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WO2023008153A1 - Procédé de production d'une composition de résine de sulfure de polyarylène - Google Patents

Procédé de production d'une composition de résine de sulfure de polyarylène Download PDF

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Publication number
WO2023008153A1
WO2023008153A1 PCT/JP2022/027192 JP2022027192W WO2023008153A1 WO 2023008153 A1 WO2023008153 A1 WO 2023008153A1 JP 2022027192 W JP2022027192 W JP 2022027192W WO 2023008153 A1 WO2023008153 A1 WO 2023008153A1
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WIPO (PCT)
Prior art keywords
resin composition
mass
alkoxysilane compound
polyarylene sulfide
parts
Prior art date
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Ceased
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PCT/JP2022/027192
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English (en)
Japanese (ja)
Inventor
良祐 立堀
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Polyplastics Co Ltd
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Polyplastics Co Ltd
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Priority to MYPI2024000592A priority Critical patent/MY207207A/en
Priority to CN202280052450.8A priority patent/CN117715957B/zh
Publication of WO2023008153A1 publication Critical patent/WO2023008153A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/54—Silicon-containing compounds
    • 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
    • C08L81/02—Polythioethers; Polythioether-ethers

Definitions

  • the present invention relates to a method for producing a polyarylene sulfide resin composition.
  • PPS resin which is a type of polyarylene sulfide (hereinafter also referred to as PAS) resin, has high heat resistance, mechanical properties, chemical resistance, and flame retardancy. Therefore, it is used in a wide range of fields such as various automobile parts, electrical and electronic equipment parts, mainly for extrusion molding and injection molding.
  • Patent Document 1 describes a method for producing a polyarylene sulfide resin composition in which an olefinic copolymer and an alkoxysilane compound are added to a PAS resin to improve toughness and moldability in a low-temperature environment.
  • Patent Document 2 describes a method for producing a polyarylene sulfide resin composition in which an alkoxyaminosilane is added to a PPS resin in order to improve weld strength for the purpose of improving toughness.
  • the PAS resin composition may leak from the tip of the nozzle of the injection molding machine after molding until the start of the next molding cycle. If the amount of leakage of the PAS resin composition is large, it is necessary to remove the leaked PAS resin composition before molding again. A decrease in continuous moldability has become a problem.
  • the present inventor found that when a basic carbonate such as calcium carbonate is contained as an inorganic filler, the amount of leakage of the PAS resin composition is particularly large, and the problem of continuous moldability deterioration of the molded product is remarkable. rice field.
  • the present invention has been made in view of the above circumstances, and provides a polyarylene sulfide having good continuous moldability while simultaneously using a polyarylene sulfide resin having a low melt viscosity, an alkoxysilane compound, and a basic carbonate.
  • An object of the present invention is to provide a method for producing a resin composition.
  • One aspect of the present invention for achieving the above object is as follows.
  • (1) Mix 0.2 to 50 parts by mass of an alkoxysilane compound with 100 parts by mass of a polyarylene sulfide resin having a melt viscosity of 5 to 80 Pa ⁇ s measured at a temperature of 310°C and a shear rate of 1200 sec -1 .
  • a step of preparing a masterbatch by Part of the alkoxysilane compound in the masterbatch is condensed, and the ratio of the condensate of the alkoxysilane compound is set to 0.5 to 60% by mass of the alkoxysilane compound, and the step B is obtained.
  • a method for producing a polyarylene sulfide resin composition comprising:
  • step D of preparing a new polyarylene sulfide resin that is the same as or different from the polyarylene sulfide resin used in step A;
  • the total amount of the alkoxysilane compound and the condensate of the alkoxysilane compound is 0.2 to 3.0 parts by mass with respect to 100 parts by mass of all the polyarylene sulfide resins.
  • alkoxysilane compound includes at least one selected from the group consisting of epoxyalkoxysilane, aminoalkoxysilane, vinylalkoxysilane, and mercaptoalkoxysilane.
  • the alkoxysilane compound is ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropylmethyldiethoxysilane, N-( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, ⁇ -diallylaminopropyltrimethoxysilane, ⁇ -diallylaminopropyltriethoxysilane, at least one selected from the group consisting of , a method for producing a polyarylene sulfide resin composition according to any one of the above (1) to (5).
  • a masterbatch means a mixture obtained by simply stirring raw materials without heating, melt-kneading, or pelletizing.
  • the polyarylene sulfide resin composition having a melt viscosity of 5 to 80 Pa ⁇ s measured at a temperature of 310° C. and a shear rate of 1200 sec ⁇ 1 is added to 100 parts by mass of the polyarylene sulfide resin.
