CN115066459A

CN115066459A - Method for producing polyarylene sulfide resin composition

Info

Publication number: CN115066459A
Application number: CN202180013613.7A
Authority: CN
Inventors: 立堀良祐
Original assignee: Polyplastics Co Ltd
Current assignee: Polyplastics Co Ltd
Priority date: 2020-02-10
Filing date: 2021-02-09
Publication date: 2022-09-16
Anticipated expiration: 2041-02-09
Also published as: WO2021161996A1; JP6968322B1; CN115066459B; MY196806A; JPWO2021161996A1

Abstract

The present invention provides a method for producing a polyarylene sulfide resin composition, including: relative to a shear rate of 1200sec at a temperature of 310 deg.C ^‑1 A step A of preparing a master batch 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 80 to 250 pas measured below; condensing a part of the alkoxysilane compound in the master batch to condense the alkoxysilane compoundA step B in which the content of the compound (A) is 10 to 60 mass% based on the alkoxysilane compound; and a step C of melt-kneading the raw materials containing the master batch obtained in the step B, that is, the master batch in which the ratio of the condensate of the alkoxysilane compound is within the above-mentioned range, and other components.

Description

Method for producing polyarylene sulfide resin composition

Technical Field

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

Background

Polyphenylene sulfide (hereinafter, also referred to as PPS) resin, which is one of polyarylene sulfide (hereinafter, also referred to as PAS) resins, has high heat resistance, mechanical and physical properties, chemical resistance, and flame retardancy, and is therefore used in a wide range of fields including extrusion molding and injection molding applications, and various automobile parts, electric and electronic parts, and the like.

Various additives are added to the PAS resin composition to improve various properties. Among such additives, it has been proposed to add an alkoxysilane compound for the purpose of improving toughness (see patent document 1).

Patent document 1 describes a method for producing a polyarylene sulfide resin composition in which an alkoxyaminosilane is added to a PPS resin for the purpose of improving toughness, thereby improving weld strength. When an alkoxysilane compound such as an alkoxyaminosilane is reacted with water (moisture in the air, etc.), a condensation reaction between the alkoxysilane compounds occurs before the alkoxysilane compound reacts with the PPS resin, and it is difficult to obtain desired mechanical physical properties. Therefore, patent document 1 uses a PPS resin to which a drying treatment is applied in advance.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2012/147185

Disclosure of Invention

Problems to be solved by the invention

However, in the case of obtaining a resin molded article having a desired shape by filling a mold with a thermoplastic resin in a molten state as in the injection molding method, a thimble (Ejector pin) or the like is generally used for the purpose of easily taking out the molded resin molded article from the mold.

However, the PPS resin composition according to patent document 1 has a high mold release resistance, and therefore, sticking to a mold is likely to occur, and further, a mold release failure is likely to occur. Therefore, when the resin molded product is ejected by an ejector pin or the like at the time of releasing the resin molded product from the mold, appearance defects, deformation, and the like of the resin molded product due to the ejector pin trace or penetration of the ejector pin occur, which is a problem. Further, as described in patent document 1, since a condensate of an alkoxysilane compound may affect mechanical properties and the like, a measure that does not cause a condensation reaction, such as a drying treatment, is generally taken.

Further, when the alkoxysilane compound is added to the PPS resin, the melt viscosity of the PPS resin composition tends to increase, and thus the fluidity of the PPS resin composition tends to be lowered. In particular, when a PPS resin having a high melt viscosity (80Pa · s or more) is used, the fluidity is remarkably reduced.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing a polyarylene sulfide resin composition having good fluidity while suppressing a mold release failure even when a polyarylene sulfide resin having a high melt viscosity and an alkoxysilane compound are used in combination.

Means for solving the problems

In the PAS resin composition containing an alkoxysilane compound, a reaction is generally adopted in which a condensate of the alkoxysilane compound which does not affect mechanical properties or the like is not generated, but the present invention has been completed by finding that when the condensate of the alkoxysilane compound is present at a predetermined ratio, a good fluidity can be obtained while suppressing a mold release failure.

An aspect of the present invention to achieve the above object is as follows.

(1) A method for producing a polyarylene sulfide resin composition, comprising:

step A: relative to a shear rate of 1200sec at a temperature of 310 DEG C ^-1 100 parts by mass of a polyarylene sulfide resin having a melt viscosity of 80 to 250 pas measured below, and 0.2 to 50 parts by mass of an alkoxysilane compoundTo prepare a masterbatch;

and a step B: condensing a part of the alkoxysilane compound in the master batch so that a ratio of the condensate of the alkoxysilane compound is 10 mass% or more and 60 mass% or less of the alkoxysilane compound; and

step C: the raw materials containing the master batch obtained in step B, that is, the master batch in which the ratio of the condensate of the alkoxysilane compound is within the above range and other components are melt-kneaded.

