JP7309790B2 - Method for producing polyarylene sulfide resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a polyarylene sulfide resin composition.

Polyphenylene sulfide (hereinafter also referred to as 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.

Various additives are added to the PAS resin composition to improve various performances. Among such additives, those to which an alkoxysilane compound is added for the purpose of improving toughness have been proposed (see Patent Documents 1 and 2).

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 for improving toughness and moldability in a low-temperature environment. Further, 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. When an alkoxysilane compound such as alkoxyaminosilane reacts with water (moisture in the air, etc.), a condensation reaction occurs between the alkoxysilane compounds before the reaction between the alkoxysilane compound and the PPS resin, and desired mechanical properties can be obtained. Have difficulty. For this reason, in Patent Document 2, a PPS resin that has been dried in advance is used.

WO2019/026869 WO2012/147185

As described above, it is common practice to add an alkoxysilane compound to a PAS resin composition to improve toughness. Such improvement in toughness is attributed to the increase in melt viscosity due to the addition of the alkoxysilane compound. However, when a PAS resin having a low melt viscosity (80 Pa·s or less) is used, the melt viscosity of the PAS resin composition tends to be low. In particular, if the condensate of the alkoxysilane compound is present, the effect of increasing the melt viscosity due to the addition of the alkoxysilane compound cannot be achieved, and the melt viscosity tends to decrease further. When the melt viscosity of the PAS resin composition is low, the fluidity is high. Therefore, during injection molding, 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. In addition, the present inventors have 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.

In the present invention, when an inorganic filler containing a basic carbonate is contained, leakage of the PAS resin composition during injection molding is remarkable, and the cause is found to be moisture in the PAS resin composition. It was made.

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 raw material containing a masterbatch having a ratio of the condensate of the alkoxysilane compound within the above range, at least one inorganic filler containing a basic carbonate, and other components Melt-kneading step C,
A method for producing a polyarylene sulfide resin composition, comprising:

(2) further 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;
In the step C, in the step B, 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. The method for producing a polyarylene sulfide resin composition according to (1) above, wherein the raw material containing the obtained masterbatch and the polyarylene sulfide resin prepared in the step D are melt-kneaded.

(3) The polyarylene sulfide resin composition according to (1) or (2), wherein in the step C, the raw materials are melt-kneaded by an extruder, and the cylinder temperature in the extruder is set to 290 to 380°C. A method of making things.

(4) Any one of (1) to (3) above, wherein the content of the inorganic filler in the raw material in the step C is 10 to 315 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin composition. A method for producing the polyarylene sulfide resin composition according to 1.

(5) Any one of (1) to (4) above, wherein the alkoxysilane compound contains at least one selected from the group consisting of epoxyalkoxysilane, aminoalkoxysilane, vinylalkoxysilane, and mercaptoalkoxysilane. A method for producing the described polyarylene sulfide resin composition.

(6) The alkoxysilane compound is γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-(β-aminoethyl) -γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-diallylaminopropyltrimethoxysilane, and γ-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).

(7) The method for producing a polyarylene sulfide resin composition according to any one of (1) to (6) above, wherein the polyarylene sulfide resin composition has a melt viscosity of 150 to 600 Pa·s.

According to the present invention, it is possible to provide a method for producing a polyarylene sulfide resin composition having good continuous moldability while using a low melt viscosity polyarylene sulfide resin, an alkoxysilane compound, and a basic carbonate in combination. can.

The present embodiment will be described in detail below, but the present embodiment is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the purpose of the present embodiment. .

In this specification and the like, a masterbatch means a mixture obtained by simply stirring raw materials without heating, melt-kneading, or pelletizing.

<Method for producing polyarylene sulfide resin composition>
In the method for producing the polyarylene sulfide resin composition of the present embodiment, 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 A of mixing 2 to 50 parts by mass of an alkoxysilane compound to prepare a masterbatch is included. Further, 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.

As described above, 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. However, even if 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]
In 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.

When 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.

[material]
(polyarylene sulfide resin)
The PAS resin is a resin mainly composed of -(Ar-S)- as a structural unit (Ar represents an arylene group). In this embodiment, a polyarylene sulfide resin having a generally known molecular structure can be used. For example, 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.

As the homopolymer, one having a p-phenylene group as an arylene group and having a p-phenylene sulfide group as a structural unit is 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.

