WO1995033008A1 - Composition de resine contenant de la resine fluoree, procede de production de ladite composition, et feuille et mousse thermoformables constituees de ladite composition - Google Patents

Composition de resine contenant de la resine fluoree, procede de production de ladite composition, et feuille et mousse thermoformables constituees de ladite composition Download PDF

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Publication number
WO1995033008A1
WO1995033008A1 PCT/JP1995/001030 JP9501030W WO9533008A1 WO 1995033008 A1 WO1995033008 A1 WO 1995033008A1 JP 9501030 W JP9501030 W JP 9501030W WO 9533008 A1 WO9533008 A1 WO 9533008A1
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WIPO (PCT)
Prior art keywords
resin composition
weight
parts
fluororesin
containing resin
Prior art date
Application number
PCT/JP1995/001030
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English (en)
Japanese (ja)
Inventor
Taizo Aoyama
Tetsuo Okura
Kazuhiro Hara
Kiyoyuki Namura
Ryuji Fukuda
Haruo Tomita
Original Assignee
Kanegafuchi Kagaku Kogyo Kabushiki Kaisha
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.)
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Publication date
Priority claimed from JP11861194A external-priority patent/JP3274934B2/ja
Priority claimed from JP11861094A external-priority patent/JP3274933B2/ja
Priority claimed from JP13228294A external-priority patent/JPH07330935A/ja
Priority claimed from JP19061194A external-priority patent/JP3563775B2/ja
Priority claimed from JP19061094A external-priority patent/JPH0853582A/ja
Priority claimed from JP31068494A external-priority patent/JPH08165358A/ja
Application filed by Kanegafuchi Kagaku Kogyo Kabushiki Kaisha filed Critical Kanegafuchi Kagaku Kogyo Kabushiki Kaisha
Publication of WO1995033008A1 publication Critical patent/WO1995033008A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • thermoforming sheets and foams Technical field
  • the present invention relates to a fluorine resin-containing resin composition, a method for producing the same, and a thermoforming sheet and a foam obtained therefrom.
  • a fluorine resin-containing resin composition has excellent impact resistance and surface properties, further improved melting properties, and improved workability (formability).
  • a fluororesin-containing resin composition suitably used for various molded articles and the like, a process for producing the same, and a molding from the fluororesin-containing resin composition.
  • a thermoforming sheet and a foam having excellent physical properties as described above.
  • propylene for example, not only has the disadvantage of poor transparency, but also has low viscosity and low tension when melted. Therefore, it is inferior to vacuum moldability (hereinafter referred to as thermoformability), calender moldability, blow moldability, foaming moldability, etc. for the sheet.
  • thermoformability vacuum moldability
  • calender moldability blow moldability
  • foaming moldability etc. for the sheet.
  • Polyethylene polyvinyl chloride
  • ABS resin Compared to ABS resin, it has low rigidity, low impact resistance at low temperatures, poor surface properties (surface gloss), poor applicability, etc., and low hardness. There is a disadvantage in workability.
  • the polypropylene and the like are generally mixed mechanically with the polypropylene. It is.
  • the effect of improving the workability by the polyethylene is insufficient, a large amount of the polyethylene is required, and a large amount of the polyethylene is required.
  • the rigidity of the obtained mixture is reduced and the transparency of the molded body is reduced.
  • a high molecular weight polyrefin is used, extrusion, one of the important processing methods, is said to be difficult. There is a big problem.
  • polyethylene In order to improve the inherent low rigidity of polyolefin, it is possible to add polyethylene to the above-mentioned polypropylene, for example.
  • inorganic fillers and the like are added to the polyrefin.
  • an inorganic filler or the like if an inorganic filler or the like is added, the compatibility between the polyolefin and the inorganic filler is reduced, and poor dispersion of the inorganic filler occurs. For example, there is a problem that the surface properties of a molded product such as a sheet are significantly reduced.
  • a rubber component such as ethylene-propylene rubber is generally used to reduce mechanical impact.
  • Poly such as by mixing or block copolymerization It is being introduced to the propylene.
  • a large amount of the rubber component is required, so that the rigidity of the obtained mixture is increased. The problem is that it drops. Further, there is a problem that the surface gloss of the obtained molded body is reduced due to the large particle diameter of the dispersed rubber component.
  • a core-type modifier which has been widely used as an impact resistance improver for polyvinyl chloride resin, has a predetermined particle size.
  • the rubber component (core layer) can be efficiently dispersed, and the impact resistance can be improved while reducing the rigidity of polyvinyl chloride resin. It is something that can be done.
  • the core-type denaturing agent has poor compatibility with non-polar porphyrins, and therefore has a low molecular weight. The problem is that they are almost inaccessible.
  • the present invention has been made in view of the conventional technology, has excellent physical properties such as impact resistance, surface properties, and workability, and is suitable for various molded articles.
  • the purpose of the present invention is to provide a resin composition to be used, a method for producing the same, and a sheet and a foam obtained therefrom. Disclosure of invention
  • the present invention comprises (1) polytetrafluoroethylene (A) and a dispersant (B) having an average particle size of 0.1 to 800 / zm.
  • the amount of tetrafluoroethylene (A) is 0.001 to 50 parts by weight with respect to 100 parts by weight of the dispersant (B), and A fluororesin-containing resin composition in which lafluoroethylene (A) is fiberized (hereinafter referred to as “resin composition (I)”), and 2 an average particle diameter of 0.1 to 80.
  • resin composition (I) A fluororesin-containing resin composition in which lafluoroethylene (A) is fiberized
  • the styrene (A) and average particle size are 0.1 l 800 ⁇ m of the dispersant (B), and the amount of the polytetrafluoroethylene (A) was 100 parts by weight of the dispersant (B).
  • resin composition (I) in which the polytetrafluoroethylene (A) is fiberized; Fluorine resin-containing resin composition consisting of refine (C) (hereinafter referred to as resin composition ( ⁇ )) ), And 100 parts by weight of a dispersant (B) having an average particle diameter of 0.1 to 800 // m per 100 parts by weight of polytetrafluoroethylene (A). ) 0.001 to 50 parts by weight are preliminarily mixed under a high shearing force, and the polytetrafluoroethylene (A) is fiberized to obtain a resin composition.
  • a method of producing a resin composition ( ⁇ ) comprising producing the resin composition (I) and mixing the resin composition (I) and a polyolefin (C). 5 Polytetrafluoroethylene (A) and a dispersant (B) having an average particle diameter of 0.1 to 800 t / m (B) The amount of the phenol oleethylene (A) is 0.001 to 50 parts by weight with respect to 100 parts by weight of the dispersant (B), and the polytetrafluoroethylene is used.
  • the resin composition (I) in which the polyethylene (A) is fiberized is And a thermoforming sheet comprising a resin composition (() comprising polyolefin (C) and polytetrafluoroethylene (() A) and a dispersant (B) having an average particle size of 0.1 to 800 / m and the amount of the polytetrafluoroethylene (A) is
  • the dispersant (B) was 0.01 to 50 parts by weight with respect to 100 parts by weight, and the polytetrafluoronorethylene (A) was fiberized.
  • the present invention relates to a foam composed of a resin composition ( ⁇ ) composed of a resin composition (I) and a polyolefin (C).
  • the resin composition (I) of the present invention comprises polytetrafluoroethylene (A) and average particles. It is composed of a dispersant (B) having a diameter of 0.1 to 800 / m, and the amount of the polytetrafluoroethylene (A) is determined by the dispersant (B) 1 0.001 to 50 parts by weight with respect to 0.0 parts by weight.
  • Trafluoroethylene (A) is a fiberized composition, and the polytetrafluoroethylene (A) used in the present invention is mainly composed of: It is a component for improving the processability of the resin composition (I) obtained.
  • the resin composition (I) is converted into a fiber by the shearing force applied when the resin composition (I) is removed. It only needs to be a polytetrafluoroethylene o
  • a dispersion obtained by an emulsion polymerization method is not agglomerated. Powders, and powders comprising polymers obtained by the suspension polymerization method, and the like. Among these, the dispersion obtained by the emulsion polymerization method is agglomerated because of the fact that the fiber is easily formed into fibers by shearing force. Uda is preferred.
  • polytetrafluoroethylene (A) include, for example, Polyfluoro TFE — F103 and Polyfluoro TFE — F10 4, Polyfluorin TFE — F201 (hereafter, manufactured by Daikin Industries, Ltd.), Teflon TFE — 6J, Teflon TFE — 7J, Teflon 6C—J (the above, manufactured by Mitsui Dupont Fluorochemical Canole Co., Ltd.).
  • the average particle size of the polytetrafluoroethylene (A) is 100 when considering the ease of mixing with the dispersant (B) and the dispersibility. ⁇ 700 / zm, preferably 300-600 ⁇ ⁇ , more preferably 400-500 im.
  • the polytetrafluoroethylene (A) is mixed with a dispersant (B) under a high shearing force and fiberized.
  • the maximum fiber diameter of the fiber-reinforced polytetrafluoroethylene (A) is 10 m or less. Preferably, it is less than 5 / m, more preferably less than 2 // m, and the smallest fiber diameter is usually 0.01 m It should be at least about 0.10 tzm, preferably about 0.01 tzm. Furthermore, since fiberized polytetrafluoroethylene (A) has a network structure, its fiber length is generally determined. Cannot be determined. The fiber length is about 3 m or more, preferably about 5 / m or more, because workability is improved by increasing the tension during melting. Preferably, it is about 1 Om or more.
  • the resin composition (I) since the polytetrafluoroethylene (A) is fiberized in the resin composition (I), the resin composition (I) ),
  • the resin composition (I) when it is mixed with a polyolefin (C) described below, the effect of improving the processability exhibited by the obtained resin composition ( ⁇ ) can be reduced. It becomes even bigger.
