JP2644468B2 - Sheet-like molded product and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a melt viscosity of 1000 to 1000.
30-95% by weight of 40000 poise substantially linear polyarylene thioether resin and 5-7 fibrous reinforcement
The present invention relates to a sheet-like molded product comprising a composition containing 0% by weight and having excellent workability, or a heat-fixed sheet-like molded product, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, in order to reduce the weight of metal structural materials such as aircraft, automobiles and small boats, which are required to have heat resistance and mechanical strength as well as corrosion resistance, a fibrous reinforcing material and a synthetic resin have been used. Composites have been developed as alternative materials for metals.

[0003]

Most of such composite materials are prepreg sheets or the like using a thermosetting resin.
Therefore, long time heat denaturation treatment (curing) during molding
And there is a problem that productivity is low. Recently, a stampable sheet and the like, which hardly requires curing, in which a thermoplastic resin is fiber-reinforced, has been developed. But,
These generally use polyolefins, polyamides, polyalkylene terephthalates, and the like, which are not high in heat resistance, as the base resin, and have a problem that they cannot be used under high temperature and corrosive conditions. Therefore, some attempts have been made on a stampable sheet or the like in which polyparaphenylene thioether, which is a thermoplastic resin, which is extremely excellent in heat resistance and corrosion resistance, is reinforced with a fibrous reinforcing material (Australia Patent No. 8,429,016). ). However, conventionally available polyparaphenylene thioethers have relatively high molecular weight polymers crosslinked by curing to increase the apparent melt viscosity. There is a problem that physical properties are unsatisfactory in practical use.

[0004]

The present inventors have made intensive studies to solve these problems, and as a result, have found that Japanese Patent Application No.
No. 126725 (Japanese Patent Application Laid-Open No. 61-7332), Japanese Patent Application No. 59-134633 (Japanese Patent Application Laid-Open No. 61-14228) or Japanese Patent Application No. 59-188533 (Japanese Patent Application Laid-Open No. 61-66720). An innovative method for economically producing a polyarylene thioether having a sufficiently high melt viscosity without cross-linking of a high molecular weight linear structure as described in (1) was developed. Since the polyarylene thioether produced by such a method is substantially linear and has a high molecular weight, a sheet-like molded product that can withstand practical use can be produced by appropriately combining the fiber with a fibrous reinforcing material. I understood. In particular, it has been found that a sheet-like molded product having both excellent workability and mechanical properties can be produced by using an arylene ether copolymer, particularly a block copolymer. The present invention has been completed based on these findings.

That is, the sheet-like molded product according to the present invention has a melt viscosity of 1,000 to 40,000 poise [temperature = 31.
0 ° C., shear rate = 200 sec ⁻¹ ], 30 to 95% by weight of a polyarylene thioether resin having a substantially linear structure and satisfying the following conditions (A) and (B): A sheet-like molded product obtained by molding a composition containing about 10% by weight into a sheet. (A) The polyarylene thioether resin is at least composed of a polyarylene thioether copolymer, and all or a part of the polyarylene thioether copolymer is a repeating unit.

[0006]

Embedded image 50-95 mol% of the block and repeating units

[0007]

Embedded image A block copolymer consisting of 5 to 50 mol% of the block. (B) In a method for obtaining a polyarylene sulfide by reacting an alkali metal sulfide with a dihalo aromatic compound in an organic amide solvent, a polyarylene thioether resin is obtained by performing this reaction in at least the following two steps. That

(1) In the presence of 0.5 to 2.4 moles of water per mole of alkali metal sulfide, 180 to 2
Carrying out a reaction at a temperature of 35 ° C. to produce polyarylene sulfide having a melt viscosity of 5 to 300 poise at a conversion of a dihalo aromatic compound of 50 to 98 mol%.

(2) Water is added so that 2.5 to 7.0 moles of water are present per mole of alkali metal sulfide, and the temperature is raised to a temperature of 245 to 290 ° C.
A step of continuing the above reaction.

Further, the method for producing a sheet-like molded product according to the present invention employs a melt viscosity of 1,000 to 40,000 poise [temperature = 3.
10 ° C., polyarylene thioether resin 30-95 wt% and fibrous reinforcing material 5-70 satisfying substantially the following with linear structural condition (i) and (ii) a shear rate = 200 sec ^-1] A method for producing a sheet-like molded product, comprising heating a composition containing at least a weight percent of the composition to a temperature equal to or higher than the melting point of the resin to be used using an extruder equipped with a T-die and extruding the composition into a sheet. (A) The polyarylene thioether resin is at least composed of a polyarylene thioether copolymer, and all or a part of the polyarylene thioether copolymer is a repeating unit.

