polytetrafluoroethylene (D) in the resin composition is 0.01 to 4 wt %, preferably 0.1 to 2 wt %, and even more preferably 0.1 to 1 wt %. If this content is less than the abovementioned lower-limit value, the effect in improving the hot-plate weldability is insufficient. On the other hand, if this content exceeds the abovementioned upper-limit value, die wells are formed, so that there is a drop in productivity when the resin is extruded.
In the composition of the present invention, hot-plate weldability is conspicuously improved as a result of the combined use of the abovementioned core-shell copolymer (C) and polytetrafluoroethylene (D). The effect of the present invention may be inferred as follows without limiting the present invention: specifically, as was described above, the polytetrafluoroethylene constituting component (D) carries the molten thermoplastic resin away from the hot plate; furthermore, the core-shell copolymer constituting component (C) strengthens the melt tension of the resin composition so that the resin that is carried away is prevented from being pulled into fine filaments. Furthermore, the core-shell copolymer (C) also acts to increase the viscosity of the resin composition, and it appears that this also inhibits the pulling of the resin into filaments. Thus, the hot-plate weldability is conspicuously improved by the addition of components (C) and (D).
Customary additives such as coloring agents (pigments or dies), thermal stabilizers, anti-oxidants, weather resistance improving agents, slip agents, mold release agents, crystal nucleus forming agents, plasticizers, flame retarding agents, fluidity improving agents, impact resistance improving agents, anti-static agents and ester interchange preventing agents, etc., may be appropriately added to the resin composition of the present invention during mixing or molding of the resin, as long as there is no loss of the object of the present invention.
There are no particular restrictions on the method used to manufacture the resin composition of the present invention; ordinary methods can be satisfactorily used. Preferably, a molten mixing method is used. Small amounts of solvents may also be used, but are ordinarily unnecessary. Examples of apparatus that can be used include extruders, Banbury mixers, rollers and kneaders, etc. Such apparatus may be operated in a batch operation or continuously.
There are no particular restrictions on the molding method used, either; various types of methods may be used. Examples include injection molding, gas-assisted molding, cold-hot cycle molding, blow molding, extrusion molding, and thermo-forming molding, etc. Injection molding is especially desirable for use.
EXAMPLES Below, the present invention will be described in greater detail in terms of working examples. However, the present invention is not limited to these examples.
I) Resins Used
The resins used in the working examples and comparative examples were as shown below.
Resins Used in Working Examples
(A) Polyester Resin
PET: MA-580, manufactured by Mitsubishi Rayon K.K.
(B) Polycarbonate Resin
PC: LEXAN 125 (trademark: manufactured by Nippon GE Plastics K.K.)
(C) Core-Shell Copolymer
MBS: KANEACE B-56 (trademark), manufactured by Kanegafuchi Kagaku Kogyo K.K.
(D) Polytetrafluoroethylene
TEFN-1: Freon CD-I (trademark), number average molecular weight (Mn) = 99,000, manufactured by Asahi ICI Fluoropolymers K.K.
Other Resins Used in Comparative Examples
SEBS: KRATON G1651, manufactured by Shell Kagaku K.K.
SEP: Septone-1001, manufactured by Kurare K.K.
TEFN-2: Lupron L-5 (trademark), number average molecular weight (Mn) = 25,000, manufactured by Daikin Kogyo K.K. Furthermore, the molecular weights of polytetrafluoroethylenes were measured using the method indicated by T. Suwa, M. Takehisa and S. Machi in "Melting and Crystallization Behavior of Poly(tetrafluoroethylene). New Method for Molecular Weight Measurement of Poly(tetrafluoroethylene) Using a Differential Scanning Calorimeter", Jr. Appl. Polym. Science, Vol. 17, pp. 3253-3257 (1973).
II) Evaluation Methods
In the present invention, the hot-plate weldability was evaluated in terms of the level of filament drawing and the amount of resin adhering to the plate (hot plate) as shown below. Details of the evaluation methods are shown below along with details of other evaluation methods used.