  • the dispersing agent (B) used in the present invention is capable of effectively dispersing and fiberizing polytetrafluoroethylene (A), and also comprises a resin. It is a component that gives the resin composition (I) the improvement effects such as impact resistance, workability, and surface properties exhibited by the composition (I).
  • the dispersant (B) effectively disperses and fibrils the poly (tetrafluoroethylene) (A) and exhibits the above-mentioned improvement effect.
  • the dispersant (B) include, for example, Coregile Powders made of foot copolymers, polyolefin powders, inorganic powders, etc., may be used alone or in combination. The above can be used in combination.
  • core shell Powders comprising a raft copolymer are preferred.
  • a polyrefin powder is preferred.
  • the core-graft copolymer includes a cross-linked rubber-like polymer as a core layer, and a hard layer made of a vinyl-based compound as a seal layer.
  • This is a core-type graphite copolymer.
  • the concept of the core-shell graph copolymer is, for example, that a cross-linked rubber-like polymer forming a core layer and a hard shell component are graph-copolymerized. And the copolymer obtained.
  • Examples of the core rubber / graft copolymer include a crosslinked rubbery polymer (b—1) and a crosslinked rubbery polymer (b—1).
  • a graphite copolymer with a polymerizable vinyl compound (b-2) is preferably used.
  • the crosslinked rubber-like polymer (b-1) includes, for example, processability and impact resistance exhibited by the obtained core-graft copolymer.
  • a polymer having a glass transition temperature of 25 ° C or less is preferred.
  • the vinyl compound (b—2) includes a glass transition temperature of the homopolymer of the vinyl compound (b—2) of 25 ° C. or more. Certain monomers are preferred to avoid agglomeration of the core-shell graft copolymer.
  • glass transition temperature and the measuring method are as follows. Speaking of Polymer Node Book (INTERSCIENCE
  • the glass transfer temperature of the polymer is based on the following formula. The value determined based on
  • T g Gas of the copolymer consisting of component a and component b
  • the rubber-like polymer used as a raw material of the crosslinked rubber-like polymer (b-1) include, for example, gen-based rubber and acryl.
  • rubber such as rubber, rubber, silicone rubber, etc. They can be used alone or as a mixture of two or more.
  • benzene rubber examples include, for example, 60 to 100% by weight of the benzene rubber and other vinyl copolymerizable with the benzene rubber.
  • diene-based rubber containing 0 to 40% by weight of metal compounds.
  • ⁇ Jenic compounds used in self-generating rubber include, for example, benzene, isoprene, and black-mouthed plane. can give . They can be used alone or as a mixture of two or more. Among them, the viewpoint that the obtained core-shell graft copolymers are much more effective in improving processability and impact resistance. Therefore, butadiene is preferred o Examples of other vinyl compounds which can be copolymerized with the above-mentioned diene compound include styrene, ⁇ -methizolestyrene and the like.
  • Aromatic vinyl compounds of the following formula methyl methacrylate, methyl methacrylate, methacryloleic acid ⁇ — petinole, methacrylic acid i-petit Metal, methacrylic acid t-butyl, methacrylic acid 2 -ethylhexyl, methacrylic acid stearylsole, etc.
  • Alkyl ester of methyl acrylate having 1 to 22 carbon atoms in the kill group methyl acrylate, methyl acrylate, ethyl acrylate Acid n—butyl alcohol, acrylic acid i-methyl, acrylic acid t—butyl, acrylic acid 2—ethyl hexyl, acrylic acid Tear lily
  • the alkyl group has 1 to 22 carbon atoms of the alkyl group, alkyl acrylate ester; acrylonitrile, metalacryloyl.
  • Unsaturated nitrinole compounds such as nitrile; maleic anhydride, methacrylic acid, acrylic acid, methacrylonitrile amide, acrylonitrile Amido, dimethyl methacrylate amino, dimethyl acrylate amino, hydroxy methacrylate, hydroxymethyl Acid-free bases such as metal, hydroxyethyl creatate, glycidyl methacrylate, glycidyl acrylate, etc.
  • vinyl compounds having a reactive functional group such as carboxyl group, amino group, hydroxy group, epoxy group, etc. can give . They can be used alone or as a mixture of two or more.
  • the rubber comprising from 0 to 40% by weight, preferably from 0 to 30% by weight of the compound is processed by the obtained core-monograft copolymer. It is desirable because it improves the effect of improving the properties, impact resistance and surface properties.
  • a typical example of the above-mentioned acrylic rubber is, for example, an alkyl ester of acrylic acid having an alkyl group of 2 to 22 carbon atoms. 100% by weight and other vinyl compounds co-polymerizable with the alkyl acrylate ester 0 to 40% by weight. Les-related rubber etc. are exposed.
  • an alkyl ester of acrylic acid having 2 to 22 carbon atoms in the alkyl group used in the acrylic rubber is, for example, Acrylic acid, acrylic acid n — butyl, acrylic acid i — butyl acrylate, acrylic acid t — butyl, acrylic acid 2 — acrylate
  • Acrylic acid n — butyl acrylic acid i — butyl acrylate
  • acrylic acid t — butyl acrylic acid 2 — acrylate
  • examples include chilled hexyl and stearinol acrylate. They can be used alone or as a mixture of two or more. Among them, the process of improving the processability and impact resistance of the obtained cohesion enograft copolymer is far superior, and it is inexpensive. From this point of view, acrylic acid n-butyl is preferred.
  • vinyl conjugates copolymerizable with the above-mentioned alkyl acrylate are, for example, copolymerizable with the above-mentioned gen-based compound.
  • vinyl compounds having a reactive functional group such as a base may be used. They can be used alone or as a mixture of two or more.
  • the acrylic rubber is 60 to 100% by weight, preferably 65 to 100% by weight, of an alkyl acrylate ester. % And other vinyl compounds from 0 to 40% by weight, preferably from 0 to 35% by weight. This is desirable because it improves the processability and impact resistance of the shell-graft copolymer.
  • ethylene-propylene-jengom, butyrum-gum and the like can be used as the above-mentioned rubbers.
  • silicone rubber examples include, for example, a polymethylsiloxango rubber.
  • cross-linking rubber-like polymers such as the aforesaid jen-type rubber, acryl-type rubber, olefin-type rubber, silicone rubber and the like.
  • a crosslinked rubbery polymer (b-1) can be obtained.
  • the method for the crosslinking is not particularly limited.
  • the bridge gel content of the obtained crosslinked rubbery polymer (b-1) is adjusted so as to be 50% by weight or more, preferably 60% by weight or more. And are desired. If the amount of the crosslinked gel is not less than the lower limit, the obtained resin composition (I) may be, for example, a polyolefin (C) described later. Distributed to In the case of using the obtained resin composition ( ⁇ ), the resin composition applied to the roll surface when performing calendar molding, etc. However, there is a tendency that no plate is formed and the effect of improving workability is sufficiently exhibited.
  • the crosslinked gel content is defined as, for example, the crosslinked rubbery polymer is immersed in a good solvent of a rubber component such as toluene or methyloketketone for 48 hours.
  • the figure shows the percentage of insoluble matter separated by the ultracentrifuge after the separation.
  • the vinyl compound (b—2) can be copolymerized with, for example, a diene compound in the example of the cross-linked rubbery polymer (b—1).
  • Aromatic vinyl compounds exemplified as other vinyl compounds; alkyl acrylates having 1 to 22 carbon atoms in the alkyl group; Alkyl acrylate having 1 to 22 carbon atoms in the alkyl group; Unsaturated nitrile compound; Acid anhydride group, carboxyl
  • vinyl compounds having a reactive functional group such as a group, an amino group, a hydroxyl group, or an epoxy group. They can be used alone or as a mixture of two or more.
  • the vinyl compound (b-2) at least one of the aromatic vinyl compound and the alkyl methacrylate ester is used. 1100% by weight ⁇ and other vinyl compounds that can be copolymerized with these components 00-50% by weight may cause a decrease in polymerizability or cost up. It is preferable because it is difficult.
  • the aromatic vinyl compounds include styrene and ⁇ -methylstyrene.
  • Particularly preferred is an alkyl ester of methacrylolinoleic acid, in which the alkyl group has 1 to 1 carbon atoms.
  • the ester of 4 is particularly preferred.
  • the core-graft copolymer is obtained by graft-polymerizing a vinyl compound (b-2) with a crosslinked rubber-like polymer (b-1). It is obtained by
  • the amount of the rubbery polymer (b-1) should be 40% by weight or more, that is, the amount of the vinyl compound (b-2) should be 60% by weight or less. Is preferred. Further, in order to prevent the core-silica-graft copolymer from agglomerating, the amount of the crosslinked rubber-like polymer (b-1) should be 95% by weight or less. In particular, the amount of the vinyl compound (b-2) should be 5% by weight or more, especially 10% by weight or less, that is, 90% by weight or less. And are preferred.
  • the core-graphite copolymer can be obtained by a conventional radical polymerization method, for example, a suspension polymerization method or an emulsion polymerization method. Any polymerization method can be employed. Among these, the emulsification polymerization method is preferred from the viewpoint that control such as particle diameter and particle structure is easy.o
  • the average particle size of the thus obtained core-shell graphit copolymer is intended to improve the surface properties of the obtained resin composition (I). Considering this, it should be less than 3 // m, preferably less than 2.5 m.
  • the obtained core-graft copolymer can be obtained by adding an acid, a salt, a coagulant and the like during the polymerization. The particles can be enlarged to form a powder having a specific average particle size described later.
  • Such Corel Graph Typical examples of copolymers include Kaneace B, Kanease M, and Kanease FM (all manufactured by Kaneka Chemical Co., Ltd.). Etc. are exterminated.
  • polyrefin powder of the dispersant (B) include, for example, polypropyrene, high-density polyethylene, and low-density polyethylene.