  • a step B is included in which a part of the alkoxysilane compound in the masterbatch is condensed so that the ratio of the condensate of the alkoxysilane compound is 0.5 to 60% by mass of the alkoxysilane compound. Furthermore, the masterbatch obtained in step B, wherein the ratio of the condensate of the alkoxysilane compound is within the above range, at least one inorganic filler containing a basic carbonate, and other components It includes a step C of melt-kneading the raw material containing and.
  • the present inventors have found that when a basic carbonate such as calcium carbonate is contained, the amount of leakage of the PAS resin composition is particularly large, and the continuous moldability of the molded article is significantly deteriorated.
  • the cause is presumed to be moisture.
  • the water content depends on the ratio of the condensate of the alkoxysilane compound, and it is presumed that the higher the ratio, the higher the water content. Therefore, it is considered that reducing the amount of condensate of the alkoxysilane compound reduces the water content and thus the amount of leakage of the PAS resin composition.
  • the amount of the condensate of the alkoxysilane compound is too small, an increase in the melt viscosity of the PAS resin composition is observed. defines the ratio of the condensate of Each step will be described below.
  • step A 0.2 to 50 parts by mass of an alkoxysilane compound is mixed with 100 parts by mass of a PAS resin having a melt viscosity of 5 to 80 Pa s measured at a temperature of 310°C and a shear rate of 1200 sec -1 . Prepare a masterbatch.
  • the content of the alkoxysilane compound mixed when preparing the masterbatch is 0.2 to 50 parts by mass with respect to 100 parts by mass of the PAS resin, the condensate of the alkoxysilane compound to the alkoxysilane compound in the masterbatch. It is easy to adjust the ratio of to a predetermined ratio. Moreover, clogging of piping can be suppressed, and handling is easy.
  • the content of the alkoxysilane compound is 0.2 to 50 parts by mass, preferably 0.3 to 25 parts by mass, and 0.5 to 15 parts by mass with respect to 100 parts by mass of the PAS resin. is more preferable, and 1.0 to 10 parts by mass is even more preferable.
  • Examples of a method for preparing the masterbatch include a method of dry blending the PAS resin and the alkoxysilane compound, and a blending method using a tumbler or a Henschel mixer is preferred.
  • the raw materials used in step A are described below.
  • the PAS resin is a resin mainly composed of -(Ar-S)- as a structural unit (Ar represents an arylene group).
  • Ar represents an arylene group
  • a polyarylene sulfide resin having a generally known molecular structure can be used.
  • arylene groups include phenylene groups such as p-phenylene group, m-phenylene group and o-phenylene group, p,p'-biphenylene group, p,p'-diphenylene ether group, p,p'-di A phenylenecarbonyl group, a p,p'-diphenylenesulfone group, a naphthylene group, and the like can be used.
  • the PAS resin can be a homopolymer using the same structural unit among the structural units represented by -(Ar-S)-, or a copolymer containing different structural units depending on the application.
  • homopolymer those having a p-phenylene group as an arylene group and having a p-phenylene sulfide group as a structural unit are preferable. This is because a homopolymer having a p-phenylene sulfide group as a structural unit has extremely high heat resistance and exhibits high strength, high rigidity, and high dimensional stability in a wide temperature range. By using such a homopolymer, it is possible to obtain a molded article having very excellent physical properties.
  • a combination of two or more different arylene sulfide groups among the arylene sulfide groups containing the above arylene groups can be used.
  • a combination containing a p-phenylene sulfide group and an m-phenylene sulfide group is preferable from the viewpoint of obtaining molded articles having high physical properties such as heat resistance, moldability and mechanical properties.
  • a polymer containing 70 mol % or more of p-phenylene sulfide groups is more preferable, and a polymer containing 80 mol % or more is even more preferable.
  • a PAS resin having a phenylene sulfide group is a polyphenylene sulfide resin (PPS resin).
  • PPS resins are known to have a substantially linear molecular structure with no branched or crosslinked structure, or to have a branched or crosslinked structure, depending on the production method. type may be used.
  • the melt viscosity of the PAS resin is 5 to 80 Pa ⁇ s under conditions of a temperature of 310° C. and a shear rate of 1200 sec ⁇ 1 from the viewpoint of toughness and fluidity.
  • the melt viscosity of the PAS resin is preferably 7 to 70 Pa ⁇ s, more preferably 10 to 60 Pa ⁇ s, even more preferably 13 to 50 Pa ⁇ s.
