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WO1991011491A1 - Composition a base de resine de sulfure polyarylene et preparation d'une telle composition - Google Patents

Composition a base de resine de sulfure polyarylene et preparation d'une telle composition Download PDF

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Publication number
WO1991011491A1
WO1991011491A1 PCT/JP1991/000120 JP9100120W WO9111491A1 WO 1991011491 A1 WO1991011491 A1 WO 1991011491A1 JP 9100120 W JP9100120 W JP 9100120W WO 9111491 A1 WO9111491 A1 WO 9111491A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin composition
resin
stabilizer
sulfide resin
inorganic filler
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP1991/000120
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English (en)
Japanese (ja)
Inventor
Toshikatsu Nitoh
Toshifumi Nonaka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Polyplastics Co Ltd
Original Assignee
Polyplastics Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Polyplastics Co Ltd filed Critical Polyplastics Co Ltd
Priority to KR1019910700722A priority Critical patent/KR920701365A/ko
Publication of WO1991011491A1 publication Critical patent/WO1991011491A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/04—Polysulfides
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Definitions

  • the present invention relates to a polyolefin sulfate resin composition having an inorganic filler and a method for preparing the same. More specifically, the present invention relates to a poly "lens sulfide resin composition which is less oxidatively degraded during the production of the composition, suppresses discoloration, has high whiteness, and has stable quality and moldability, and a method for preparing the same.
  • Polyarylene sulfide (PAS) resin typified by polyphenylene sulfide (PPS) resin is often used as a composition containing an inorganic filler as a composition with excellent mechanical properties, high heat resistance, and heat resistance.
  • chemical resistance has a flame retardant, also processing productivity and: in Aimatsu also cost Topafu O over Ma Nsu, in recent years, electric and electronic equipment parts materials and automotive parts material, as the chemical equipment unit product material, market needs Demand is growing because it is well suited to No
  • Stabilizers proposed by the present inventors such as Japanese Patent Application Nos. 1-164310 and 1-1644311, are relatively effective, but may not be sufficient.
  • the present inventors have developed a method for maintaining excellent heat resistance, solvent resistance, flame retardancy, mechanical properties, and crystallinity of a PAS resin composition, particularly a PPS resin composition, and reducing gas generation during molding.
  • a resin composition that suppresses discoloration has little discoloration, has high whiteness, and has stable quality
  • intensive studies have been conducted.
  • the inorganic filler brings in a large amount of oxygen (air) during the melt extrusion with the filler, and the filler may react at the interface where it comes into contact with the hot resin, causing discoloration.
  • fillers such as glass fibers are generally treated with various organic surface treatment agents to increase the affinity (adhesion) with the resin, and various organic substances are used as a binder for handling and the like.
  • various organic surface treatment agents to increase the affinity (adhesion) with the resin
  • various organic substances are used as a binder for handling and the like.
  • these deposits may decompose at high temperatures and cause problems such as discoloration due to aging, if stabilizers such as antioxidants are concentrated at the interface of the filler, We anticipate that the effect of preventing discoloration will be doubled.As a result of adding a stabilizer etc. to the surface of the filler and adding it, the amount of the added stabilizer will be lower than when adding the stabilizer directly to the blend material.
  • the present invention was found to improve the generation of decomposed gas and thereby the generation of deposits on a molding die and the like, and to obtain a molded product having a high whiteness.
  • an organic stabilizer is previously added to the surface of 100 to 100 parts by weight of the polyolefin sulfide resin.
  • 5% by weight ( ⁇ inorganic filler) A method for preparing a polyarylene sulfide resin composition comprising 5 to 400 parts by weight of an inorganic filler adhered thereto, and a method for preparing the same. It relates to the obtained resin composition.
  • the base resin used in the composition of the present invention is mainly composed of a PAS resin, and is mainly composed of a repeating unit "( ⁇ Ar-S) ⁇ (where Ar is an arylene group).
  • Ar is an arylene group.
  • the arylene group include p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group, p, p, diphenylene sulphone group, p, p, A biphenylene group, a p, p'-diphenylene ether group, a p, p, a diphenylenecarbonyl group, a naphthalene group, and the like can be used.
  • a polymer using the same repeating unit that is, a homopolymer can be used among the arylene sulfide groups composed of the above-mentioned arylene group, and from the viewpoint of the processability of the composition, different types are used. Copolymers containing repeat units may be preferred.