  • Polyethylene Linear Low Density Polyethylene, Poly1 — Butene, Polyisobutylene, Propylene and Echilen, and Z Or 1-random or block copolymer in any ratio with butene, in any ratio of ethylene and propylene Ethylene-Propylene-Jen terpolymer, Polymethylenolepentene, Cyclopentene having 10% or less by weight of a gen component Cyclic polyolefins, such as copolymers of evening gen with ethylene and / or propylene, ethylene or propylene Pyrene and 50% by weight or less, such as vinyl acetate, alkyl methacrylate ester, alkyl acrylate ester, and Yoshika Random, block or graphitic copolymers with vinyl compounds such as group vinyl, etc. have
  • propylene powder obtained by polymerizing a monomer component containing 50% by weight or more of propylene is used.
  • Powder comprising a polyolefin and a propylene polyolefin, and a simple substance containing 50% by weight or more of ethylene. It is a mixture with an ethylene-based olefin obtained by polymerizing the monomer components, and the amount of the ethylene-based olefin is determined by the amount of the ethylene-based olefin.
  • a mixture of 0.1 to 100 parts by weight based on 100 parts by weight is preferred because it is versatile and low cost
  • Representative examples of the inorganic powder of the dispersant (B) include, for example, heavy calcium carbonate, light calcium carbonate, evening water, and glass fiber. , Magnesium carbonate, my strength, kaolin, calcium sulfate, barium sulfate, titanium dioxide, white carbon, carbon Inorganic powders such as bomb black, hydroxide hydroxide, alumina oxide, magnesium hydroxide, molten silica, etc. It is. They can be used alone or as a mixture of two or more. Among them, from the viewpoint of availability, heavy calcium carbonate, light potassium carbonate and talc are preferred.
  • a powder, a polyrefin powder and an inorganic substance comprising the above-mentioned core-graft copolymer.
  • thermoplastics there are also thermoplastic elastomers such as blocks of styrene and butadiene or random copolymers.
  • a powder consisting of a crosslinked elastomer such as hydrogenated product, polybutadiene and the like and a hydrogenated product thereof are mixed with a dispersant (B).
  • the dispersant (B) has an average particle diameter of 0.1 to 800 m.
  • the average particle size of the dispersant (B) is less than 0.1 m and if it exceeds 800 / m, polytetrafluoroethylene is used.
  • the resin (A) is not sufficiently dispersed and fibrous, the molded product obtained by using the resin composition (I) is treated with polytetrafluoroethylene (A). Lumps remain and surface properties As a result, the effects of improving impact resistance, surface properties, workability, etc., become insufficient.
  • the average particle size is 50 m or more, preferably 100 m or more, and 700 m / m or less, preferably 500 m or less. I want something o
  • the average particle size of the dispersant (B) is such that different tile sizes of about 6 sizes are piled up in descending order of the mesh size. Pour the dispersant (B) dispersed in water using a surfactant, and calculate from the weight ratio of the dispersant (B) accumulated in each mesh according to the particle size diagram. Get out.
  • the average particle diameter can be measured by other general powder measurement methods.
  • the method for adjusting the average particle diameter of the dispersant (B) so as to fall within the above range is not particularly limited.
  • any method of controlling the particle size of the powder such as agglomeration, grinding, sieving, etc., can be used.
  • the average particle size of a powder composed of a coercie-dahlaf copolymer can be adjusted by agglomeration as described above. it can .
  • the average particle size of the polyrefin powder can be adjusted by controlling the particle size during polymerization or changing the conditions during freeze-milling.
  • the average particle size of the inorganic powder can be adjusted by pulverization and sieving.
  • the resin composition (I) of the present invention is obtained by mixing a polytetrafluoroethylene (A) and a dispersant (B) under a high shear force. By making the fiber (A) sufficiently fibrous, it can be strengthened.
  • the amount of the polytetrafluoroethylene (A) is from 0.001 to 50 parts by weight based on 100 parts by weight of the dispersant (B). It is. As long as the amount of such polytetrafluoroethylene (A) is extremely small, the processability imparted to the resin composition (I) is not sufficient. Any improvement effect will be insufficient. In addition, when the amount of polytetrafluoroethylene (A) is too large, it is difficult to reduce the cost. The versatility is reduced, and the fiberized polytetrafluoroethylene (A) is more likely to form aggregates. From the above viewpoint, the amount of polytetrafluoroethylene (A) is preferably at least 0.01 part by weight based on 100 parts by weight of the dispersant (B). More than 0.05 parts by weight, more preferably more than 0.01 parts by weight, and less than 50 parts by weight, preferably less than 40 parts by weight. More preferably not more than 30 parts by weight
  • Polytetrafluoroethylene (A) and a dispersant (B) are mixed under high shear to disperse Polytetrafluoroethylene (A).
  • a stirring and mixing method using a stirrer such as a hensyl mixer, for example, a single screw extruder, a twin screw extruder, etc.
  • a melt kneading method using an extruder, a roll kneader, or the like can be employed.
  • the above-mentioned stirring and mixing is carried out. There are no particular restrictions on operating conditions such as the method and the melt-kneading method.
  • the stirring and mixing method has an advantage of low cost, and the melt-kneading method can use a pellet-shaped resin composition (I). There are advantages.
  • the poly (tetrafluoroethylene) (A) and the dispersant (B) are mixed at room temperature.
  • the mixture may be stirred and mixed with each other, or both may be heated to a temperature at which both are not deteriorated or deteriorated, and then mixed with stirring.
  • the stirring and mixing method and the melt-kneading method can be used in combination.
  • the mixture is obtained.
  • the extruded mixture can be melt-kneaded using an extruder and extruded to produce pellets 0
  • the resin composition (I) of the present invention is produced as described above, and the resin composition (I) expresses the resin composition (I).
  • Add additives such as stabilizers, lubricants, nucleating agents, etc., as needed, in order to further enhance the effect of improving, for example, surface properties. be able to .
  • the additive may be added to other components at the time of stirring and mixing or melt kneading, for example, and the timing of addition is not particularly limited.
  • stabilizers include, for example, pentaerythritolyl teretrax [3— (3,5—di-t-butynole 4-hide) Roxy vinyl) Propirate], Tri-legging connector [3-(3-t-Petit 5-Metizoret) 4—Hydroxyphenyl) propionate] and other phenolic stabilizers, and tris (monononylvinyl) phospho Phosphites and other phosphorus-based stabilizers, such as phosphates and tris (2, 4—Jetyl phenyl phenyl), dilauryl thiodipro Dioxin-based stabilizers such as pionates are required.
  • pentaerythritolyl teretrax 3— (3,5—di-t-butynole 4-hide) Roxy vinyl) Propirate
  • Tri-legging connector [3-(3-t-Petit 5-Metizoret) 4—H
  • the amount of the stabilizer is usually about 0.01 to 3 parts by weight relative to 100 parts by weight of the dispersant (B). Preferably, it is about 0.05 to 2 parts by weight.
  • Typical examples of the lubricant include saturated or unsaturated fatty acids such as, for example, raurilic acid, palmitic acid, oleic acid, and stearic acid. Sodium, cascade, magnesium salt, etc. are exposed. They can be used alone or as a mixture of two or more.
  • the amount of the lubricant is usually about 0.1 to 3 parts by weight, preferably about 0.1 to 2 parts by weight, based on 100 parts by weight of the dispersing agent (B). Is desired.
  • nucleating agent examples include, for example, sodium benzoate, bisbenzylidene sonore, and vis (p-methyl) Benzylidene) Solbitol, bis (p-ethylbenzylidene) Sonorebito Nore, Sodium 1-2, 2—Methylenbi (4, 6 — di-t — butyl phenol) Phosphite, phenol, titanium oxide, azo phenol — T — Petite Benzoate. They can be used alone or as a mixture of two or more.
  • the amount of the nucleating agent is usually about 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the resin composition (I). It is hoped that it is about.
  • the nucleating agent is used in an amount of about 0.01 to 10 parts by weight, preferably 0,:! To 5 parts by weight, based on 100 parts by weight of the resin composition (I). It can be added to the dispersant (B) so that the amount becomes about parts.
  • the resin composition (I) of the present invention can impart physical properties such as excellent workability, impact resistance, surface properties, and the like, as described later. It can be used as a modifier for the resin composition (II) containing the polyolefin (C).
  • the resin composition ( ⁇ ) of the present invention has a polytetrafluorophenol (A) and an average particle size of 0.1 to 800 / zm. (B), and the amount of the poly (ethylene glycol) ethylene (A) is 0.0 with respect to 100 parts by weight of the dispersant (B). 0 to 50 parts by weight, and a resin composition in which the polytetrafluoroethylene (A) is fiberized.
  • a composition comprising (I) and a polyolefin (C).
  • the core-graft copolymer is a polytetrafluoroethylene copolymer. It is preferable from the viewpoint of the dispersibility of the polyethylene (A), the impact resistance of the obtained molded article, and the like, and among them, the obtained resin composition (II) In consideration of the thermal coloring of the resulting molded article, a copolymer that does not deteriorate thermally at the molding temperature of polyolefin (C) is preferred.
  • the above-mentioned polyrefin powder of the dispersant (B) is easily dispersed in the polyrefin (C) and is inexpensive. Is better. Among them, powders that can easily mix the resin composition (I) and the polyolefin (C) are obtained. O It is preferable because it does not leave foreign matter on the molded body and improves its surface properties and transparency.
  • the melt flow of the polyolefin (C) is used.
  • a polyrefined powder that has a similar amount of index to the index as the dispersant (B).
  • the refractive index of the dispersant (B) is determined from the viewpoint that the transparency of the obtained resin composition ( ⁇ ) can be further improved. Preferably, it is substantially the same as that of the refine (C).