  • the problem of deterioration in continuous moldability that can occur when a PAS resin having a melt viscosity of 80 Pa ⁇ s or less and an alkoxysilane compound are used is intended to be solved. Therefore, a PAS resin having a melt viscosity of more than 80 Pa ⁇ s is out of the scope of this embodiment.
  • alkoxysilane compound is not particularly limited, and examples thereof include epoxyalkoxysilane, aminoalkoxysilane, vinylalkoxysilane, mercaptoalkoxysilane, etc. One or more of these may be used.
  • the number of carbon atoms in the alkoxy group is preferably 1-10, more preferably 1-4.
  • epoxyalkoxysilanes include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, and the like.
  • aminoalkoxysilanes include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropylmethyldiethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, ⁇ -diallylaminopropyltrimethoxysilane, ⁇ -diallylaminopropyltriethoxysilane and the like, one or more of these is used.
  • vinylalkoxysilanes examples include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris( ⁇ -methoxyethoxy)silane.
  • Examples of mercaptoalkoxysilanes include ⁇ -mercaptopropyltrimethoxysilane and ⁇ -mercaptopropyltriethoxysilane.
  • epoxyalkoxysilanes and aminoalkoxysilanes are preferred, and ⁇ -aminopropyltriethoxysilane is particularly preferred.
  • Step B part of the alkoxysilane compound in the masterbatch is condensed so that the ratio of the condensate of the alkoxysilane compound is 0.5 to 60 mass % of the alkoxysilane compound.
  • the ratio of the condensate in the alkoxysilane compound in the masterbatch is 0.5 to 60% by mass.
  • the ratio of the condensate is preferably 0.6 to 50% by mass, more preferably 0.7 to 45% by mass. If the ratio of the condensate is less than 0.5% by mass, the melt viscosity may become too high when the amount of the inorganic filler in the PAS resin composition is large.
  • the amount of the condensate of the alkoxysilane compound depends on the amount of the hydrolyzed alkoxysilane compound.
  • Methods for adjusting the amount of condensate of the alkoxysilane compound include, for example, the following (1) to (3). (1) Adjust the humidity of the environment in which the alkoxysilane compound and the masterbatch are stored and the water vapor transmission rate of the system. (2) Adjust the storage time of the alkoxysilane compound and masterbatch. (3) Adjust the mixing ratio of the PAS resin and the alkoxysilane compound in the masterbatch in step A.
  • the masterbatch in step A is prepared by mixing 2 parts by mass of an alkoxysilane compound with 100 parts by mass of a PAS resin, and is stored at a temperature of 40 ° C. and a humidity of 80% RH for 40 minutes to condense. The amount becomes 43% by mass.
  • the masterbatch in step A is prepared by mixing 25 parts by mass of an alkoxysilane compound with 100 parts by mass of the PAS resin, and when stored for 10 minutes at a temperature of 23 ° C. and a humidity of 40% RH, the amount of condensate is 1% by mass. becomes.
  • the amount of condensate of the alkoxysilane compound is 0.5 to 60% by mass, a PAS resin composition having excellent continuous moldability can be obtained.
  • an alkoxysilane compound is newly added to decrease the ratio of the condensate, thereby producing the alkoxysilane compound.
  • the amount of condensate can be adjusted. For example, even if the ratio of the condensate exceeds 60% by mass, the ratio of the condensate can be finally adjusted to 0.5 to 60% by mass by adding an alkoxysilane compound.
  • PAS resin composition which is the final product
  • the masterbatch contains at least a PAS resin, an alkoxysilane compound, and a condensate of the alkoxysilane compound produced by hydrolysis of the alkoxysilane compound.
  • the alkoxysilane compound is soluble in acetone, while the condensate of the alkoxysilane compound is insoluble in acetone.
  • the mass A of the aluminum cup is measured with a precision balance (step 1).
  • the membrane filter is placed on the aluminum cup, and the mass B of the membrane filter is measured (step 2).
  • the weighed membrane filter is placed in a suction funnel (step 3). At this time, the precision balance has only an aluminum cup.
  • step 4 put the masterbatch in an aluminum cup and measure the mass C (step 4).
  • step 4 put the weighed masterbatch into a funnel equipped with a membrane filter. Wash the aluminum cup with acetone, and put the washing liquid into the funnel (step 5).
  • step 6 add acetone while washing the area around the funnel, stir with a spatula for about 3 seconds, and suction-filter.
  • the process of adding acetone, stirring with a spatula and suction filtering is carried out two more times (step 6).
  • step 7 the residue and membrane filter are placed on an aluminum cup, dried at 40°C for 2 hours using a vacuum dryer, and the mass D is measured (step 7).
  • the ratio of the condensate in the alkoxysilane compound is represented by the following formula.
