JP6968322B1 - Method for Producing Polyarylene Sulfide Resin Composition - Google Patents

Abstract

An alkoxysilane compound having a melt viscosity of 80 Pa · s or more and 250 Pa · s or less measured at a temperature of 310 ° C. and a shear rate of 1200 sec-1 with respect to 100 parts by mass of a polyarylene sulfide resin of 0.2 parts by mass or more and 50 parts by mass or less. In step A to prepare a master batch by mixing the above, a part of the alkoxysilane compound in the master batch is condensed, and the ratio of the condensate of the alkoxysilane compound is set to 10% by mass or more and 60% by mass or less of the alkoxysilane compound. The master batch obtained in the step B and the step B includes a step C of melt-kneading a raw material containing the master batch having a condensate ratio of the alkoxysilane compound within the above range and other components. This is a method for producing a polyarylene sulfide resin composition.

Description

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 polyphenylene sulfide (hereinafter, also referred to as PAS) resin, has high heat resistance, mechanical properties, chemical resistance, and flame retardancy. It is used in a wide range of fields such as various automobile parts and electrical / electronic equipment parts, mainly for extrusion molding and injection molding.

In the PAS resin composition, various additives are added in order 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 Document 1).

Patent Document 1 describes a method for producing a polyarylene sulfide resin composition in which 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 between the alkoxysilane compounds occurs before the alkoxysilane compound and the PPS resin react, and desired mechanical properties can be obtained. Have difficulty. Therefore, in Patent Document 1, a PPS resin that has been previously dried is used.

International Publication No. 2012/147185

By the way, as in the injection molding method, when a molten thermoplastic resin is filled in a mold to obtain a resin molded product having a desired shape, the purpose is to make it easier to remove the molded resin molded product from the mold. Usually, an ejector pin or the like is used.
However, since the PPS resin composition according to Patent Document 1 has a high mold release resistance, sticking to the mold is likely to occur, and mold release defects are likely to occur. For this reason, when the resin molded product is ejected from the mold with an ejector pin or the like, the appearance of the resin molded product may be poor or deformed due to the ejector pin marks or the ejector pin penetrating, which is a problem. It has become. Further, as described in Patent Document 1, since the condensate of the alkoxysilane compound may affect the mechanical properties and the like, it is common to take measures such as drying treatment so that the condensation reaction does not occur. It is a target.

Further, when the alkoxysilane compound is added to the PPS resin, the melt viscosity of the PPS resin composition tends to increase, so that the fluidity of the PPS resin composition tends to decrease. In particular, when a PPS resin having a high melt viscosity (80 Pa · s or more) is used, the decrease in fluidity is remarkable.

The present invention has been made in view of the above circumstances, and while using a polyarylene sulfide resin having a high melt viscosity and an alkoxysilane compound in combination, it suppresses mold release defects and provides good fluidity. It is an object of the present invention to provide a method for producing a polyarylene sulfide resin composition having.

In the PAS resin composition to which the alkoxysilane compound is added, it is common to take measures so that a condensate of the alkoxysilane compound that affects the mechanical properties and the like is not generated, whereas in the present invention, the alkoxy is used. It was discovered that when a condensate of a silane compound is present in a predetermined ratio, good fluidity can be obtained while suppressing mold release defects.

One aspect of the present invention that achieves the above object is as follows.

(1) 0.2 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polyarylene sulfide resin having a melt viscosity of 80 Pa · s or more and 250 Pa · s or less measured at a temperature of 310 ° C. and a shear rate of 1200 sec-1. Step A to prepare a masterbatch by mixing alkoxysilane compounds,
Obtained in step B and step B in which a part of the alkoxysilane compound in the master batch is condensed so that the ratio of the condensate of the alkoxysilane compound is 10% by mass or more and 60% by mass or less of the alkoxysilane compound. Step C of melt-kneading a raw material containing a master batch in which the ratio of the condensate of the alkoxysilane compound is within the above range and other components in the master batch.
A method for producing a polyarylene sulfide resin composition, which comprises.