  • those having a p-phenylene sulfide group as a repeating unit using a p-phenylene group as an arylene group are particularly preferably used.
  • arylene sulfide groups composed of the above-mentioned arylene groups
  • p-phenylene sulfide group and m-phenylene sulfide group are preferred.
  • a combination containing a thio group those containing 50 mol% or more, preferably 70 mol% or more of p-phenylene sulfide group are suitable in terms of physical properties such as heat resistance, moldability, and mechanical properties.
  • a copolymer containing 5 to 50 mol%, particularly 10 to 25 mol% of m-phenylene sulfide group is preferable as a copolymer.
  • those in which the repeating units of the components are contained in a block form are more excellent in processability than those in a random form, and Excellent in heat resistance and mechanical properties, preferred Can be used well. -..
  • a polymer having a substantially linear structure obtained by condensation polymerization from a monomer mainly containing a bifunctional halogen aromatic compound can be particularly preferably used.
  • polymers that partially form cross-linked structures by using a small amount of a cross-linking agent such as a polyaromatic compound having three or more halogen substituents during condensation polymerization are also used.
  • a polymer in which the linear polymer described above is heated at a high temperature in the presence of oxygen at a high temperature to increase the melt viscosity and thereby improve the formability.
  • Kasori Borima that high-temperature heating is one 1.
  • purpose of the present invention for coloring brown, high resin composition whiteness can not be obtained.
  • the resin stabilization effect was some. Me, molding This is effective in obtaining a resin composition in which gas generation at the time, deposits on the mold and the like are reduced and physical properties are hardly reduced.
  • the melt viscosity (temperature 310, shear rate 1200 / sec) of the polyolefin resin as a base resin used in the present invention is 10 or more: preferably L0000 poise.
  • Those having a melt viscosity in the range of 5000 vise are particularly preferred because of their excellent balance between mechanical properties and fluidity, and melt viscosity less than 10 vise is not preferred because of insufficient mechanical strength.
  • melt viscosity exceeds 10,000 voids, it is not preferable because the flowability of the resin composition is poor at the time of injection molding and the molding operation becomes difficult.
  • the base resin of the present invention the resin is in a range not adversely affected.
  • Other thermoplastic resin besides arylene sulfide resin ⁇ It is also possible to use a small amount together.
  • thermoplastic resin Any other thermoplastic resin may be used as long as it is stable at high temperatures.
  • aromatic polyesters composed of aromatic dicarboxylic acids such as polyolefin (co) polymers, poly (ethylene terephthalate), polybutylene terephthalate and diols or oxycarboxylic acids, polyamide polymers, polyamides, etc. Examples thereof include carbonate, ABS, polyphenylene oxide, polyalkyl acrylate, polyacetal, polysulfone, polyethersulfone, polyetherimide, polyetherketone, and fluorine resin.
  • These thermoplastic resins can be used as a mixture of two or more kinds.
  • any filler generally used for thermoplastic resins can be used, and fibrous, granular, and plate-like fillers are used. .
  • fibrous fillers include glass fiber, aspect fiber, carbon fiber, silicon fiber, silica / alumina fiber, zirconium fiber, boron nitride fiber, silicon nitride fiber, boron fiber, Titanic acid fibers and inorganic and fibrous materials such as stainless steel, aluminum, titanium, copper, brass and other metal fibrous materials.
  • Particularly typical fibrous fillers are glass fibers or carbon fibers.
  • High melting point organic fibrous substances such as polyamides, fluororesins, and acrylic resins can also be used.
  • powdered particulate fillers include carbon black, silica, and quartz powder.
  • examples of the plate-like filler include my strength, glass flake, various metal foils, and the like.
  • inorganic fillers can be used alone or in combination of two or more.
  • the amount of the inorganic filler to be used is 5 to 400 parts by weight, preferably 10 to 200 parts by weight, per 100 parts by weight of the polystyrene sulfide resin. If the amount is less than 5 parts by weight, the mechanical strength is not sufficient. If the amount is too large, molding work becomes difficult.
  • fillers are preferably subjected to a surface treatment or a convergence treatment with a functional compound such as an epoxy compound, an isocyanate compound, a silane compound, a titanate compound or a polymer.
  • a functional compound such as an epoxy compound, an isocyanate compound, a silane compound, a titanate compound or a polymer.
  • a feature of the present invention resides in that an organic stabilizer is previously attached to such an inorganic filler and added to the resin.
  • Organic stabilizers that adhere to the surface of inorganic fillers include phenolic, amine, zeolite, and linoleic organic compounds that are generally used to prevent the oxidation of resin and rubber. .
