JPH0258568A - Polyarylene thioether ketone composition having improved melt-stability and crystallinity - Google Patents

Abstract

PURPOSE:To provide a polyarylene thioether ketone composition containing a heat-stabilized polyarylene thioether ketone having a specific physical property and a specific basic compound and having improved melt-stability and crystallinity. CONSTITUTION:The objective composition contains (A) 100 pts.wt. of a heat- stabilized polyarylene thioether ketone containing the unit of formula (CO and S are bonded to para positions of a benzene ring) as a main constituent unit and having a melting point of 310-380 deg.C, melt-crystallization temperature of >=210 deg.C (420 deg.C/10min), a residual melt-crystallization enthalpy of >=10J/g (420 deg.C/10min) and a reduced viscosity if 0.2-2dl/g (in 98% sulfuric acid at a concentration of 0.5g/dl at 25 deg.C) and (B) 0.1-30 pts.wt. of a basic compound selected from hydroxide, oxide or aromatic carboxylic acid salt of a group IIA metal (excluding Mg) and a hydrocarbyl oxide, aromatic carboxylic acid salt, etc., of a group IA metal.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a polyarylene thioetherketone-based jA composition with improved melt stability and crystallinity, and more specifically, it is applicable to general melt processing. The present invention relates to a composition containing a thermostable polyarylene thioether ketone and a stabilizer consisting of a basic compound.

When the composition of the present invention is melt-molded, it can provide a molded article with little change in melt viscosity and improved crystallinity.

[Conventional technology]

In recent years, with the progress of light l1iI miniaturization technology in the electronics and electric industry fields and the progress of light weight reduction technology in the automobile, aircraft, and space industries, it has become possible to develop heat-resistant materials with a melting point of approximately 3°C or higher, and to melt them. There has been a strong demand for crystalline thermoplastic resins that are easy to process.

Examples of crystalline, heat-resistant thermoplastic resins that have been developed to date include polybutylene terephthalate, polyacetal, and polyP-phenylenethioether, but these resins do not meet the latest requirements for heat resistance. I couldn't be more satisfied.

Recently, polyetheretherketone (hereinafter abbreviated as PEEK) and polyetherketone (hereinafter abbreviated as PEK) have been developed as thermal resins having a melting point of approximately 300"C or higher. Because it is a thermoplastic resin, general melt processing methods such as extrusion molding, injection molding, and melt spinning can be applied to extrusion moldings, injection moldings, moldings, films, etc. It is known that it can be easily molded into various molded products.

However, since these resins use expensive fluorine-converted aromatic compounds such as 4,4'-difluorobenzophenone as raw materials, it is said that there is a limit to cost reduction, and there are problems with quantitative expansion. It has been pointed out that there is.

By the way, below polyarylene thioether ketone C,
rPTK) has a similar chemical structure to PEEK and PEK, so some studies have been conducted based on the assumption that it could be a thermoplastic resin with similar thermal properties. For example, Japanese Unexamined Patent Publication No. 1986
-58435 Publication (hereinafter referred to as "Document A"), West German Publication DE-3405523AI (hereinafter referred to as "Document B"), Publication No. 60-104126 (hereinafter referred to as "Document C"), Unexamined Japanese Patent Publication No. 13347/1983 (hereinafter referred to as "Bun pADJ"), magazine Indian
J, Cbem, 21A (Ma2. +982)
pp 501-502 (hereinafter referred to as "Document E") and JP-A-61-221229 (hereinafter referred to as "Document #F")
) is full of disclosures regarding PTK.

However, regarding the PTK described in the above literature, no successful molding process has been achieved so far using a general melt processing method. Note that the term "general melt processing method" here refers to the four normal melt processing methods for thermoplastic resins. It is. This means extrusion molding, injection molding, melt spinning, etc.

The reason why PTK molding processing using general melt processing methods has not been successful is that PTK produced using conventional technology has poor thermal stability, resulting in loss of crystallinity during melt processing or cross-linking accompanied by an increase in melt viscosity. This is presumed to be because it was easy to cause reactions and carbonization reactions.

In Document #A and Document B, attempts have been made to make some molded products made by yJ, but since these PTKs also have poor thermal stability, a large amount of fiber reinforcement is impregnated with or mixed with PTK as a type of binder. Due to the special molding method of press molding, only a limited number of molded products can be obtained.

As described above, all conventional PTKs have insufficient thermal stability, so it has not been possible to obtain molded products by applying general melt processing methods.

The inventors have conducted intensive studies on a method for economically producing PTK having thermal stability applicable to general melt processing methods.

The present inventors first decided to use inexpensive dichloropentuphenone and dibromobenzophenone as raw materials instead of using expensive fluorine-substituted aromatic compounds. Then, we devised a monopolymerization method! The amount of coexisting water in the i-combination system is extremely large compared to the methods reported so far, and
An attempt was made to carry out polymerization by adding a polymerization aid and appropriately controlling the polymerization temperature profile. As a result, it was found that high molecular weight PTK can be obtained economically.

However, the high molecular weight PTK obtained by this new method was still unsatisfactory in terms of thermal stability. Therefore, as a first step, the inventors further devised the IX mixing method, and added no FR mixing agent, and
By carrying out single polymerization with consideration to the selection of monomer charging ratio, shortening of polymerization time at high temperatures, selection of material for double polymerization reactor, etc.

In addition, by performing stabilization treatment at the final stage of polymerization as necessary, thermal stability is dramatically improved compared to conventional PTK, resulting in a PTK that is easy to apply general melt processing methods. I found out that it can be done. Then, from such thermally stable PTK, by a general melt processing method,
It has been found that molded products such as extrusion molded products, injection molded products, fibers, and films can be easily obtained.

However, even with thermostable PTK that can be applied to this general melt processing method, some degree of thermal denaturation and thermal deterioration is unavoidable when melt processing from polymer powder to pellets or molded products, resulting in a decrease in melt viscosity. This causes problems such as increase in the melting temperature, decrease in crystallinity, and adhesion of thermal decomposition products to the resin retention area of the melt processing equipment, making it difficult to grasp the appropriate melt processing conditions.

Therefore, regarding this thermally stable PTK, it is important to consider further improving the thermal stability during melt processing.
6 The present inventors have developed the above-mentioned thermally stable material for the purpose of preventing an increase in melt viscosity, a decrease in crystallinity, and adhesion of thermal decomposition products to resin retention parts of melt processing equipment during melt processing. By adding various heat stabilizers such as those shown below, which are conventionally known as heat stabilizers for polyarylene thioether (FATE), to PTK,
Attempts were made to improve the physical properties.

