JP6960229B2 - Method for manufacturing PAS resin-impregnated long fiber pellets - Google Patents

Description

The present invention relates to a method for producing long fiber pellets impregnated with a polyarylene sulfide resin and a method for producing a composition containing the pellets.

Polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) resin and other polyarylene sulfide (hereinafter sometimes abbreviated as PAS) resin have high heat resistance, chemical resistance, dimensional stability, and flame retardancy. Therefore, it is widely used in electrical and electronic equipment parts materials, automobile equipment parts materials, chemical equipment parts materials, and the like. The high temperature rigidity of the molded product may be insufficient with the PAS resin alone, but the heat resistance and rigidity of the PAS resin containing an inorganic filler such as glass fiber are improved.

Molded products of long fiber reinforced thermoplastic resin pellets, which are obtained by impregnating continuous fibers such as glass fibers arranged in parallel with a thermoplastic resin and then cutting them to a required length, are compared with those reinforced with short fibers. Due to its excellent mechanical strength, it is widely used as a molding material.
The invention of Patent Document 1 describes a method for continuously producing pellets of a coated fiber-reinforced composite material structure in which a first fixed die and a second fixed die having different temperatures are combined. Thermoplastic materials are described in paragraphs 0015 and 0017, and fiber strands are described in paragraph 0016.

Japanese Patent No. 4405080

An object of the present invention is to provide a method for producing PAS resin-impregnated long fiber pellets and a method for producing a composition containing the pellets.

In the present invention, a continuous fiber bundle in which continuous fibers are aligned in the length direction is impregnated with a molten polyarylene sulfide (PAS) resin in a heated die and integrated. A method for producing PAS resin-impregnated long fiber pellets, which is cut to a length of 4 to 50 mm.
The content ratio of the continuous fiber in the PAS resin-impregnated long fiber pellet is 20 to 60% by mass.
The viscosity of the PAS resin used (temperature 310 ° C., shear rate 1200s ^-1 ) is 50 to 250 Pa · s.
Provided is a method for producing PAS resin-impregnated long fiber pellets, wherein the set temperature of the die is 340 ° C. or higher and 390 ° C. or lower.

In the present invention, after producing PAS resin-impregnated long fiber pellets by the above production method, 0.005 to 0.1 parts by mass of fatty acid amide, fatty acid ester, and fatty acid with respect to 100 parts by mass of the PAS resin-impregnated long fiber pellets. Provided is a method for producing a PAS resin composition, which comprises adding and mixing one or more lubricant components selected from the group consisting of a metal salt and a polyethylene wax.

The PAS resin-impregnated long fiber pellets obtained by the production method of the present invention have high tensile strength of the molded product.

<Manufacturing method of PAS resin impregnated long fiber pellets>
In the production method of the present invention, a continuous fiber bundle in which continuous fibers are aligned in the length direction is impregnated with a molten polyarylene sulfide (PAS) resin in a heated die and integrated. It has a step of cutting into a length of 4 to 50 mm after sulphurization.

Examples of the PAS resin include polyphenylene sulfide (PPS) resin and the like.

In order to obtain a fiber-reinforced PAS resin molded product having excellent mechanical properties such as tensile strength, it is preferable that the molecular weight of the PAS resin used as a raw material is high, but if the molecular weight is too high, the fluidity in the molten state deteriorates. ..
^{The viscosity at a temperature of 310 ° C. and a shear rate of 1200 sec -1} , which is an index of the molecular weight and fluidity of the PAS resin, is preferably 50 to 250 Pa · s, more preferably 60 to 230 Pa · s, still more preferably 70 to 220 Pa · s. .. If the viscosity of the PAS resin under the above conditions is less than 50 Pa · s, the mechanical properties of the molded product, particularly the tensile strength, will be low. On the other hand, if it is larger than 250 Pa · s, the impregnation property of the PAS resin into the continuous fiber bundle in the heated die is lowered.
As the PAS resin used in the present invention, one in which the PAS resins having different viscosities are mixed so as to be in the above viscosity range can also be used.