  • the fact that the refractive indices are practically the same means that the difference between the two refractive indices is 0 to 0.02. Further, from the viewpoint that the transparency of the resin composition (() can be further improved, the difference in the refractive index is 0 to 0.01, Preferably it is between 0 and 0.05.
  • the refractive index is determined, for example, by Polymer Handbook (John Wiley and Sands Inc.). ), Third Edition, 1989), and the refractive index of the polymer is calculated proportionally based on the weight fraction of the constituent monomers. This is the value obtained.
  • dispersant (B) which is a core-graft copolymer.
  • a powder having a refractive index substantially the same as that of polypropylene for example, has an emulsifying weight.
  • the resulting powder, n-acrylic acid n-butyl 70% by weight, and the styrene 30% by weight Ingredient 100% by weight 70% by weight of cross-linked acrylic rubber obtained by emulsion polymerization of a monomer to which 1 part by weight of acrylic acid was added, and methyl methacrylate 2 Monomer composition consisting of 7% by weight and 3% by weight of styrene
  • a powder made of a copolymer obtained by copolymerizing a component with a polymer is obtained.
  • Polyolefins (C) used in the resin composition ( ⁇ ) include, for example, polypropylene, high-density polyethylene, and low-density polyethylene.
  • Polyethylene Linear Low Density Polyethylene, Poly1 — Butene, Polyisobutylene, Propylene and Echilen, and Or 1 — random or block copolymer in any ratio with the pentene, any ratio between the ethylene and the propylene in any ratio Ethylene-Propylene-Jen ternary copolymers, polymethylpentenes, cyclopentanes with a gen content of 10% by weight or less Cyclic polyolefins, such as copolymers of tagenes with ethylene and propylene, or ethylene, or propylene Less than 50% by weight of len, such as vinyl acetate, alkyl acrylate methyl ester, alkyl acrylate acrylic ester, and aromatic compounds Random, block or graft copolymers with vinyl compounds such as
  • propylene obtained by polymerizing a monomer component containing 50% by weight or more of propylene is used.
  • Polymerization of propylene-based olefins, and the propylene-based olefins, and a monomer component containing 50% by weight or more of ethylene It is a mixture with the obtained ethylene-based olefin, and the amount of the ethylene-based olefin is the amount of the propylene-based olefin.
  • Mixtures in an amount of 0.1 to 100 parts by weight to 100 parts by weight of fine powder are preferred from the viewpoint that they are easily available and inexpensive.
  • propylene-based olefins described above At least one selected from propylene, ethylene-propylene random copolymer and ethylene-propylene block copolymer.
  • propylene ethylene-propylene random copolymer
  • ethylene-propylene block copolymer One is preferred because it is readily available and inexpensive.
  • ethylene-based polyolefins low-density polyethylene, linear low-density polyethylene, and high-density polyethylene are included. At least one selected from the group is preferred because it is readily available and inexpensive.
  • the index of melt mouth is less than 10 g ⁇ 10 minutes, preferably 5 g 10. Or less, more preferably 2.5 g Z 10 minutes or less, the effect of high tension on melting and excellent workability. Is desired because it is sufficiently expressed.
  • the melt flow index can be weighed 2.16 kg in accordance with the method described in ASTMD 1 238, and is a propylene-based polyreflection. The temperature is measured at 230 ° C for olefins, and at 190 ° C for ethylene-based polyrefin.
  • the refractive index of the dispersant (B) and the refractive index of the polyolefin (C) are practically the same. It is preferred that the dispersant (B) and the polyrefin (C) are appropriately selected and used so that
  • the refractive index of a typical polyolefin (C) is, for example, that the refractive index of polypropylene is 1.503, and that of high-density polyolefin.
  • the refractive index of the lens is 1.545
  • the refractive index of the low-density polyethylene is 1.51
  • the refractive index of the linear low-density polyethylene is 1.52
  • the refractive index of the port Li main Chi le pen Te emissions is Ru 1. 4 5 9 to 1.4 6 5 teeth 5 fit.
  • the resin composition ( ⁇ ) of the present invention comprises the resin composition (I). And a polyrefin (C) can be obtained by mixing them.
  • the amount of the resin composition (I) is determined in order to sufficiently improve the effect of the obtained resin composition ( ⁇ ) such as processability imparted to the obtained resin composition ( ⁇ ). It is preferred that the amount be 0.01 parts by weight or more, preferably 0.05 parts by weight or more, based on 100 parts by weight of the olefin (C). In order to reduce the cost and enhance the versatility, the amount of the resin composition (I) is set to 100 parts by weight of the polyolefin (C). It is desired that the amount be no more than 20 parts by weight, preferably no more than 10 parts by weight, and more preferably no more than 6 parts by weight.
  • the amount of the resin composition (I) with respect to the polyrefin (C) is adjusted so as to be within the above range.
  • the polytetrafluoroethylene (A) and the dispersant (B) that constitute the resin composition (I) are each used. Is preferably contained in the resin composition (II) within the following range.
  • the amount of the polytetrafluoroethylene (A) is set so that the effect of improving the workability can be sufficiently improved. It is desired that the amount be at least 0.01 parts by weight, preferably at least 0.05 parts by weight, based on 0 parts by weight. In addition, the amount of the polytetrafluoroethylene (A) is set to a value that is low in order to reduce cost and enhance versatility. (C) 100 parts by weight or less, preferably not more than 10 parts by weight, preferably not more than 5 parts by weight, and more preferably not more than 3 parts by weight. Yes.
  • the amount of the dispersant (B) is such that the polytetrafluoroethylene (A) is effectively dispersed and fiberized. In order to achieve this, at least 0.002 parts by weight, and preferably at least 0.25 parts by weight, of 100 parts by weight of the polyolefin (C). I want to. In addition, the amount of the dispersant (B) is determined by the amount of the polyolefin (C) in order to sufficiently exhibit the inherent properties such as heat resistance and rigidity. (C) 100 parts by weight or less, preferably 100 parts by weight or less, more preferably 70 parts by weight or less, and more preferably 50 parts by weight or less. I want it.
  • the method of mixing the master batch and the polyrefin (C) is not particularly limited, and includes, for example, an extrusion mixing method and a roll mixing method. Which can be adopted.
  • the mixing conditions depend on the types of polytetrafluoroethylene (A), dispersant (B), and polyolefin (C) used. It is preferable to adjust it appropriately.
  • the resin composition ( ⁇ ) of the present invention is produced as described above.
  • the resin composition ( ⁇ ) may be, for example, an inorganic filler or a nucleator. Agents, stabilizers, lubricants, etc. can be mixed. Such inorganic fillers, nucleating agents, stabilizers and lubricants are used, for example, when the resin composition (I) is mixed with the polyolefin (C). O o
  • the inorganic filler is used in a calendar molding process to improve the rigidity, heat resistance, paintability, printability, etc. of the obtained resin composition ( ⁇ ). Prevents sticking to the roll surface, improves the additivity, improves the surface properties of the obtained molded body, and has the property of realizing a lower cost.
  • a typical example of the inorganic filler is heavy carbonic acid.
  • Carbonate such as canole gum, light calcium carbonate, etc., talc, glass fiber, magnesium carbonate, my strength, kaolin, Calcium sulfate, sulfuric acid sulfate, titanium dioxide, white carbon, carbon black, hydroxylated aluminum, Magnesium hydroxide, molten silica, etc. are required. They can be used alone or as a mixture of two or more. Among them, from the viewpoint of availability, calcium carbonate such as heavy calcium carbonate and light calcium carbonate, and tanole Is preferred.
  • the average particle diameter of the inorganic filler is about 10 // m or less, and preferably about 5 m or less, depending on the resin composition ( ⁇ ) obtained. This is desirable from the viewpoint of improving the surface properties.
  • the amount of the inorganic filler is 0.1 part by weight with respect to 100 parts by weight of the polyolefin (C) so that the effect of improving rigidity and the like can be sufficiently exhibited. It should be at least 1 part by weight, preferably at least 1 part by weight.
  • the amount of the inorganic filler is preferably 100 parts by weight of polyolefin (C). It is desired to be less than 400 parts by weight, preferably less than 350 parts by weight, and more preferably less than 300 parts by weight.
  • the nucleating agent is a component having the property of improving the transparency, surface properties, and rigidity of the obtained resin composition ( ⁇ ).
  • nucleating agent examples include, for example, compounds exemplified as nucleating agents that can be used in the production of the resin composition (I). Is exacerbated. They can be used alone or as a mixture of two or more.
  • the amount of the nucleating agent has the effect of improving transparency and surface properties. In order to sufficiently improve the content, it is required to be at least 0.01 part by weight, preferably at least 0.05 part by weight, based on 100 parts by weight of the resin composition. This is what you want.
  • the amount of the nucleating agent is 2 parts by weight with respect to 100 parts by weight of the resin composition (() so as not to reduce the transparency. Less than 1.5 parts by weight, preferably less than 1.5 parts by weight.
  • the stabilizer examples include the compounds exemplified as the stabilizer that can be used in the production of the resin composition (I). . They can be used alone or as a mixture of two or more.
  • the amount of the stabilizer is usually about 0.01 to 3 parts by weight, preferably 0.05 to 100 parts by weight of the polyolefin (C). It is desired to be about 2 parts by weight.
  • the lubricant examples include the compounds exemplified as lubricants that can be used in the production of the resin composition (I). They can be used alone or as a mixture of two or more.
  • the amount of the lubricant is usually about 0.1 to 3 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the polyolefin (C). Parts.
  • polytetrafluoronorylene (A) and a dispersant (B) having a specific average particle size are used in a specific weight ratio, and these are used.
  • the resin composition (I) is produced by mixing under high shearing force to make the polytetrafluoroethylene (A) into fibers, and then preparing the resin composition (I).
  • One of the great features is that the mixture of I) and the polyrefin (C).
