WO1999005211A1 - Compositions de resine a base de fluorure de vinylidene et articles moules correspondants - Google Patents

Compositions de resine a base de fluorure de vinylidene et articles moules correspondants Download PDF

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Publication number
WO1999005211A1
WO1999005211A1 PCT/JP1997/002596 JP9702596W WO9905211A1 WO 1999005211 A1 WO1999005211 A1 WO 1999005211A1 JP 9702596 W JP9702596 W JP 9702596W WO 9905211 A1 WO9905211 A1 WO 9905211A1
Authority
WO
WIPO (PCT)
Prior art keywords
vinylidene fluoride
weight
compound
fluoride resin
phosphite
Prior art date
Application number
PCT/JP1997/002596
Other languages
English (en)
Japanese (ja)
Inventor
Seiichi Ohira
Kazuyuki Munakata
Toshiya Mizuno
Nobuyuki Masumura
Original Assignee
Kureha Chemical Industry Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to JP8037316A priority Critical patent/JPH09208783A/ja
Application filed by Kureha Chemical Industry Co., Ltd. filed Critical Kureha Chemical Industry Co., Ltd.
Priority to PCT/JP1997/002596 priority patent/WO1999005211A1/fr
Publication of WO1999005211A1 publication Critical patent/WO1999005211A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3