[0011]

Embedded image 50-95 mol% of the block and repeating units

[0012]

Embedded image A block copolymer consisting of 5 to 50 mol% of the block. (B) In a method for obtaining a polyarylene sulfide by reacting an alkali metal sulfide with a dihalo aromatic compound in an organic amide solvent, a polyarylene thioether resin is obtained by performing this reaction in at least the following two steps. That

(1) In the presence of 0.5 to 2.4 moles of water per mole of alkali metal sulfide, 180 to 2
Carrying out a reaction at a temperature of 35 ° C. to produce polyarylene sulfide having a melt viscosity of 5 to 300 poise at a conversion of a dihalo aromatic compound of 50 to 98 mol%.

(2) Water is added so that 2.5 to 7.0 mol of water is present per 1 mol of alkali metal sulfide, and the temperature is raised to a temperature of 245 to 290 ° C.
A step of continuing the above reaction. Effect Since the sheet-like molded product of the present invention is composed of a substantially linear high molecular weight polyarylene thioether and a fibrous reinforcing material, the polyarylene thioether and the fiber reinforcing material whose apparent melt viscosity is increased by low molecular weight or crosslinking are provided. Compared to the sheet-like molded product obtained from the above, it is possible to obtain a product having remarkably excellent mechanical properties such as impact strength and bending strength. It can be suitably used for parts.

Further, the obtained sheet-like molded article can be subjected to vacuum molding or compression molding, and a uniform and tough secondary molded article can be obtained as compared with a low-molecular-weight polyarylene thioether sheet-like molded article.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION

<Molding Material> Material Resin One of the features of the present invention is that the resin component of the composition used for the sheet-like molded product is substantially a linear high molecular weight polyarylene thioether resin (AT polymer). That is.

Here, the AT polymer is a repeating unit

[0018]

Embedded image (Ar: arylene group) is a main component.

As the arylene group, those having a paraphenylene group as a main component are preferred from the viewpoint of physical properties such as heat resistance, moldability and mechanical properties.

As the arylene group other than the paraphenylene group, those shown in Table 1 below can be used.

[0021]

[Table 1] In general, the composition is formed into a sheet, and from the viewpoint of workability such as stamping of the obtained sheet,

[0022]

Embedded image AT copolymers containing heterologous repeating units are preferred over AT homopolymers containing only repeating units.

The block copolymer used in the present invention comprises:
Repeat unit

[0024]

Embedded image 50-95 mol% of the block and repeating units

[0025]

Embedded image 5 to 50 mol% of When such a block copolymer is used, it is almost the same in terms of processability (has a crystallization rate suitable for sheet processing), but it is difficult in terms of physical properties (heat resistance, mechanical properties, etc.). From the viewpoint of (3), the use of a random copolymer is remarkably superior to that of the case using a random copolymer. In the block copolymer

[0026]

Embedded image The content of the repeating unit is particularly preferably from 10 to 25 mol%.

The material used as the material resin of the sheet-shaped molded product of the present invention has the above-mentioned chemical constitution,
And a melt viscosity of 1000 to 40000 poise [temperature = 31
0 ° C., shear rate = 200 sec ⁻¹ ], particularly preferably 300
0 to 20,000 poise, substantially linear polyarylene thioether. With a low melt viscosity polymer of less than 1000 poise, drawdown tends to occur during processing,
Mechanical properties are also poor. On the other hand, in the case of a polymer having a high melt viscosity exceeding 40,000 poise, the flowability deteriorates, so that the adhesiveness with the fiber reinforcement deteriorates, and the molded product often contains microvoids, and the mechanical properties deteriorate, which is preferable. Absent.

Furthermore, the AT polymer used in the present invention has a substantially linear structure. Therefore, for example, a crosslinked product obtained by using a crosslinking agent (for example, 1,2,4-trihalobenzene) of 0.5 mol or more per 100 mol of an arylene group at the time of polymerization or a polymer is subjected to high temperature treatment in the presence of O ₂ or the like. A crosslinked product having apparently increased the melt viscosity by a factor of 2 or more by crosslinking by the method of the present invention is not used in the present invention. Incidentally, these crosslinked products are usually extremely weak mechanically, which is not only unfavorable in terms of physical properties, but also
Sheets using these as a material resin are poor in elongation, making it difficult to perform deep drawing and the like, which is not preferable from the viewpoint of workability.