(2) Further including step D for 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, the said step C so that the total amount of the alkoxysilane compound and the condensate of 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 all the polyarylene sulfide resin. The method for producing a polyarylene sulfide resin composition according to (1) above, wherein the raw material containing the masterbatch obtained in step B and the polyarylene sulfide resin prepared in step D is melt-kneaded.

(3) The polyarylene according to (1) or (2) above, 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.

(4) The alkoxysilane compound is γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, (1) to (3) above, which comprises at least one selected from the group consisting of N-phenyl-γ-aminopropyltrimethoxysilane, γ-diallylaminopropyltrimethoxysilane, and γ-diallylaminopropyltriethoxysilane. The method for producing a polyarylene sulfide resin composition according to any one of the above.

(5) The method for producing a polyarylene sulfide resin composition according to any one of (1) to (4) above, wherein the mold release resistance of the polyarylene sulfide resin composition is 410 N or less.

(6) The polyarylene sulfide according to any one of (1) to (5) above, wherein the melt viscosity of the polyarylene sulfide resin composition measured at a temperature of 310 ° C. and a shear rate of 1000 sec ^{-1 is 470 Pa · s or less.} A method for producing a resin composition.

(7) 1. The method for producing a polyarylene sulfide resin composition according to any one.

An embodiment of the present invention is a method for producing a polyarylene sulfide resin composition which suppresses mold release defects and has good fluidity while using a polyarylene sulfide resin having a high melt viscosity and an alkoxysilane compound in combination. Can be provided.

1A and 1B are views for explaining a double-cylindrical molded product, where FIG. 1A is a top view, FIG. 1B is a bottom view, FIG. 1C is a perspective view, and FIG. 1D is a dimensional view.

Hereinafter, the present embodiment will be described in detail, but the present embodiment is not limited to the following embodiments, and can be carried out 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 the raw materials without heating / melt-kneading or pelletizing.

<Manufacturing method of polyarylene sulfide resin composition>
The method for producing the polyarylene sulfide resin composition of the present embodiment is based on 100 parts by mass of the polyarylene sulfide resin having a melt viscosity of 80 Pa · s or more and 250 Pa · s or less measured at a ^{temperature of 310 ° C. and a shear rate of 1200 sec -1.} , A step A of mixing 0.2 parts by mass or more and 50 parts by mass or less of an alkoxysilane compound to prepare a masterbatch is included. Further, the step B is included in which a part of the alkoxysilane compound in the master batch is condensed so that the ratio of the condensate of the alkoxysilane compound is 10% by mass or more and 60% by mass or less of the alkoxysilane compound. Further, the master batch obtained in the step B includes a step C in which a raw material containing the master batch having a condensate ratio of the alkoxysilane compound within the above range and other components is melt-kneaded.

If water (moisture in the PAS resin or moisture in the air) is present when the alkoxysilane compound is mixed with the PAS resin to prepare a master batch, the alkoxysilane compound is hydrolyzed and the alkoxysilane compound is condensed. The formation of the condensate means that the amount of the alkoxysilane compound decreases, and as the amount of the condensate increases, the effect of increasing the melt viscosity by the alkoxysilane compound decreases, and the fluidity improves. Further, in the past, since the presence of a condensate of an alkoxysilane compound affects the mechanical properties, it was common to take measures so that the condensation reaction does not occur.
On the other hand, as a result of diligent research, the present inventor has found that the condensate of the alkoxysilane compound is a factor that increases the mold release resistance when the melt viscosity of the PAS resin is 80 Pa · s or more and 250 Pa · s or less. I found that. That is, in order to improve the releasability, the smaller the condensate of the alkoxysilane compound, the better. Therefore, when the condensate of the alkoxysilane compound is present in an appropriate ratio, the melt viscosity is lowered, the fluidity is improved, and the increase in the mold release resistance is suppressed. Therefore, in the present embodiment, while intentionally producing a condensate of the alkoxysilane compound, the content ratio of the condensate is specified to improve the fluidity and suppress the mold release defect.
Hereinafter, each step will be described.

[Step A]
In step A, 0.2 parts by mass or more and 50 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin having a melt viscosity of 80 Pa · s or more and 250 Pa · s or less measured at a temperature of 310 ° C. and a shear rate of 1200 sec ^-1. The following alkoxysilane compounds are mixed to prepare a masterbatch.