The continuous fiber is preferably selected from glass fiber, carbon fiber, stainless steel fiber, and aramid fiber.
The number of fibers in the continuous fiber bundle is preferably 100 to 30,000, more preferably 500 to 25,000, still more preferably 1,000 to 15,000, and particularly preferably 2000 to 10,000.

A method for producing resin-impregnated fiber bundle long fiber pellets using a thermoplastic resin (excluding PAS resin) is known. For example, Japanese Patent Application Laid-Open No. 2013-107979 (resin-impregnated glass long fiber bundle of Production Example 1) is known. , JP 2013-121988 (manufacturing of resin-impregnated glass fiber bundle of Production Example 1), JP 2012-52093 (Examples 1 to 9), JP 2012-131104 (manufacturing). Production of resin-impregnated glass long fiber bundle of Example 1, production of resin-impregnated carbon fiber long fiber bundle of Production Example 2), Japanese Patent Application Laid-Open No. 2012-131918 (Production of resin-impregnated carbon fiber bundle of Production Example 1, Production Example 2) (Production of resin-impregnated glass fiber bundle), JP-A-2011-162905 (Example 1), JP-A-2004-14990 (Examples 1 to 7).

In the production method of the present invention, the set temperature of the die is 340 ° C. or higher, preferably 345 ° C. or higher, and more preferably 350 ° C. or higher.
When the temperature is lower than 340 ° C., the fluidity of the molten PAS resin is not sufficient, the impregnation property of the PAS resin into the continuous fiber bundle in the heated die is lowered, and the PAS resin impregnated long fiber pellets. Is difficult to manufacture.
On the other hand, if the set temperature of the die is too high, the mechanical properties of the molded product, particularly the tensile strength, will decrease. When the viscosity of the PAS resin used is high, that is, when the molecular weight is high, the temperature can be set from 380 ° C. to 390 ° C., but when the viscosity is low, about 370 ° C. is used as a guideline for the upper limit setting temperature. It is preferable to do so. If the viscosity of the PAS resin used is 250 Pa · s or less, the PAS resin-impregnated long fiber pellets of the present invention can be produced at a set temperature of 370 ° C.
In the production method of the present invention, the upper limit of the set temperature of the die is 390 ° C. or lower, preferably 380 ° C. or lower, more preferably 370 ° C. or lower. If the set temperature of the die is too high, the mechanical properties such as tensile strength will be significantly reduced.

The content ratio of continuous fibers in the PAS resin-impregnated long fiber pellets is preferably 20 to 60% by mass, preferably 25 to 55% by mass, more preferably 30 to 50% by mass, further preferably 40 to 50% by mass, and a total of 100% by mass. The remaining ratio to be% is PAS resin. The ratio is substantially the same as the raw material standard.
The length of the fiber contained in the PAS resin-impregnated long fiber pellet is the same as that of the PAS resin-impregnated long fiber pellet.

<Manufacturing method of PAS resin composition>
The method for producing the composition of the present invention is a method for producing PAS resin-impregnated long fiber pellets by the above-mentioned method for producing PAS resin-impregnated long fiber pellets, and then further adding and mixing lubricant components.
The lubricant component is selected from the group consisting of fatty acid amides, fatty acid esters, fatty acid metal salts, and polyethylene wax. One of these may be used alone, or two or more thereof may be used in combination. The boiling point of the lubricant component is not observed, or it is preferably 300 ° C. or higher, and more preferably 330 ° C. or higher.

Specific examples of the aliphatic amide include stearic acid amide, oleic acid amide, erucic acid amide, behenic acid amide, ethylene bisstearic acid amide, ethylene bisoleic acid amide, ethylene biserucic acid amide, and ethylene bislauric acid amide. And so on. One of these may be used alone, or two or more thereof may be used in combination.