(2) The process for producing a polyarylene sulfide resin composition according to the above (1),

further comprising a step D of preparing a new polyarylene sulfide resin which is the same as or different from the polyarylene sulfide resin used in the step A,

in the step C, a raw material containing the master batch obtained in the step B and the polyarylene sulfide resin prepared in the step D is melt-kneaded so that the total amount of the condensate of the alkoxysilane compound and the alkoxysilane compound is 0.2 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the entire polyarylene sulfide resin.

(3) The process for producing a polyarylene sulfide resin composition according to the above (1) or (2),

the alkoxysilane compound contains at least 1 selected from the group consisting of an epoxyalkoxysilane, an aminoalkoxysilane, a vinylalkoxysilane, and a mercaptoalkoxysilane.

(4) The process for producing a polyarylene sulfide resin composition according to any one of the above (1) to (3),

the alkoxysilane compound includes at least 1 selected from the group consisting of gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, gamma-diallylaminopropyltrimethoxysilane, and gamma-diallylaminopropyltriethoxysilane.

(5) The method for producing a polyarylene sulfide resin composition according to any one of the items (1) to (4),

the polyarylene sulfide resin composition has a mold release resistance of 410N or less.

(6) The process for producing a polyarylene sulfide resin composition according to any one of (1) to (5),

at a temperature of 310 ℃ and a shear rate of 1000sec ^-1 The polyarylene sulfide resin composition has a melt viscosity of 470 pas or less as measured below.

(7) The process for producing a polyarylene sulfide resin composition according to any one of (1) to (6),

and an inorganic filler which is contained in the polyarylene sulfide resin composition in an amount of 10 to 190 parts by mass based on 100 parts by mass of the polyarylene sulfide resin.

Effects of the invention

Embodiments of the present invention can provide a method for producing a polyarylene sulfide resin composition having good fluidity while suppressing poor mold release even when a polyarylene sulfide resin having a high melt viscosity and an alkoxysilane compound are used in combination.

Drawings

Fig. 1 is a diagram illustrating a double cylindrical molded article, in which (a) is a plan view, (b) is a bottom view, (c) is a perspective view, and (d) is a dimensional view.

Detailed Description

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

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

< method for producing polyarylene sulfide resin composition >

The method for producing the polyarylene sulfide resin composition of the present embodiment includes: relative to a shear rate of 1200sec at a temperature of 310 deg.C ^-1 100 parts by mass of a polyarylene sulfide resin having a melt viscosity of 80 pas to 250 pas measured below,and a step A of mixing 0.2 to 50 parts by mass of an alkoxysilane compound to prepare a master batch. Further, the method comprises a step (B) of condensing a part of the alkoxysilane compound in the master batch so that the ratio of the condensate of the alkoxysilane compound is 10 to 60 mass% based on the alkoxysilane compound. Further, the method comprises a step C of melt-kneading the raw materials containing the master batch obtained in the step B, that is, the master batch in which the ratio of the condensate of the alkoxysilane compound is in the above-mentioned range, and other components.

When water (moisture in the PAS resin or moisture in the air) is present in the master batch prepared by mixing the alkoxysilane compound with the PAS resin, the alkoxysilane compound is hydrolyzed and the alkoxysilane compound is condensed. The condensate formation means that the alkoxysilane compound is decreased, and the effect of increasing the melt viscosity of the alkoxysilane compound is decreased and the fluidity is improved as the condensate is increased. Further, conventionally, the presence of a condensate of an alkoxysilane compound has affected mechanical properties, and therefore, it is generally dealt with so as not to cause a condensation reaction.

On the other hand, the present inventors have conducted intensive studies and, as a result, have found that: when the melt viscosity of the PAS resin is 80Pa · s or more and 250Pa · s or less, the condensate of the alkoxysilane compound increases the mold release resistance. That is, in order to improve the releasability, the smaller the condensate amount of the alkoxysilane compound, the better. Therefore, when the condensate of the alkoxysilane compound is present at an appropriate ratio, the melt viscosity decreases to improve the fluidity, and the increase in the mold release resistance can be suppressed. Therefore, in the present embodiment, by intentionally generating a condensate of an alkoxysilane compound and defining the content ratio of the condensate, improvement in fluidity and suppression of mold release failure are achieved.

The respective steps will be explained below.