As the copolymer, a combination of two or more different arylene sulfide groups among the arylene sulfide groups containing the above arylene groups can be used. Among these, 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).

In general, 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.
In addition, in the present embodiment, 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)
The 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.

Examples of epoxyalkoxysilanes include γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and the like.

Examples of aminoalkoxysilanes include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-(β-aminoethyl)- γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-diallylaminopropyltrimethoxysilane, γ-diallylaminopropyltriethoxysilane and the like, one or more of these is used.

Examples of vinylalkoxysilanes include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, and the like.

Examples of mercaptoalkoxysilanes include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and the like.

Among these, epoxyalkoxysilanes and aminoalkoxysilanes are preferred, and γ-aminopropyltriethoxysilane is particularly preferred.

[Step B]
In the 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.

From the viewpoint of obtaining excellent continuous moldability of the PAS resin composition, the proportion 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 (1) adjusting the humidity of the environment in which the alkoxysilane compound and masterbatch are stored and the water vapor transmission rate of the system, and (2) the storage time of the alkoxysilane compound and masterbatch. (3) adjusting the mixing ratio of the PAS resin and the alkoxysilane compound in the masterbatch in step A, and the like. As a specific example, for example, 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. In addition, 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. When 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.
Alternatively, after the condensate of the alkoxysilane compound is produced by the methods (1) to (3) above, 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.

In the PAS resin composition, which is the final product, a distinction is made between a condensate of the alkoxysilane compound condensed by reacting with the PAS resin and a condensate of the alkoxysilane compound condensed by reacting with water. I can't. Therefore, it is necessary to adjust the amount of the condensate of the alkoxysilane compound that reacts with water and condenses in the state of the masterbatch.

Here, an example of a method for calculating the ratio of the condensate of the alkoxysilane compound in the masterbatch will be described.

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.

First, the mass A of the aluminum cup is measured with a precision balance (step 1).

Next, the aluminum cup is placed on a precision balance, and zero adjustment is performed. Further, the membrane filter is placed on the aluminum cup, and the mass B of the membrane filter is measured (step 2). Next, the weighed membrane filter is placed in a suction funnel (step 3). At this time, the precision balance has only an aluminum cup.

Next, put the masterbatch in an aluminum cup and measure the mass C (step 4). Next, 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).

Next, while washing around the funnel, add acetone, 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).

Next, the residue and the membrane filter are put 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

In the above formula, E represents the concentration (g/g) of the alkoxysilane compound in the masterbatch, and F represents the concentration (g/g) of acetone-soluble substances other than the alkoxysilane compound in the masterbatch.

Through the above steps, the ratio of the condensate of the alkoxysilane compound in the masterbatch can be calculated.

In the present embodiment, 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.
However, even if 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. For example, when the ratio of the condensate in the condensate in the masterbatch is increased, the ratio of the amount of the condensate can be lowered by newly adding an alkoxysilane compound when charging the masterbatch into the extruder.

[Step C]
In 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.

(Inorganic filler)
In this embodiment, from the viewpoint of improving mechanical properties, 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 μm) manufactured by Toyo Fine Chemical Co., Ltd.).

In the present embodiment, when 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.

Next, inorganic fillers other than basic carbonates will be described.

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 μm) manufactured by Nippon Electric Glass Co., Ltd., chopped glass fiber (CS03DE 416A, average fiber diameter: 6 μm) manufactured by Owens Corning Japan (same). Fiber diameter: 6 μm), manufactured by Nippon Electric Glass Co., Ltd., chopped glass fiber (ECS03T-747H, average fiber diameter: 10.5 μm), manufactured by Nippon Electric Glass Co., Ltd., chopped glass fiber (ECS03T-747, average fiber diameter) : 13 μm), Nitto Boseki Co., Ltd., modified cross-section chopped strand CSG 3PA-830 (major axis 28 μm, minor axis 7 μm), Nitto Boseki Co., Ltd., modified cross-section chopped strand CSG 3PL-962 (major axis 20 μm, minor axis 10 μm) ) and the like.

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.