Definitions

  • Vinylidene fluoride resin composition and molded article Vinylidene fluoride resin composition and molded article
  • the present invention relates to a thermally stable vinylidene fluoride resin composition.
  • a specific amount of phosphite compound is blended with vinylidene fluoride-based resin.
  • the present invention relates to a vinylidene fluoride resin composition that can be formed without foaming or coloring.
  • the present invention also relates to a molded product formed from the composition.
  • Vinylidene fluoride resin is a thermoplastic resin that has good mechanical properties and is excellent in weather resistance, chemical resistance, and abrasion resistance, and is formed into various molded products.
  • the vinylidene fluoride resin is molded at a molding temperature of 200 to 350 ° C by operations such as compression molding, injection molding, extrusion molding, and blow molding. At such a molding temperature, the vinylidene fluoride resin is thermally degraded.
  • additives such as antioxidants are used to ensure the stability during processing.
  • 53-44953 discloses that a vinylidene fluoride resin and an organic phosphite of a polyhydric alcohol and a penter, a dipenter and a tripentaerythritol are used. Disclosed are compositions of a stabilizer and vinylidene fluoride resin, alone or in combination with a mixture. In the invention of this publication, when used as a coating composition, the deterioration time and adhesion time of the organic phosphite alone of polyhydric alcohol added to the fusibinylidene resin are hardly improved.
  • Deterioration time by adding 0.5 to 5% by weight of an organic phosphite of a polyhydric alcohol in the presence of 0.1 to 2% by weight of a polyhydric alcohol such as penter, dipenter, and tripentaerythritol, An improvement in the adhesion time has been observed.
  • a polyhydric alcohol such as penter, dipenter, and tripentaerythritol
  • the effect is recognized when the organic phosphite of the polyhydric alcohol is 0.5% by weight or more based on the vinylidene fluoride resin and the amount is equal to or more than that of the phenol erythritol added at the same time. It is also described that in this case as well, when only 2% by weight of an organic phosphite of a polyhydric alcohol is added, coloring occurs.
  • a phenolic antioxidant is generally used as an antioxidant for improving the heat-resistant life during molding of a thermoplastic resin.
  • Japanese Patent Application Laid-Open No. H 1-25256769 discloses that a composition obtained by adding a specific cyclic phosphate compound and a phenol compound to various thermoplastic resins improves the thermal stability of the thermoplastic resin.
  • the specific addition ratios of these compounds are such that the amount of the phenol compound added is the same as or smaller than that of the cyclic phosphite compound.
  • thermoplastic resin As described above, various compositions for forming a thermoplastic resin are known, but a vinylidene fluoride resin composition capable of sufficiently suppressing a foaming phenomenon and coloring at a processing temperature is not known.
  • the fusibinylidene-based resin composition obtained by mixing has heat resistance at a processing temperature of 280 ° C or higher, and suppresses thermal deterioration.As a result, a molded product without coloring can be obtained without causing a foaming phenomenon. And that a specific amount of a phenol compound is allowed to coexist in this composition. Thus, the present inventors have found that there is an effect of preventing the foaming phenomenon and coloring even at a high temperature, and reached the present invention.
  • an object of the present invention is to provide a stable vinylidene fluoride resin composition which does not cause a foaming phenomenon or coloring at a processing temperature. Disclosure of the invention
  • the present invention 1 0 0 parts by weight of vinylidene fluoride resin and Hosufai DOO compound 0. 0 1 ⁇ 0. 5 c
  • the above composition characterized in that it is a vinylidene fluoride resin composition comprising by weight parts, This is a vinylidene fluoride resin composition to which a phenol compound is added in an amount of 0 to 10 times the weight of a phosphite compound. Further, it is a molded product obtained from these compositions.
  • a preferred embodiment is a vinylidene fluoride resin composition comprising a phenol compound in an amount of 2 to 6 times the phosphite compound in the above composition, and is obtained from these compositions. It is a molded product.
  • a vinylidene fluoride resin is a vinylidene fluoride homopolymer, a copolymer physically and chemically similar to the homopolymer, and containing 70% by mole or more of vinylidene fluoride as a structural unit. And a mixture of these polymers.
  • Monomers that copolymerize with vinylidene fluoride include tetrafluoroethylene, propylene hexafluoride, ethylene trifluoride, ethylene trifluoride, vinyl fluoride, and the like.One or more of these may be used. Can be used.
  • the phosphite compound used in the present invention includes a polyhydric alcohol having 3 to 5 carbon atoms such as pentaerythritol and propanetriol or an oligomer thereof having 1 to 3 phosphorus atoms (trivalent) formed through an ester bond.
  • tri (alkyl-substituted or unsubstituted phenyl) phosphites such as tris (nonylphenyl) phosphite, trialkyl phosphites such as tris (2-ethylhexyl) phosphite and tris (tridecyl) phosphite
  • diphenylmono (2-ethylhexyl) phosphite can also be used.
  • the phenolic compound used in the present invention is preferably a compound having 1 to 4 benzene rings substituted with 1 to 3 alkyl groups and hydroxy groups in a molecule and having a phenolic OH group. More specifically, tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-14-hydroxyphenyl) propionate] methane, 4,4,1-isopropylidene diphenol, stearyl (3,5) -Di-tert-butyl_4-hydroxyphenyl) propionate, thiodiethylene glycol bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3 , 5-Di-tert-butyl-1-hydroxyphenyl) propioic acid amide], 2,2'-methylenebis (4-ethyl-1-6-tert-butylphenol, 4,4,1-butylidenebis (6-tert
  • the vinylidene fluoride-based resin is Thermal stability is improved and no coloring occurs during molding.
  • the phosphite compound is less than 0.01 parts by weight and when the phosphite compound is more than 0.5, there is no heat stabilizing effect, and coloring or foaming phenomenon occurs at the processing temperature. happenss.
  • the thermal stability is further improved, and when the heat history is large, for example, when processing at a high temperature, it is preferable to use the phenol compound in combination.
  • the phosphite compound when the phosphite compound is lacking even when the phenol compound is added, the phenol compound itself is undesirably colored due to decomposition.
  • the amount of the phenol compound to be added is preferably not more than 10 times by weight of the phosphite compound, more preferably more than the phosphite compound and not more than 8 times by weight of the phosphite compound, more preferably 2 to 6 times by weight of the phosphite compound. is there.
  • the ratio of the phenol compound to the phosphite compound is equal to or less than that of the phosphite compound, the effect of adding the phenol compound is not sufficiently exhibited. On the other hand, if the amount exceeds 10 times by weight, the phenol compound present in a large amount is decomposed, and conversely, the degree of foaming and coloring increases.
  • the vinylidene fluoride-based resin composition as described above can be molded into various molded products such as films, sheets, and fibers, and molded products can be obtained without fear of foaming and coloring at the processing temperature.
  • compression molding, injection molding, extrusion molding, blow molding and other ordinary molding operations are performed at a molding temperature of 200 to 350 ° C. Shaped.
  • the amount ratio is selected within the above composition range according to the target molded product.
  • processing aids usually used for the molding process of the vinylidene fluoride resin such as a lubricant and a pigment, may be added.
  • a composition comprising a vinylidene fluoride homopolymer having a 77, nh of 1.3 dl / g and a phosphite compound and a phenol compound in an amount shown in Table 2 with respect to 100 parts by weight of the polymer was prepared.
  • the sheet was pressed at 0 ° C to prepare a sheet with a size of 5 cm x 5 cm and a thickness of 1 m2, and a thermal stability test was performed.
  • V force ⁇ 1.3 dl / g of vinylidene fluoride homopolymer 100 parts by weight, phosphite compound 0.05 parts by weight and phenol compound 0.15 parts by weight Extruded at 35 ° C from a 35mm0 extruder. This was extruded from a nozzle with a discharge diameter of 1.5 cm ⁇ , and then cooled in water at 30 ° C to obtain a 75-monofilament. The hue of this monofilament was white and there was no change in hue due to extrusion. Comparative Example 6
  • the vinylidene fluoride-based resin composition of the present invention is obtained by blending a specific amount of a phosphite compound with a vinylidene fluoride-based resin, and can be formed without foaming or coloring at a processing temperature. Therefore, the present invention provides a vinylidene fluoride-based resin molded product without foaming and coloring.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)