[ Process A ]

In the step A, 0.2 to 50 parts by mass of an alkoxysilane compound is mixed with 100 parts by mass of a polyarylene sulfide resin having a melt viscosity of 80 to 250 pas measured at a temperature of 310 ℃ and a shear rate of 1200sec-1 to prepare a master batch.

When the content of the alkoxysilane compound mixed at the time of preparing the master batch is 0.2 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the PAS resin, the ratio of the condensate of the alkoxysilane compound with respect to the alkoxysilane compound in the master batch can be easily adjusted to a predetermined ratio. Further, clogging of the piping can be suppressed, and handling is facilitated. The content of the alkoxysilane compound is 0.2 to 50 parts by mass, preferably 0.3 to 25 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 1.0 to 10 parts by mass, based on 100 parts by mass of the PAS resin.

Examples of a method for producing the master batch include a method of dry-blending a PAS resin and an alkoxysilane compound, and a mixing method using a tumbler, a henschel mixer, or the like is preferable.

The raw materials used in step A will be described below.

[ raw materials ]

(polyarylene sulfide resin)

The PAS resin is a resin mainly composed of- (Ar-S) -as a structural unit (Ar represents an arylene group). In the present embodiment, a polyarylene sulfide resin having a generally known molecular structure can be used. For example, as the arylene group, a phenylene group such as a p-phenylene group, a m-phenylene group, and an o-phenylene group, a p, p '-biphenylene group, a p, p' -diphenylene ether group, a p, p '-diphenylene carbonyl group, a p, p' -diphenylene sulfo group, and a naphthylene group can be used.

The PAS resin may be a copolymer containing different structural units depending on the application, in addition to a homopolymer having the same structural unit, among the structural units represented by- (Ar-S) -.

The homopolymer is preferably a homopolymer having a p-phenylene group as an arylene group and a p-phenylene sulfide group as a structural unit. 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 region. By using such a homopolymer, a molded article having very excellent physical properties can be obtained.

As the copolymer, can use containing arylene sulfide, different 2 or more different aryl sulfide combination. Among them, a combination containing a p-phenylene sulfide group and a m-phenylene sulfide group is preferable from the viewpoint of obtaining a molded article having high physical properties such as heat resistance, moldability, and mechanical properties.

More preferably, the polymer contains 70 mol% or more of p-phenylene sulfide groups, and still more preferably 80 mol% or more of p-phenylene sulfide groups. The PAS resin having a phenylene sulfide group is a polyphenylene sulfide resin (PPS resin).

Generally, PPS resins are known to have a molecular structure substantially linear without a branched or crosslinked structure and a molecular structure having a branched or crosslinked structure, depending on the production method thereof, but any type of PAS resin may be used.

From the viewpoint of toughness and fluidity, the temperature was 310 ℃ and the shear rate was 1200sec ^-1 Under the condition (1), the PAS resin has a melt viscosity of 80 PAS to 250 PAS. Preferably 85 to 230 pas, more preferably 90 to 220 pas, and still more preferably 95 to 200 pas.

Further, the present embodiment has achieved a problem of causing a mold release failure and a decrease in flowability, which may occur when a PAS resin having a melt viscosity of 80Pa · s or more and 250Pa · s or less and an alkoxysilane compound are used. Therefore, the present embodiment does not include a PAS resin having a melt viscosity of less than 80Pa · s.

(alkoxysilane compound)

The alkoxysilane compound is not particularly limited, and examples thereof include epoxyalkoxysilane, aminoalkoxysilane, vinylalkoxysilane, mercaptoalkoxysilane, and the like, and 1 or 2 or more of these may be used. The number of carbon atoms of the alkoxy group is preferably 1 to 10, and particularly preferably 1 to 4.

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

Examples of aminoalkoxysilanes include gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane, N- (. beta. -aminoethyl) -gamma-aminopropyltrimethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, gamma-diallylaminopropyltrimethoxysilane, and gamma-diallylaminopropyltriethoxysilane.

Examples of the vinyl alkoxysilane include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (. beta. -methoxyethoxy) silane, and the like.

Examples of the mercaptoalkoxysilane include γ -mercaptopropyltrimethoxysilane and γ -mercaptopropyltriethoxysilane.

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

[ Process B ]

In the step B, a part of the alkoxysilane compound in the master batch is condensed to make the ratio of the condensate of the alkoxysilane compound to 10 mass% or more and 60 mass% or less of the alkoxysilane compound.

From the viewpoint of obtaining excellent flowability and mold releasability of the PAS resin composition, the ratio of the condensate in the alkoxysilane compound in the master batch is 10 mass% or more and 60 mass% or less. The ratio of the condensate is preferably 15 to 55 mass%, more preferably 20 to 50 mass%.