That is, as heat stabilizers, organic thiols (US Pat. No. 3,388,950), organic hydroxyamines (US Pat. No. 3,408,342 fi),
Fiphosphine #rf48 and organic phosphites (US Patent No. 3,858,753), inorganic nitrite group (US Patent No. 4,405,745),
Organotin compounds (U.S. Pat. No. 4,411,853), dithiocaroctamates (U.S. Pat. No. 4,413)
, 081), alkaline earth metal fatty acid #i (U.S. Pat. No. 4,418,029), dithiophosphine a salt (U.S. Pat. No. 4,421,910),
Phenolamides and phenol esters (U.S. Pat. No. 4.434□122), aminotriazoles (U.S. Pat. No. 4.478.1189),
Sorbates (U.S. Pat. No. 4,535,117, U.S. Pat. No. 4,543,224), aromatic ketones and amines, aromatic amides and imides (U.S. Pat. An attempt was made to improve the thermal stability of thermally stable PTK during melt processing by adding materials such as those disclosed in Japanese Patent No. 4,482,883.

However, none of these compounds was found to have an effect of improving thermal stability on PTK.

[Problem to be solved by the invention]

An object of the present invention is to provide a PTK-based composition that has excellent thermal stability during melt processing.

Another object of the present invention is to obtain a PTK composition that is prevented from increasing melt viscosity, decreasing crystallinity, and adhering thermal decomposition products to the resin retention portion of melt processing equipment during melt processing. .

As a result of further investigation, the present inventors found that , hydroxides (excluding magnesium), # compounds, aromatic carboxylates, and the first periodic table
When basic compounds such as hydrocarbyl oxides, aromatic carboxylates, carbonates, hydroxides, phosphates, and borates of Group A metals were added to the thermostable PTK, the thermostability during melt processing was improved. It has been found that the increase in melt viscosity and decrease in crystallinity due to crosslinking reactions etc. can be effectively reduced or prevented. Further, as a result of thermogravimetric analysis, it was found that by adding these basic compounds, the decomposition initiation temperature of thermally stable PTK was improved.

By the way, FATE is treated with a water-soluble monovalent or polyvalent metal solution of an alkali or alkaline earth metal element of Group 1A or FFA metal of the W1 table, thereby reducing the melt flow of FATH. , a method of increasing the melt viscosity and influencing the crystallization of PATH (Japanese Unexamined Patent Publication No. 149661/1983), by reacting FATE with a strong basic metal compound to form the m-form,
Method for significantly increasing the melt viscosity of ATE
-240731 Publication), a method for using hydroxides or oxides of metals of Group ■A of the periodic table, aromatic carboxylates of metals of Groups IA and ■A of the periodic table to prevent corrosion of melt-forming equipment by FATH ( Japanese Unexamined Patent Publication No. 82-109850) and the like have been disclosed so far.

However, the present inventors have found that when a blend of FATE and an alkali metal salt or an alkaline earth metal salt is held at a high temperature above the processing temperature, the melt viscosity of FATH decreases.

The effect of improving melt stability due to the basic compound, that is, there is less fluctuation in melt viscosity at high temperatures.

Moreover, the effect of preventing or reducing the decrease in crystallinity is due to FA
It was found that this is a novel effect that is not observed in TE or conventionally known PTKs with poor thermostability, but is specifically expressed in the thermostable PTKs used in the present invention. This fact is unexpected and interesting.

Note that basic compounds that have low heat resistance and easily volatilize at the processing temperature of a composition containing thermally stable PTK, such as fatty acid salts and aryl fatty acid salts, are undesirable because they tend to volatilize and foam during melt processing.

Furthermore, thermostable PTK with a basic compound added to it can be used as a thermoplastic resin or polymer that can be mixed with PTK as desired.
! ! Mixed fillers and/or free fillers! This product has excellent physical properties that have significantly improved problems such as increased melt viscosity, decreased crystallinity, and adhesion of thermal decomposition products to the resin retention area of melt processing equipment during general melt processing. It has been found that molded products such as extrusion molded products, injection molded products, 1 m thick products, and films can be obtained.

The present inventors have completed the present invention based on these findings.

[Means to solve the problem]

That is, the gist of the present invention is as follows.

[In the formula, the -co- group and -S- group are bonded to the para position via a benzene ring] as a main constituent, and have the following physical properties (a) to (c). Ingredient A) 100 parts by weight, and (B) hydroxides, oxides, aromatic carbon salts of metals from Group IA of the Periodic Table (excluding magnesium), and hydrocarbyls of metals from Group IA of the Periodic Table. Oxides, aromatic carboxylates, carbonates.

At least one basic compound (component B) selected from the group consisting of hydroxide, phosphate (including condensate), and borate (including condensate) 0.1 to 30 heavy f1 heavy electric 1 A polyarylene thioetherketone composition having improved melt stability and crystallinity.

(a) The melting point Tm is 310 to 380°C, and (b) The melt crystallization temperature Tmc (420°C/10 minutes) is 210″C
This is the above, and the enthalpy of crystallization ΔHmc (
420℃/710 minutes) is IOJ/g or more [However, Tmc (420℃/10 minutes) and ΔHmC (420℃/10 minutes)
20'C/10 minutes] is a differential scanning calorimeter in which polyarylene thioetherketone is held at 50°C for 5 minutes in an inert gas atmosphere, then heated to 420°C at a rate of 75°C/min, and then heated to 420°C. These are the melt crystallization peak temperature and melt crystallization enthalpy when the temperature was lowered at a rate of 10° C./min after holding the temperature for 10 minutes.

(c) Reduced viscosity (in 98% sulfuric acid, degree of oxidation 0.5 g/di,
25°C) is 0.2 to 2 d/g.

The composition of the present invention may contain a thermoplastic resin (component C), a fibrous filler material and/or an inorganic filler (component D) that can be mixed with PTK, as desired. From this composition, problems such as increase in melt viscosity, decrease in crystallinity, and attachment of thermal decomposition products to the resin retention part of melt processing equipment during general melt processing have been improved by Lil. Extruded products, injection molded products, and fibers with excellent physical properties! Molded products such as i4 films are obtained.

Each component of the present invention will be explained in detail below.