The linear polyarylene thioether satisfying the conditions of the resin of the present invention as described above is disclosed in Japanese Patent Application No. 59-126725 filed by the present inventors (Japanese Patent Application Laid-Open No. 61-73).
No. 32), in a method of reacting an alkali metal sulfide with a dihaloaromatic compound in an organic amide solvent to obtain a polyarylene sulfide, the reaction is carried out in at least the following two steps. It was done. (1) 0.5 to 2.4 per mole of alkali metal sulfide
The reaction is carried out at a temperature of 180 to 235 ° C. in the presence of moles of water to convert a polyarylene sulfide having a melt viscosity of 5 to 300 poise to a dihalo aromatic compound conversion of 50 to 50.
(2) 2.5 to 7.0 per mole of alkali metal sulfide
A step of adding water so as to be in a state where moles of water are present, and increasing the temperature to 245 to 290 ° C. to continue the above reaction.

The material resin is preferably contained in the composition in an amount of 30 to 95% by weight, particularly 40 to 80% by weight. If the amount is less than 30% by weight, it is difficult to bond the fiber reinforced material firmly, so that the strength is weak. If the amount exceeds 95% by weight, the composite effect of improving the mechanical properties when the fiber reinforced material is uniformly dispersed is not sufficiently exhibited. Fibrous Reinforcement The fibrous reinforcement to be used in the fiber-reinforced sheet-like molded product of the present invention includes carbonaceous fiber, glass fiber, silica fiber, alumina fiber, ceramic fiber, rock wool, potassium whisker titanate. Inorganic fibers such as fibrous metal or organic fibers such as aramid fibers are preferable, and among them, carbonaceous fibers, glass fibers and aramid fibers are particularly preferable from the viewpoint of heat resistance, mechanical strength and economy.

The fibrous reinforcing material may be of various shapes such as cloth, mat, felt, paper, roving, chopped fiber, milled fiber, whisker and the like.

The mixing amount of the fibrous reinforcing material in the composition sheet of the present invention is preferably in the range of 5 to 70% by weight, more preferably 20 to 60% by weight in the composition. In addition, the composition of the present invention contains the AT polymer of the material resin and the fibrous reinforcing material as essential components. However, if necessary, as long as it does not hinder molding, an inorganic filler or other thermoplastic resin may be used. Resins, various auxiliaries and the like can also be added.
The inorganic filler is added in the form of powder or fine particles for improving dimensional stability, heat deformation temperature, flame retardancy, mechanical strength, hardness, etc., or for cost reduction. For example, calcium carbonate, calcium silicate, talc, silica, mica, TiO ₂ , carbonaceous (including carbon black and graphite), alumina, silica alumina, glass, iron oxide, gypsum, sand, cement, or various metals Equivalent to. The addition amount is preferably from 0 to 50% by weight. If it exceeds 50%, the processability of the composition sheet deteriorates, which is not preferable.

Further, for the purpose of improving the lubricating property and impact resistance or reducing the cost, another thermoplastic resin can be mixed if necessary. As the thermoplastic resin, for example, fluorine resin, polyalkylene terephthalate, polyolefin, polycarbonate, polyphenylene ether, polyamide, silicone, ABS resin, polyetheretherketone, polysulfone, polyethersulfone, etc., decompose or change It is preferable because it can be kneaded without rubbing. 0-40% by weight
Is preferred. If it exceeds 40%, the original heat resistance of the material resin,
It is not preferable because characteristics such as flame retardancy and workability are impaired.

Further, for the purpose of color tone improvement, thermal stability improvement, weather resistance improvement, processability improvement, rust prevention, lubricity improvement, crystallinity adjustment, coloring, etc., if necessary, the periodic table IA group,
Salt hydroxides, oxides or hydrocarbyl oxides of Group IIA or IIB metals, stabilizers, lubricants, mold release agents, pigments, nucleating agents, etc. can also be added.

The composition comprising the above components can be used as a powder mixture directly as a raw material for a sheet-like molded product, or once formed into a composition pellet and then formed into a sheet-like molded product. It can be used for melt molding as a raw material.