The amount of the condensate of the alkoxysilane compound depends on the amount of the hydrolyzed alkoxysilane compound. Examples of the method for adjusting the amount of the condensate of the alkoxysilane compound include (1) adjusting the humidity of the environment in which the alkoxysilane compound and the master batch are stored and the water vapor transmission rate of the system, (2) adjusting the storage time of the alkoxysilane compound and the master batch, and (3) adjusting the mixing ratio of the PAS resin and the alkoxysilane compound in the master batch in the step a. As a specific example, the master batch in the step a is adjusted to 2 parts by mass of an alkoxysilane compound with respect to 100 parts by mass of the PAS resin, and the amount of the condensate is 24% by mass when stored at 40 ℃ and a humidity of 80% RH for 20 minutes, and the master batch in the step a is adjusted to 25 parts by mass of the alkoxysilane compound with respect to 100 parts by mass of the PAS resin, and the amount of the condensate is 1% by mass when stored at 23 ℃ and a humidity of 40% RH for 10 minutes. When the amount of the condensate of the alkoxysilane compound is 10 to 60% by mass, a PAS resin composition having excellent flowability and releasability can be obtained.

Further, the amount of the condensate of the alkoxysilane compound can also be adjusted by forming a condensate of the alkoxysilane compound by the methods (1) to (3) and then adding a new amount of the alkoxysilane compound to reduce the quantitative ratio of the condensate. For example, even if the ratio of the condensate exceeds 60 mass%, the ratio of the condensate can be finally adjusted to more than 5 mass% and 60 mass% or less by further adding the alkoxysilane compound.

In addition, in the PAS resin composition as a final product, a condensate of an alkoxysilane compound condensed by reacting with a PAS resin and a condensate of an alkoxysilane compound condensed by reacting with water cannot be distinguished. Therefore, it is necessary to adjust the amount of the condensate of the alkoxysilane compound which is condensed by reaction with water in the form of a master batch.

An example of a method for calculating the condensate ratio of the alkoxysilane compound in the master batch is described here.

The master batch contains at least a PAS resin, an alkoxysilane compound, and a condensate of an alkoxysilane compound produced by hydrolysis of the alkoxysilane compound.

In addition, the alkoxysilane compound is soluble in acetone, and the condensate of the alkoxysilane compound is insoluble in acetone.

First, the mass a of the aluminum cup was weighed by a precision balance (step 1).

Next, the aluminum cup was set to zero with the precision balance placed thereon, and then the membrane filter was placed on the aluminum cup, and the mass B of the membrane filter was weighed (step 2). Next, the membrane filter after the measurement is set on a suction funnel (step 3). At this time, only an aluminum cup is arranged on the precision balance.

Next, the master batch was put into an aluminum cup, and mass C was weighed (step 4). Next, the weighed master batch was put into a funnel provided with a membrane filter. The aluminum cup was washed with acetone, and the washing solution was also put into the funnel (step 5).

Next, acetone was added while washing the periphery of the funnel, stirred with a spatula for about 3 seconds, and suction-filtered. The step of adding acetone, stirring with a spatula, and suction-filtering was further performed 2 times (step 6).

Next, the residue and the membrane filter were placed on an aluminum cup, dried at 40 ℃ for 2 hours with a vacuum dryer, and weighed for mass D (step 7).

The condensate ratio in the alkoxysilane compound is represented by the following formula.

The condensate ratio (% by mass) is (mass of condensate in alkoxysilane compound contained in master batch/mass of alkoxysilane compound mixed at the time of master batch preparation) × 100 { [ { mass D- (mass a + mass B) } -mass C × (1-E-F) ]/(mass C × E) } × 100 { [ mass D { [ mass a + mass B) } -mass C × (1-E-F) ]/(mass C × E) } × 100 { (mass C × C { (mass B) } mass C { (mass B) } B { (mass C { (mass B) } B { (mass C { (B) } B)

In the above formula, E represents the concentration (g/g) of the alkoxysilane compound in the master batch, and F represents the concentration (g/g) of acetone other than the alkoxysilane compound dissolved in the master batch.

Through the above steps, the condensation product ratio of the alkoxysilane compound in the master batch can be calculated.

In the present embodiment, a part of the alkoxysilane compound in the master batch prepared in step a is condensed in step B, and when the time between step a and step B is long, it is preferable to store the master batch in a dry state so that the condensation reaction does not occur due to moisture.

Alternatively, when the time from the end of the steps a and B to the end of the step C is long, it is preferable to store the master batch obtained in the step B in a dry state so that the ratio of the condensate does not change.