(The following is a blank space) Component A (8-stable PTK) The thermostable PTK used in the present invention is a repeating unit of arylene thioetherketone [in the formula].

-co- group and -S- group are bonded to the rose position via the benzene ring].

In order for the PTK used in the present invention to be a heat-resistant polymer, the above-mentioned repeating unit should be 50% by weight or more, preferably 6% by weight.
0% by weight or more, more preferably 70%! It is preferable that tji is 1% or more. If the above-mentioned repeating unit is less than 50% by weight, crystallinity may decrease and heat resistance may also decrease accordingly.

As a different repeating unit other than the above repeating unit -3-
(excluding those in which the group is bonded to the rose position via a benzene ring)
.

(However, R is an alkyl group having carbon a5 or less, 2m is 0 to 4
), etc.

The thermostable PTK used in the present invention includes uncured m
- Polymers, more preferably uncured linear polymers are desirable.

In the present invention, the term "cure" refers to a molecular weight increasing treatment by a crosslinking, one branch, one molecular chain extension reaction, etc. other than a normal polycondensation reaction, particularly a molecular weight increasing treatment by a high temperature heat treatment. The term "uncured polymer" as used herein refers to a polymer that is not subjected to post-treatment to increase the molecular weight by curing and to increase the degree of melting of the polymer.In general, curing refers to the thermal stability and Loss or decreases crystallinity, etc.

Note that, as long as thermal stability, fluidity, and crystallinity are not impaired, PTK with a slight crosslinked structure and/or branched structure is acceptable as the PTK of the present invention. PTK obtained by polymerization using polychlorobenzophenone, polybromobenzophenone, etc.) and PTK that has been lightly cured are acceptable as PTK used in the present invention.

It is preferable that the PTK used in the filtration process has the following physical properties.

(B) As an indicator of poor heat resistance, the melting point Tm is 31
Must be between 0 and 380°C.

(b) As an index showing the thermal stability of the polymer in the molten state, the melt crystallization temperature Tmc (420°C ZlO min) is 21
The temperature is 0°C or higher, and the residual melt crystallization enthalpy ΔHmc (420°C/10 minutes) is 10 J/g or higher.

(c) Reduced viscosity ηr, which is an indicator of the molecular weight of the polymer
ed should be 0°2 to 2d or/g.

In the present invention, the reduced viscosity ηred is expressed as a value at 25° C. of a solution of 0.5 g/d day using 98% sulfuric acid as a solvent.

(d) As an index showing the properties of crystalline polymers, the density (
25°C) is 1.34 g/cm3 or more.

Next, we will discuss the characteristics of the PTK used in the present invention.

(1) Melting point Tm of a heat-resistant polymer is an index representing the heat resistance of the polymer.

The PTK used in the present invention is preferably 310 to 380°C, more preferably 320 to 375°C, and even more preferably 330 to 375°C.
It has a melting point Tm of 370°C. Tm is 310
If the temperature is lower than ℃, the heat resistance is insufficient;
If the temperature exceeds 80°C, it will be difficult to melt-process without being decomposed, so any of them is not preferred.

(2) Thermal stability The most important feature of the PTK used in the present invention is that it has sufficient thermal stability for application to general melt processing methods.

All PTKs according to the prior art have low thermal stability, and are prone to crosslinking reactions and carbonization reactions accompanied by a decrease in fit dynamics, loss of crystallinity, or increase in melt viscosity during melt processing.

Therefore, by examining the residual crystallinity of PTK after it is maintained at a high temperature higher than the melt processing temperature for a certain period of time, it can be used as an index of the melt processing suitability of PTK. Residual crystallinity is determined by measuring the enthalpy of melt crystallization using a differential scanning calorimeter (F4r
DscJ) can be quantitatively evaluated. Specifically, after holding PTK at 50°C for 5 minutes in an inert gas atmosphere, it was heated at a rate of 75°C/min for 4
The melt crystallization temperature Tmc (420 °C
/10 minutes) and the residual melt delivery enthalpy ΔHmc (420° C./10 minutes) can be used as a measure of thermal stability. If PTK has poor thermal stability, it will undergo a crosslinking reaction and lose most of its crystallinity under the above-mentioned high temperature conditions of 420°C.

The high thermal stability PTK used in the present invention is ΔHmc (420
°C/10 min) is 10 J/g or more, more preferably 15
J/g or more, more preferably 20 J/g or more, and has a Tmc (420°C for 710 minutes) of 210
C. or higher, more preferably 220.degree. C. or higher, and even more preferably 230.degree. C. or higher. ΔHmc(420
°C/10 minutes) is less than 17g or Tmc
(420° C./10 minutes) of less than 210° C. tends to lose crystallinity and increase viscosity during melt processing, making it difficult to apply a sterilization melt processing method.

(3) Molecular Weight The molecular weight, which is related to the melt viscosity of PTK, is an important factor governing melt processing characteristics. The molecular weight of a polymer can be indexed by the reduced viscosity ηred of the polymer.

PTK suitable for melt processing has a reduced viscosity ηred of 0.2
It is desirable that the PTK has a polymer density of ~2d di/g, preferably 0.3 to 2 di/g, more preferably 0.5 to 2 di/g.

r) red is less than 0.2 di/g0) PTK has a low melt viscosity and a large drawdown property, making it difficult to apply a -sterilization melt processing method. Furthermore, the resulting molded product also has insufficient mechanical properties.

On the other hand, r) PTK with red exceeding 2 di/g is difficult to manufacture and process.

(4) The density of the polymer is employed as an index of the crystallinity of the crystalline polymer.

The PTK used in the present invention is a crystallized product (280°C/30°C).
The density (25℃) of 1.34
g/crrr' or more, more preferably 1.35 g/cm
Polymer chains of 3 or more are desirable.

If the density of the crystallized product is less than 1.34 g/crrr', the crystallinity may be low and the heat resistance may be insufficient.
Furthermore, processability such as injection moldability and mechanical properties of the obtained molded product may also be insufficient.

In particular, highly cross-linked PTK (PTK described in Document A, etc.)
has lost its crystallinity and its density is usually 1.34g/c.
much lower than rrr'.

The thermostable PTK used in the present invention is an alkali metal sulfide and a dihaloaromatic compound, preferably dichlorobenzophenone, in an aprotic polar organic solvent, preferably an organic amide solvent (including carbamate amides). and/or dibromobenzophenone in a system with an extremely large amount of coexisting water compared to conventionally reported polymerization methods, and in the substantial absence of polymerization aids (carboxylic acid salts, etc.), the temperature profile can be adjusted appropriately. 〃With controlled and short polymerization time.