Sheet-like molding A sheet-like molded product can be obtained from the composition using the AT polymer of the present invention as a material resin by a molding method using a melt extrusion method. The contents are as follows.

Sheet-like molded product by melt extrusion method It is obtained by a method in which a raw resin or a raw resin composition and a fibrous reinforcing material are melt-mixed in an extruder and extruded into a sheet. When the shape of the fiber reinforcement is short, such as chop, milled fiber, whisker, etc., a mixture (powder or pellet) of the fiber reinforcement and the material resin or the material resin composition is extruded with a T-die. It is preferable that the mixture is heated and melted while being supplied to a machine via a hopper, and extruded into a sheet. If the shape of the fiber reinforcement is long, such as a roving cloth or mat, use a vented extruder, the raw resin or raw resin composition is passed through a hopper, and the fibrous reinforcement is passed through a vent hole. It is preferable to extrude into a sheet by heating and melting while continuously supplying the extruder.

The sheet-shaped molded product of the present invention is characterized by high bending strength and impact resistance, and high heat distortion temperature (HDT). The flexural strength obtained by a measuring method according to ASTM D-790 is generally 20 kg / cm ² or more.
The impact strength obtained by a measuring method according to STM D-256 is 30 kg · cm / cm or more, preferably 40 k · cm / cm.
g · cm / cm or more, and HDT is 180 ° C.
Or higher, preferably 230 ° C. or higher.

Deformation of sheet-like molded article The sheet-like molded article of the present invention can be deformed into molded articles of various shapes by a high-temperature vacuum molding method, a high-temperature compression molding method, a mandrel method or the like. High Temperature Vacuum Forming Method One or several sheets of the composition sheet of the present invention or, if necessary, a sheet-like material made of a fiber reinforced material and a composition sheet of the present invention stacked on each other, the softening temperature of the material resin To the decomposition initiation temperature, particularly preferably from 80 ° C to 380.
Heating to a temperature in the range of ° C., a vacuum mold is used, and the mold is brought into close contact with the mold in a vacuum to form a desired shape.

This molded product is optionally subjected to a heat treatment at a temperature slightly lower than its heat deformation temperature,
It is possible to further improve the heat distortion temperature of molded products [Plastic Engineering Handbook (P
LASTIC. ENG. HANDBOOK) Third Edition, p. 48 (1960)]. High Temperature Compression Molding In a vacuum molding method, a compression mold is used instead of a vacuum mold, and the sheet is brought into close contact with the mold by high pressure instead of vacuum, and can be processed into a desired shape. Compared with the vacuum molding method, the compression molding method is superior in that a molded product having few voids and defects can be easily obtained, a thick product can be processed, and deep drawing can be performed. Mandrel method One or several sheets of the composition of the present invention are used by using a mandrel instead of a vacuum mold or a compression mold, and if necessary, the composition sheet of the present invention and a fiber reinforced material (especially cloth). , Mat, paper, etc.), heated to the range from the softening temperature of the resin used to the decomposition temperature, wound around a mandrel, pressed using a mold, cooled, and pulled out of the mandrel Can also be processed. This method is suitable for forming pipes and tubes.

Heat fixing of sheet-like molded product and deformed product The sheet-like molded product of the present invention and its deformed molded product are:
Further, when heat resistance and mechanical properties are required, it is preferable to perform heat fixing. Heat setting is performed by holding the molded product at a temperature of 150 to 260 ° C. for 0.3 to 100 hours. When the temperature is lower than 150 ° C., it takes a long time for heat setting, which is disadvantageous in terms of productivity. When the temperature is higher than 260 ° C., the resin may be melted, which is not preferable. If it is less than 0.3 hours, the heat setting is insufficient, and if it exceeds 100 hours, it is disadvantageous in terms of productivity.

The heating can be performed in air or in a non-oxidizing atmosphere.

Product sheet-like molded product and its deformed product The sheet-like molded product of the composition of the present invention may be, for example, an automobile,
Applications such as flooring, wall materials, tanks, housings, etc. for vehicles or aircraft, housings for electronics, electricity, equipment, wiring boards, range parts, bobbins, etc., or various industrial pipes, tubes, etc. Widely applicable to

[0044]

EXAMPLES Synthesis Example 1 (Comparative Example) An autoclave was charged with 1400 kg of N-methylpyrrolidone (abbreviated as NMP), 1.5 Kmol of Na ₂ S.3H ₂ O and 3 Kmol of CaO, and heated at 160 ° C. for 2 hours. To remove water of crystallization with CaO
110 kg and para-dichlorobenzene (p-DCB
1.51 Kmol) and polymerized at 205 ° C. for 7 hours to obtain poly-para-phenylene thioether (L1). Melt viscosity of L1 (temperature = 310 ° C.,
Shear rate = 200 sec- ¹ ) was 300 poise.