  • Condensate ratio (% by mass) (mass of condensate in alkoxysilane compound contained in masterbatch/mass of alkoxysilane compound blended during masterbatch preparation)
  • ⁇ 100 ⁇ [ ⁇ mass D - (mass A + Mass B) ⁇ -mass C ⁇ (1-EF)] / (mass C ⁇ E) ⁇ ⁇ 100
  • E represents the concentration (g/g) of the alkoxysilane compound in the masterbatch
  • F represents the concentration (g/g) of substances dissolved in acetone other than the alkoxysilane compound in the masterbatch.
  • the ratio of the condensate of the alkoxysilane compound in the masterbatch can be calculated.
  • step B part of the alkoxysilane compound in the masterbatch prepared in step A is condensed in step B, but if the period between steps A and B is long, the condensation reaction does not occur due to moisture. It is preferable to store it in a dry state. Since the present embodiment contains an inorganic filler containing a basic carbonate, the PAS resin composition tends to leak during injection molding, particularly due to the influence of moisture. It is therefore particularly important to store the masterbatch in a dry state. Alternatively, if it takes a long time to reach Step C after Steps A and B are completed, it is preferable to store the masterbatch in a dry state so that the ratio of the condensate in the masterbatch obtained in Step B does not change.
  • the ratio of the condensate in the masterbatch changes, it is sufficient that the amount of the condensate in the masterbatch when fed into the extruder satisfies the specified range.
  • the ratio of the amount of the condensate in the masterbatch can be lowered by newly adding an alkoxysilane compound when charging the masterbatch into the extruder.
  • step C the masterbatch obtained in step B, wherein the ratio of the condensate of the alkoxysilane compound is within the above range, at least one inorganic filler containing a basic carbonate, A raw material containing other components is melt-kneaded.
  • the PAS resin composition contains at least one inorganic filler containing a basic carbonate.
  • Inorganic fillers other than basic carbonates include fibrous inorganic fillers (but excluding basic carbonates), powdery and granular inorganic fillers (but excluding basic carbonates), and plate-like inorganic fillers. Fillers (with the exception of basic carbonates) may be mentioned. One of these may be used, or two or more may be used in combination.
  • Basic carbonates include calcium carbonate, magnesium carbonate, sodium carbonate, potassium carbonate, ammonium carbonate, zinc carbonate, and the like.
  • Examples of commercially available products of calcium carbonate include Whiten P-30 (average particle size (50%d): 5 ⁇ m) manufactured by Toyo Fine Chemical Co., Ltd.).
  • the content of the basic carbonate is 0.5 to 315 parts by mass with respect to 100 parts by mass of the PAS resin, the effect of reducing leakage of the PAS resin composition during injection molding is exhibited. can.
  • Fibrous inorganic fillers other than basic carbonates include glass fibers, carbon fibers, zinc oxide fibers, titanium oxide fibers, wollastonite, silica fibers, silica-alumina fibers, zirconia fibers, boron nitride fibers, and silicon nitride fibers. , boron fibers, potassium titanate fibers, mineral fibers, stainless steel fibers, aluminum fibers, titanium fibers, copper fibers, brass fibers, and other metal fibrous substances. One or more of these can be used. . Among them, glass fiber is preferable.
  • Examples of commercially available glass fiber products include chopped glass fiber (ECS03T-790DE, average fiber diameter: 6 ⁇ m) manufactured by Nippon Electric Glass Co., Ltd., chopped glass fiber (CS03DE 416A, average fiber diameter: 6 ⁇ m) manufactured by Owens Corning Japan (same), Fiber diameter: 6 ⁇ m), manufactured by Nippon Electric Glass Co., Ltd., chopped glass fiber (ECS03T-747H, average fiber diameter: 10.5 ⁇ m), manufactured by Nippon Electric Glass Co., Ltd., chopped glass fiber (ECS03T-747, average fiber diameter) : 13 ⁇ m), manufactured by Nitto Boseki Co., Ltd., modified cross-section chopped strand CSG 3PA-830 (long diameter 28 ⁇ m, short diameter 7 ⁇ m), manufactured by Nitto Boseki Co., Ltd., modified cross-section chopped strand CSG 3PL-962 (long diameter 20 ⁇ m, short diameter 10 ⁇ m ) and the like.
  • ECS03DE 416A average
  • the fibrous inorganic filler may be surface-treated with various surface treatment agents such as generally known epoxy-based compounds, isocyanate-based compounds, silane-based compounds, titanate-based compounds, and fatty acids. Adhesion to the PAS resin can be improved by surface treatment.