(1) IZOD Impact Strength
This was measured according to ASTM D256.
(2) Heat Deformation Temperature
This was measured according to ASTM D648 at a load of 4.6 kg.
(3) Melt Flow Index (MI)
This was measured according to ASTM D1238 at a temperature of 266°C and a load of 2.16 kg.
(4) Level of Filament Drawing
A Teflon sheet was placed on a hot plate heated to 300°C or 370°C, and a sample piece was light pressed against this. The sample piece used in each case was lA bar, and a Vi x Vi inch cross section was subjected to testing. After heating for 15 seconds, the sample piece was pulled away, and the cross section was examined. The length of the filament-form resin that was extended when the pressed cross section was stripped away was measured. This test was performed three times, and the maximum value obtained was recorded.
(5) Amount of Resin Adhering to Plate
A Teflon sheet was placed on a hot plate heated to 300°C or 370°C, and a sample piece was light pressed against this. The sample piece used in each case was Vi bar, and a Vi x Vi inch cross section was subjected to testing. After heating for 15 seconds, the sample piece was pulled away, and the extent of filament drawing was observed. The weight of the sample piece was measured before and after this welding test, and the difference between the two values obtained was taken as the amount of resin adhering to the plate. This test was performed three times, and the mean value obtained was recorded.
Working Examples 1 Through 4 and Comparative Examples 1 Through 9
The respective components used were mixed in the proportions shown in Table 1, and pellets were manufactured by extruding the respective mixtures at a set temperature of 280 to 300°C and an rpm of 300 to 400 rpm using a two-shaft extruding machine. Various evaluation sample pieces (described below) were injection-molded from these pellets, and were used in testing. The evaluation results are shown in Table 1.
TABLE 1
Figure imgf000014_0001
2) Hot-plate welding test performed at 300°C
It is seen that when a specified amount of a core-shell copolymer (MBS) (Comparative Example 2) is added to a composition containing a polyester resin and a polycarbonate resin (Comparative Example 1), the level of filament drawing is conspicuously reduced. The rubbers used in Comparative Examples 3 and 4 are not core-shell copolymers, and have no strengthening effect on the melt tension of the resin composition; accordingly, compared to a core-shell copolymer, these rubbers have little effect in reducing the level of filament drawing.
Furthermore, the level of filament drawing is reduced as the amount of core-shell copolymer increases, in the order of Comparative Example 1 (containing no MBS), Comparative Example 2 (5 wt % MBS), Comparative Example 5 (10 wt % MBS) and Comparative Example 6 (20 wt %). However, as is seen from a comparison of Comparative Examples 5 and 6, the heat resistance (HDT) of the resin composition drops, and problems appear in the mechanical strength (IZOD), when the MBS content exceeds a certain level.
It is seen from a comparison of Working Examples 1 through 4 with Comparative Examples 5 and 7 that the amount of resin adhering to the hot plate and the level of filament drawing at a high temperature (370°C) are further ameliorated by the addition of component (D), i. e., a polytetrafluoroethylene, along with the core-shell copolymer. When a rubber (SEBS) other than the abovementioned core-shell copolymer is added along with the polytetrafluoroethylene (D) (Comparative Example 9), some amelioration of the amount of adhering resin is seen; however, the improvement in terms of level of filament drawing is small compared to that seen in Working Examples 1 through 4.
Furthermore, in cases where the molecular weight of the polytetrafluoroethylene is less than 30,000, almost no improvement is seen in terms of the level of filament drawing or amount of resin adhering to the plate (Comparative Example 8).
Thus, in the thermoplastic resin composition of the present invention, the hot-plate weldability is conspicuously improved as a result of the presence of a core-shell copolymer (C) and polytetrafluoroethylene (D) with a specified molecular weight in the composition.