L1 16.2 kg, NMP 180 kg
And 30 kg of water were charged into an autoclave and stirred,
Further, 400 g of C ₂ H ₅ ONa was charged and 265 ° C.
For 3 hours to obtain poly-para-phenylene thioether L2. The melt viscosity of L2 was 18,000 poise.

A part of L1 was put in a hot air drier and
Heat treatment was performed at 3 ° C. for 3 hours to obtain a crosslinked poly-para-phenylene thioether C1. The melt viscosity of C1 is 410
It was 0 poise. Synthesis Example 2 (Comparative Example) In an autoclave, 110 kg of NMP and Na ₂ S ·
5H ₂ O 250 mol was charged, and the temperature was raised to about 200 ° C. to distill water of crystallization, and 33 kg of NMP and p-DCB
Then, 250 mol was added and polymerization was carried out at 220 ° C. for 6 hours. Then, 600 mol of water was added, and the temperature was raised to 260 ° C. to carry out polymerization for 4 hours to obtain poly-para-phenylene thioether L3. The melt viscosity of L3 was 4000 poise. Synthesis Example 3 (Comparative Example) Instead of 250 mol of p-DCB, 210 mol of p-DCB and 40 meta-dichlorobenzene (abbreviated as m-DCB) 40
And polymerization was performed in the same manner as in Synthesis Example 2 except that polymerization was performed at a temperature of 260 ° C. for 15 hours.
(Phenylene thioether / m-phenylene thioether) random copolymer R1 was obtained. The melt viscosity of the obtained R1 was 3,800 poise, and the composition ratio of (p-phenylene thioether / m-phenylene thioether) was (87 mol / 13 mol). Synthesis Example 4 In an autoclave, 110 kg of NMP and Na ₂ S ·
200 mol of 5H ₂ O was charged and the temperature was raised to 205 ° C. to distill water of crystallization, and then 33 kg of NMP and m-
200 mol of DCB was charged and polymerization was carried out at 230 ° C. for 8 hours to prepare a reaction mixture A. On the other hand, NMP 620 kg and _{Na 2} S · 5H 2 to another autoclave
1.11 Kmol of O was charged, the temperature was raised to about 205 ° C., and about 70% of the water of crystallization was distilled off to prepare a mixed solution B. The reaction mixture A was added thereto, and NMP 170
22 kg and 1.11 Kmol additional p-DCB
The reaction was carried out at 0 ° C. for 10 hours, and then 3.5 Kmol of water was added to carry out polymerization at 255 ° C. for 6 hours. Four polymerizations were repeated in the same manner. The melt viscosity of the obtained (p-phenylene thioether / m-phenylene thioether) block copolymer B1 was 4100 poise, and the composition ratio of (p-phenylene thioether / m-phenylene thioether) was (84 mol / 16 mol). Was. Synthesis Example 5 Reaction mixture A and mixture B in the same manner as in Synthesis Example 4.
And polymerization was carried out in the same manner as in Synthesis Example 4 except that 1/3 of the reaction mixture A was added to the mixture B.
A block copolymer B2 was obtained. The melt viscosity of B2 is 510
0 poise, and the composition ratio of (p-phenylene thioether / m-phenylene thioether) was (94 mol / 6 mol). Examples 1-2, Comparative Examples 1-5 Each of AT polymers L1, L2, L3, R1, B1, B2 and C1 was continuously supplied to a vented extruder through a hopper and heated to 350 ° C. Melt and glass chop [Nittobo Co., Ltd.]
: CS3PE-471S] is continuously supplied at a constant supply speed, melt-extruded into a 2 mm-thick sheet from a T-die attached to the tip of the extruder, and immediately cooled with water to obtain a sheet-like molded product. It was kept at 205 ° C. for 4 hours and heat-fixed.
Sheet-shaped moldings (L1-S1-1), (L2-S1-
1), (L3-S1-1), (R1-S1-1), (B
1-S1-1), (B2-S1-1) and (C1-S1)
-1) was obtained.