  • organic phosphorus-based stabilizers and phenolic antioxidants are particularly effective in suppressing discoloration and produce less gas during molding.]: Is preferred. ⁇
  • organic phosphorus-based stabilizer for example, phosphite-based and phosphonite-based organic compounds described in Japanese Patent Application Nos. 11-164310 and 11-164431 are preferable.
  • Triaryl phosphite such as it, tri (nonyl phenyl), phosphite, etc., Jisteria J Lepenta erythritol disulfide, cyclic neopentente Tris-bis (2,4-di-tert-butylphenylene phosphite), G- (2,6-di-tert-butyl-14-methyl phenyl) Penta erythritol diphenyl phosphite Heat-resistant phosphites such as butyl ether, tetrakis (2,4-di-t-butylphenyl) —4,4-biphenylene phosphonite and other phosphonite compounds Etc.
  • inorganic phosphorus-based compounds such as hypophosphorous acid or salts thereof, have a low heat-resistant temperature and are easily decomposed, and the inclusions tend to affect the crystallinity of PAS and lower the crystallinity. Not good.
  • phenol-based antioxidant a series of phenol derivatives, which is generally referred to as hindered phenol, is effective.
  • high heat resistant high molecular weight type compounds have a good balance between moldability and resin stabilization.
  • Compounds of this type include, for example, pentaerythritol tetrakis [3- (3,5-di-t-butyl-14-hydroxy-4-phenyl) probionate] and triethylene glycol Le-bis [3- (3-t-butyl-1-5-methyl-1-4-hydroxyphenyl) propionate] is a typical example.
  • a solution obtained by dissolving or dispersing the stabilizer in a solvent is spray-stirred and dispersed in an inorganic filler in a Henschel mixer :
  • the method of evaporating the solvent including the method of performing the sizing treatment and adhering to the sizing treatment, by adding a stabilizer to the sizing agent when the inorganic filler is collected, and the like. Any method can be applied as long as it can be uniformly attached to the surface of the filler, and the method is not limited to the method of attachment.
  • the amount of the stabilizer to be attached to the surface of the inorganic filler is preferably 0.01% to 2.5% by weight, and more preferably 0.02% to 1% by weight.
  • the effect of the invention such as improvement in whiteness, is not sufficient. If the effect is large, odor or gas is generated during processing, which is not preferable.
  • organic stabilizer of the present invention may be used as a mixture of two or more kinds.
  • composition of the present invention further includes known substances generally added to thermoplastic resins and thermosetting resins, that is, coloring agents such as antistatic agents, flame retardants, dyes and pigments, lubricants and crystallization. Accelerators, crystal nucleating agents, etc. can also be added as appropriate according to the required performance.
  • the polyarylene sulfide resin composition of the present invention can be prepared by equipment and a method generally used for preparing a synthetic resin composition. That is, necessary components can be mixed, kneaded using a single-screw or twin-screw extruder, and extruded into a pellet for a ⁇ -shape.
  • the method in which the fat component is added in the middle of melting is less likely to damage the fibrous filler, and the effect of the present invention is sufficiently exhibited. It is. --As is clear from the above description and Examples, the PAS resin composition produced by the method of the present invention has little discoloration in processing such as extrusion and molding, and a molded article with high stability and whiteness can be obtained.
  • the generation of gas during processing is small, the generation of deposits on the mold tends to be suppressed, and expensive stabilizers are used because they are effective even in a small amount compared to the usual method of using stabilizers. It also has the advantage of minimizing the rise in cost, and can be expected as a material for various functional components, especially electronic components assembled using surface-mount technology.
  • the commercially available organic stabilizers shown in Tables 1, 2, and 3 are included in sizing agents or binders and adhered to inorganic fillers, and sizing is performed as shown in Tables 1-3. Then, it was mixed with polyphenylene sulfide resin (Kureha Chemical Industry Co., Ltd., trade name "Photo KP") for 30 seconds in a blender. Next, this mixture was melt-kneaded with an extruder having a cylinder temperature of 310 * C to prepare a pellet of a polyolefin sulfide resin composition. .
  • an ASTM test piece was molded using an injection molding machine at a cylinder temperature of 320 and a mold temperature of 150, and the tensile strength and tensile elongation were measured.
  • the gas generated from the nozzle during extrusion and molding is used to remove the odor during molding.
  • the degree of adhesion was determined from the surface state of the mold after repeated detection and detection by air and visual observation.
  • Ratio 2 100 force 'Las Phino, '70 A 0.1 66.2 Fine ⁇ Fine loon 1 0
  • Ciba gigineilgafos P-EPQ FF tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylenephosphonite

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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)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)

Abstract

L'invention se rapporte à une composition à base de résine de sulfure polyarylène, qui ne cause que peu de dégradation acide, qui a d'excellentes propriétés anti-ternissement et dans laquelle un stabilisant peut être utilisé efficacement. Cette composition contient 100 parties en poids d'une résine de sulfure polyarylène et 5 à 400 parties en poids d'une charge inorganique ayant une surface sur laquelle a été déposé un pourcentage en poids de 0,01 à 2,5, calculé sur la base de la charge, d'un stabilisant organique.
PCT/JP1991/000120 1990-02-02 1991-01-31 Composition a base de resine de sulfure polyarylene et preparation d'une telle composition Ceased WO1991011491A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1019910700722A KR920701365A (ko) 1990-02-02 1991-01-31 폴리아릴렌 설파이드 수지조성물 및 그의 조제법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2/24188 1990-02-02
JP2024188A JP2547266B2 (ja) 1990-02-02 1990-02-02 ポリアリーレンサルファイド樹脂組成物及びその調製法

Publications (1)

Publication Number Publication Date
WO1991011491A1 true WO1991011491A1 (fr) 1991-08-08

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PCT/JP1991/000120 Ceased WO1991011491A1 (fr) 1990-02-02 1991-01-31 Composition a base de resine de sulfure polyarylene et preparation d'une telle composition

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JP (1) JP2547266B2 (fr)
KR (1) KR920701365A (fr)
WO (1) WO1991011491A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4266609B2 (ja) 2002-10-08 2009-05-20 株式会社プライムポリマー 成形方法および樹脂成形体

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01311171A (ja) * 1988-06-10 1989-12-15 Asahi Fiber Glass Co Ltd ポリフェニレンサルファイド補強用ガラス繊維束並びに樹脂体の製造方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01311171A (ja) * 1988-06-10 1989-12-15 Asahi Fiber Glass Co Ltd ポリフェニレンサルファイド補強用ガラス繊維束並びに樹脂体の製造方法

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JP2547266B2 (ja) 1996-10-23
JPH03229760A (ja) 1991-10-11
KR920701365A (ko) 1992-08-11

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