JP3049107B2 - Flex-resistant polyarylene sulfide sheet-like molded product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyarylene sulfide sheet shaped article having high rigidity and good flexibility.

[0002]

2. Description of the Related Art It is known that a conventional polyarylene sulfide resin sheet-like molded product is weak in bending. In particular, the crystallization sheet is weak. Further, when an inorganic filler or the like is added, the bending strength tends to decrease.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a sheet-like molded product having high rigidity and excellent flexibility and excellent workability.

[0004]

[Means for Solving the Problems]

The gist of the present invention is that 100 parts by weight of a polyarylene sulfide resin having a melt viscosity of 2,000 to 30,000 poise and at least 90% by weight of the following mica powder have a particle size of 1 to 8 μm. The iron component in mica is 3.5% by weight or less The weight ratio of magnesium component in mica to the iron component in mica is less than 1 Bound water is 2% by weight or less, and the dehydration start temperature is 400% A flexible polyarylene sulfide sheet-like molded product comprising 1 to 80 parts by weight of mica powder having a characteristic of not less than ℃. Hereinafter, the present invention will be described in detail.

The polyarylene sulfide referred to in the present invention means a polymer having-(-Ar-S-)-(where Ar means an arylene group) as a main component. Here, as the arylene group, for example, -Ph- (where P
h means a phenylene group), -Ph-CO-Ph-
Is used in a broad sense that includes The aromatic ring may have a substituent, but a substituent having no substituent is preferably used. The main constituent means 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol%.
The above is used.

The melt viscosity of the polyarylene sulfide used in the present invention is from 2,000 to 30,000 poise. If it is smaller than 2,000 poise, a sheet having sufficient flexibility cannot be obtained, and if it exceeds 30,000 poise, troubles such as surface roughening of the sheet-like molded product during melt extrusion occur. Preferably 3,000-20,
000 poise, more preferably 4,000 to 15,000
The one having 0 poise is used. The melt viscosity as used herein refers to a value obtained by melt extruding a polyarylene sulfide into a pellet and measuring it at 310 ° C. at a shear rate of 200 sec ⁻¹ .

[0008] As the polyarylene sulfide used in the present invention, a substantially straight-chain high molecular weight one is suitably used. Here, “substantially linear” means that the melt viscosity is 310 ° C., and the shear rate is 200 seconds ⁻¹ to 2,000 to 3,000.
10,000 poise, 310 ° C., shear rate 1200
310 ° C., shear rate 20 for melt viscosity in sec ⁻¹
The melt viscosity ratio at 0 sec ^-1 is 3.0 or less, more preferably 2.8 or less, and the melt crystallization temperature is 170 ° C.
Above, more preferably obtained from a substantially bifunctional monomer-based monomer having a temperature of 180 ° C. or higher, and 1 mol% or less, more preferably 0.5 mol% or less, Preferably, 0.3 mol% or less of a polyfunctional monomer may be present as a constituent unit.

The term "melt crystallization temperature" as used herein refers to a temperature of 23 ° C. being raised to 380 ° C. at a rate of 10 ° C./min by using a differential scanning calorimeter. The exothermic peak temperature of crystallization that appears when the temperature is decreased at a rate. When the polyarylene sulfide has two or more melt crystallization temperatures, for example, a block copolymer or a composition of polyphenylene sulfide and polyphenylene sulfide ketone, the main peak is the melt crystal. Temperature.

As a method for producing polyarylene sulfide which satisfies the above conditions, a known polymerization method for a linear polyarylene sulfide having a high degree of polymerization is employed. For example, as described in JP-B-63-33775. An alkali metal sulfide and a dihalo aromatic compound are
In an organic amide solvent such as methylpyrrolidone or the like, in the presence of water, a method based on a specific two-stage temperature-increasing polymerization method is suitably employed. Further, those obtained by copolymerizing a polyhaloaromatic compound substituted with three or more halogens, such as trichlorobenzene, as a small component can also be suitably used.