Table 2 shows the physical properties of the obtained sheet-like molded product. (L1-S1-1) and (C1) using L1 of low melt viscosity (low molecular weight) and C1 of crosslinked type as materials.
-S1-1) Sheet-shaped molded product [Comparative Examples 1 and 5]
Had insufficient strength. (R1-S1-1) using the random copolymer R1 as a material had sufficient strength, but heat resistance was somewhat insufficient. Examples 3 to 4 An AT polymer (B1) was blended with a carbonaceous fiber chop (C-101F, manufactured by Kureha Chemical Co., Ltd.) and an aramid fiber cloth (Conex, manufactured by Teijin Limited), and the mixture was extruded using an extruder. Each of the composition pellets was prepared, and each pellet was fed to an extruder equipped with a T-die, melt-extruded at 350 ° C. from a T-die into a sheet, quenched with water, and cooled to a thickness of 2 mm.
And then heat-set at 205 ° C. for 4 hours to obtain (B1-S1-2) and (B1-S1-
3) was obtained.

Table 2 also shows the physical properties of the obtained sheet-like molded product. Reference Examples 1-2 The AT polymers (L3) and (B1) were each reduced to a fine powder of 150 μm or less by a pulverizer, and the water / acetone ratio was 70.
Each slurry was prepared by dispersing in a (weight) / 30 (weight) aqueous solution to a concentration of 20% by weight.

Each of these slurries was mixed with a glass chopped strand mat [Nittobo Co., Ltd. (MC60)
0A)], squeezed, and then heated with hot air to remove the dispersion medium. The same operation was performed with a fiber content of about 30% by weight.
Repeated until.

Each of the AT polymer-impregnated mats was alternately laminated and subjected to a pressure of 200 kg / cm ² and 350 ° C. for 1 hour.
It was melt-pressed for 0 minutes, and then quenched with water to obtain a sheet-shaped molded product having a thickness of 2 mm. Thereafter, it was held at 205 ° C. for 4 hours and heat-set to obtain (L3-S2-1) and (L3-S2-1). B1-S2-
I made 1).

Table 3 shows the physical properties of the obtained sheet-like molded product. Reference Examples 3 to 4 Using an extruder equipped with a crosshead die, glass roving with a crosshead die [manufactured by Nitto Boseki Co., Ltd.] while melt-extruding AT polymers (L3) and (B1):
RS240PE-535] was gel-coated with each polymer and immediately cooled with water to prepare a polymer-coated roving. Cut this polymer coated roving
The operation of arranging one layer in the direction and repeating the operation of arranging and stacking the next layer in the orthogonal direction is repeated to form a laminate in which the fiber is oriented in two directions, and is melt-pressed with a hot press at a pressure of 200 kg / cm ² and a temperature of 350 ° C. for 10 minutes. Then, a sheet-shaped molded product having a thickness of 2 mm was obtained, and then held at 205 ° C. for 4 hours and heat-set to obtain (L3-S3-1) and (B1-S3-
1) was obtained.

Table 3 shows the physical properties of the obtained sheet-like molded product. Reference Examples 5 to 6 Each of AT polymers (L3) and (B1) was supplied to an extruder equipped with a T-die, heated and melted at 350 ° C., extruded into a sheet, and cooled with water to obtain a polymer having a thickness of about 0.10 mm. I made a sheet.

A glass cloth [Nittobo Co., Ltd.]
: WF230N-100] is sandwiched and melt-pressed at a pressure of 20 kg / cm ² and a temperature of 350 ° C. for 10 minutes to obtain a composite sheet having a fiber content of 41% by weight and a thickness of 0.3 mm. This was heat-set at 205 ° C. for 4 hours to give (L3-S4-1) and (B1-S4-
1) was obtained.

[0054]

[Table 2]

[0055]

[Table 3] Reference Examples 7 to 10 Sheet-shaped moldings (L1-S1-1), (L3-S1-
1), (B1-S1-1) and (C1-S1-1) are each preheated at 290 ° C., supplied to a pair of male and female dies set at 135 ° C., and subjected to a pressure of about 90 kg / cm ^2. ,
A 100 mm × 100 mm × 15 mm square tray-like molding was produced.