In addition, it can be obtained by a method of selecting and polymerizing the material of the stretching device as required.

Specifically, the thermostable PTK used in the present invention is prepared by combining an alkali metal sulfide with 4,4'-dichlorohensiphenone and/or if4,4'-dibromobenzene in an organic amide solvent. It can be suitably produced by a method of subjecting a dihaloaromatic compound containing phenone as a main component to a dehetagenation/sulfurization reaction under the following conditions (a) to (c).

(a) The ratio of coexisting moisture Ji/organic amide solvent charge is 2.
Must be in the range of 5 to 15 (mol/kg).

(b) The ratio of the amount of dihaloaromatic compound charged/the amount of alkali metal sulfide charged is in the range of 0.95 to 1.2 (1 mol).

(c) carrying out the reaction at a temperature in the range of 60 to 300°C;
However, the reaction time at 210°C or higher must be within 10 hours.

Further, if a reactor is used in which at least the part in contact with the reaction liquid is made of titanium material, a highly thermally stable PTK can be obtained more preferably.

Furthermore, if desired, at least one halogen-substituted aromatic compound containing one or more substituents having an electron-withdrawing property equal to or higher than that of the (-CO-) group at the final stage of polymerization (preferably 4, 4 or 4 used as a monomer)゛-Dichlorohensiphenone and/or 4,
By adding and reacting (stabilizing treatment at the final stage of polymerization) 4'-dibromobenzophenone), PTK with further improved thermal stability can be obtained.

As mentioned above, the thermostable PTK used in the present invention is preferably an uncured polymer, but it may also be a PTK with a slight crosslinked structure and/or branched structure. In order to obtain the introduced PTK, as a polyhalo compound as a crosslinking agent, in particular, a polyhalobenzophenone having a trihalo or higher content is added to the polymerization reaction system at a ratio of monomer dihaloaromatic compound charge/polyhalobenzophenone charge of 10010 to 100. It is preferable that the amount of polyhalobenzophenone be present within the range of 9515 (1 mole).If the amount of polyhalobenzophenone is too large, physical properties such as melt processability, density, and crystallinity of PTK will deteriorate, which is undesirable.

Component B (basic compound) Basic compound used as a stabilizer in the present invention (component B)
is added to reduce and prevent increases in melt viscosity and decreases in crystallinity due to thermal denaturation and thermal deterioration during melt processing of PTK, as well as adhesion of thermal decomposition products in resin retention areas of melt processing equipment. This is the greatest feature of the present invention.

As mentioned above, compounds conventionally known as stabilizers for FATH have poor stabilizing effects on melt viscosity and crystallinity, or may even worsen them, even when added to heat-stable PTK. . Additionally, #-type inorganic substances, neutral inorganic substances, and oxidizing basic inorganic substances may have poor improvement effects or may even cause deterioration.

Stabilizers effective for improving the melt stability and crystallinity deterioration of heat-stable PTK include non-oxidizing, heat-resistant and hardly volatile basic compounds.

As a basic compound, specifically, the 11th periodic table 11A
Hydroxides, oxides, and aromatic carboxylates of Group 1A metals (excluding magnesium) and hydrocarbyl oxides, aromatic carboxylates, carbonates, hydroxides, and phosphorus salts of Group 1A metals (with the exception of magnesium). Examples of highly effective substances include borates (including condensates), borates (including condensates), and basic double salts containing these.

From the viewpoint of improving the increase in melt viscosity of PTK, the decrease in crystallinity, and the adhesion of thermal decomposition products to the resin retention part of melt processing equipment, calcium and barium hydroxides or oxides, or naphthalene monomers are used. or polycarboxylic acid,
Arylbenzoic acid.

Particularly preferred are the lithium, titrium or potassium salts of aromatic carboxylic acids such as benzene mono- or polycarboxylic acids and hydroxybenzoic acid.

The mixing ratio of component B in the PTK composition of the present invention is 0.1 to 30 parts by weight, more preferably 0.2 to 25 parts by weight, and even more preferably 0.3 to 2 parts by weight per part of component Al0Qt.
0! The range is in parts.

If the B component is less than 0.1 parts by weight, the stabilizing effect will be insufficient, and if it exceeds 30 parts by weight, there is a risk of decomposing PTK or deteriorating other physical properties (eg, electrical properties).

(The following is a blank space) Component C (thermoplastic resin) The PTK-based composition of the present invention optionally contains a thermoplastic resin (component C) that is miscible with the component in an amount of 0 to 400 parts by weight, preferably 0 parts by weight, per 00 parts by weight of component Al. .1 to 200 parts by weight,
More preferably, it can be mixed in a proportion of 11 to 90 parts by weight.

If component C exceeds 400 parts by weight, the characteristics of the heat-stable PTK, which is a heat-resistant, crystalline thermoplastic resin, may be substantially impaired in the two compositions, which is not preferable.

Thermoplastic resins that can be used in the present invention include polyarylene thioethers, aromatic polyether ketones such as PEEK and PEK, polyamides (including aramids), polyamideimide polyesters (including aromatic polyesters and liquid crystal polyesters), Resins such as polysulfone, polyethersulfone, polyetherimide, polyarylene, polyphenylene ether, polycarbonate, polyester carbonate, polyacetal, fluorine polymer, polyolefin, polystyrene, polymethyl methacrylate, ABS, or fluorine rubber, silicone rubber, olefin Examples include elastomers such as rubber, acrylic rubber, polyimbutylene (including butyl rubber), hydrogenated SBR, polyamide elastomer, and polyester elastomer. Among them, polyarylene thioethers, aromatic polyetherketones such as PEEK and PEK, polyesters, polysulfones, polyethersulfones, polyetherimides, fluoropolymer-
etc., each of these polymers alone is preferably
Alternatively, multiple types can be used in combination. Among the above-mentioned thermoplastic resins, polyarylene thioethers, especially those containing 50% by weight or more of repeating units, have improved mechanical properties when blended with thermostable PTK compared to PTK alone, and -Improved heat resistance compared to lylenthioether alone,
Heat Resistance 1 A composition with well-balanced mechanical properties and flow properties.