Specific examples of the aliphatic ester include isopropyl palmitate, octyl palmitate, octyl palm fatty acid ester, octyl stearate, octyl beef fatty acid fatty acid ester, lauryl laurate, stearyl stearate, behenyl behenyl, cetyl myristate, and carbon. 28-30 linear, non-branched saturated monocarboxylic acids (hereinafter abbreviated as montanic acid) and ethylene glycol esters, montanic acid and glycerin esters, montanic acid and butylene glycol esters, montanic acid and trimethylol Examples thereof include an ester of ethane, an ester of montanoic acid and trimethylolpropane, and an ester of montanoic acid and pentaerythritol. One of these may be used alone, or two or more thereof may be used in combination.
When the montanic acid ester wax forms a metal salt, it also suitably contributes to the mold releasability during molding. Furthermore, a mixed wax of a montanic acid esterified product and a saponified product of montanic acid and calcium hydroxide can also be used.

The aliphatic ester also includes a glycerin organic acid ester, a polyglycerin organic acid ester, a sorbitan organic acid ester, a propylene glycol organic acid ester, and a higher alcohol organic acid ester. Most preferably, these are derived from fatty acids having less than 40 carbon atoms. Specific examples thereof include stearic acid monoglyceride, citric acid saturated fatty acid monoglyceride, sorbitan stearate, propylene glycol monostearate, stearyl steerate, and polyglycerin stearate. One of these may be used alone, or two or more thereof may be used in combination.

Further, as the polyethylene wax, for example, any polyethylene wax polymerized by a Ziegler catalyst can be used without any problem. Further, it is preferable that the polyethylene wax is oxidized in order to improve the compatibility with the polar plastic. The melt viscosity is preferably 3000 mPa · s or less at 140 ° C.

The fatty acid metal salt is preferably a metal salt of a higher fatty acid having 16 to 36 carbon atoms, for example, magnesium stearate, calcium stearate, barium stearate, calcium montanate, sodium montanate, zinc stearate, aluminum stearate, and the like. Examples thereof include sodium stearate and lithium stearate. One of these may be used alone, or two or more thereof may be used in combination.
Of these, calcium stearate, magnesium stearate and the like are preferable.

Among these specific compounds, the lubricant component is one or more selected from the group consisting of ethylene bisstearic acid amide, montanic acid ester wax, polyglycerin stearate, calcium stearate, magnesium stearate and polyethylene wax. Is preferable, and one or more selected from the group consisting of montanic acid ester wax, calcium stearate, and magnesium stearate is more preferable.

The composition of the present invention does not require any other external lubricant except for the group consisting of fatty acid amides, fatty acid esters, fatty acid metal salts, and polyethylene wax, but when used in combination with other external lubricants, the fatty acids in the external lubricant The content ratio of the group consisting of amide, fatty acid ester, fatty acid metal salt, and polyethylene wax is preferably 95% by mass or more, and more preferably 98% by mass or more.

The content ratio of the PAS resin-impregnated long fiber pellets and the lubricant is 0.005 to 0.1 parts by mass, preferably 0.005 to 0.05 parts by mass, and more preferably 0.005 parts by mass of the lubricant with respect to 100 parts by mass of PAS. ~ 0.02 parts by mass.
The lubricant has a particle size of 100 μm or less, which is represented as a particle size (D90) corresponding to a cumulative distribution value of 90%, preferably 5 to 75 μm, more preferably 10 to 60 μm.
The particle size (D90) corresponding to the cumulative distribution value of 90% of the lubricant component was determined by using a laser diffraction / scattering type particle size distribution measuring device (for example, "Microtrac MT3300EX II" (trade name), manufactured by Microtrac) as a dispersion medium. For example, it can be measured using a solvent such as ethanol.

Known additives can be added to the composition of the present invention depending on the use of the composition.
Known additives, stabilizers, plasticizers, light stabilizer, antistatic agent, there may be mentioned, such as wearing color agent, a flame retardant is not included.

(1) PPS viscosity (Pa · s)
The PPS pellets were dried at 140 ° C. for 3 hours, and then the melt viscosity was measured with Capillograph 1B manufactured by Toyo Seiki Co., Ltd.
At this time, the capillary used a flat die of 1 mmφ × 20 mmL, and the set temperature was set to 310 ° C. PPS pellets were introduced into the apparatus and held for 5 minutes, after which the melt viscosity was measured at a ^{shear rate of 1200 sec -1.} The higher the melt viscosity, the higher the molecular weight and the lower the fluidity, so this was used as an index of the molecular weight and fluidity.