On the other hand, at least 90% by weight of the mica powder used in the present invention has a particle size of 1.0 to 8.0 μm. Here, the particle size is the arithmetic mean of the major axis and the minor axis of the mica powder. The measuring method is obtained by enlarging and projecting a length measured by an optical microscope photograph on a screen. In the case of mica powder having an average particle diameter of 1 to 8 μm and less than 90% by weight, if the amount exceeds 8 μm, the smoothness of the sheet becomes poor, resulting in an adverse effect on the flexibility. To bring about. Conversely, if the particle size is less than 1 μm, agglomeration occurs in the extruder, resulting in clogging and poor running performance, and also in this case, bending resistance is reduced.

The iron component present in the mica used in the present invention is 3.5% by weight or less, preferably 1 to 3% by weight in the mica. The magnesium component in mica has a weight ratio of less than 1 to the iron component in mica, preferably less than 0.5. Furthermore, the water of crystallization (bound water) of mica is 2% by weight or less,
Preferably it is 1% by weight. Moreover, the dehydration start temperature is 400 ° C. or higher. Otherwise, kneading of polyarylene sulfide and mica is performed at a high temperature of 280 to 400 ° C., so that dehydration from mica during kneading causes a decrease in productivity.

Such mica can be obtained by, for example, wet-milling muscovite (muscovite) and filtering it by wet filtration to obtain a mica having an average diameter of 1 to 8 μm. The amounts of magnesium component and iron component are measured by melting mica with lithium metaborate, dissolving with hydrochloric acid, and quantifying various elements by induction plasma emission spectrometry. The mica used in the present invention may or may not be subjected to silane coupling treatment. In addition, the treatment may be carried out on the mica surface in advance, or in a kneading step of an extruder, a coupling agent may be directly added to a mixture of polyarylene sulfide and mica for kneading.

[0014] The sheet-like molded product of the present invention is prepared by mixing mica powders 1 to 8 with respect to 100 parts by weight of the polyarylene sulfide.
0 parts by weight, preferably 2 to 60 parts by weight, more preferably 4 to 40 parts by weight. By using the above mica, the effect of improving the bending resistance and rigidity appears even in a small amount as compared with ordinary mica, but the effect of improvement is more remarkable when more mica is used. On the other hand, if the ratio exceeds the above upper limit, the bending resistance decreases. The molded article of the present invention may contain other thermoplastic resins or other fillers at all.

In the present invention, the sheet-like molded product has a broad concept including a thin film. That is, the thickness is not particularly limited, and usually about 5 to 500 μm is employed. The shape is not limited to a flat shape, but broadly includes a wide shape such as a cylindrical shape, a belt shape, a tape shape and the like.

The method for forming the polyarylene sulfide sheet-like molded article of the present invention may be a known method. Preferably, the material comprising the polyarylene sulfide is made of T-die, circular die, or the like. A method is employed in which the material is melt-extruded in a sheet form from a slit-shaped die and cooled and solidified on a metal roll or in a cooling medium and crystallized simultaneously or thereafter. In this case, the resin may be oriented or non-oriented. By using the mica according to the present invention, the draft rate after melt extrusion can be increased as compared with other mica, and a thin sheet can be stably obtained.

In addition to the above-mentioned molding method, a method in which the material is melt-extruded while maintaining an amorphous state or crystallized, stretched, and subjected to a tension heat treatment may be used.

[0018]

[Example] [Measurement method] (Bending resistance)
JISL1021 test items (15)
It was measured according to the method for measuring the bending resistance.

(Bending resistance) A measurement sample was 100 mm long,
A sample was cut out to a width of 15 mm, and a sample was set at 55 mm between chucks according to JIS-8115 using a MIT massaging fatigue tester manufactured by Toyo Seiki Co., Ltd., at a load of 1.25 kg, a bending angle of 135 degrees, and a bending speed of 175 times / The number of bends until the sheet was cut by turning the sheet left and right in minutes was determined and used as an index of the bending resistance.