In the PTK composition of the present invention, if desired, an inorganic filler and/or a fibrous filler (component D) may be added to the total amount of resin components (component A yield C). 0-400 per part by weight
It can be included in an amount of parts by weight, preferably 1 to 300 parts by weight, more preferably 10 to 200 parts by weight.

If the component exceeds 400 parts by weight, processability may deteriorate, which is not preferable.

Inorganic fillers (other than component B) include talc,
Mica, kaolin, clay, silica, alumina, silica alumina, titanium oxide, iron oxide.

Chromium oxide, calcium silicate, calcium phosphate, calcium sulfate, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium phosphate, barium sulfate, silicon, carbon (including carbon black), graphite, silicon nitride, molybdenum disulfide , glass, /
Examples include powders such as hydrotalcite, ferrite, samarium powder, neodymium/iron-poron, etc.

m Male fillers include glass, carbon, and graphite.

Fibers such as silica, alumina, zirconia, silicon carbide, athemid, potassium titanate, calcium silicate (including wollastonite), calcium sulfate,
Examples include whiskers such as carbon, silicon nitride, and poron. Among them.

As the la female filler, glass fibers, carbon fibers, and aramid w1 fibers are particularly preferred from the viewpoint of physical properties or economical efficiency.

Note that these inorganic fillers and fibrous fillers can be used alone or in combination.

The PTK composition of the present invention also contains light stabilizers, rust inhibitors, lubricants, roughening agents, crystal nucleating agents, mold release agents, colorants, coupling agents, anti-fog agents, antistatic agents, etc. Auxiliaries can be added in small amounts.

Kumihigashi Toyotachi 11 (1) Melt stability The amount of change in melt viscosity of a polymer at melt processing temperature can be used as an index of melt stability.

Generally, when thermoplastic polymers are held at high temperatures, their melt viscosity decreases due to decomposition, crosslinking reactions, etc.

On the contrary, an increase is observed. - When applying the sterilization melt processing method, it is strongly desired that the change in melt viscosity be small.

Conventional PTK, which has poor thermal stability, shows a rapid increase in melt viscosity in a short time due to crosslinking reaction when kept at a high temperature above the melting point, and in some cases carbonizes.

On the other hand, one thermostable PTK used in the present invention (component A)
Since the thermal stability of PTK is greatly improved compared to conventional PTK, the increase in melt viscosity is quite gradual. Moreover, by adding a stabilizer (component B) consisting of the basic compound of the present invention, the increase in the temperature can be further prevented or reduced.

However, for conventional PTK with poor thermal stability, the effect of the basic compound (component B) is not expressed, and P
Polyarylene thioethyl (FATE) other than TK,
For example, even if the stability stabilizer of the present invention is blended with poly-P-phenylenethioether, the melt stability will not be improved but will instead deteriorate.

The change in melt viscosity is determined by the melt viscosity η: (shear rate: 1200 sec") and 38
The melt viscosity after being maintained at a temperature of 5°C for 60 minutes is η6° (shear rate: 1200 sec-') at a ratio η60/η5.

The PTK-based composition (here, it means a blend of component A and component B) with improved melt stability and crystallinity of the present invention.

η6o/η5 is 0.5 or more and 10 or less, more preferably 0
．． 6 or more and 8 or less, more preferably 0.7 or more and 7 or less. If η6o/η exceeds 10, the effect of improving melt stability will be unsatisfactory, and the long run time of melt processing will not be extended too much. I can't hope anymore.

(2) Decreased crystallinity The crystallinity of a crystalline polymer can be evaluated by residual melting enthalpy ΔHmc or density. Therefore, the amount of decrease in crystallinity can be evaluated by the amount of decrease Δ(ΔHmc) in ΔHmc, the amount of decrease in density, etc.

In the present invention, the amount of decrease in crystallinity is evaluated by Δ(ΔHmc) for reasons of simplicity.

That is, the value of Δ(ΔHmc) in the present invention is PT
The ΔHmc (420°C/10 minutes) of a product obtained by melt-extruding K or its composition powder into a strand under the conditions of a cylinder temperature of 385°C and an average resin residence time of 1 minute in the cylinder was measured, and it was found that it did not contain basic compounds. It is expressed as the difference from ΔHmc (420°C/10 minutes) of PTKm powder.

PTK (component A) generally has ΔHm when melt extruded.
It has the property of decreasing c. However, by adding the basic compound (component B) of the present invention, this decrease can be prevented or reduced. In other words, since thermal history causes a decrease in crystallinity, by determining Δ(ΔHmc), which is the difference between ΔHmc of the melt extrudate (pellet) and ΔHmc of the original powder PTK, PTK can be changed from a powder state. Decrease in crystallinity due to thermal history during pelletization by melt-kneading shall be quantitatively evaluated.

The decrease in crystallinity of the present invention has been prevented or reduced! l#:
As Th (blended product of component A and component B), ΔHmc (420"C/10 minutes) by melt extrusion
It is preferable that the decrease amount Δ(ΔHmc) is less than 25 J per Ig of PTK (component A), more preferably 20 J or less, and even more preferably 15 J or less. If Δ(ΔHmc) is 25 J or more, the long run time of melt processing will be extended. There is a possibility that the effect of improving physical properties such as heat resistance due to the improvement in the degree of crystallinity of the resulting molded product may become insufficient.

Compounding method PT with improved melt stability and reduced crystallinity of the present invention
Among the K compositions, the composition consisting of component A and component B is
r#, Mix component B with component A and y
You can do 4w. Furthermore, if necessary, a melt-kneaded product can be prepared by melt-kneading these blends.

A dry blending method is usually preferred from the viewpoint of convenience as it does not require a drying step.
That is, when adding component C1, component D8, and other auxiliaries, they may be added to the composition of component A and component B, or may be added to component A at the same time as component B is added.
Also, it may be added to component A before thrust a of component B.
The blending method in this case can be the same as the blending method for component B described above.6 The PTK-based composition of the invention can be made into a melt-molded product by melt processing. can.

This melt-molded product is obtained by applying a sterilization melt-processing method, that is, a melt-processing method such as extrusion molding, injection molding, and melt spinning, to the PTK-based composition that has improved melt stability and reduced solidity. That's what you get. Furthermore, stretching processing of the molded product, thermoforming (T) IERMOFO
It is also possible to obtain a PTK molded product through secondary processing such as RM ING) or tertiary processing.