When the content of the alkoxysilane compound to be mixed when preparing the masterbatch 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 alkoxysilane compound with respect to the alkoxysilane compound in the masterbatch It is easy to adjust the ratio of the condensate of the above to a predetermined ratio. In addition, clogging of the piping can be suppressed and handling is easy. The content of the alkoxysilane compound is 0.2 parts by mass or more and 50 parts by mass or less, preferably 0.3 parts by mass or more and 25 parts by mass or less, and 0.5 parts by mass with respect to 100 parts by mass of the PAS resin. It is more preferably 1 part or more and 15 parts by mass or less, and further preferably 1.0 part by mass or more and 10 parts by mass or less.

Examples of the method for preparing the masterbatch include a method of dry blending a PAS resin and an alkoxysilane compound, and a blending method using a tumbler or a Henschel mixer is preferable.
The raw materials used in step A will be 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, as the arylene group, a phenylene group such as a p-phenylene group, an m-phenylene group, and an o-phenylene group, a p, p'-biphenylene group, a p, p'-diphenylene ether group, a p, p'-di A phenylene carbonyl group, a p, p'-diphenylene sulfone group, a naphthylene group and the like can be used.
The PAS resin can be a copolymer containing homopolymers using the same structural unit among the structural units represented by − (Ar—S) −, and different structural units depending on the application.

As the homopolymer, a homopolymer 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 homopolymers having a p-phenylene sulfide group as a structural unit have extremely high heat resistance, and exhibit high strength, high rigidity, and high dimensional stability in a wide temperature range. By using such a homopolymer, a molded product having very excellent physical properties can be obtained.

As the copolymer, a combination of two or more different arylene sulfide groups among the above-mentioned arylene sulfide groups including an arylene group 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 a molded product having high physical properties such as heat resistance, moldability and mechanical properties.
A polymer containing 70 mol% or more of p-phenylene sulfide group is more preferable, and a polymer containing 80 mol% or more is further preferable. The PAS resin having a phenylene sulfide group is a polyphenylene sulfide resin (PPS resin).

Generally, a PPS resin is known to have a molecular structure that is substantially linear and does not have a branched or crosslinked structure, or a structure that has a branched or crosslinked structure, depending on the production method. Type may be used.

From the viewpoint of toughness and fluidity, the melt viscosity of the PAS resin is 80 Pa · s or more and 250 Pa · s or less under the conditions of ^{a temperature of 310 ° C. and a shear rate of 1200 sec-1.} It is preferably 85 Pa · s or more and 230 Pa · s or less, more preferably 90 Pa · s or more and 220 Pa · s or less, and further preferably 95 Pa · s or more and 200 Pa · s or less.
In this embodiment, the problem of mold release failure and deterioration of fluidity that may occur when a PAS resin having a melt viscosity of 80 Pa · s or more and 250 Pa · s or less and an alkoxysilane compound is used is solved. It is a plan. Therefore, PAS resins having a melt viscosity of less than 80 Pa · s are outside the scope of this embodiment.

(Alkoxysilane compound)
The alkoxysilane compound is not particularly limited, and examples thereof include epoxyalkoxysilane, aminoalkoxysilane, vinylalkoxysilane, and mercaptoalkoxysilane, and one 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 epoxyalkoxysilane 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, and N- (β-aminoethyl)-. Examples thereof include γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-diallylaminopropyltrimethoxysilane, and γ-diallylaminopropyltriethoxysilane.

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

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

Among these, epoxyalkoxysilane and aminoalkoxysilane are preferable, and γ-aminopropyltriethoxysilane is particularly preferable.

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

From the viewpoint of obtaining excellent fluidity and releasability of the PAS resin composition, the ratio of the condensate among the alkoxysilane compounds in the masterbatch is 10% by mass or more and 60% by mass or less. The ratio of the condensate is preferably 15% by mass or more and 55% by mass or less, and more preferably 20% by mass or more and 50% by mass or less.