  • the surface treatment agent may be applied to the fibrous inorganic filler in advance for surface treatment or convergence treatment prior to material preparation, or may be added simultaneously during material preparation.
  • the fiber diameter of the fibrous inorganic filler is not particularly limited, it can be, for example, 5 ⁇ m or more and 30 ⁇ m or less in the initial shape (shape before melt-kneading).
  • the fiber diameter of the fibrous inorganic filler refers to the major diameter of the fiber cross section of the fibrous inorganic filler.
  • Powdery inorganic fillers other than basic carbonates include talc (granular), carbon black, silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, silicates such as diatomaceous earth, and iron oxide. , titanium oxide, zinc oxide, alumina (granular) and other metal oxides, calcium sulfate, barium sulfate and other metal sulfates, silicon carbide, silicon nitride, boron nitride, various metal powders, etc., and one of these Or 2 or more types can be used. Among them, glass beads are preferred.
  • Examples of commercially available glass beads include EGB731A (average particle size (50% d): 20 ⁇ m) manufactured by Potters Ballotini Co., Ltd., EMB-10 (average particle size ( 50% d): 5 ⁇ m) and the like.
  • the powdery inorganic filler may also be surface-treated in the same manner as the fibrous inorganic filler.
  • Plate-like inorganic fillers other than basic carbonates include, for example, glass flakes, talc (plate-like), mica, kaolin, clay, alumina (plate-like), and various metal foils. Or 2 or more types can be used. Among them, glass flakes and talc are preferable. Examples of commercially available glass flakes include REFG-108 (average particle diameter (50% d): 623 ⁇ m) manufactured by Nippon Sheet Glass Co., Ltd., Fine Flake (average particle diameter (50% d) manufactured by Nippon Sheet Glass Co., Ltd.
  • talc PP manufactured by Matsumura Sangyo Co., Ltd.
  • Talcan Powder PKNN manufactured by Hayashi Kasei Co., Ltd.
  • the plate-like inorganic filler may also be surface-treated in the same manner as the fibrous inorganic filler.
  • the inorganic filler other than the basic carbonate is preferably one or more selected from the group consisting of glass fibers, glass beads, glass flakes and talc.
  • the inorganic filler containing basic carbonate is preferably included in an amount of 10 to 315 parts by mass with respect to 100 parts by mass of the PAS resin contained in the PAS resin composition. That is, the content of the inorganic filler in the raw material in step C is preferably 10 to 315 parts by mass with respect to 100 parts by mass of the PAS resin.
  • the content of the inorganic filler is more preferably 20 to 300 parts by mass, even more preferably 30 to 280 parts by mass, and particularly preferably 35 to 250 parts by mass.
  • PAS resin prepared separately and/or other additives described later other than the inorganic filler.
  • the PAS resin will be described in step D.
  • the inorganic filler and other components may be added when the PAS resin and masterbatch are blended and melt-kneaded.
  • the inorganic filler, other additives, etc., and the masterbatch may be mixed by a method such as dry blending, and the resulting mixture and the PAS resin may be blended and melt-kneaded.
  • an inorganic filler, and other components for example, the masterbatch, inorganic filler, and other components may be supplied to an extruder.
  • the masterbatch, inorganic fillers, and other ingredients may be dry blended prior to feeding to the extruder.
  • a part of raw materials may be supplied by a side feed system.
  • the present inventors found that when the PAS resin composition contains a basic carbonate, if the amount of heat received by the PAS resin composition in the melt-kneading in step C is further increased, during subsequent injection molding, after molding , the amount of leakage of the PAS resin composition from the tip of the nozzle of the injection molding machine before the start of the next molding cycle can be further suppressed. It is presumed that this is because the amount of CO 2 generated during molding, in addition to the water content described above, also contributes to the leakage amount of the PAS resin composition. CO2 is believed to be generated by the reaction of acid gas derived from PAS resin and basic carbonate.
  • step C it is preferable to melt-knead the raw materials in an extruder and set the cylinder temperature in the extruder to 290 to 380°C. That is, it is preferable to set the set temperature of the cylinder of the extruder during melt-kneading within the above range.
  • the melt-kneading of the raw materials may be performed by an extruder, and the rotational speed of the cylinder of the extruder may be increased.
  • the screw design of the extruder may be changed to a design that increases the heat generation of the PAS resin composition during melt-kneading.
  • the cylinder temperature is preferably 290° C. or higher, more preferably 300° C. or higher, particularly preferably 310° C. or higher, particularly preferably 320° C. or higher, and even more preferably 330° C. or higher.
  • 380 degrees C or less is preferable and 370 degrees C or less is more preferable.