  • the obtained resin composition ( ⁇ ) the fully fiberized polytetrafluoroethylene (A) is uniformly obtained. By dispersing, the appearance of the molded article obtained from the resin composition (II) is improved.
  • the tension at the time of melting increases, causing the sheet to be easily taken off during molding of the calendar, and the molten resin to be drawn down during thermoforming or blow molding.
  • cell foaming during foam molding is improved, and the moldability by calendar molding, thermoforming, pro-molding, foaming molding, etc. is improved.
  • the amount of discharge during extrusion and the surface condition of the extruded body such as a sheet and a film are improved, and the extrudability is improved.
  • the polytetrafluoroethylene can be obtained.
  • the blocking of the styrene (A) has been improved, and the mixing of the polytetrafluoroethylene (A) and the polyolefin (C) has been improved. It has become easier.
  • the resin composition ( ⁇ ) of the present invention has significantly improved workability, impact resistance, and surface properties. Therefore, when the conventional resin composition is used, the resin composition (III) is used even if it is difficult to mold the resin composition. In some cases, various useful moldings can be produced.
  • Examples of the molding method used for the resin composition (II) include a calendar molding method, an extrusion molding method, a thermal molding method, an injection molding method, and a blow molding method. -Molding method, foam molding method, etc. are required.
  • the molding method used to produce the thermoforming sheet of the present invention does not impair the transparency of the resulting sheet.
  • an extrusion molding method using, for example, a single-screw extruder or a twin-screw extruder is preferably used.
  • calendar molding it is possible to perform calendar molding on the sheet for thermal molding obtained by the extrusion molding method, for example.
  • the thickness of the thermoforming sheet obtained as described above is not particularly limited, and may be appropriately adjusted according to the purpose of use.
  • the thickness of such a sheet is usually preferably about 0.05 to 3 mm.
  • the sheet for thermoforming of the present invention has improved transparency, and particularly improved workability and surface properties. Therefore, when the conventional sheet was used, the thermoforming sheet was used even if the method was difficult to mold. In some cases, it is possible to produce various useful thermoformed bodies.
  • thermoforming method applied to the thermoforming sheet of the present invention include, for example, a vacuum forming method and a pressure forming method. By these thermoforming methods, it is possible to obtain a thermoformed body having excellent transparency, surface properties, etc.
  • the foam of the present invention can be obtained by performing foam molding using the resin composition ( ⁇ ) and a foaming agent.
  • the foaming agents used in the present invention include volatile foaming agents (physical foaming agents) and decomposable foaming agents (chemical foaming agents), and have a high foaming ratio.
  • a volatile foaming agent is preferable from the viewpoint that a foam is easily obtained.
  • volatile foaming agents include, for example, aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons, and fluorinated aliphatic hydrocarbons.
  • aliphatic hydrocarbon For example, propane, butane, pentane, hexane, etc. are given.
  • chlorinated aliphatic hydrocarbon include, for example, methyl chloride, methylene dichloride and the like.
  • the above-mentioned fluorinated aliphatic hydrocarbons include, for example, trichloro-mouth monofunctional fluoromethane (Fleon-11), dichlorodiphenylene For example, Rometan (Freon-1 12), dichlorotetrafluorofluoroethane (Freon-1 114), etc. can be produced. They can be used alone or as a mixture of two or more. Of these, aliphatic hydrocarbons are the most preferred, given the recent environmental concerns.
  • decomposable foaming agent examples include, for example, azodicarbonamide, trihydrazinotriazine, benzenesulfur Semi-solid Solenoid, Jizoamino Benzene, N, ⁇ '— Ginitorosopentamethylenetetramine, ⁇ , N'- Chinole N, N '— Ginitroterev olenoic acid imide, azodicarboxylic acid olevonic acid, rhodium, ⁇ , ⁇ ' — oxbisbenzene Surhonyl hydrazide, etc. can be obtained. They can be used alone or as a mixture of two or more. ⁇
  • the amount of the foaming agent is from 1 to 50 parts by weight based on 100 parts by weight of the resin composition ( ⁇ ) from the viewpoints of the expansion ratio of the foam to be obtained, the stability of the cells, and the surface properties. It is desired to be present in parts by weight, preferably 5 to 40 parts by weight.
  • the foam molding method for example, a molding method such as an extrusion foam molding method or a bead foam molding method can be employed.
  • the extrusion foaming method is preferred from the viewpoint that the productivity of the foam is excellent, and a foam having a high expansion ratio is obtained.
  • Bead foam molding is preferred from the viewpoint of It is better.
  • the foam obtained by the extrusion foaming method is a low cost foam, and the foam obtained by the bead foaming method is It is a foam with excellent dimensional accuracy, appearance, etc.
  • a single-axis extrusion in which a die having a shape corresponding to the shape of a desired molded body is attached. It is preferable to use a machine or a twin-screw extruder.
  • the molding temperature is a temperature equal to or higher than the melting point of the polyolefin (C) or a temperature equal to or higher than the decomposition temperature if a decomposable foaming agent is used. It is preferred that the temperature be lower than the temperature at the tip of the cylinder.
  • the expansion ratio of the foam obtained as described above is preferably 2 to 10 times, preferably 3 to 8 times, and the foam is preferably For example, it can be used for thermal insulation, building materials, structural materials, etc.
  • the pellet of the resin composition ( ⁇ ) and the volatile foaming agent are hermetically sealed. After encapsulating the pellet in a container and holding it at about 20 to 90 ° C for 5 to 20 hours to impregnate the pellet with the volatile foaming agent, remove the pellet from the closed container. The pellets are heated and pre-foamed by water steam, hot water, hot air, etc. to produce pre-foamed particles. Next, the obtained pre-expanded particles are filled into a mold having, for example, a water vapor passage hole, and heated to obtain a foam.
  • the expansion ratio of the foam obtained as described above is 10
  • the foam may be, for example, insulation, cushioning material, bumper core, etc. It can be used as a material.
  • the resin composition ( ⁇ ) may be produced by calendar molding or extrusion molding to produce a film-shaped molded article. And can be done. Also, for example, by injection molding or blow molding using a pellet produced by molding from the resin composition (II), It is possible to produce injection moldings or hollow moldings, respectively.
  • the crosslinked polybutadiene rubber was obtained by emulsion polymerization of butadiene.
  • the average particle size of the obtained crosslinked polybutadiene rubber was 0.25 / im, and the crosslinked gel content was 85% by weight.
  • the latex (glass transfer temperature: 180 ° C) of the crosslinked polybutadiene rubber was added to 75 parts by weight (solid content) of methyl methacrylate.
  • Glass transition temperature: 100 ° C.) 25 parts by weight of a monomer component consisting of 10 parts by weight was added, and no graphite copolymerization was carried out by emulsion polymerization.
  • a core copolymer copolymer (hereinafter referred to as copolymer (b) -1) was obtained.
  • the final conversion was 98%, and the average particle size of the copolymer (b) -1 was 0.26 m.
  • Acrylic acid n-butyl alcohol 100 parts by weight and a monomer component consisting of 1 part by weight of methacrylic acid acrylate are cross-linked acrylic by emulsion polymerization. I got rubber.
  • methacrylic acid was used as a cross-linking agent and a graphitizing agent.
  • the average particle size of the obtained bridged acrylic rubber was 0.2 m, and the crosslinked gel content was 85% by weight.
  • the latex (glass transition temperature: about 154 ° C.) of the crosslinked acrylic rubber was added to 70 parts by weight (solid content) of methyl methacrylate (methyl methacrylate).
  • copolymer (Glass transition temperature when used as a homopolymer: 20 ° C) A monomer component consisting of 5 parts by weight (only the monomer component was used as a polymer. (Glass transition temperature at this time: about 8.8 ° C) 30 parts by weight are added, and graphite copolymerization is not performed by emulsification polymerization. Foot copolymer (hereinafter referred to as copolymer)
  • Polypropylene (Mesolet flow index at 230 ° C: 0.5 g Z 10 min, powder (average particle size): 250 m, below , PP-1) 100 parts by weight of polytetrafluoroethylene (Polyflon TFE-F104, 2 parts by weight of B are added, and these are stirred at a high speed for 5 minutes at room temperature using a benzyl mixer. PTFE was fiberized to obtain a resin composition (A).
  • a resin composition (B) was prepared in the same manner as in Example 1 except that the amount of PTFE was changed to 20 parts by weight in Example 1.
  • Example 1 except that the copolymer (b) -1 was used instead of PP_1, a resin composition (C) was obtained in the same manner as in Example 1. Was.
  • Example 2 PP—110 parts by weight was changed to PP—150 parts by weight and copolymer (b) —150 parts by weight.
  • Resin composition (D) was obtained in the same manner as in (2).
  • Example 4 a resin composition (A ') was obtained in the same manner as in Example 4 except that PPTFE was not used.
  • Example 5 PP—250 parts by weight and copolymer (b) —250 parts by weight were changed to PP—110 parts by weight, and the amount of PTFE was 2 parts by weight. Other than the above, a resin composition (F) was obtained in the same manner as in Example 5.
  • Example 7 the resin compositions (H) to (L) and the resin composition were changed in the same manner as in Example 7 except that the composition was changed as shown in Table I-11. (B ') to (D').
  • PP-3 in Table 1 indicates the melt-to-inlet force at 230 ° C. 3.
  • the average particle size is 700 / m. Represents propylene powder.
  • Resin composition Example No. Components agitated with a henshenole mixer Components kneaded with a twin-screw extruder
  • the melt tension (g) of the obtained pellets was determined using a capillary graph (manufactured by Toyo Seiki V) having a die with a diameter of 2 mm and a length of 10 mm. , At 200 ° C, at an extrusion speed of 20 mm, and at a pull-out speed of 1 m / min. The results are shown in Table I-12.
  • the pellets obtained were roll-kneaded at 200 ° C to prepare a sheet.