The amount of condensate of the alkoxysilane compound depends on the amount of the alkoxysilane compound to be hydrolyzed. As a method for adjusting the amount of condensate of the alkoxysilane compound, (1) the humidity of the environment in which the alkoxysilane compound or the masterbatch is stored and the water vapor permeability of the system are adjusted, and (2) the storage time of the alkoxysilane compound or the 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, when the master batch in step A is adjusted to 100 parts by mass of PAS resin and 2 parts by mass of an alkoxysilane compound and stored at a temperature of 40 ° C. and a humidity of 80% RH for 20 minutes, the amount of condensate is 24% by mass. %, The amount of the condensate becomes 1% by mass when the master batch in step A is adjusted with 25 parts by mass of the alkoxysilane compound with respect to 100 parts by mass of the PAS resin and stored at a temperature of 23 ° C. and a humidity of 40% RH for 10 minutes. When the amount of the condensate of the alkoxysilane compound is 10% by mass or more and 60% by mass or less, a PAS resin composition having excellent fluidity and releasability can be obtained.
Further, by producing a condensate of the alkoxysilane compound by the methods (1) to (3) above, and then adding a new alkoxysilane compound to lower the condensate amount ratio, the condensation of the alkoxysilane compound can also be performed. The quantity 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 be larger than 5% by mass and 60% by mass or less by further adding an alkoxysilane compound.

In the PAS resin composition which is the 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 are distinguished. Can't. Therefore, it is necessary to adjust the amount of 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 condensate ratio of the alkoxysilane compound in the masterbatch will be described.

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

Next, the masterbatch is placed in an aluminum cup and the mass C is measured (step 4). Next, put the weighed masterbatch in the funnel equipped with the membrane filter. Wash the aluminum cup with acetone and put the cleaning solution in the funnel (step 5).

Next, add acetone while washing the area around the funnel, stir with a spatula for about 3 seconds, and perform suction filtration. Acetone is added, the mixture is stirred with a spatula, and suction filtration is performed twice more (step 6).

Next, the residue and the 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 condensate ratio in the alkoxysilane compound is represented by the following formula.
Condensate ratio (mass%) = (mass of condensate in alkoxysilane compound contained in master batch / mass of alkoxysilane compound compounded at the time of master batch preparation) × 100 = {[{mass D- (mass A + mass) B)}-Mass C x (1-EF)] / (Mass C x E)} x 100

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

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

In the present embodiment, a part of the alkoxysilane compound in the masterbatch prepared in step A is condensed in step B, but when the period between step A and step B is long, the condensation reaction does not occur due to moisture. It is preferable to store it in a dry state.
Alternatively, when the period from the completion of the step A and the step B to the step C is long, it is preferable to store the condensate in a dry state so that the ratio of the condensate in the master batch obtained in the step B does not change.
However, even when the ratio of the condensate in the masterbatch changes, it is sufficient that the amount of the condensate in the masterbatch at the time of feeding into the extruder satisfies the specified range. For example, when the ratio of the condensate in the condensate in the masterbatch increases, the ratio of the amount of the condensate can be lowered by adding a new alkoxysilane compound when the compound is put into the extruder.

[Process C]
In step C, the masterbatch obtained in step B and the masterbatch obtained in step B, the raw material containing the masterbatch in which the ratio of the condensate of the alkoxysilane compound is within the above range and other components. Is melt-kneaded.

Examples of other components include PAS resins prepared separately and / or inorganic fillers and other additives described later. Among them, the PAS resin will be described in step D.
Other components may be added when the PAS resin and the masterbatch are blended and melt-kneaded. Further, the other additives and the masterbatch may be mixed by a method such as dry blending, and the obtained mixture and the PAS resin may be mixed and melt-kneaded.

As a method of melt-kneading the raw material containing the masterbatch and other components, for example, PAS resin and masterbatch may be supplied to the extruder, respectively, or PAS resin, masterbatch, other additives and the like may be supplied. It may be dry-blended and then supplied to the extruder, or some raw materials may be supplied by a side feed method.

When the step C is completed, the total amount of the condensate of the alkoxysilane compound and the alkoxysilane compound in the finally obtained PAS resin composition is 0.2 parts by mass or more and 3.0 parts by mass with respect to 100 parts by mass of the PAS resin. It is preferable to mix the masterbatch with the PAS resin and melt-knead it so that the amount is less than or equal to the part.