Claims

1. A resin composition which contains
(A) a polyester resin at the rate of 98 to 1 wt %,
(B) a polycarbonate resin at the rate of 1 to 98 wt %,
(C) a core-shell copolymer at the rate of 0.5 to 18 wt %, and
(D) a polytetrafluoroethylene with a number average molecular weight of 30,000 or greater at the rate of 0.01 to 4 wt % (with the total of A through D being 100 wt %).
2. The resin composition claimed in Claim 1, which is characterized by the fact that the core-shell polymer (C) is formed by polymerizing at least one type of shell-forming monomer selected from a set consisting of vinyl aromatic compounds, vinyl cyanide, alkyl acrylates, alkyl methacrylates, acrylic acid and methacrylic acid with a core consisting of an acrylate rubber or butadiene rubber.
PCT/US2000/018294 1999-07-02 2000-06-30 Polyester-polycarbonate composition with improved hot-plate weldability WO2001002487A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP00946995A EP1115790A1 (en) 1999-07-02 2000-06-30 Polyester-polycarbonate composition with improved hot-plate weldability
KR1020017002487A KR20010073015A (en) 1999-07-02 2000-06-30 Polyester- polycarbonate composition with improved hot-plate weldability

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11/189435 1999-07-02
JP18943599A JP4486180B2 (en) 1999-07-02 1999-07-02 Resin composition with improved hot plate weldability

Publications (1)

Publication Number Publication Date
WO2001002487A1 true WO2001002487A1 (en) 2001-01-11

Family

ID=16241211

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2000/018294 WO2001002487A1 (en) 1999-07-02 2000-06-30 Polyester-polycarbonate composition with improved hot-plate weldability

Country Status (5)

Country Link
EP (1) EP1115790A1 (en)
JP (1) JP4486180B2 (en)
KR (1) KR20010073015A (en)
CN (1) CN1321180A (en)
WO (1) WO2001002487A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006039110A1 (en) * 2004-09-29 2006-04-13 General Electric Company Method for reducing stringiness of a resinous composition during hot plate welding
EP2287249A1 (en) 2008-04-08 2011-02-23 Sumitomo Chemical Company, Limited Methacrylic resin composition for hot plate melt-bonding, use of the same for hot plate melt-bonding, and melt-bonding method
WO2016076666A1 (en) * 2014-11-14 2016-05-19 에스케이케미칼주식회사 Polymer resin composition
WO2016099179A1 (en) * 2014-12-19 2016-06-23 에스케이케미칼주식회사 Polymer resin composition with excellent flame retardancy

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5233063B2 (en) * 2004-09-17 2013-07-10 東レ株式会社 Resin composition and molded article comprising the same
KR100604735B1 (en) * 2004-12-20 2006-07-28 에스케이씨 주식회사 Polyester-based optical film having improved polarization
KR100831083B1 (en) * 2005-12-27 2008-05-20 제일모직주식회사 Polyester Thermoplastic Resin Compositions Having High Melt Strength
KR100878571B1 (en) * 2007-12-31 2009-01-15 제일모직주식회사 Transparent thermoplastic resin composition
CN105612213A (en) * 2013-09-04 2016-05-25 Sk化学株式会社 Polymer resin composition and molded product thereof
JP6218344B1 (en) * 2017-01-25 2017-10-25 ユーエムジー・エービーエス株式会社 Thermoplastic resin composition for hot plate welding, molded article thereof, and resin joined body
CN111698798B (en) * 2020-06-17 2023-02-03 浙江南洋科技有限公司 Preparation method of heat-resistant and flame-retardant polyester film for electrothermal film

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2197930A1 (en) * 1972-08-30 1974-03-29 Teijin Ltd
EP0162382A2 (en) * 1984-05-19 1985-11-27 Bayer Ag Thermoplastic molding compounds on the basis of polyalkylene terephthalate, polycarbonate and polymerisate and process for their fabrication
DE4040243A1 (en) * 1990-03-10 1991-09-12 Bayer Ag Fire resistant thermoplastic polycarbonate moulding materials - contg. aromatic ester] aromatic carbonate] opt. graft copolymer, anti-drip additive and non-volatile tri:aryl phosphate as fire retardant
WO1993018090A1 (en) * 1992-03-10 1993-09-16 The Dow Chemical Company Ignition resistant polycarbonate blends
JPH0912902A (en) * 1995-06-30 1997-01-14 Sumika A B S Ratetsukusu Kk Resin composition for fusing heat plate
JPH10298422A (en) * 1997-04-25 1998-11-10 Mitsubishi Eng Plast Kk Thermoplastic resin composition excellent in weldability and welded molding
JPH10310676A (en) * 1997-05-12 1998-11-24 Mitsubishi Rayon Co Ltd Thermoplastic resin composition for heat-plate welding and automotive lamp using the same
US5871570A (en) * 1995-05-26 1999-02-16 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Flame-retardant resin composition

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2197930A1 (en) * 1972-08-30 1974-03-29 Teijin Ltd
US3864428A (en) * 1972-08-30 1975-02-04 Teijin Ltd Polyester/polycarbonate/graft copolymer thermoplastic resin composition
EP0162382A2 (en) * 1984-05-19 1985-11-27 Bayer Ag Thermoplastic molding compounds on the basis of polyalkylene terephthalate, polycarbonate and polymerisate and process for their fabrication
DE4040243A1 (en) * 1990-03-10 1991-09-12 Bayer Ag Fire resistant thermoplastic polycarbonate moulding materials - contg. aromatic ester] aromatic carbonate] opt. graft copolymer, anti-drip additive and non-volatile tri:aryl phosphate as fire retardant
WO1993018090A1 (en) * 1992-03-10 1993-09-16 The Dow Chemical Company Ignition resistant polycarbonate blends
US5871570A (en) * 1995-05-26 1999-02-16 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Flame-retardant resin composition
JPH0912902A (en) * 1995-06-30 1997-01-14 Sumika A B S Ratetsukusu Kk Resin composition for fusing heat plate
JPH10298422A (en) * 1997-04-25 1998-11-10 Mitsubishi Eng Plast Kk Thermoplastic resin composition excellent in weldability and welded molding
JPH10310676A (en) * 1997-05-12 1998-11-24 Mitsubishi Rayon Co Ltd Thermoplastic resin composition for heat-plate welding and automotive lamp using the same