  • the sheet was press-molded to obtain a test piece compliant with the following ASTM test.
  • test piece Using the test piece, apply the method described in ASTM-D256 and the method described in ASTM-D790, and conduct a razor impact resistance test and a bending elasticity test in accordance with the method described in ASTM-D790. Was carried out. The results are shown in Table I-12.
  • a sheet having a size of 100 mm X 10 mm and a thickness of 1.5 mm is formed from the pellet, and an opening of the sheet has a width of 76 mm.
  • the sheet was fixed with a clamp to a size of X76 mm and left for 30 minutes in an oven set at 190 ° C. Then, the K-down (mm) at the center of the sheet was measured. The results are shown in Table I-12.
  • A The surface is homogenous, and no fibrous aggregates are observed.
  • a pellet was manufactured in the same manner as in Example 13 except that the composition was changed as shown in Tables I-12 and I-3 in Example 13; Test pieces and sheets were prepared using the pellets.
  • the LDPE in Table I-2 and Table I-13 has a melt flow index at 190 ° C of 0.25 g Z10 min. Represents density polyethylene.
  • composition (weight part)
  • the polyrefin (C) and the polyrefin and / or core-graft copolymer are A resin composition (A) in which the poly (tetrafluoroethylene) (A) is mixed with the poly (tetrafluoroethylene) (A), and the polytetrafluoroethylene (A) is fiberized.
  • (L) has a higher melting tension than the resin compositions obtained in Comparative Examples 5 to 11, and can be formed by thermoforming or blow molding. It can be seen that the drawdown power, which is an indicator, is extremely small and has a significantly improved workability. Furthermore, the surface condition of the molded article (sheet) obtained from the resin composition ( ⁇ ) of Examples 13 to 28 was good, and the appearance was improved. This is the strength.
  • Example 16 a very thin section cut out of the roll sheet obtained in Example 16 was stained with ruthenium tetroxide, and this was used as a transmission type.
  • the resin composition ( ⁇ ) was observed under an electron microscope (magnification: ⁇ 1000) to examine the presence of polytetrafluoroethylen (A) in the resin composition ( ⁇ ).
  • PTF E had a diameter of about 0.05 to 0.3 / / 1 and a length of about 5 to 20 ⁇ , and was fibrous.
  • Example 13 light-weight calcium carbonate (average particle diameter: 0.15 m) surface-treated with a fatty acid as an inorganic filler was used. Same as Example 13 except that 50 parts by weight of the light calcium carbonate was added to 100 parts by weight of indium (C), and the composition was changed as shown in Table I-14. Then, a pellet was manufactured, and a test piece and a sheet were prepared using the pellet.
  • composition (weight part)
  • Resin composition index rate (kg / down
  • Pellet of phomopolypropylene which is a polyolefin (C) with the amount of resin composition shown in Table II-1 (trade name: Hypopoly) Ru-B200, manufactured by Mitsui Petrochemical Industry Co., Ltd., refractive index: 1.503, methylo-fluoro-index: 0.5 g ZIO, below, high Using a single-screw extruder (screw diameter: 40 mm, LZD: 28) at 100 ° C, 500 parts by weight (port B) The mixture was extruded and kneaded at rpm to obtain a pellet of the resin composition.
  • Table II-1 trade name: Hypopoly
  • Ru-B200 manufactured by Mitsui Petrochemical Industry Co., Ltd.
  • refractive index 1.503
  • methylo-fluoro-index 0.5 g ZIO
  • the core phenolic copolymers having an average particle size of 24.6 m, 14.7 m or 7 O / zm used in Examples 3 to 5 were obtained from Prepare Ness FM by sieving using a 60-mesh timer tile or a 140-mesh timer.
  • the average particle size of the core-graft copolymer remaining on the 60-mesh tile flyer was 24 6 / m, and the 60-mesh
  • the average particle size of the core-graft copolymer that has passed through the insulators and remained in the mesh-type tire tray is 140. 4 7 // m, the average particle diameter of the core graft copolymer passed through the mesh tile array was 140 m. .
  • Comparative Example 2 a predetermined amount of Hyper B and TFE-F was used without using the core-graft copolymer and the single-screw extruder was used. And extruded and kneaded in the same manner to obtain pellets of the resin composition.
  • the resin composition was roll-kneaded at 200 ° C. for 3 minutes to produce a sheet having a thickness of 1 mm. Two sheets obtained are overlapped and this is 200. After press-molding with C at 30 kg Z cm 2 and 10 minutes, this is referred to as 50 kg cm 2 and 10 minutes at room temperature. After cooling under the following conditions, a sheet having a thickness of 1.5 mm was obtained. A 300 mm X 400 mm test piece was cut from this sheet.
  • test piece is applied to the opening force of the sheet. Secure the sheet with clamps to a size of 98 mm and place it in an oven set at 190 ° C for 10 minutes. After leaving, the drawdown (mm) at the center of the sheet was measured.
  • the melt tension of the resin composition was measured at a take-up speed of 20 m / min and a take-up speed of 1 m / min.
  • the resin composition was roll-kneaded and press-molded at 200 ° C. to produce a 1.5-mm-thick sheet.
  • the surface condition of the obtained sheet was visually observed, and evaluated based on the following evaluation criteria.
  • Average particle size (m) (parts by weight)
  • the sheet obtained from the resin composition ( ⁇ ) was used.
  • a very thin section cut out was stained with ruthenium tetroxide and observed with a transmission electron microscope (magnification: 10000).
  • the amount of the case FM was set to 25 weight in Example 1. Parts, and the amount of TFE-F was changed to 0.5 parts by weight, except that the resin composition (II) produced in the same manner as in Example 1 was used as a sample.
  • Example 1 instead of the core-graft copolymer, as shown in Table III-3, the flop plane QB 200 was obtained.
  • 50 P Suditomo Seika Co., Ltd., homopolypropylene frozen-pulverized powder, average particle size 250 ⁇ m, refractive index 1.53, below -Plan QB
  • Snow Light SSS manufactured by Maruo Calcium Co., Ltd., calcium carbonate, average particle diameter 1.8 m
  • Hypolite B200P Mitsubishi Chemical Industries, Ltd., Polypropylene Powder, average particle diameter: 100 m
  • a resin composition was prepared in the same manner as in Example 1, and the physical properties of the obtained resin composition were evaluated. The results are shown in Table II-4.
  • Example 1 When using SSS), as in Example 1, the drawdown of the sheet is greatly improved, and the appearance of the sheet is also greatly improved. You can see. On the other hand, a polypropreneno having an average particle diameter of 1000 ⁇ m. When using powder (no dipole B200P), the improvement effect of the sheet drawdown is small and the portability It can be seen that the fluoroethylene is not sufficiently dispersed and the appearance of the sheet is poor. Examples 8-9 and Comparative Examples 5-6 (Nucleating agent or inorganic filler) Example using filler)
  • the flop plane QB (average particle diameter 250 / m) or the case FM (average particle diameter 180 ⁇ m) and TFE-F were used.
  • the resin composition was manufactured by high-speed stirring with a helix mixer to form TFE-F into fibers.
  • the obtained resin composition and Hyper B were added to the nucleating agent (Gel All DH (manufactured by Shin Nihon Rika Co., Ltd.) in the amount shown in Table II-5.
  • Bis (p-methyl benzylidene) sono-reitol or heavy calcium carbonate (trade names: Snolite SSS, Maruo Calushiu) was added, and a resin composition was prepared in the same manner as in Example 1, and the physical properties of the obtained resin composition were evaluated. The transparency was evaluated by the method, and the results are shown in Table II-6.
  • test piece having a thickness of 1.0 mm and a size of 3 O mm x 3 O mm was prepared in the same manner as in the method described in (Workability) above, and conformed to the method described in ASTM-D1003. Then, the transparency of the test piece was examined.
  • T represents total light transmittance (%)
  • HAZE represents turbidity (%).
  • Example 9 obtained by mixing a specific amount of an inorganic filler (calcium carbonate) with the resin composition and the polyolefin (c) was used.
  • the obtained sheet was obtained by mixing only the inorganic filler (calcium carbonate) with Hyperpole.
  • the sheet has the same appearance and rigidity as the sheet made of the resin composition of Example 6, has an increased melt tension, and is an indicator of workability. It can be seen that the drawdown has been greatly improved, and the shock resistance and stiffness of the lance have been greatly improved.
  • Butadiene was polymerized by the usual emulsion polymerization method to obtain a bridged polybutadiene rubber. No cross-linking agent was used.
  • the obtained rubber had a glass transition temperature of 180 ° C, a particle diameter of 0.25 // m, and a crosslinked gel content of 85% by weight.
  • 75 parts by weight (solid content) of the obtained polybutadiene rubber, 15 parts by weight of methyl methacrylate and 15 parts by weight of styrene 25 parts by weight of a monomer component consisting of 0 parts by weight was subjected to graph-polymerization by a usual emulsion polymerization method to obtain a polymer.
  • the conversion of the obtained polymer was 98%, and the particle size was 0.2 to ⁇ m.
  • the obtained dispersion of the polymer is salted out, dehydrated and dried by a usual method, and the powder of the core-shell graph copolymer ( ⁇ ) -1 is removed. Yes.
  • the average particle size of the powder was 250 / m.
  • a monomer component consisting of 100 parts by weight of n-butyl acrylate and 1 part by weight of methacrylic acid is polymerized by a usual emulsion polymerization method.
  • a crosslinked polyethylene acrylate rubber The obtained rubber had a glass transition temperature of 55 ° C, a particle size of 0.2 // m, and a crosslinked gel content of 85% by weight.