  • the total amount of the condensate of the alkoxysilane compound and the alkoxysilane compound in the finally obtained PAS resin composition is 0.2 to 3.0 parts by mass based on 100 parts by mass of the PAS resin. It is preferable that the masterbatch is blended with the PAS resin and melt-kneaded so that
  • step D When using a raw material containing a PAS resin as another component in step C, it is preferable to provide the following step D.
  • step D a new polyarylene sulfide resin that is the same as or different from the polyarylene sulfide resin used in step A is prepared. Then, in step C, the total amount of the alkoxysilane compound and the condensate of the alkoxysilane compound is 0.2 to 3.0 parts by mass with respect to 100 parts by mass of all polyarylene sulfide resins.
  • the raw materials containing the masterbatch and the polyarylene sulfide resin prepared in step D are melt-kneaded. All the PAS resins are the PAS resin used in the preparation of the masterbatch in step A and the new PAS resin used in step D.
  • the new PAS resin prepared in step D may be the same as or different from the PAS resin used in step A.
  • the melt viscosity of each PAS resin is different, the molecular structure of each PAS resin is different, and the like.
  • Examples of different molecular structures include the following (1) to (3). (1) There is a difference between a molecular structure that is substantially linear and does not have a branched or crosslinked structure and a structure that has a branched or crosslinked structure.
  • the arylene sulfide groups of the structural units are different (for example, the p-phenylene sulfide group and the m-phenylene sulfide group are different).
  • the total amount of the alkoxysilane compound and the condensate of the alkoxysilane compound in the finally obtained PAS resin composition is 0.2 to 3.0 parts by mass with respect to 100 parts by mass of the PAS resin. It is preferable to blend in By blending in such a manner, the fluidity and toughness of the PAS resin composition can be imparted in a well-balanced manner. In addition, the adhesiveness to the inorganic filler is increased, and the mechanical properties are likely to be improved.
  • the total amount of the condensate of the alkoxysilane compound and the alkoxysilane compound is more preferably 0.3 to 2.0 parts by mass with respect to 100 parts by mass of the PAS resin. 0.5 to 1.5 parts by mass is more preferable.
  • the melt viscosity of the PAS resin composition is preferably 150 to 600 Pa s under conditions of a temperature of 310 ° C. and a shear rate of 1000 sec -1 , and preferably 200 to 500 Pa s. more preferred.
  • the PAS resin composition is generally a thermoplastic resin and a thermosetting resin in order to impart desired properties according to its purpose within a range that does not impair the effects (specifically, excellent continuous moldability) of the present embodiment.
  • Known additives that are added to flexible resins can be contained according to the required performance. Additives include flash inhibitors (excluding alkoxysilane compounds), release agents, lubricants, plasticizers, flame retardants, coloring agents such as dyes and pigments, crystallization accelerators, crystal nucleating agents, various oxidation Inhibitors, heat stabilizers, weather stabilizers, corrosion inhibitors, and the like can be mentioned.
  • flash inhibitors include branched polyphenylene sulfides with very high melt viscosities, such as those described in WO 2006/068161 and WO 2006/068159. system resin and the like.
  • release agents include polyethylene wax, fatty acid esters, fatty acid amides, and the like.
  • Crystal nucleating agents include boron nitride, talc, kaolin, carbon black, carbon nanotubes, and the like. Zinc oxide etc. can be mentioned as a corrosion inhibitor.
  • the content of the above additives can be 5% by mass or less in the total resin composition.
  • thermoplastic resins used herein may be any resins that are stable at high temperatures.
  • polyethylene terephthalate, polybutylene terephthalate, etc. aromatic polyesters composed of aromatic dicarboxylic acids and diols, or oxycarboxylic acids, polyamides, polycarbonates, ABS resins (acrylonitrile-butadiene-styrene copolymer synthetic resins), polyphenylene oxides, Polyalkyl acrylates, polysulfones, polyethersulfones, polyetherimides, polyetherketones, fluororesins, liquid crystal polymers, cyclic olefin copolymers and the like can be mentioned.
  • these thermoplastic resins can also be used in mixture of 2 or more types.
  • the content of other thermoplastic resin components can be, for example, 20% by mass or less in the total
  • PAS resin composition in this embodiment can be used for various purposes.
  • PAS resin compositions include automobile cooling system parts, ignition-related parts, distributor parts, various sensor parts, various actuator parts, throttle parts, power module parts, ECU parts, and various connector parts.