Abstract

L"invention, qui a trait à une composition de résine à base de fluorure de vinylidène thermostable ne se gonflant pas ni ne se décolorant et ce, même à la température de traitement, concerne également des articles moulés à l"aide de cette composition. La composition de résine comporte 100 parties en poids d"une résine à base de fluorure de vinylidène et de 0,01 à 0,05 partie en poids d"un composé de phosphite. Elle est également susceptible de renfermer en outre un composé phénolé.
PCT/JP1997/002596 1996-01-31 1997-07-28 Compositions de resine a base de fluorure de vinylidene et articles moules correspondants WO1999005211A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP8037316A JPH09208783A (ja) 1996-01-31 1996-01-31 フッ化ビニリデン系樹脂組成物および成形物
PCT/JP1997/002596 WO1999005211A1 (fr) 1996-01-31 1997-07-28 Compositions de resine a base de fluorure de vinylidene et articles moules correspondants

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP8037316A JPH09208783A (ja) 1996-01-31 1996-01-31 フッ化ビニリデン系樹脂組成物および成形物
PCT/JP1997/002596 WO1999005211A1 (fr) 1996-01-31 1997-07-28 Compositions de resine a base de fluorure de vinylidene et articles moules correspondants

Publications (1)

Publication Number Publication Date
WO1999005211A1 true WO1999005211A1 (fr) 1999-02-04

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Application Number Title Priority Date Filing Date
PCT/JP1997/002596 WO1999005211A1 (fr) 1996-01-31 1997-07-28 Compositions de resine a base de fluorure de vinylidene et articles moules correspondants

Country Status (2)

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JP (1) JPH09208783A (fr)
WO (1) WO1999005211A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09208783A (ja) * 1996-01-31 1997-08-12 Kureha Chem Ind Co Ltd フッ化ビニリデン系樹脂組成物および成形物

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52119652A (en) * 1976-02-05 1977-10-07 Ciba Geigy Ag Triarylphosphiteephenol series compound stabilizers
JPS5774345A (en) * 1980-10-27 1982-05-10 Adeka Argus Chem Co Ltd Halogen-containing resin composition
JPS60135445A (ja) * 1983-12-24 1985-07-18 Katsuta Kako Kk 含ハロゲン樹脂安定化組成物
JPS60188447A (ja) * 1984-02-16 1985-09-25 オウシモント・ユーエスエイ・インコーポレーテッド 安定化したフルオロポリマー組成物
JPS6433147A (en) * 1987-07-06 1989-02-03 Chiyandorasekaran Suwayanbu Improved stable melt-processable composition
JPH01254769A (ja) * 1988-04-02 1989-10-11 Adeka Argus Chem Co Ltd 安定化された合成樹脂組成物
JPH03177442A (ja) * 1989-11-14 1991-08-01 Ciba Geigy Ag エラストマーのための安定剤混合物
JPH09208783A (ja) * 1996-01-31 1997-08-12 Kureha Chem Ind Co Ltd フッ化ビニリデン系樹脂組成物および成形物

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52119652A (en) * 1976-02-05 1977-10-07 Ciba Geigy Ag Triarylphosphiteephenol series compound stabilizers
JPS5774345A (en) * 1980-10-27 1982-05-10 Adeka Argus Chem Co Ltd Halogen-containing resin composition
JPS60135445A (ja) * 1983-12-24 1985-07-18 Katsuta Kako Kk 含ハロゲン樹脂安定化組成物
JPS60188447A (ja) * 1984-02-16 1985-09-25 オウシモント・ユーエスエイ・インコーポレーテッド 安定化したフルオロポリマー組成物
JPS6433147A (en) * 1987-07-06 1989-02-03 Chiyandorasekaran Suwayanbu Improved stable melt-processable composition
JPH01254769A (ja) * 1988-04-02 1989-10-11 Adeka Argus Chem Co Ltd 安定化された合成樹脂組成物
JPH03177442A (ja) * 1989-11-14 1991-08-01 Ciba Geigy Ag エラストマーのための安定剤混合物
JPH09208783A (ja) * 1996-01-31 1997-08-12 Kureha Chem Ind Co Ltd フッ化ビニリデン系樹脂組成物および成形物

Also Published As

Publication number Publication date
JPH09208783A (ja) 1997-08-12

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