  • the amount of the resin composition shown in Table m-1 and the amount of the polyolefin (c :) homopolypropylene (trade name noisypore B2 Melt D-index, manufactured by Mitsui Petrochemical Industry Co., Ltd .: 0.5 g Z 10 minutes, hereinafter referred to as Hyper B 9) 100 weight Using a single-screw extruder (screw diameter: 40 mm ⁇ L / D: 28), the parts were extruded and kneaded at 200 ° C and 50 rpm, and the resin composition was extruded. Based on the pellet of
  • the resin composition was not prepared from the core-shell graphite copolymer and TFE-F in advance, and a predetermined amount of high Pole B, core shell graft copolymer and TFE-F were similarly extruded and kneaded with the single-screw extruder to obtain a resin composition pellet.
  • the resin composition was roll-kneaded at 200 ° C. for 3 minutes to prepare a sheet having a thickness of 1 min. Two sheets obtained are overlapped, and this is 200. After press molding with C at 30 kg Z cm 2 and 10 min, at room temperature, 50 kg / cm 2 and L 0 min. After cooling, a 1.5 mm thick sheet was obtained. A 100 mm x 100 mm specimen was cut from this sheet.
  • test piece was clamped with a frame having an opening of 76 mm x 76 mm in size, and was dropped on the leg of the frame. Attach the metal object for the drop measurement and leave the sheeted frame in an oven set at 190 ° C for 30 minutes. After that, I measured the draw down mm at the center of the sheet.o
  • a 4 inch thick ⁇ piece was prepared in the same manner as in the above (workability), and the test piece was knocked in accordance with the method described in ASTM-D256. Izzt with lip Impact resistance was measured ⁇
  • the bending elastic modulus was measured according to the method described in AST II-D790.
  • the surface condition of the sheet obtained by rolling and kneading the resin composition at 200 ° C was visually observed, and evaluated based on the following evaluation criteria.
  • melt flow index The melt flow index was measured at 230 in accordance with the method described in ASTM — D1238.
  • the core siezograft copolymer and TFE-F were mixed with a helical mixer, and TFE-F To produce a resin composition, and the resin composition of Examples 1 to 4 obtained by using the resin composition.
  • the molded article made of the resin composition ( ⁇ ) was cut.
  • the resulting very thin sections were stained with ruthenium tetroxide and observed with a transmission electron microscope (magnification: 100,000).
  • a transmission electron microscope magnification: 100,000
  • the core shell graph in Example 1 was used. Resin produced in the same manner as in Example 1 except that the amount of polymer (B)-1 was changed to 25 parts by weight and the amount of TFE-F was changed to 0.5 part by weight.
  • the composition ( ⁇ ) was used as a sample.
  • Examples 5 to 8 The core-graft copolymer shown in Table m-3 and the amount of TFE-F and TFE-F shown in Table m-3 After blending 5 parts by weight of the high-pole B with these, the two-screw extruder screw diameter: 44 mm, LZD: 30) At 200 ° C and 100 rpm After kneading, the TFE-F was fiberized to produce a resin composition (I).
  • Example 9 The amount of core-shell graft copolymer and TFE-F shown in Table III-3 were measured with a Henschel mixer. The mixture was stirred at a high speed for 10 minutes at room temperature to fibrillate TFE-F to obtain a mixture. After this mixture and the amount of nipple B in the amount shown in Table m-3 were subjected to node blending, biaxial extrusion was performed in the same manner as in Examples 5 to 8 above. The resin composition (I) was manufactured using a machine.
  • the core-graft copolymer, TFE-F and a part of Hypo-B were kneaded with a twin-screw extruder. Then, TFE-F is fiberized to produce a resin composition (I), and the resin composition ( ⁇ ) obtained by using the resin composition (I) is used.
  • the melt tension has been increased and the melt flow index has been reduced, which is an indicator of workability. It can be seen that the drawdown of the vehicle has been greatly improved, and the appearance of the seat has also been improved.
  • the core copolymer graft copolymer and TFE-F were stirred at a high speed with a heterogeneous mixer, and the TFE-F was allowed to react with a fiber.
  • a part of Hyper B are kneaded with a twin screw extruder to produce a resin composition (I), and the resin composition obtained by using the resin composition (I) is obtained.
  • the melt tension is increased and the melt flow index is reduced. It can be seen that the drawdown of the sheet, which is an indicator of workability, has been improved, and the appearance of the sheet has been further improved. .
  • Acrylic acid n A monomer component consisting of 70 parts by weight of butylene, 30 parts by weight of styrene, and 1 part by weight of methacrylic acid 100 parts by weight A part by weight was subjected to emulsion polymerization to obtain a crosslinked acrylic rubber.
  • methacrylic acid was used as a cross-linking agent and a graphitizing agent.
  • the average particle size of the obtained crosslinked acrylic rubber is 0.2 m, and the crosslinked gel content is 85% by weight.
  • Acrylic rubber rubber (glass transfer temperature: approx. 23 ° C) 70 mass parts of methacrylic acid methyl (solid content) (Glass transition temperature when used as a homopolymer: 105 ° C) 27 parts by weight and styrene (when used as a homopolymer) (Glass transition temperature: 100 ° C) 30 parts by weight of a monomer component consisting of 3 parts by weight are added, and these are subjected to a graphitization copolymerization by an emulsion polymerization method.
  • a corecyanoleft copolymer (b) hereinafter, referred to as a copolymer (b) was obtained.
  • the final conversion was 98%, and the refractive index of the copolymer (b) was 1.503.
  • the wax of the copolymer (b) was salted, dehydrated and dried to obtain a powder of the copolymer (b) having an average particle size of 180 ⁇ m.
  • Polypropylene (Melt flow index at 230 ° C: 0.5 g Z 10 min, refractive index: 1.503 (Polymer No. 3rd edition, listed value), powder (average particle diameter): 250 // m, hereinafter referred to as PP-1) 100 parts by weight of poly Add 2 parts by weight of tetrafluorophenol (Polyflon TFE-F104, manufactured by Daiken Industries, Ltd .; hereinafter, referred to as PTFE). These were stirred at a high speed for 5 minutes at room temperature using a helical mixer to fibrillate the PTFE and obtain a resin composition (A).
  • Preparation Example 2 the polymer composition (b) was used in place of PP-1, except that the resin composition was changed in the same manner as in Preparation Example 2.
  • a resin composition (D) was obtained in the same manner as in Production Example 3 except that the amount was changed to 50 parts by weight.
  • Example 5 PTFE was not used.
  • a resin composition ( ⁇ ′) was obtained in the same manner as in Preparation Example 5.
  • melt tip at 230 ° C has an index of 3. Og ZIO and a refractive index of 1.53 (poly It represents polypropylene powder with an average particle size of 700 zm (Marhandbook, 3rd edition, published values).
  • the melt tension (g) of the obtained pellets was measured using a capillary graph (manufactured by Toyo Seiki Co., Ltd.) having a die with a diameter of 2 mm and a length of 10 mm. Yes, 200.
  • C Measured at an extrusion speed of 20 mm / min and a take-up speed of 1 mZ. The results are shown in Table IV-2.
  • the obtained pellets were roll-kneaded at 200 ° C to produce a sheet, and the sheet was press-molded to obtain each of the following ASTMs. A test piece conforming to the test was obtained.
  • a sheet having a size of 100 mm x OO mm and a thickness of 1.5 mm is formed from the pellet, and the opening of the sheet has a width of 76 mm.
  • a sheet having a size of 100 mm X 100 mm and a thickness of 1.5 mm is formed from the pellet in the same manner as described above, and the sheet is formed.
  • the surface condition (appearance) was visually observed, and evaluated based on the following 5 parity standards. The results are shown in Table IV-2.
  • A The surface is homogenous, and no fibrous aggregates are observed.
  • Example 1 except that the composition was changed as shown in Table IV-2 and Table IV-3, a pellet was produced in the same manner as in Example 1 and the pellet was produced. Specimens and sheets were prepared using the rod.
  • the LDPE in Tables W-2 and W-3 has a refractive index of 0.25 g Z at 10 ° C at 190 ° C, and is refracted. Represents low-density polyethylene with a rate of 1.51 (Polymer Handbook, 3rd edition, published values).
  • Table IV
  • composition (weight part)
  • the polyrefin (C) and the polyrefin were obtained. Or copolymer core copolymer and polytetrafluoroethylene (A) are mixed together, and the polytetrafluoroethylene (A) is mixed.
  • a resin composition ( ⁇ ) consisting of a resin composition (A) to (L) in which fluoroethylene (A) is fiberized is used, a specific ratio is required.
  • the HAZE turbidity
  • the transparency is improved, and the melt tension is increased.
  • PTFE had a diameter of about 0.05 to 0.3 zm and a length of about 5 to 20 / zm, and was fibrous.
  • Example 1 bis (p-methylbenzylidene) solvitol was added as a nucleating agent to 100 parts by weight of the pellet of the resin composition.
  • pellets were produced in the same manner as in Example 1 except that 0.5 parts by weight were added, and the composition was changed as shown in Table W-4, and the pellets were produced.
  • the test pieces and sheets were prepared using the method. Factory -r
  • Rubber-based core copolymer (Kaneace M511, manufactured by Kanegafuchi Chemical Industry Co., Ltd., average particle size: 200 / m, refractive index: 1) 5 2) 5 parts by weight and polytetrafluoroethylene phenyl, 0 powder (Polyfluoro TFE-F104, Daikin Industries, Ltd.) (Average particle size: 500 ⁇ m) 0.1 parts by weight was stirred at room temperature for 10 minutes in a helical mixer and mixed at the same time. Shearing force was applied to the fiber to make the polytetrafluoronorylene ethylene.