Although the fiber diameter of the fibrous inorganic filler is not particularly limited, it can be, for example, 5 μm or more and 30 μm or less in the initial shape (shape before melt-kneading). Here, 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 μm) manufactured by Potters Ballotini Co., Ltd., EMB-10 (average particle size ( 50% d): 5 μm) 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 μm) manufactured by Nippon Sheet Glass Co., Ltd., Fine Flake (average particle diameter (50% d) manufactured by Nippon Sheet Glass Co., Ltd. d): 169 μm), manufactured by Nippon Sheet Glass Co., Ltd., REFG-301 (average particle size (50% d): 155 μm), manufactured by Nippon Sheet Glass Co., Ltd., REFG-401 (average particle size (50% d): 310 μm ) and the like.
Examples of commercially available talc products include Crown Talc PP manufactured by Matsumura Sangyo Co., Ltd., Talcan Powder PKNN manufactured by Hayashi Kasei Co., Ltd., and the like.
The plate-like inorganic filler may also be surface-treated in the same manner as the fibrous inorganic filler.

In the present embodiment, 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.
From the viewpoint of improving mechanical properties, 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.

Other components include the PAS resin prepared separately and/or other additives described later other than the inorganic filler. Among them, 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. Alternatively, 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.

In order to melt-knead the raw material containing the masterbatch, the inorganic filler, and other components, for example, the masterbatch, the inorganic filler, and the other components may be supplied to an extruder, or the master The batch, inorganic fillers, and other ingredients may be dry-blended and then fed into the extruder, or some raw materials may be side-fed.

On the other hand, 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 from the PAS resin and basic carbonate. It is presumed that the amount of CO ₂ generated during molding is suppressed by increasing the amount of heat given to the PAS resin composition during melt-kneading. Therefore, in order to increase the amount of heat given to the PAS resin composition during melt-kneading, in 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. In addition, in order to increase the amount of heat given to the PAS resin composition during melt-kneading, the melt-kneading of the raw materials may be performed using an extruder, and the number of rotations of the cylinder of the extruder may be increased, or the screw design of the extruder may be adjusted to the melting point. The design may be changed so that the PAS resin composition generates more heat during 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. Moreover, 380 degrees C or less is preferable and 370 degrees C or less is more preferable. In addition, regarding the number of rotations of the cylinder, it cannot be said unconditionally because the preferable number of rotations is not uniquely determined depending on the discharge amount and the size of the extruder. However, for example, in the case of an extruder having a cylinder diameter of 30 mm, Q (kg/h) (discharge rate)/Ns (rpm) (screw rotation speed) is preferably 0.07 to 0.20.

When the step C is finished, 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

In step C, when using a raw material containing a PAS resin as another component, it is preferable to provide the following step D.

[Step D]
In 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. When the new PAS resin prepared in step D is 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: (1) a structure that is substantially linear and does not have a branched or crosslinked structure, and a structure that has a branched or crosslinked structure, and (2) a homopolymer and a copolymer. , (3) different arylene sulfide groups in structural units (for example, different p-phenylene sulfide groups and m-phenylene sulfide groups);

In step C, 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. In the finally obtained PAS resin composition, 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.

Further, from the viewpoint of improving moldability, the melt viscosity of the PAS resin composition is preferably 150 to 600 Pa s under the conditions of a temperature of 310 ° C. and a shear rate of 1000 sec ^-1 , and preferably 200 to 500 Pa s. more preferred.

Other components used as part of the raw materials in step C are described below.

(other additives, etc.)
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. Examples of flash inhibitors (excluding alkoxysilanes) 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. Examples of 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.

In addition to the components described above, the PAS resin composition may optionally contain a small amount of other thermoplastic resin components in addition to the components described above. Other thermoplastic resins used herein may be any resins that are stable at high temperatures. For example, 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. Moreover, 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 resin composition.

The PAS resin composition in this embodiment can be used for various purposes. Examples of 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.

In addition, as other applications, for example, LEDs, sensors, sockets, terminal blocks, printed circuit boards, motor parts, electric and electronic parts such as ECU cases, lighting parts, TV parts, rice cooker parts, microwave oven parts, iron parts, It can be used for domestic and office electrical product parts such as copier-related parts, printer-related parts, facsimile-related parts, heaters, and air-conditioner parts.

EXAMPLES The present embodiment will be more specifically described below with reference to Examples, but the interpretation of the present embodiment is not limited by these Examples.