Of course, even when the ratio of the condensate in the master batch is changed, the amount of the condensate in the master batch when fed to the extruder may satisfy a predetermined range. For example, when the ratio of the condensate in the master batch is increased, the alkoxysilane compound can be newly added to reduce the ratio of the amount of the condensate when the master batch is fed into the extruder.

[ Process C ]

In the step C, the master batch containing the master batch obtained in the step B, that is, the condensate of the alkoxysilane compound in a ratio within the above range and other components are melt-kneaded.

Examples of the other components include a separately prepared PAS resin, an inorganic filler described later, and other additives. The PAS resin will be described in step D.

The other components may be added when the PAS resin and the master batch are mixed and melt-kneaded. Further, the other additives and the master batch may be mixed by a method such as dry blending, and the obtained mixture and the PAS resin may be mixed together and melt-kneaded.

As a method of melt-kneading raw materials containing a master batch and other components, for example, the PAS resin and the master batch may be supplied separately to an extruder, or the PAS resin, the master batch, other additives, and the like may be dry-blended and then supplied to the extruder, or a part of the raw materials may be supplied by side feeding.

Preferably, at the end of step C, the PAS resin composition finally obtained is melt-kneaded by mixing the master batch with the PAS resin so that 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 the PAS resin.

In the case where a raw material containing a PAS resin is used as another component in the step C, the following step D is preferably provided.

[ Process 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 raw material containing the master batch obtained in step B and the polyarylene sulfide resin prepared in step D is melt-kneaded so that the total amount of the condensate of the alkoxysilane compound and the alkoxysilane compound is 0.2 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the entire polyarylene sulfide resin. All PAS resins refer to the PAS resin used for preparing the master batch 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 new PAS resin prepared in step D is different from the PAS resin used in step a, and examples thereof include different melt viscosities of the PAS resins and different molecular structures of the PAS resins. As examples of the difference in molecular structure, there are the following: (1) a molecular structure having a substantially linear structure and no branched or crosslinked structure, a structure different from a structure having a branched or crosslinked structure, (2) a homopolymer different from a copolymer, (3) an arylthioether group different from a structural unit (for example, a p-phenylene thioether group and a m-phenylene thioether group), and the like.

In the step C, the total amount of the alkoxysilane compound and the condensate of the alkoxysilane compound in the finally obtained PAS resin composition is preferably 0.2 to 3.0 parts by mass based on 100 parts by mass of the PAS resin. By mixing in this manner, the flow properties and mold release properties of the PAS resin composition can be imparted in a well-balanced manner. In addition, when an inorganic filler is used, the adhesion with the inorganic filler is improved, and the mechanical properties are easily improved. In the finally obtained PAS resin composition, the total amount of the alkoxysilane compound and the condensate of the alkoxysilane compound is more preferably 0.3 parts by mass or more and 2.0 parts by mass or less, and still more preferably 0.5 parts by mass or more and 1.5 parts by mass or less, with respect to 100 parts by mass of the PAS resin.

Further, the PAS resin composition has a melt viscosity at a temperature of 310 ℃ and a shear rate of 1000sec ^-1 Under the condition (2), 470Pa · s or less is preferable, and 465Pa · s or less is more preferable.

Further, the mold release resistance (double cylinder mold release resistance) of the PAS resin composition is preferably 410N or less, more preferably 400N or less, and further preferably 350N or less.

In the present embodiment, the mold release resistance of the PAS resin composition is the resistance at the time of releasing the double cylindrical molded article shown in fig. 1 from the mold. Fig. 1 (a) is a plan view of a double-cylindrical molded article, fig. 1 (b) is a bottom view of the double-cylindrical molded article, fig. 1 (c) is a perspective view of the double-cylindrical molded article, fig. 1 (d) is a dimensional view of the double-cylindrical molded article, and the unit of the dimensions in fig. 1 (a) and (d) is "mm". The gate size of the double cylindrical molded article was 5mm × 2.5 mm.

The double cylindrical molded article shown in fig. 1 has a double cylindrical shape in which a first cylindrical body 1 is provided on the inside and a second cylindrical body 2 is provided on the outside, and the first cylindrical body 1 and the second cylindrical body 2 are connected by a 4mm shaft. Further, the height of the first cylindrical body 1 was 20mm, the outer diameter was 18mm, and the inner diameter was 9mm, the height of the second cylindrical body 2 was 40mm, the outer diameter was 40mm, and the inner diameter was 30mm, the thickness of the side surface portion of the first cylindrical body 1 was 4.5mm, and the thickness of the bottom portion and the side surface portion of the second cylindrical body 2 was 5 mm. The second cylindrical body 2 is a bottomed cylindrical body, but is open in a portion of the first cylindrical body 1.