Extrusion product An extrusion product from a PTK-based composition is prepared by, for example, supplying the PTK-based material to an extruder equipped with a shaping die or nozzle in the atmosphere, or more preferably under an inert gas atmosphere. The cylinder temperature is 320 to 450°C, and the average resin residence time in the cylinder is 0.5 to 60 minutes, preferably 2 to 30 minutes. It can be manufactured by annealing for 1 to 100 hours.

The extruder used here is preferably one in which the portion that comes into contact with the resin melt is made of a non-ferrous corrosion-resistant metal, and is more preferably equipped with two vents.

Injection molded products from the PTK-based compositions include, for example, the PTK compositions described above.
The K-based composition is supplied to an injection molding machine equipped with a molding die in the atmosphere, or more preferably under an inert gas atmosphere, and the cylinder temperature is 320 to 450°C and the mold temperature is 50°C.
~250℃, resin average residence time in cylinder 1~300
0 seconds, more preferably 3 to 1000 seconds flfl, injection holding pressure 10 to 10' Kg/ctr? It can be manufactured by injection molding under molding conditions of an injection cycle of 1 to 3000 seconds, and optionally annealing at 200 to 370° C. for 1 to 100 hours.

In addition, the injection molding machine used here is preferably one in which the portion that comes into contact with the resin melt is made of a non-ferrous corrosion-resistant metal.

Moreover, one with a vent is more preferable.

Ii & fibrous molded product P-Km with improved melt stability and crystallinity reduction
For example, the composition is fed into an extruder equipped with a melt-spinning nozzle in the atmosphere, or more preferably under an inert gas atmosphere, and melt-extruded from the nozzle. Take the yarn at a pick-up speed ratio of 1 to too many times, and
Stretched 1.2 to 8 times at a temperature of 0 to 200°C, 130 to
A fibrous molded product is obtained by heat setting at 370°C for 0.1 to 1000 seconds.

The spinning extruder used here is preferably one in which the part that comes into contact with the resin melt is made of a non-ferrous corrosion-resistant metal, and is more preferably equipped with a vent.

The PTK composition with improved melt stability and reduced crystallinity is fed into an extruder equipped with a T-die in the atmosphere, or more preferably under an inert gas atmosphere, Shaped into a film by a method of melt extruding and shaping into a film (T-die method), or a method of pressing while melting and heating using a high-temperature press (hot press method), ℃ or above and below the melting point of PTK, limit the deformation to within ±20% while applying stress (pressure), and heat set for 1 to 3000 seconds, and if necessary, fix it at a temperature of 200 to 360℃ to virtually eliminate it. 1-300 under stress
A film-like molded product is obtained by thermally relaxing for 0 seconds.

The T-die extruder used here is preferably one in which the portion that comes into contact with the resin melt is made of a non-ferrous corrosion-resistant metal, and is more preferably equipped with a vent.

A film-like molded product can also be obtained from the PTK composition by an inflation molding method or a compression molding method. PTK
From the system compositions, it is also possible to obtain various thermosetting resins or multilayer films in combination with thermosetting resins.

Other molten acids/PTK with improved melt stability and crystallinity reduction of the present invention
Hollow carved objects such as bottles, tanks, pipes, tubes, etc. can be obtained from the Ml composition by blow molding or the like. Further, elongated molded products such as plates, pipes, tubes, rods, profiles, etc. can be obtained from the PTK composition by pultrusion molding or the like.

Secondary and third processing The PTK-based Jl acid is supplied to an extruder equipped with, for example, a T-die or a ring die in the atmosphere, or more preferably under an inert gas atmosphere, and is melt-extruded. A method in which a PTK-based composition is formed into a film and then rapidly cooled (T-die method or inflation method), or a method in which a PTK-based composition is melted and heated using a high-temperature press, pressurized, used as a film, and then rapidly cooled (hot press method) ), an amorphous film-like molded product can be obtained. Furthermore, this amorphous film-like molded product is stretched in the axial direction or in the bidirectional direction (in the case of bidirectional stretching) at a temperature of 100 to 180° C. using a roll, tenter, or the like.

The film was stretched 1.5 to 7 times in each direction (sequentially or simultaneously), deformed within ±20% while applying stress (tension), and heat-set for 1 to 3000 seconds.

If necessary, a stretched film can be obtained by thermal relaxation for 1 to 3000 seconds at a temperature of 200° C. or higher and lower than the melting point of PTK under substantially no stress.

The T-die extruder used here is preferably one in which the part that comes into contact with the resin melt is made of a non-ferrous corrosion-resistant metal, and one with a vent is more preferable. A method of forming a composition in which a small amount of solid fine powder (calcium carbonate, kaolin, alumina, silica, # titanium, clay, etc.) is further added into a film, and a film obtained from the PTK-based composition of the present invention. A method in which the surface of a molded product is treated with an organic solvent that has high affinity with PTK and then stretched, jt-all-invention PTK system! Dynamic friction coefficient (film-to-film, 25°C, ASTM-01894)
) It is possible to obtain an easily slippery film of 0.7 or less.

PT with improved melt stability and crystallinity reduction of the present invention
Also from K-based compositions. Secondary processing such as heat-forming method, stretching process, etc.
Various molded products can be obtained through tertiary processing.

Application: PT with improved melt stability and crystallinity reduction that has not yet been invented.
The K-based composition can be used to obtain various molded products for various uses through a sterilization melt processing method.

Injection molded products are, for example, various electronic/electrical parts (wiring boards, electronic part sealants, connectors, etc.), automotive parts (
Various parts around engines, etc.), precision parts (parts for cameras, watches, etc.), plastic magnets, sealants, sliding members, friction materials 1 food containers, cooking utensils, etc.

Extrusion moldings, blow moldings, and pultrusion moldings are, for example,
Sheet-plates (stampable sheets, trays, etc.),
Pipes and tubes (chemical industry piping, hot/hot water piping,
(tm piping, etc.), heat-resistant coatings for wires, blow bottles, mouthpieces, profiles, etc.

Examples of fibrous molded products include industrial filter insulation materials, reinforcing magnets, insulating tapes, insulating cloths, fireproof layers, high-temperature gloves, prepreg fiber 2 prepreg tapes, infusible tension members for optical cables, carbon fibers, Used for various textiles.