Example 1 A polyphenylene sulfide polymerized using paradichlorobenzene and sodium sulfide by the method described in JP-B-63-33775 was used. The melt viscosity of this resin is 4400 poise, 3
310 for melt viscosity at 1200C- ^{1 at} 10 ° C.
The ratio of the melt viscosity at 200 ° C. and 200 sec ⁻¹ was 1.6. The melt crystallization temperature was 180 ° C. A composition in which mica A-150 (a muscovite, and other characteristics are as shown in Table 1; trade name of Tsuchiya Kaolin Co., Ltd.) was added to 100 parts by weight of the resin and melt-extruded, Pelletized.

Using this pellet, 35 mmφ, L /
Lip Clearance Attached to D = 28 Extruder
Extruded in a sheet form with a T-die having a lip of 55 mm in width and 250 mm in width, crystallized while being taken up by a castin roll, and further contacted with a heating roll at 165 ° C. for about 20 seconds to proceed with crystallization. Was. The melting temperature of the resin is 310 ° C
And the extrusion rate was 3.0 kg / hour. Approximately 10 mm between the tip of the T-die and the upper end of the castin gall
And the surface temperature of the castin roll was set at 155 ° C. The diameter of the castin roll was 300 mm. The obtained sheet had a thickness of 50 μm. The results obtained are shown in the figure for flex resistance. Table 1 shows only the case where mica is 30 parts by weight with respect to 100 parts by weight of polyphenylene sulfide.

[0022]

[Table 1]

[Comparative Examples 1 to 5] Example 1 was the same as Example 1 except that mica having the characteristics shown in Table 1 was used instead of the mica of Example 1.
Was performed in the same manner as described above. The results obtained are shown in the figure for the flex resistance only in Comparative Example 1, and in the case of polyphenylene sulfide 10
Table 1 shows only the case where mica is 30 parts by weight with respect to 0 parts by weight.

Example 2 Paradichlorobenzene 100 was used in place of the polyphenylene sulfide used in Example 1.
Polyphenylene sulfide polymerized in the same manner as in Example 1 except that 0.2 mol of trichlorobenzene was used per mol was used. Its melt viscosity is 12,000 poise, 310
° C., 310 ° C. for a melt viscosity at 1200 sec ^-1,
The melt viscosity ratio at 200 sec ^-1 was 2.6. The melt crystallization temperature was 185 ° C. Molding was performed under the same conditions as in Example 1 except that the melt extrusion temperature was changed to 340 ° C. using pellets prepared by adding 7.5 parts by weight of mica as in Example 1 to 100 parts by weight of this resin. did. The results obtained are as shown in Table 1.

[0025]

According to the present invention, there is provided a method for producing a sheet-like molded product having high flexibility and excellent workability while maintaining high rigidity as compared with the case where ordinary mica is used. Therefore, such a sheet is suitably used for, for example, a flexible printed circuit board, an insulation-resistant sheet, a heat-resistant release sheet, and the like.

[0026]

[Brief description of the drawings]

The figure shows the number of times of refraction resistance for various addition amounts of mica in Example 1 and Comparative Example 1.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-4-72356 (JP, A) JP-A-62-132962 (JP, A) JP-A-61-174262 (JP, A) JP-A-59-1984 179639 (JP, A) JP-A-57-63355 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 81/00-81/10

Claims (1)

(57) [Claims] 1. 100 parts by weight of a polyarylene sulfide resin having a melt viscosity of 2,000 to 30,000 poise;
At least 90% by weight of the mica powder has a particle size of 1 to 8 μm. The iron component in the mica is 3.5% by weight or less. The weight ratio of the magnesium component in the mica to the iron component in the mica is less than 1. A bend-resistant polyarylene sulfide sheet-like molded product comprising 1 to 80 parts by weight of mica powder having a characteristic that bound water is 2% by weight or less and dehydration start temperature is 400 ° C. or more.