  • Example 1 PPS resin (manufactured by Kureha Co., Ltd., Fortron KPS (melt viscosity: 20 Pa s (shear rate: 1200 sec -1 , 310 ° C.)) 100 parts by mass, an alkoxysilane compound ( ⁇ -aminopropyltriethoxysilane (Shin-Etsu Chemical "KBE-903P" manufactured by Kogyo Co., Ltd.))) to prepare a masterbatch, and exposed to an environment at a temperature of 40° C.
  • an alkoxysilane compound ⁇ -aminopropyltriethoxysilane (Shin-Etsu Chemical "KBE-903P" manufactured by Kogyo Co., Ltd.)
  • melt viscosity of PPS resin was measured as follows.
  • the melt viscosities of the PPS resins obtained in Examples 3 and 4 and Comparative Example 1 were also measured as follows.
  • the melt viscosity was measured at a barrel temperature of 310° C. and a shear rate of 1200 sec ⁇ 1 using a capilograph manufactured by Toyo Seiki Seisakusho Co., Ltd. using a flat die of 1 mm ⁇ 20 mmL as a capillary.
  • Example 2 Each resin composition was obtained under the same conditions as in Example 1, except that the ratio of the condensate in the alkoxysilane compound in the masterbatch was changed to the ratio shown in Table 1.
  • Examples 3 and 4, Comparative Example 1 PPS resin (manufactured by Kureha Co., Ltd., Fortron KPS (melt viscosity: 20 Pa s (shear rate: 1200 sec -1 , 310 ° C.)) 100 parts by mass, an alkoxysilane compound ( ⁇ -aminopropyltriethoxysilane (Shin-Etsu Chemical "KBE-903P" manufactured by Kogyo Co., Ltd.))) to prepare a masterbatch, and exposed to an environment at a temperature of 40° C.
  • PPS resin manufactured by Kureha Co., Ltd., Fortron KPS (melt viscosity: 20 Pa s (shear rate: 1200 sec -1 , 310 ° C.)
  • an alkoxysilane compound ⁇ -aminopropyltriethoxysilane (Shin-Etsu Chemical "KBE-903P" manufactured by Kogyo Co., Ltd.)
  • PPS resin manufactured by Kureha Co., Ltd., Fortron KPS (melt viscosity: 20 Pa s (shear rate: 1200 sec -1 , 310 ° C.) 100 parts by mass, 25.9 parts by mass of the masterbatch prepared above, Glass fiber (Owens Corning Japan (same), chopped strand, diameter 10.5 ⁇ m, length 3 mm) 122 parts by mass, calcium carbonate (manufactured by Toyo Fine Chemicals Co., Ltd., Whiten P-30, average particle size (50% d ): 5 ⁇ m) 122 parts by mass were put into a twin-screw extruder at a cylinder temperature of 290° C. and melt-kneaded to obtain a resin composition. The glass fiber was separately added from the side feed section of the extruder. .
  • melt viscosity of resin composition For each resin composition obtained, the melt viscosity was measured at a barrel temperature of 310° C. and a shear rate of 1000 sec ⁇ 1 using a capilograph manufactured by Toyo Seiki Seisakusho Co., Ltd. using a flat die of 1 mm ⁇ 20 mm as a capillary.
  • the cylinder temperature of the injection molding machine was adjusted to 310°C.
  • the inside of the cylinder was replaced with the evaluation sample by purging.
  • the resin composition was injected once, the inside of the cylinder was emptied, the resin composition was measured by 30 mm with a back pressure of 2 MPa, and the resin composition that leaked from the tip of the nozzle was removed immediately after being sucked back by 5 mm.
  • the mass of the leaked resin composition was measured for ⁇ 1 minute after removal.
  • the above measurements were performed 5 times, and the average of the measured values was defined as the amount of resin composition leaking from the tip of the nozzle (g/min).
  • Table 1 shows the evaluation results of each resin composition.
  • Examples 5 to 11 The same conditions as in Example 1 except that the ratio of the condensate in the alkoxysilane compound in the masterbatch was changed to 30% by mass, and the cylinder temperature and cylinder rotation speed of the twin-screw extruder were changed as shown in Table 2. to obtain each resin composition. Then, under the same conditions as in Example 1, the amount (g/min) of the resin composition leaking from the tip of the nozzle and the melt viscosity of the resin composition were measured. Table 2 shows the measurement results. In addition, each resin composition obtained was subjected to the following pretreatment, and then the amount of CO 2 generated was measured by barrier discharge ionization detection gas chromatography.
  • the CO 2 generation amount was rated A when it was 45 ⁇ mol/g or less, and rated B when it was more than 45 ⁇ mol/g and 55 ⁇ mol/g or less.