In step C, when the raw material contains 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, step B so that the total amount of the alkoxysilane compound and the condensate of 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 all the polyarylene sulfide resin. The raw material containing the masterbatch obtained in step 1 and the polyarylene sulfide resin prepared in step D is melt-kneaded. All PAS resins are the PAS resin used for preparing 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 the step D and the PAS resin used in the step A are different, 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 molecular structure that is substantially linear and does not have a branched or crosslinked structure, and (2) a homopolymer and a copolymer that differ between a structure having a branched or crosslinked structure. , (3) The arylene sulfide group of the structural unit is different (for example, the p-phenylene sulfide group and the m-phenylene sulfide group are different), and the like.

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 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the PAS resin. It is preferable to mix them so as to be. By blending in this way, the fluidity and releasability of the PAS resin composition can be imparted in a well-balanced manner. Further, when the inorganic filler is used, the adhesion with the inorganic filler is enhanced, and the mechanical properties are likely to be improved. In the finally obtained PAS resin composition, the total amount of the alkoxysilane compound and the condensate of the alkoxysilane compound is 0.3 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the PAS resin. It is preferably 0.5 parts by mass or more and 1.5 parts by mass or less, more preferably.

The melt viscosity of the PAS resin composition is preferably 470 Pa · s or less, and more preferably 465 Pa · s or less under the conditions of a temperature of 310 ° C. and a shear rate of 1000 sec- ^1.

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

In the present embodiment, the mold release resistance of the PAS resin composition means the resistance when the double cylindrical molded product shown in FIG. 1 is released from the mold. 1 (a) is a top view of the double-cylindrical molded product, FIG. 1 (b) is a bottom view of the double-cylindrical molded product, and FIG. 1 (c) is a perspective view of the double-cylindrical molded product. 1 (d) is a dimensional drawing of a double-cylindrical molded product, and the dimensional unit in FIGS. 1 (a) and 1 (d) is "mm". The gate size of the double-cylindrical molded product is 5 mm × 2.5 mm.

The double-cylindrical molded product shown in FIG. 1 has a double-cylindrical shape with the first cylinder 1 on the inside and the second cylinder 2 on the outside. The second cylinder 2 is connected by a 4 mm shaft. The height of the first cylinder 1 is 20 mm, the outer diameter is 18 mm, the inner diameter is 9 mm, and the height of the second cylinder 2 is 40 mm, the outer diameter is 40 mm, and the inner diameter is 30 mm. The thickness of the side surface portion of the cylindrical body 1 is 4.5 mm, and the thickness of the bottom portion and the side surface portion of the second cylindrical body 2 is 5 mm. Although the second cylinder 2 is a bottomed cylinder, it has an opening in the portion of the first cylinder 1.

Hereinafter, other components used as a part of the raw material in the step C will be described.

(Inorganic filler)
In the present embodiment, it is preferable to include an inorganic filler in the PAS resin composition from the viewpoint of improving the mechanical properties. Examples of the inorganic filler include a fibrous inorganic filler, a plate-like inorganic filler, and a powder-granular inorganic filler, and one of these may be used alone or two or more thereof may be used in combination. ..

Examples of the fibrous inorganic filler include glass fiber, carbon fiber, zinc oxide fiber, titanium oxide fiber, wollastonite, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, and titanium acid. Examples thereof include mineral fibers such as potash fibers, stainless fibers, aluminum fibers, titanium fibers, copper fibers, and metal fibrous substances such as brass fibers, and one or more of these can be used. Of these, glass fiber is preferable.

Examples of marketed products of glass fiber are chopped glass fiber (ECS03T-790DE, average fiber diameter: 6 μm) manufactured by Nippon Electric Glass Co., Ltd., Owens Corning Japan (same), chopped glass fiber (CS03DE 416A, average). 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 Spinning Co., Ltd., modified cross-section chopped strand CSG 3PA-830 (major axis 28 μm, minor axis 7 μm), Nitto Spinning Co., Ltd., irregular cross-section chopped strand CSG 3PL-962 (major axis 20 μm, minor axis 10 μm) ) Etc. can be mentioned.