  • This mixture was mixed with homopolypropylene (melt flow index at 230 ° C: SgZ10O, refractive index: 1.503) ) Pellet of 100 parts by weight and sorbitol-based nucleating agent (C1, bis (p-methisolenbenzylidene) solvitol) 0.3 parts by weight of a single-screw extruder (screw diameter: 50 mm, L / D: 28) with a T die attached at 200 ° C and 50 rpm (The content of fiberized polytetrafluoroethylene: 0.1 part by weight based on 100 parts by weight of homopolypropylene) , And extruded to obtain a lmm thick sheet. The obtained sheet had sufficient impact resistance as a sheet for thermoforming.
  • C1 bis (p-methisolenbenzylidene) solvitol
  • the transparency of the obtained sheet is defined as the total light transmittance (%) (in Table V-1, denoted as T) and HAZE (turbidity). (%) was measured. In addition, 45 ° dalo (%) was measured in terms of luminous intensity in accordance with the method described in JISK7105. The results are shown in Table V-1.
  • Example 1 a sheet having a thickness of 1 mm was obtained in the same manner as in Example 1, except that the composition was changed as shown in Table V-1.
  • the sheets obtained in Examples 2 to 11 had sufficient impact resistance as a sheet for thermoforming.
  • the content of the polished polytetrafluoroethylene in any of the polyolefins (C) It is the same as the amount of polytetrahydronorethole ethylene added to 100 parts by weight (parts by weight).
  • Comparative Examples 3 and 4 the rubber-based coresile graph copolymer and the polytetrafluoroethylene were used as the phenols.
  • the mixture was agitated in a mixer, and when they were mixed, a shearing force was applied at the same time, but the polytetrafluoroethylene remained in powder form. However, it was not fiberized.
  • B-1 Gum-based core schizograft copolymer (Kaneace M511, manufactured by Kanegafuchi Chemical Industry Co., Ltd., average particle size: 200; tm, refractive index: 1.5 2)
  • B-2 homopolypropylene (Melt flow index at 230 ° C: 3 g Z 10 min) , Refraction index: 1.503) frozen crushed powder (average particle diameter: 250 ⁇ m)
  • D 2 Lin-based nucleating agent SODIUM 2,2—Methylenvis (4,6—Di-t-butylphenol) Phosphite
  • the sheet obtained from the resin composition consisting of an olefin ( ⁇ ) is a resin composition in which no polytetrafluoroethylene is used.
  • Example 3 a very thin section cut out from the sheet obtained in Example 3 was stained with ruthenium tetroxide, and this was then transmitted through a transmission electron microscope. Observation was carried out at a magnification of 100,000 times) to examine the form of polytetrafluoroethylene in the resin composition ( ⁇ ). As a result, it was confirmed that the polytetrafluoroethylene had a diameter of about 0.1 to 1 lm, a length of about 3 to 10 / m, and was fibrous.
  • the sheet for thermoforming according to the present invention can be readily translucent, and at the same time, can be readily surface and workable. This was due to the fact that the resin composition (() contained fiberized polytetrafluoroethylene. .
  • the dispersants (B) shown in Table VI-1 and Table VI-2 and the polytetrafluoronorethylene shown in Table VI-1 and Table VI-2 (A) with a powder mixer The mixture was stirred at high speed for 5 minutes at room temperature, and at the same time, high shear was applied at the same time to form the polytetrafluoroethylene (A) into a fiber, thereby preparing a mixture.
  • blowing agent a mixture having a higher content of i-butane than that of n-butane is added to this pellet, and these are tandem extruded.
  • Machine screw diameter: 1 40 mm, 2 50 mm, rotation speed: 1 70 rpm, 2 20 rpm
  • a 0.6 mm slit die temperature approx. From C
  • the foaming agent was used in an amount of 3 parts by weight based on 100 parts by weight of the pellet of the resin composition.
  • the foam obtained had excellent surface properties and had sufficient impact resistance as a building material.
  • Example 5 a mixture of citric acid and sodium bicarbonate, which are foaming nucleating agents, was added in an amount of 0.1 parts by weight to 100 parts by weight of the resin composition. Parts by weight were added, and these were extruded and foamed from a slit die of a tandem extruder in the same manner as described above.
  • Comparative Examples 1 to 5 only the dispersant (B) was stirred with a Henschel mixer without using the polytetrafluoroethylene (A). Then, this was mixed with a polyrefin (C).
  • Comparative Examples 6 and 7 polytetrafluoroethylene (A) and a dispersant (B) were mixed under high shearing force.
  • Frozen pulverized powder having an average particle size of 0.5 g Z: 10 min, refractive index: 1.53) (average particle size: 250 um) )
  • the piston speed is 5 mm
  • the bow I speed is 1 m / min
  • the temperature in the pallet was measured at 200 ° C (crystallization temperature).
  • the density of the foam was measured according to the method described in JIS K7222, and the following formula was obtained.
  • the expansion ratio was determined based on the above.
  • the closed cell ratio was measured using a multi-type chromometer (manufactured by Yuasa Aionix Co., Ltd.) according to the method described in ASTM D2856-.
  • Example Resin composition Bubble number Melt tension Crystallization temperature Expansion ratio Closed cell ratio
  • the resin compositions ( ⁇ ) of Examples 1 to 10 obtained by mixing the mixture obtained from (B) have a high crystallization temperature, a high melt tension, and a high workability.
  • the foam obtained from (ii) has a favorable expansion ratio and a high closed cell rate.
  • the fluororesin-containing resin composition of the present invention has excellent impact resistance and surface properties, and further has improved and improved melting properties. Shows workability (formability).
  • the resin composition (I) is, for example, a modifier for the resin composition ( ⁇ ). Therefore, it can be suitably used. Further, from the resin composition ((), various moldings such as the thermoforming sheets and foams of the present invention having excellent physical properties as described above can be obtained.
  • the body is shaped.
  • the fluororesin-containing resin composition can be easily produced by the production method of the present invention.

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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)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine contenant une résine fluorée, comprenant 0,001-50 parties en poids de polytétrafluoroéthylène fibreux (A) et 100 parties en poids d'un dispersant (B), dont le diamètre moyen des particules est de 0,1-800 νm, ainsi qu'un procédé de production de ladite composition. L'invention concerne ágalement une autre composition de résine contenant de la résine fluorée, constituée de la composition de résine sus-mentionnée et d'une polyoléfine (C), ainsi que son procédé de production. L'invention concerne en outre une feuille et une mousse thermoformables produites à partir desdites compositions.
PCT/JP1995/001030 1994-05-31 1995-05-29 Composition de resine contenant de la resine fluoree, procede de production de ladite composition, et feuille et mousse thermoformables constituees de ladite composition WO1995033008A1 (fr)

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
JP6/118611 1994-05-31
JP11861194A JP3274934B2 (ja) 1994-05-31 1994-05-31 ポリオレフィン系樹脂組成物の製造法
JP6/118610 1994-05-31
JP11861094A JP3274933B2 (ja) 1994-05-31 1994-05-31 ポリオレフィン系樹脂組成物の製法
JP13228294A JPH07330935A (ja) 1994-06-14 1994-06-14 結晶性ポリオレフィン発泡体
JP6/132282 1994-06-14
JP6/190610 1994-08-12
JP19061194A JP3563775B2 (ja) 1994-08-12 1994-08-12 ポリオレフィン用樹脂組成物
JP19061094A JPH0853582A (ja) 1994-08-12 1994-08-12 ポリオレフィン系樹脂組成物
JP6/190611 1994-08-12
JP31068494A JPH08165358A (ja) 1994-12-14 1994-12-14 熱成形用ポリオレフィンシート
JP6/310684 1994-12-14

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022127858A1 (fr) * 2020-12-18 2022-06-23 金发科技股份有限公司 Matériau de polypropylène à résistance élevée à l'état fondu, son procédé de préparation et son utilisation

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50119040A (fr) * 1974-03-06 1975-09-18
JPS5385845A (en) * 1977-01-03 1978-07-28 American Cyanamid Co Method of improving wear resistance of elastomer
JPS5649740A (en) * 1979-07-30 1981-05-06 Lion Corp Production of filled polyolefin resin foam
JPS6090260A (ja) * 1982-09-29 1985-05-21 ボルカー・インコーポレイテッド ポリマ−相互分散物および関連組成物
JPH01172453A (ja) * 1987-12-28 1989-07-07 Teijin Ltd アラミド押出成形物とその製造方法
JPH026536A (ja) * 1988-06-24 1990-01-10 Teijin Chem Ltd 熱可塑性樹脂成形物の製造法
JPH03122008A (ja) * 1989-10-05 1991-05-24 Tokai Carbon Co Ltd 活性炭シートとその製造方法
JPH05214184A (ja) * 1992-02-07 1993-08-24 Mitsubishi Rayon Co Ltd 加工性の改良されたポリプロピレン樹脂組成物

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50119040A (fr) * 1974-03-06 1975-09-18
JPS5385845A (en) * 1977-01-03 1978-07-28 American Cyanamid Co Method of improving wear resistance of elastomer
JPS5649740A (en) * 1979-07-30 1981-05-06 Lion Corp Production of filled polyolefin resin foam
JPS6090260A (ja) * 1982-09-29 1985-05-21 ボルカー・インコーポレイテッド ポリマ−相互分散物および関連組成物
JPH01172453A (ja) * 1987-12-28 1989-07-07 Teijin Ltd アラミド押出成形物とその製造方法
JPH026536A (ja) * 1988-06-24 1990-01-10 Teijin Chem Ltd 熱可塑性樹脂成形物の製造法
JPH03122008A (ja) * 1989-10-05 1991-05-24 Tokai Carbon Co Ltd 活性炭シートとその製造方法
JPH05214184A (ja) * 1992-02-07 1993-08-24 Mitsubishi Rayon Co Ltd 加工性の改良されたポリプロピレン樹脂組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022127858A1 (fr) * 2020-12-18 2022-06-23 金发科技股份有限公司 Matériau de polypropylène à résistance élevée à l'état fondu, son procédé de préparation et son utilisation

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