[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 (γ-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. and a humidity of 70% RH for 5 minutes.Alkoxysilane compound in the masterbatch The ratio of the condensate in the medium was 33% by mass.The amount of condensate described below was prepared by appropriately changing the exposure time in an environment of temperature 40° C. and humidity 70% RH, as described above.
Next, 100 parts by mass of the masterbatch prepared above, 97 parts by mass of glass fiber (manufactured by Owens Corning Japan (the same company), chopped strand, diameter 10.5 μm, length 3 mm), calcium carbonate (manufactured by Toyo Fine Chemical Co., Ltd. , Whiten P-30, average particle size (50% d): 5 μm) 97 parts by mass are melt-kneaded by introducing them into a twin-screw extruder having a cylinder temperature of 290 ° C. and a cylinder rotation speed of 240 rpm to obtain a resin composition. got The glass fiber was separately added from the side feed section of the extruder.

(Measurement of melt viscosity of PPS resin)
The melt viscosity of the 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 mmφ×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 (γ-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. and a humidity of 70% RH for 5 minutes.Alkoxysilane compound in the masterbatch The ratio of condensate in the mixture was 29% by mass.The amount of condensate described below was prepared by appropriately changing the exposure time in an environment of temperature 40° C. and humidity 70% RH, as described above.
Next, 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 μm, 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 μm) 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. .

(Measurement of 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 mmφ×20 mm as a capillary.

[evaluation]
For each of the obtained resin compositions, the amount of resin composition leaking from the nozzle tip of an injection molding machine ("EC60Ni1.5A" manufactured by Toshiba Machine Co., Ltd.) after injection molding was evaluated. The evaluation method is shown below.

First, the cylinder temperature of the injection molding machine was adjusted to 310°C. Next, the inside of the cylinder was replaced with the evaluation sample by purging. Next, 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.

From Table 1, it can be seen that as the ratio of the condensate in the alkoxysilane compound in the masterbatch increases, the amount of the PPS resin composition leaking from the tip of the nozzle increases and the continuous moldability deteriorates. Therefore, a PPS resin composition having excellent continuous moldability can be obtained when the ratio of the condensate in the alkoxysilane compound in the masterbatch is in the range of 0.5 to 60% by mass.

[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 µmol/g or less, and rated B when it was more than 45 µmol/g and 55 µmol/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). .
<Pretreatment>
After freeze-milling, the pellets were dried at 140° C. for 2 hours and then heated at 340° C. for 15 minutes.

From Table 2, comparison between 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. In addition, from the comparison of Example 5, Example 7, Example 9, and Example 11, and the comparison of Example 6, Example 8, and Example 10, in which the cylinder rotation speed is the same and the cylinder temperature is different, the cylinder It can be seen that the leakage amount of the PPS resin composition tends to decrease as the temperature increases.
On the other hand, 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.

Claims (7)

A masterbatch is prepared by mixing 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 . Step A of preparing
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 raw material containing a masterbatch having a ratio of the condensate of the alkoxysilane compound within the above range, at least one inorganic filler containing a basic carbonate, and other components Melt-kneading step C,
A method for producing a polyarylene sulfide resin composition, comprising: Further 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,
In the step C, in the step B, 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. 2. The method for producing a polyarylene sulfide resin composition according to claim 1, wherein the raw material containing the obtained masterbatch and the polyarylene sulfide resin prepared in step D are melt-kneaded. 3. The method for producing a polyarylene sulfide resin composition according to claim 1, wherein in the step C, the raw materials are melt-kneaded by an extruder, and the cylinder temperature in the extruder is set to 290 to 380° C. The content of the inorganic filler in the raw material in the step C is 10 to 315 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin composition, The poly according to any one of claims 1 to 3 A method for producing an arylene sulfide resin composition. The polyarylene according to any one of claims 1 to 4, wherein the alkoxysilane compound contains at least one selected from the group consisting of epoxyalkoxysilane, aminoalkoxysilane, vinylalkoxysilane, and mercaptoalkoxysilane. A method for producing a sulfide resin composition. The alkoxysilane compound is γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-(β-aminoethyl)-γ- The claim comprising at least one selected from the group consisting of aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-diallylaminopropyltrimethoxysilane, and γ-diallylaminopropyltriethoxysilane. 6. A method for producing the polyarylene sulfide resin composition according to any one of 1 to 5. The method for producing a polyarylene sulfide resin composition according to any one of claims 1 to 6, wherein the polyarylene sulfide resin composition has a melt viscosity of 150 to 600 Pa·s.