Film-like molded products (including sheets) include, for example, magnetic recording material base films (especially films for vapor deposition or sputtering, 4 also include perpendicular magnetization type magnetic recording films), capacitor films (especially for chip-type capacitors). film), printed wiring boards (including flexible and rigid types), insulating films, printer tapes, stampable sheets, various trays, and containers.

Separation membranes, filtration membranes, ion exchange! ! j! Used as a membrane, etc.

〔Effect of the invention〕

The PTK-based composition of the present invention is a composition in which the thermal denaturation of PTK during melt processing, the decrease in crystallinity and the fluctuation in melt viscosity caused by thermal deterioration are greatly improved, so the long run time of melt processing can be significantly reduced. It has become possible to extend the molding cycle time and significantly shorten the molding cycle time of injection molding processing, and as a result, it has become possible to significantly reduce melt processing costs.

In addition, the crystallinity of the melt-molded product is increased, and accordingly,
It has become possible to significantly improve physical properties such as heat resistance and mechanical properties of the resulting molded product.

Furthermore, the adhesion of thermal decomposition products to the molten resin contact surface of the melt processing equipment has been significantly reduced, and the cleaning of the processing equipment has become easier.

〔Example〕

EXAMPLES The present invention will be explained in more detail below using Examples, Experimental Examples, and Comparative Examples. However, the present invention is not limited to the following Examples and Experimental Examples unless the gist thereof is exceeded.

(Left below blank) Example 4.4'-dichlorobenzophenone (hereinafter referred to as "DCBPJ")
) (manufactured by Ihara Chemical Industry ■) 90 mol, hydrated sodium sulfide (water content 53.6% by weight) (Sankyo Kasei [11) 9
0 mol and N-methylpyrrolidone (rNMPJ)
90 kg (abbreviated as ) was charged into a titanium-lined polymerization can (coexisting moisture content/NMP = 5.0 mol/kg), and after nitrogen gas M inspection,
The temperature was raised from room temperature to 240°C over 1.5 hours, maintained at 240°C for 1.5 hours, and then a mixture of 9.0 mol of DCBP, 18 kg of NMP, and 90 mol of water was injected for stabilization treatment at the final stage of polymerization. 280℃ for 0.5 hours
The temperature was raised to 260° C., and the temperature was further maintained at 260° C. for 1.0 hour to cause a reaction.

After the reaction was completed, the pulp of the polymerization can was opened and the contents were taken out while flushing into the can, thereby volatilizing a considerable portion of the solvent. The obtained solvent-containing mixture was supplied to a small rotary dryer, and the temperature was gradually increased while flowing nitrogen gas to distill off most of the solvent.

The obtained solid was ground in a mill, washed with chloroform and acetone, then dispersed in water to elute and remove water-soluble components (mainly sodium chloride), and filtered. Furthermore, a wet polymer was obtained by washing with acetone, washing with chloroform, washing with acetone, washing with hot water, and then separating by filtration. The obtained wet polymer was dried under reduced pressure at 80°C for 712 hours to obtain polymer PI (eye poly-colored powder).

Synthesis Experiment Example 2 (Conventional Synthesis of PTK) 10 moles of sodium sulfide nonahydrate, 5.0 liters of NMP, and 10 moles of lithium acetate were placed in a 5US316 polymerization reactor and heated to 200°C under a nitrogen stream to dehydrate. . 1580 g of distilled water containing NMP104+r was obtained.

After cooling the Nz system to 120°C, DCBPIO moles and NM
Coexistence moisture content to charge the solution with Po, 8 liters/
NMP = 1.4 mol/kg), 2 h at 230 °C and 1 h at 250 °C under nitrogen pressure with stirring.
After the polymerization reaction, the slurry of the reaction solution was poured into water, washed with water and washed with acetone repeatedly, and then dried to prepare Polymer F2 (brown powder).

A portion of polymer P2 was heated in air at 250° C. for 2 hours to obtain cured polymer CP2 (black powder).

Synthesis experiment example 3 (conventional PTK synthesis) Sodium sulfide 3 1.0 mol of wood salt, 800 ml of NMP and 1.0 g of sodium hydroxide were added to 5US316
Pour into a polymerization can, heat up to 210°C,
42g of distilled water containing 3g of
cooled down to.

While stirring strongly, 1.0 mol of 4,4'-difluorobenzophenone and 0.033 mol of sodium sulfite were added (coexisting water content/NMP = 0°9 mol/kg), pressurized to 5 atm with nitrogen, and After the 0 reaction, which was maintained at ℃ for 4 hours, the polymerization vessel was cooled to 100 ℃, the slurry, which is the reaction solution, was taken out, the produced polymer was separated, and the resulting polymer was washed with hot water and acetone. After thorough cleaning, After thorough drying, Polymer P3 (yellowish brown powder) was obtained.

4 PTK combination 4-(4-chlorobenzoyl)thiophenol 0.80
4 mol, potassium hydroxide aqueous solution 45.1 g (114,5
1 molar solution), 300 g of 1,1-dioquinethiolane and 300 g of diphenylsulfone were added under reduced pressure (15 molar solution).
rr) The mixture was heated for 3 hours.

The produced water and 1,1-dioxothiolane were removed by heating from 20°C to 260°C.

The reaction mixture became solid (the amount of coexisting water was essentially O). This mixture was cooled and heated in the first stage at 350° C. for 3 hours under a nitrogenous atmosphere. This mixture has approximately 340
It becomes liquid at a temperature of ℃. The mixture is allowed to cool and solidify;
It was taken out from the flask, crushed, extracted 4 times with 4 liters of hot methanol, twice with 4 liters of hot water, once again with 4 liters of hot methanol, and then dried to obtain the polymer P.
4 (yellow powder) was obtained.

5 DCBPI of PTK
O mol was dissolved in 30 kg of dimethylformamide (hereinafter abbreviated as "rDMF").

10 mol of sodium sulfide nonahydrate was placed in a 5US316 polymerization reactor, and the above solution was added (coexisting water content/DMF = 3 mol/kg). After purging with nitrogen, the reactor was reacted at about 175°C for 27 hours. The resulting reaction solution was washed 5 times with hot water and 5 times with DMF to obtain polymer P5 (yellow powder).

In addition, polymer P2, CF2 (′+ near type),
P3. P4 and P5 are from documents A, A, B, and C, respectively.
and D, and was used as a conventional PTK model.

For each PTK obtained by the company, the melting point T is used as an index of heat resistance.
m was measured. The measurement method is to measure each PTK (powder) by approximately 10
ong weighed, D SC (Kettler TGI)
OA type) for 5 minutes at 50°C in an inert gas atmosphere.
gI: Measured by heating at a rate of 10° C./min.