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE CHEMABS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; XP002151407, retrieved from STN Database accession no. 126:200522/DN HCAPLUS *
DATABASE CHEMABS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; XP002151408, retrieved from STN Database accession no. 130:53089/DN HCAPLUS *
DATABASE CHEMABS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; XP002151409, retrieved from STN Database accession no. 130:67522/DN HCAPLUS *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006039110A1 (en) * 2004-09-29 2006-04-13 General Electric Company Method for reducing stringiness of a resinous composition during hot plate welding
EP2287249A1 (en) 2008-04-08 2011-02-23 Sumitomo Chemical Company, Limited Methacrylic resin composition for hot plate melt-bonding, use of the same for hot plate melt-bonding, and melt-bonding method
WO2016076666A1 (en) * 2014-11-14 2016-05-19 에스케이케미칼주식회사 Polymer resin composition
WO2016099179A1 (en) * 2014-12-19 2016-06-23 에스케이케미칼주식회사 Polymer resin composition with excellent flame retardancy

Also Published As

Publication number Publication date
CN1321180A (en) 2001-11-07
KR20010073015A (en) 2001-07-31
JP4486180B2 (en) 2010-06-23
EP1115790A1 (en) 2001-07-18
JP2001011293A (en) 2001-01-16

Similar Documents

Publication Publication Date Title
US5416148A (en) Blends of polycarbonate and ethylene polymers
JP4378130B2 (en) Aromatic polycarbonate resin composition
CN111801386B (en) Thermoplastic resin composition and molded article using the same
JP5111458B2 (en) Method for reducing pearl luster of aromatic polycarbonate resin composition
US4880876A (en) Thermoplastic polyester molding materials having low-temperature impact strength
JPWO2001072872A1 (en) Block copolymer
US6894112B1 (en) Thermally stable polyester molding materials
JP2008524397A (en) Optically clear polycarbonate / polyester composition
US5124402A (en) Thermoplastic molding compositions with improved solvent resistance and impact strength, and methods for preparation thereof
US5525651A (en) Blends of polycarbonate and chlorinated polyethylene
WO2001002487A1 (en) Polyester-polycarbonate composition with improved hot-plate weldability
JP2008519874A (en) Polymer blend consisting of polyester and linear oligomeric polycarbonate
JP5277833B2 (en) Polycarbonate resin composition and buffer material for profile extrusion molding
EP3992248A1 (en) Thermoplastic resin composition and molded product using same
JPH075825B2 (en) Improved polyester composition
US5021508A (en) Thermoplastic molding materials consisting of polyesters and polycarbonates and having a good low-temperature impact strength
US20120309889A1 (en) Polyesters with styrene copolymers
JP5111456B2 (en) Method for using aromatic polycarbonate resin composition for exterior material of OA equipment or home appliance
MXPA01002239A (en) Polyester-polycarbonate composition with improved hot-plate weldability
KR20030011351A (en) Product from melt of wholly aromatic polyester and aromatic polycarbonate and process for producing the same
JP7334732B2 (en) Resin composition, method for producing resin composition, and method for producing resin molding
KR910007597B1 (en) Polycarbonate composition
JPH0739536B2 (en) Polyarylate composition
JP5136924B2 (en) Thermoplastic elastomer resin composition for composite molding and composite molded body
JP5111457B2 (en) Method for producing aromatic polycarbonate resin composition

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 00801902.9

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): CN KR MX SG

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

WWE Wipo information: entry into national phase

Ref document number: 2000946995

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 1020017002487

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: PA/a/2001/002239

Country of ref document: MX

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWP Wipo information: published in national office

Ref document number: 2000946995

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1020017002487

Country of ref document: KR

WWW Wipo information: withdrawn in national office

Ref document number: 2000946995

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1020017002487

Country of ref document: KR