The other components used as part of the raw materials in the step C will be described below.

(inorganic Filler)

In the present embodiment, it is preferable that the PAS resin composition contains an inorganic filler from the viewpoint of improving mechanical and physical properties. The inorganic filler includes a fibrous inorganic filler, a plate-like inorganic filler, and a particulate inorganic filler, and 1 kind of the inorganic filler may be used alone or 2 or more kinds may be used in combination.

Examples of the fibrous inorganic filler include mineral fibers such as glass fibers, carbon fibers, zinc oxide fibers, titanium oxide fibers, wollastonite, silicon fibers, silicon-aluminum fibers, zirconium oxide fibers, boron nitride fibers, silicon nitride fibers, boron fibers, potassium titanate fibers, etc., and metal fibrous materials such as stainless steel fibers, aluminum fibers, titanium fibers, copper fibers, brass fibers, etc., and 1 or 2 or more of them can be used. Among them, glass fiber is preferable.

Examples of commercially available products of glass fibers include chopped glass fibers (ECS03T-790DE, average fiber diameter: 6 μm), Owens Corning Japan (same name), chopped glass fibers (CS03DE 416A, average fiber diameter: 6 μm), available from Nippon electric glass Co., Ltd., chopped glass fibers (ECS03T-747H, average fiber diameter: 10.5 μm), available from Nippon electric glass Co., Ltd., chopped glass fibers (ECS03T-747, average fiber diameter: 13 μm), available from Nippon textile company Ltd., profiled chopped strand CSG 3PA-830 (long diameter 28 μm, short diameter 7 μm), available from Nippon textile company Ltd., profiled chopped strand CSG 3PL-962 (long diameter 20 μm, short diameter 10 μm), and the like.

The fibrous inorganic filler can be surface-treated with various conventionally known surface-treating agents such as epoxy compounds, isocyanate compounds, silane compounds, titanate compounds, and fatty acids. The adhesion to the PAS resin can be improved by the surface treatment. The surface treatment agent may be previously applied to the fibrous inorganic filler to apply a surface treatment or a convergence treatment before the material is prepared or may be added simultaneously at the time of the material preparation.

The fiber diameter of the fibrous inorganic filler is not particularly limited, and may be, for example, 5 μm or more and 30 μm or less as the initial shape (shape before melt-kneading). The fiber diameter of the fibrous inorganic filler herein means the major axis of the cross section of the fiber of the fibrous inorganic filler.

Examples of the particulate inorganic filler include 1 or 2 or more kinds of powdery or granular inorganic fillers such as talc (particulate), carbon black, silica, quartz powder, glass beads, glass powder, silicate such as calcium silicate, aluminum silicate and diatomaceous earth, metal oxide such as iron oxide, titanium oxide, zinc oxide and alumina (particulate), metal carbonate salt such as calcium carbonate and magnesium carbonate, metal sulfate such as calcium sulfate and barium sulfate, and other silicon carbide, silicon nitride, boron nitride, and various metal powders. Among them, glass beads and calcium carbonate are preferable.

Examples of commercially available products of calcium carbonate include Whiten P-30 (average particle size (50% d): 5 μm) manufactured by Toyo Seiki Kagaku K.K. Further, examples of commercially available glass beads include those manufactured by Potters-Ballotini, EGB731A (average particle size (50% d): 20 μm), those manufactured by Potters-Ballotini, EMB-10 (average particle size (50% d): 5 μm), and the like.

The inorganic filler in the form of powder or granule may be surface-treated in the same manner as the fibrous inorganic filler.

Examples of the plate-like inorganic filler include glass flakes, talc (plate-like), mica, kaolin, clay, alumina (plate-like), and various metal foils, and 1 or 2 or more of them can be used. Among them, glass flake and talc are preferable.

Examples of commercially available glass sheets include REFG-108 (average particle diameter (50% d): 623 μm), (manufactured by NIPPHIZI K.K.), fine flakes (fine flake) (average particle diameter (50% d): 169 μm), REFG-301 (average particle diameter (50% d): 155 μm), manufactured by NIPPHIZI K.K., REFG-401 (average particle diameter (50% d): 310 μm), and the like.

Examples of commercially available products of talc include crow talc PP manufactured by sonmura industries, ltd, and Talcum Powder PKNN manufactured by linchen chemicals.

The plate-like inorganic filler may be surface-treated in the same manner as the fibrous inorganic filler.