The fibrous inorganic filler may be surface-treated with various surface treatment agents such as generally known epoxy compounds, isocyanate compounds, silane compounds, titanate compounds, and fatty acids. The surface treatment can improve the adhesion with the PAS resin. The surface treatment agent may be applied to the fibrous inorganic filler in advance for surface treatment or convergence treatment before material preparation, or may be added at the same time as material preparation.

The fiber diameter of the fibrous inorganic filler is not particularly limited, but 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 means the major axis of the fiber cross section of the fibrous inorganic filler.

Examples of the powdery inorganic filler include talc (granular), carbon black, silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, silicate such as diatomaceous earth, iron oxide, titanium oxide, zinc oxide. , Metal oxides such as alumina (granular), metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, other silicon carbide, silicon nitride, boron nitride, various metal powders and the like. , These can be used alone or in combination of two or more. Of these, glass beads and calcium carbonate are preferable.
Examples of products on the market for calcium carbonate include Whiten P-30 (average particle size (50% d): 5 μm) manufactured by Toyo Fine Chemicals Co., Ltd. Examples of commercially available glass beads include Potters Barotini Co., Ltd., EGB731A (average particle size (50% d): 20 μm), Potters Barotini Co., Ltd., EMB-10 (average particle size). Diameter (50% d): 5 μm) and the like can be mentioned.
The powdery granular inorganic filler may also be surface-treated in the same manner as the fibrous inorganic filler.

Examples of the plate-shaped inorganic filler include glass flakes, talc (plate-shaped), mica, kaolin, clay, alumina (plate-shaped), various metal foils, and the like, and one or more of these may be used. Can be done. Of these, glass flakes and talc are preferable.
Examples of marketed glass flakes are Nippon Plate Glass Co., Ltd., REFG-108 (average particle size (50% d): 623 μm), (Nippon Plate Glass Co., Ltd., fine particle size (50%)). d): 169 μm), manufactured by Nippon Plate Glass Co., Ltd., REFG-301 (average particle size (50% d): 155 μm), manufactured by Nippon Plate Glass Co., Ltd., REFG-401 (average particle size (50% d): 310 μm) ) Etc. can be mentioned.
Examples of talc products on the market include Crown Talc PP manufactured by Matsumura Sangyo Co., Ltd. and talcan powder PKNN manufactured by Hayashi Kasei Co., Ltd.
The plate-shaped inorganic filler may also be surface-treated in the same manner as the fibrous inorganic filler.

In the present embodiment, among the above-mentioned inorganic fillers, one or more selected from the group consisting of glass fibers, glass beads, glass flakes, calcium carbonate and talc is preferable. Further, from the viewpoint of improving the mechanical properties, the inorganic filler preferably contains 10 to 190 parts by mass with respect to 100 parts by mass of the PAS resin contained in the PAS resin composition, and more preferably 20 to 150 parts by mass. It is more preferable to contain 30 to 110 parts by mass, and particularly preferably 35 to 90 parts by mass.

(Other additives, etc.)
The PAS resin composition is generally a thermoplastic resin and thermosetting in order to impart desired properties according to the purpose within a range that does not impair the effect (specifically, excellent releasability) of the present embodiment. A known additive added to the sex resin can be contained according to the required performance. Additives include burr suppressors (excluding alkoxysilane compounds), mold release agents, lubricants, plasticizers, flame retardants, colorants such as dyes and pigments, crystallization accelerators, crystal nucleating agents, and various oxidations. Examples thereof include an inhibitor, a heat stabilizer, a weather resistant stabilizer, a corrosion inhibitor and the like. Examples of the burr inhibitor (excluding alkoxysilane) include branched polyphenylene sulfide having a very high melt viscosity, as described in International Publication No. 2006/068161 and International Publication No. 2006/068159. Examples include system resins. Examples of the release agent include polyethylene wax, fatty acid ester, fatty acid amide and the like. 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 additive can be 5% by mass or less in the total resin composition.