(2) Tensile strength (MPa)
Measured according to ISO527.
An ISO multipurpose test piece A-shaped product (thickness 4 mm) was prepared under the following conditions and used as a test piece for measuring tensile strength.
Equipment: J-150EII manufactured by Japan Steel Works, Ltd.
Cylinder temperature 330 ℃
Mold temperature: 160 ° C
Screw: Screw for long fibers Screw diameter: 51 mm
Gate shape 20 mm wide side gate

PAS resin used A-1: PPS resin manufactured by Polyplastics Co., Ltd., DURAFIDE 0220C9 (310 ° C., viscosity 210 Pa · s at ^{shear rate 1200 sec -1)}
A-2: PPS resin manufactured by Polyplastics Co., Ltd., DURAFIDE 0203C6 (viscosity 28 Pa · s at ^{310 ° C. and shear rate 1200 sec -1)}
A-3: PPS resin in which A-1 and A-2 are mixed at a mass ratio of 1: 1 (viscosity 72 Pa · s at a ^{shear rate of 1200 sec -1)}
A-4: PPS resin in which A-1 and A-2 are mixed at a mass ratio of 1: 2 (viscosity 51 Pa · s at a ^{shear rate of 1200 sec -1)}

Example 1 (PPS resin impregnated carbon long fiber pellet)
Long carbon fibers (24,000 fiber bundles made of Trading Card T700S (manufactured by Toray Industries, Inc.)) were passed through a crosshead die after being heated at 230 ° C. by a preheating device.
At that time, a dry blend of 99.7 parts by mass of PPS resin (A-3) and 0.3 parts by mass of IRGAFOS168 manufactured by BASF Japan Ltd. was charged from the resin feeder, and a twin-screw extruder (cylinder). It was melted at a maximum temperature of 345 ° C.) and supplied to a crosshead die (set temperature of 360 ° C.), and the fiber bundle was impregnated with PPS resin at the ratio shown in Table 1.
Then, it was shaped with a shaping nozzle at the outlet of the crosshead die, shaped with a shaping roll, and then cut with a pelletizer to obtain PPS resin-impregnated carbon long fiber pellets.
When the PPS resin-impregnated carbon long fiber pellets were cut and confirmed, the carbon long fibers were substantially parallel in the length direction, and the resin was impregnated up to the center.

Example 2
PPS resin-impregnated carbon long fiber pellets were obtained in the same manner as in Example 1 except that the set temperature of the crosshead die was 380 ° C.

Example 3 (PPS resin impregnated glass long fiber pellet)
A fiber bundle (glass fiber: a bundle of about 4000 fibers) bundled with a sizing agent composed of long glass fibers was passed through a crosshead die.
At that time, a dry blend of 99.7 parts by mass of PPS resin (A-1) and 0.3 parts by mass of IRGAFOS168 manufactured by BASF Japan Ltd. was charged from the resin feeder, and a twin-screw extruder (cylinder). It was melted at a maximum temperature of 345 ° C.) and supplied to a crosshead die (set temperature of 350 ° C.), and the fiber bundle was impregnated with PPS resin at the ratio shown in Table 2.
Then, it was shaped with a shaping nozzle at the outlet of the crosshead die, shaped with a shaping roll, and then cut to a predetermined length with a pelletizer to obtain PPS resin-impregnated glass long fiber pellets.
When the PPS resin-impregnated glass long fiber pellets thus obtained were cut and confirmed, the glass long fibers were substantially parallel in the length direction, and the resin was impregnated to the center.

Example 4 (PPS resin impregnated glass long fiber pellet)
PPS resin-impregnated glass long fiber pellets were obtained in the same manner as in Example 3 except that the PPS resin used was A-3.