In the present embodiment, among the inorganic fillers, 1 or 2 or more selected from the group consisting of glass fibers, glass beads, glass flakes, calcium carbonate, and talc are preferable. In addition, from the viewpoint of improving mechanical physical properties, the inorganic filler is contained in an amount of preferably 10 to 190 parts by mass, more preferably 20 to 150 parts by mass, still more preferably 30 to 110 parts by mass, and particularly preferably 35 to 90 parts by mass, based on 100 parts by mass of the PAS resin contained in the PAS resin composition.

(other additives, etc.)

The PAS resin composition may contain known additives that are generally added to thermoplastic resins and thermosetting resins in accordance with performance requirements, in order to impart desired characteristics according to the purpose of the PAS resin composition, within a range that does not interfere with the effects (specifically, excellent mold release properties) achieved by the present embodiment. Examples of the additives include burr inhibitors (except for alkoxysilane compounds), mold release agents, lubricants, plasticizers, flame retardants, colorants such as dyes and pigments, crystallization accelerators, crystal nucleating agents, various antioxidants, heat stabilizers, weather-resistant stabilizers, and corrosion inhibitors. Examples of burr inhibitors (except for alkoxysilane) include branched polyphenylene sulfide resins having a very high melt viscosity as described in International publication No. 2006/068161 and International publication No. 2006/068159. Examples of the release agent include polyethylene wax, fatty acid ester, and fatty acid amide. Examples of the crystal nucleating agent include boron nitride, talc, kaolin, carbon black, carbon nanotubes, and the like. Examples of the corrosion inhibitor include zinc oxide and zinc carbonate. The content of the above-mentioned additive may be 5% by mass or less in the whole resin composition.

In addition, in the PAS resin composition, in addition to the purpose of the corresponding components, can also be a small amount of auxiliary and other thermoplastic resin components. The other thermoplastic resin used herein may be any resin that is stable at high temperatures. Examples thereof include aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate, which are composed of an aromatic dicarboxylic acid and a diol, or a hydroxycarboxylic acid (oxycarboxylic acid), etc., polyamides, polycarbonates, ABS resins (acrylonitrile-butadiene-styrene copolymerized synthetic resins), polyphenylene ethers, polyalkylacrylates, polysulfones, polyether sulfones, polyether imides, polyether ketones, fluororesins, liquid crystal polymers, and cyclic olefin copolymers. Further, 2 or more of these thermoplastic resins may be mixed and used. The content of the other thermoplastic resin component may be, for example, 20% by mass or less in the entire resin composition.

The PAS resin composition of the present embodiment can be used for various purposes. Examples of the PAS resin composition include various cooling system components, ignition-related components, distributor components, various sensor components, various actuator components, throttle components, Power module (Power module) components, ECU components, various connector components, and the like of automobiles.

In addition, the present invention can be used for other applications, for example, for home/office electric appliance parts such as LEDs, sensors, sockets, wiring boards, printed circuit boards, motor parts, and ECU housings, lighting parts, television parts, rice cooker parts, microwave oven parts, iron parts, copy-related parts, print-related parts, facsimile-related parts, heaters, and air-conditioning parts.

Examples

The present embodiment will be described more specifically with reference to the following examples, but the present embodiment is not to be construed as being limited thereto.

[ example 1]

PPS resin (manufactured by Kureha, Fortron KPS (melt viscosity: 130 pas (shear rate: 1200 sec)) ^-1 310 ℃ C.) and 9.4 parts by mass of an alkoxysilane compound (. gamma. -aminopropyltriethoxysilane ("KBE-903P" manufactured by shin-Etsu chemical Co., Ltd.) were mixed to prepare a master batch, and the master batch was exposed to an atmosphere having a temperature of 40 ℃ and a humidity of 80% for 10 minutes. The condensate ratio in the alkoxysilane compound in the master batch was 24% by mass. The amount of the condensate described below was prepared by appropriately changing the time of exposure to an environment at 40 ℃ and a humidity of 80% in the same manner as described above.

Next, a PPS resin (manufactured by Kureha, Fortron KPS (melt viscosity: 130 pas (shear rate: 1200 sec)) ^-1 310 ℃ C.)), 10.7 parts by mass of the master batch prepared as described above, and glass fibers (manufactured by Nippon Denko K.K.)And a strand broken line ECS 03T-717, diameter 13 μm, length 3mm)74 parts by mass (glass fiber separately added from the side feed part of the extruder) were fed into a twin-screw extruder having a cylinder temperature of 320 ℃ and melt-kneaded to obtain a resin composition.

(measurement of melt viscosity of PPS resin)

The melt viscosity of the PPS resin is measured as follows.