Further, in addition to the above-mentioned components, other thermoplastic resin components may be supplementarily used in a small amount in combination with the PAS resin composition depending on the purpose. The other thermoplastic resin used here may be any resin as long as it is stable at high temperatures. For example, aromatic polyesters, polyamides, polycarbonates, ABS resins (acrylonitrile-butadiene-styrene copolymer synthetic resins), polyphenylene oxides, etc., which are composed of aromatic dicarboxylic acids and diols such as polyethylene terephthalates and polybutylene terephthalates, or oxycarboxylic acids. Examples thereof include polyalkyl acrylates, polysulfones, polyether sulfones, polyetherimides, polyetherketones, fluororesins, liquid crystal polymers, cyclic olefin copolymers and the like. Moreover, these thermoplastic resins can also be used by mixing two or more kinds. The content of the other thermoplastic resin component 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 the PAS resin composition include various cooling system parts of automobiles, ignition-related parts, distributor parts, various sensor parts, various actuator parts, throttle parts, power module parts, ECU parts, various connector parts and the like.

Other uses include, for example, LEDs, sensors, sockets, terminal blocks, printed circuit boards, motor parts, electrical and electronic parts such as ECU cases, lighting parts, TV parts, rice cooker parts, microwave parts, iron parts, etc. It can be used for household and office electrical product parts such as copier-related parts, printer-related parts, facsimile-related parts, heaters, and air conditioner parts.

Hereinafter, the present embodiment will be described in more detail 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: 130 Pa · s (shear velocity: 1200 sec- ¹ , 310 ° C)) 100 parts by mass and an alkoxysilane compound (γ-aminopropyltriethoxysilane (Shin-Etsu Chemical)) 9.4 parts by mass of "KBE-903P")) manufactured by Kogyo Co., Ltd. was mixed to prepare a master batch, which was exposed to an environment at a temperature of 40 ° C. and a humidity of 80% for 10 minutes. The alkoxysilane compound in the master batch. The condensate ratio in the medium was 24% by mass. The amount of the condensate described below was prepared by changing the exposure time in an environment of a temperature of 40 ° C. and a humidity of 80% as described above.
Next, 100 parts by mass of PPS resin (manufactured by Kureha Co., Ltd., Fortron KPS (melt viscosity: 130 Pa · s (shear rate: 1200 sec- ¹ , 310 ° C.)), 10.7 parts by mass of the master batch adjusted above, Glass fiber (manufactured by Nippon Electric Glass Co., Ltd., chopped strand ECS 03 T-717, diameter 13 μm, length 3 mm) 74 parts by mass (glass fiber is added separately from the side feed part of the extruder) at a cylinder temperature of 320 ° C. A resin composition was obtained by putting it into a shaft extruder and melt-kneading it.

(Measurement of melt viscosity of PPS resin)
The melt viscosity of the PPS resin was measured as follows.
Using a capillary graph manufactured by Toyo Seiki Seisakusho Co., Ltd., a flat die of 1 mmφ × 20 mmL was used as a capillary, and the melt viscosity was measured at a ^{barrel temperature of 310 ° C. and a shear rate of 1200 sec -1.}

[Example 2, Comparative Examples 1 and 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 set to the ratio shown in Table 1.

(Measurement of melt viscosity of resin composition)
In each of the obtained resin compositions, a capillary graph manufactured by Toyo Seiki Seisakusho Co., Ltd. was used, and a flat die having a diameter of 1 mm φ × 20 mm was used as a capillary, and the melt viscosity was measured at a ^{barrel temperature of 310 ° C. and a shear rate of 1000 sec -1.}

[evaluation]
The cylindrical molded product shown in FIG. 1 was molded using an injection molding machine under the following conditions, the force when the molded piece was extruded from the mold was measured, and the measured value was taken as the mold release resistance value.
Pressure sensor: "Indirect type in-mold sensor" manufactured by Nippon Kistler Co., Ltd. (Model: 9221A)
Injection molding machine: "EC60Ni1.5A" manufactured by Toshiba Machine Co., Ltd.
Cylinder temperature: 320 ° C
Injection time: 12 seconds Cooling time: 45 seconds Mold temperature: 150 ° C

The evaluation results of each resin composition are shown in Table 1.

From Table 1, it can be seen that as the amount of the condensate in the alkoxysilane compound in the masterbatch increases, the melt viscosity of the PPS resin composition decreases and the fluidity improves. It can also be seen that the mold release resistance of the PPS resin composition increases as the amount of condensate in the alkoxysilane compound in the masterbatch increases. Therefore, a PPS resin composition having excellent fluidity and releasability can be obtained in the range where the amount of condensate is 10% by mass or more and 60% by mass or less.