Example 5 (PPS resin composition)
PPS resin-impregnated glass long fibers by dry-blending 0.01 parts by mass of calcium stearate (SC-100 manufactured by Sakai Chemical Industry Co., Ltd.) with 100 parts by mass of PPS resin-impregnated glass long fiber pellets produced in Example 4. Pellets were obtained.

Example 6 (PPS resin impregnated glass long fiber pellet)
PPS resin-impregnated glass long fiber pellets were obtained in the same manner as in Example 4 except that the set temperature of the crosshead die was 370 ° C.

Example 7 (PPS resin impregnated glass long fiber pellet)
PPS resin-impregnated glass long fiber pellets were obtained in the same manner as in Example 3 except that the PPS resin used was A-4 and the set temperature of the crosshead die was 370 ° C.

Example 8 (PPS resin impregnated glass long fiber pellet)
PPS resin-impregnated glass long fiber pellets were obtained in the same manner as in Example 7 except that the set temperature of the crosshead die was 390 ° C.

Comparative Example 1 (PPS resin impregnated glass long fiber pellet)
PPS resin-impregnated glass long fiber pellets were obtained in the same manner as in Example 3 except that the PPS resin used was A-2, the mass fraction of the glass fiber was 40%, and the set temperature of the crosshead die was 390 ° C. rice field.

Comparative Example 2 (PPS resin impregnated glass long fiber pellet)
PPS resin-impregnated glass long fiber pellets were obtained in the same manner as in Comparative Example 1 except that the set temperature of the crosshead die was 370 ° C.

Comparative Example 3 (PPS resin impregnated glass long fiber pellet)
PPS resin-impregnated glass long fiber pellets were obtained in the same manner as in Example 3 except that the PPS resin used was A-2.

In Comparative Examples 1 to 3, the viscosity of the PAS resin used was too low, so that sufficient tensile strength could not be obtained.
Further, when Example 4 and Example 5 were compared, there was a difference of 9 MPa in tensile strength depending on the presence or absence of the external lubricant.

The PAS resin-impregnated long fiber pellets obtained by the production method of the present invention maintain the heat resistance, chemical resistance, and heat resistance and water resistance originally exhibited by the PPS resin and are excellent in mechanical properties (tensile strength). It can be used for electrical / electronic applications, automobile applications, water-related applications, general miscellaneous goods applications, building materials, etc.

Claims (5)

A continuous fiber bundle in which continuous fibers are aligned in the length direction is impregnated with a molten polyarylene sulfide (PAS) resin in a heated die and integrated, and then 4 to 50 mm. It is a method for producing PAS resin-impregnated long fiber pellets that are cut to the length of
The PAS resin impregnated long fiber pellet does not contain a flame retardant and
The content ratio of the continuous fiber in the PAS resin-impregnated long fiber pellet is 20 to 60% by mass.
The viscosity of the PAS resin used (temperature 310 ° C., shear rate 1200s ^-1 ) is 50 to 250 Pa · s.
A method for producing PAS resin-impregnated long fiber pellets, wherein the set temperature of the die is 340 ° C. or higher and 390 ° C. or lower. The method for producing PAS resin-impregnated long fiber pellets according to claim 1 or 2, wherein the PAS resin has a viscosity of 50 to 220 Pa · s, and the set temperature of the die is 340 ° C. or higher and 370 ° C. or lower. The method for producing PAS resin-impregnated long fiber pellets according to claim 1 or 2, wherein the continuous fiber is selected from glass fiber, carbon fiber, stainless fiber, and aramid fiber. After producing the PAS resin-impregnated long fiber pellets by the production method according to any one of claims 1 to 3, 0.005 to 0.1 parts by mass with respect to 100 parts by mass of the PAS resin-impregnated long fiber pellets. A method for producing a PAS resin composition, which comprises adding and mixing one or more lubricant components selected from the group consisting of fatty acid amides, fatty acid esters, fatty acid metal salts, and polyethylene wax. The fourth aspect of claim 4, wherein the lubricant component comprises one or more selected from the group consisting of ethylene bisstearic acid amide, montanic acid ester wax, polyglycerin stearate, calcium stearate, magnesium stearate and polyethylene wax. A method for producing a PAS resin composition.