  • the device configuration of the barrier discharge ionization detection gas chromatography is HS (headspace sampler, Perkin Elmer, TurboMatrix HS40) and GC/BID (Shimadzu Corporation, GC-2010Plus and BID-2010Plus). .
  • HS headspace sampler, Perkin Elmer, TurboMatrix HS40
  • GC/BID Shiadzu Corporation, GC-2010Plus and BID-2010Plus
  • Example 5 and Example 6, Example 7 and Example 8, and Example 9 and Example 10 where the cylinder temperature is the same and the cylinder rotation speed is different, it can be seen that the leakage amount of the PPS resin composition decreases as the cylinder rotation speed increases.
  • the cylinder It can be seen that the leakage amount of the PPS resin composition tends to decrease as the temperature increases.
  • the amount of CO 2 generated can be reduced by setting the cylinder temperature to 290 to 380°C, and the higher the cylinder temperature and the higher the cylinder rotation speed, the more the amount of CO 2 generated tends to decrease. I understand.

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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)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un procédé de production d'une composition de résine de sulfure de polyarylène, le procédé comprenant : une étape A pour préparer un mélange maître par mélange de 0,2 à 50 parties en masse d'une composition d'alcoxysilane avec 100 parties en masse d'une résine de sulfure de polyarylène ayant une viscosité à l'état fondu prescrite; une étape B pour condenser une partie de la composition d'alcoxysilane dans le mélange maître de telle sorte que la proportion de condensat de la composition d'alcoxysilane représente de 0,5 à 60 % en masse de la composition d'alcoxysilane; et une étape C pour faire fondre et malaxer une matière première qui contient le mélange maître obtenu à l'étape B, au moins un type de charge inorganique comprenant un carbonate basique, et un autre composant.
PCT/JP2022/027192 2021-07-30 2022-07-11 Procédé de production d'une composition de résine de sulfure de polyarylène Ceased WO2023008153A1 (fr)

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MYPI2024000592A MY207207A (en) 2021-07-30 2022-07-11 Method for producing polyarylene sulfide resin composition
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JPH07258543A (ja) * 1994-03-22 1995-10-09 Polyplastics Co ポリアリーレンサルファイド樹脂組成物及びその製造方法
JP2006143827A (ja) * 2004-11-18 2006-06-08 Polyplastics Co ポリアリーレンサルファイド樹脂組成物
WO2013141363A1 (fr) * 2012-03-23 2013-09-26 Dic株式会社 Composition de résine de sulfure de polyarylène et corps moulé
JP2013256082A (ja) * 2012-06-13 2013-12-26 Toray Ind Inc 樹脂複合成形体および樹脂複合成形体を製造する方法
JP2021105112A (ja) * 2019-12-26 2021-07-26 ポリプラスチックス株式会社 インサート成形品用ポリアリーレンサルファイド樹脂組成物及びインサート成形品

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US4451601A (en) * 1981-09-10 1984-05-29 Phillips Petroleum Company Glass-filled polyarylene sulfide compositions containing organosilanes
JPH01146955A (ja) * 1987-12-03 1989-06-08 Kureha Chem Ind Co Ltd ポリフェニレンスルフィド樹脂組成物
JP4954516B2 (ja) * 2005-09-14 2012-06-20 ポリプラスチックス株式会社 ポリアリーレンサルファイド樹脂組成物
JP2009249492A (ja) * 2008-04-07 2009-10-29 Toray Ind Inc ポリアリーレンスルフィド樹脂組成物およびポリアリーレンスルフィドフィルム
JP5456983B2 (ja) * 2008-04-17 2014-04-02 ポリプラスチックス株式会社 ポリアリーレンサルファイド樹脂組成物の製造法
JP6201456B2 (ja) * 2013-06-28 2017-09-27 Dic株式会社 ポリアリーレンスルフィド樹脂組成物、成形体およびそれらの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07258543A (ja) * 1994-03-22 1995-10-09 Polyplastics Co ポリアリーレンサルファイド樹脂組成物及びその製造方法
JP2006143827A (ja) * 2004-11-18 2006-06-08 Polyplastics Co ポリアリーレンサルファイド樹脂組成物
WO2013141363A1 (fr) * 2012-03-23 2013-09-26 Dic株式会社 Composition de résine de sulfure de polyarylène et corps moulé
JP2013256082A (ja) * 2012-06-13 2013-12-26 Toray Ind Inc 樹脂複合成形体および樹脂複合成形体を製造する方法
JP2021105112A (ja) * 2019-12-26 2021-07-26 ポリプラスチックス株式会社 インサート成形品用ポリアリーレンサルファイド樹脂組成物及びインサート成形品

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JP7309790B2 (ja) 2023-07-18

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