[Examples 3 to 4]
In each example, the PPS resin was changed to Fortron KPS (melt viscosity: 100 Pa · s (shear velocity: 1200 sec- ¹ , 310 ° C.)) manufactured by Kureha Corporation, and in the alkoxysilane compound in the master batch. Each resin composition was obtained under the same conditions as in Example 1 except that the condensate ratio was set to the ratio shown in Table 2. Moreover, the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 2.

From Table 2, it can be seen that even when a PPS resin having a melt viscosity of 100 Pa · s is used, the same tendency is shown as when a PPS resin having a melt viscosity of 130 Pa · s is used. Therefore, a PPS resin composition having excellent fluidity and releasability can be obtained in the range where the amount of condensate is 10% by mass or more and 60% by mass or less.

[Comparative Example 3]
In each comparative example, the PPS resin was changed to Fortron KPS (melt viscosity: 60 Pa · s (shear velocity: 1200 sec- ¹ , 310 ° C.)) manufactured by Kureha Corporation, and in the alkoxysilane compound in the master batch. Each resin composition was obtained under the same conditions as in Example 1 except that the condensate ratio was set to the ratio shown in Table 3. Moreover, the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 3.

From Table 3, when a PPS resin having a low melt viscosity of 60 Pa · s was used, a mold release defect was observed even when the condensate ratio of the alkoxysilane compound was within a predetermined range.

Claims (7)

An alkoxysilane compound having a melt viscosity of 80 Pa · s or more and 250 Pa · s or less measured at a temperature of 310 ° C. and a shear rate of 1200 sec-1 with respect to 100 parts by mass of a polyarylene sulfide resin of 0.2 parts by mass or more and 50 parts by mass or less. Step A to prepare a masterbatch by mixing
Obtained in step B and step B in which a part of the alkoxysilane compound in the master batch is condensed so that the ratio of the condensate of the alkoxysilane compound is 10% by mass or more and 60% by mass or less of the alkoxysilane compound. Step C of melt-kneading a raw material containing a master batch in which the ratio of the condensate of the alkoxysilane compound is within the above range and other components in the master batch.
A method for producing a polyarylene sulfide resin composition, which comprises. Further comprising step D to prepare a new polyarylene sulfide resin that is the same as or different from the polyarylene sulfide resin used in the step A.
In the step C, the said step C so that the total amount of the alkoxysilane compound and the condensate of 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 all the polyarylene sulfide resin. The method for producing a polyarylene sulfide resin composition according to claim 1, wherein the raw material containing the masterbatch obtained in step B and the polyarylene sulfide resin prepared in step D is melt-kneaded. The preparation of the polyarylene sulfide resin composition according to claim 1 or 2, wherein the alkoxysilane compound contains at least one selected from the group consisting of epoxyalkoxysilane, aminoalkoxysilane, vinylalkoxysilane, and mercaptoalkoxysilane. Method. The alkoxysilane compound is γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N-phenyl. The item according to any one of claims 1 to 3, which comprises at least one selected from the group consisting of −γ-aminopropyltrimethoxysilane, γ-diallylaminopropyltrimethoxysilane, and γ-diallylaminopropyltriethoxysilane. The method for producing a polyarylene sulfide resin composition according to the above method. The method for producing a polyarylene sulfide resin composition according to any one of claims 1 to 4, wherein the release resistance of the polyarylene sulfide resin composition is 410 N or less. The polyarylene sulfide resin composition according to any one of claims 1 to 5, wherein the polyarylene sulfide resin composition measured at a temperature of 310 ° C. and a shear rate of 1000 sec ^{-1 has a melt viscosity of 470 Pa · s or less.} Production method. The invention according to any one of claims 1 to 6, wherein an inorganic filler of 10 parts by mass or more and 190 parts by mass or less is further blended with respect to 100 parts by mass of the polyarylene sulfide resin contained in the polyarylene sulfide resin composition. A method for producing a polyarylene sulfide resin composition.

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