The tray made from (L1-S1-1) had remarkably thin tops and ridges. The thickness of the others was almost uniform. Those obtained from (L1-S1-1) and (C1-S1-1) (Reference Examples 7, 10) are as follows:
It was very brittle and broke with little stress. Reference Examples 11 to 12 Sheet-like molded products (L3-S4-1) obtained in Reference Examples 5 to 6
And (B1-S4-1) are each preheated at 290 ° C. and wound on a mandrel, then placed in a cylindrical mold set at 135 ° C., formed into a cylindrical shape at a pressure of about 30 kg / cm ² , and cooled. After that, pull out the mandrel, inner diameter 30mmφ,
A pipe having a thickness of about 2 mm was formed.

The pipe from (L3-S4-1) was conspicuous with voids, but the pipe from (B1-S4-1) was apparently dense.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08G 75/02 NTX C08G 75/02 NTX B29K 81:00 105: 12 B29L 7:00

Claims (6)

(57) [Claims] 1. A polyarylene thioether having a substantially linear structure having a melt viscosity of 1,000 to 40,000 poise [temperature = 310 ° C., shear rate = 200 sec− ¹ ] and satisfying the following conditions (a) and (b): A sheet-like molded product obtained by substantially molding a composition containing 30 to 95% by weight of a resin and 5 to 70% by weight of a fibrous reinforcing material into a sheet. (A) The polyarylene thioether resin is at least composed of a polyarylene thioether copolymer, and all or a part of the polyarylene thioether copolymer is a repeating unit. 50 to 95 mol% of a block and a repeating unit A block copolymer consisting of 5 to 50 mol% of the block. (B) In a method for obtaining a polyarylene sulfide by reacting an alkali metal sulfide with a dihalo aromatic compound in an organic amide solvent, a polyarylene thioether resin is obtained by performing this reaction in at least the following two steps. That (1) 0.5 to 2.4 per mole of alkali metal sulfide
The reaction is carried out at a temperature of 180 to 235 ° C. in the presence of moles of water to convert a polyarylene sulfide having a melt viscosity of 5 to 300 poise to a dihalo aromatic compound conversion of 50 to 50.
Producing at 98 mol%. (2) 2.5 to 7.0 per mole of alkali metal sulfide
A step of adding water so as to be in a state where moles of water are present, and raising the temperature to a temperature of 245 to 290 ° C. to continue the reaction. 2. The sheet-shaped molded product according to claim 1, which is heat-set. 3. The sheet-like molded product according to claim 1, wherein the fibrous reinforcing material contains at least one kind of fiber selected from glass fiber, carbonaceous fiber and aramid fiber. 4. The method according to claim 1, wherein the resin is embossed at a temperature equal to or higher than the softening point of the resin used to form a three-dimensional shape.
Item. 5. The sheet-shaped molded product according to claim 1, wherein the sheet-shaped molded product is wound into a tube and the contact layers are joined. 6. A polyarylene thioether having a substantially linear structure having a melt viscosity of 1,000 to 40,000 poise [temperature = 310 ° C., shear rate = 200 sec− ¹ ] and satisfying the following conditions (a) and (b): A composition containing 30 to 95% by weight of a resin and 5 to 70% by weight of a fibrous reinforcing material is heated and melted to a temperature equal to or higher than the melting point of the used resin by using an extruder equipped with a T-die, and extruded into a sheet. A method for producing a sheet-like molded product, characterized in that: (A) The polyarylene thioether resin is at least composed of a polyarylene thioether copolymer, and all or a part of the polyarylene thioether copolymer is a repeating unit. 50 to 95 mol% of a block and a repeating unit A block copolymer consisting of 5 to 50 mol% of the block. (B) In a method for obtaining a polyarylene sulfide by reacting an alkali metal sulfide with a dihalo aromatic compound in an organic amide solvent, a polyarylene thioether resin is obtained by performing this reaction in at least the following two steps. That (1) 0.5 to 2.4 per mole of alkali metal sulfide
The reaction is carried out at a temperature of 180 to 235 ° C. in the presence of moles of water to convert a polyarylene sulfide having a melt viscosity of 5 to 300 poise to a dihalo aromatic compound conversion of 50 to 50.
Producing at 98 mol%. (2) 2.5 to 7.0 per mole of alkali metal sulfide
A step of adding water so as to be in a state where moles of water are present, and raising the temperature to a temperature of 245 to 290 ° C. to continue the reaction.