The capillary rheometer (Capillograph) manufactured by Toyo Seiki Seisaku-Sho was used, and the capillary was used

Flat die to determine the shear rate at 310 ℃ in the barrel of material, 1200sec ^-1 Melt viscosity of (b).

Example 2 and comparative examples 1 to 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 master batch was changed to the ratio shown in table 1.

(measurement of melt viscosity of resin composition)

In each of the obtained resin compositions, a capillary rheometer manufactured by Toyo Seiki Seisaku-Sho was used, and the capillary was used

Flat die to determine the barrel temperature of 310 ℃ and the shear rate of 1000sec ^-1 Melt viscosity of (b).

[ evaluation ]

The cylindrical molded article shown in fig. 1 was molded using an injection molding machine under the following conditions, and the force at the time of extruding the molded piece from the mold was measured, and the measured value was taken as the mold release resistance value.

A pressure sensor: "Indirect type model inner sensor" manufactured by Nippon strange Stone Co., Ltd. (type: 9221A)

An injection molding machine: "EC60Ni1.5A" manufactured by Toshiba mechanical Co., Ltd "

Temperature of the cylinder: 320 deg.C

Injection time: 12 seconds

Cooling time: 45 seconds

Temperature of the die: 150 ℃ C

The evaluation results of the respective resin compositions are shown in table 1.

[ Table 1]

As is clear from table 1, as the amount of the condensate in the alkoxysilane compound in the master batch increases, the melt viscosity of the PPS resin composition decreases and the flowability improves. Further, it is also known that as the amount of the condensate in the alkoxysilane compound in the master batch increases, the mold release resistance of the PPS resin composition increases. Therefore, the amount of the condensate is in the range of 10 to 60 mass%, and a PPS resin composition having excellent fluidity and mold release properties can be obtained.

[ examples 3 to 4]

In each example, except that the PPS resin was changed to Fortron KPS (melt viscosity: 100 pas (shear rate: 1200 sec), manufactured by Kureha Co., Ltd ^-1 310 ℃ C.) and the ratio of the condensate in the alkoxysilane compound in the master batch were ratios shown in Table 2, and each resin composition was obtained under the same conditions as in example 1. The same evaluation as in example 1 was performed. The evaluation results are shown in table 2.

[ Table 2]

As is clear from Table 2, the use of a PPS resin having a melt viscosity of 100 pas showed the same tendency as the use of a PPS resin having a melt viscosity of 130 pas. Therefore, the amount of the condensate is in the range of 10 to 60 mass%, and a PPS resin composition having excellent fluidity and mold release properties can be obtained.

Comparative example 3

In each comparative example, except that the PPS resin was changed to Fortron KPS (melt viscosity: 60 pas (shear rate: 1200 sec.) manufactured by Kureha Co., Ltd.) ^-1 310 ℃ C.) and the ratio of the condensate in the alkoxysilane compound in the master batch were set to the ratios shown in Table 3, and resin compositions were obtained under the same conditions as in example 1. The same evaluation as in example 1 was performed. The evaluation results are shown in table 3.

[ Table 3]

As is clear from Table 3, even when a PPS resin having a low melt viscosity of 60 pas was used, the condensate of the alkoxysilane compound was within a predetermined range, and a mold release failure was observed.

Claims

1. A process for producing a polyarylene sulfide resin composition, characterized in that the composition has a temperature of 310 ℃ and a shear rate of 1200sec ^-1 A step A of preparing a master batch 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 80 to 250 pas measured below;

a step (B) of condensing a part of the alkoxysilane compound in the master batch so that the ratio of the condensate of the alkoxysilane compound is 10 to 60 mass% of the alkoxysilane compound; and

and a step C of melt-kneading the raw materials containing the master batch obtained in the step B, that is, the master batch having a ratio of the condensate of the alkoxysilane compound within the above-mentioned range and other components.

2. The method for producing a polyarylene sulfide resin composition according to claim 1,

further comprising a step D: a new polyarylene sulfide resin which is the same as or different from the polyarylene sulfide resin used in the step A is prepared,

3. The method for producing a polyarylene sulfide resin composition according to claim 1 or 2,

4. The method for producing a polyarylene sulfide resin composition according to any one of claims 1 to 3,

5. The method for producing a polyarylene sulfide resin composition according to any one of claims 1 to 4,

6. The method for producing a polyarylene sulfide resin composition according to any one of claims 1 to 5,

at a temperature of 310 ℃ and a shear rate of 1000sec ^-1 The polyarylene sulfide resin composition has a melt viscosity of 470 pas or less, as measured below.

7. The method for producing a polyarylene sulfide resin composition according to any one of claims 1 to 6,