The results are summarized in Table 1.

For each PTK powder obtained by fusion enthalpy polymerization, the residual melt lj! is used as an index of thermal stability. Delivery enthalpy ΔHmc (
420°C ZlO min) was measured. That is, the temperature at the peak of melt crystallization measured using DSC is Tmc (
420° C./10 minutes), and the residual melt crystallization enthalpy ΔHmc (420° C./10 minutes) was calculated from the peak area. Specifically, approximately 10% of each PTK (powder)
mg, held at 50°C for 5 minutes in an inert gas atmosphere, and then heated to 420°C at a rate of 75°C/min.
After that, while decreasing the temperature at a rate of 10°C/min, Tmc (420°C/10 min) and ΔHmc
(420°C/10 minutes). The results are summarized in Table 1.

(The following margins) Symptoms: To evaluate the melt extrudability of a PTKjA product containing a basic compound as a stabilizer, 100 parts of each PTK obtained by polymerization were added to 100 parts of IE. 5 parts by weight of calcium hydroxide Ca(OH)20, which is a basic compound, was added, triblended using a tumbler blender, and fed to a single screw extruder with a cylinder diameter of 19 mmφ and L/D = 25. The mixture was melt-kneaded at a temperature of 75,375°C, extruded into a strand, and its melt extrudability was observed.At the same time, the strand was cooled and pulverized to obtain an extrudate sample.

Polymer P2. which is a conventional PTK. CP2, P3. P4
The PTK compositions from P5 and P5 caused decomposition reactions and crosslinking reactions during melt extrusion, and a rapid increase in extrusion torque was observed.
It gave only partially carbonized and foamed melt extrudates.

Next, in order to evaluate the melt moldability of the obtained basic stabilizer-blended PTK melt extrudates, sheet-like products were melt-molded from each melt-extruded sample and their densities were measured.

First, a Ca (OH) 2 additive extrusion sample of each PTK was inserted between two polyimide [phase] films (“Kapton ■” manufactured by DuPont) and heated using a hot press.
The mixture was heated to 385° C./2 molecules, shaped by applying pressure at 385° C. for 10.5 minutes, and rapidly cooled to prepare amorphous sheets with thicknesses of approximately 0 and 5 mm, respectively.

Part of the amorphous sheet was used as a sample as it was, and the other part was used as an anil sample with increased crystallinity by annealing at 280° C. for 30 minutes. The density was measured at 25° C. using a [lithium bromide/wood] density gradient tube. The results are shown in Table 2.

Polymer P2. which is a conventional PTK. CP2゜P3,
From the extrudates of the compositions P4 t3 and P5.

Only sheets with defects that were partially foamed and carbonized were obtained. On the other hand, - Polymer P with sterilization melt processing suitability
An extruded sample of composition I yielded a light-colored sheet with a smooth appearance.

The results are summarized in Table 2.

As is clear from Table 2, polymer P2゜CF2 Ca of It is The carving is Ta.

P3, P4, and P5 had poor melt extrudability even when a basic stabilizer (OH) was added, and the sheet-form density prepared from the extrudates was extremely low and non-uniform (
(Left below) Table 2 (1) There is a lot of variation in density in some areas due to foaming, etc.

(Ko) A melt-formed sheet of PTK alone was prepared and its density was measured in the same manner as the density measurement of a melt-formed sheet from a basic stabilizer-blended PTK melt-extrudate.

Next, for the PTK polymer Pl, which has good melt processability, the solution viscosity (reduced viscosity ηred
) was investigated. That is, PTK powder was dissolved in 98% sulfuric acid to a concentration of 0.5 g/d, and the viscosity was measured at 25° C. using an Ubbelohde-type original tube. ηred is o
, 82d sentence/g.

Polymer P1 was blended with various stabilizers to examine its effect on improving melt stability and delivery performance.

That is, dry powders of various stabilizers were added to Polymer PI, blended using a tumbler/blender, and then fed to an axle extruder with a cylinder diameter of 19 mmφ and L/D = 25, and the cylinder temperature was 385°C and the resin inside the cylinder. Melt and knead with an average residence time of 1 minute, extrude into strands,
Cool, cut and pellet each stabilized composition)
- Prepared the sample. Some of these were used as samples for evaluating melt stability and crystallinity reduction.

The melt stability of each stabilizer-blended composition pellet was evaluated as follows. In other words, a pellet of approximately 20 ff was placed in the barrel of a cavilograph heated to 385°C, and
Measure the melt viscosity after 30 minutes, 30 minutes and 60 minutes. ,
η and η: 0 (both at a shear rate of 1200 se
c) was calculated.

Similarly, measurements of conventional PTK polymers were attempted using samples prepared in melt processing tests.

η is an index of melt stability. /η: and η6o/η
The results of No. 5 are summarized in Table 3.

Evaluation of the decrease in crystallinity due to melt processing of each stabilizer-containing composition was performed in the following manner. That is, for each stabilizer-blended composition pellet, ΔHmc and Tmc were measured in the same manner as the residual melt crystallization enthalpy measurement of PTK powder, and these values were compared with ΔHmc and Tmc of Polymer P+ powder, and the respective values were determined. From the difference Δ(ΔHmc) and Δ(Tmc), the effect of improving the crystallinity reduction due to the thermal history while the powder polymer P1 was pelletized by melt-kneading was evaluated.

The results (excluding Tmc and Δ(Tmc)) are summarized in Table 3.

It has been found that certain basic compounds have a remarkable effect of improving melt stability and M quality deterioration.

In other words, as is clear from Table 3, the melt stability of the product without a basic compound (experiment number 1) was such that η/η5 was 10 or more, and a crosslinking reaction occurred within 60 minutes, resulting in an increase in melt viscosity. It shows. There was also some decomposition material adhering to the barrel of the cavilograph.

On the other hand, 1. For example, η*60/η of a mixture containing 0.5 parts by weight of Ca (OI() 2 (experiment number 2)) is 1°3, and the melt stability of the Ca (OH) 2 mixture is It has been greatly improved, and the adhesion of decomposed substances to the barrel has been greatly reduced.

Furthermore, as is clear from Table 3, the amount of decrease Δ (ΔHmc) in the enthalpy of melt crystallization in the case where #i base injection compound was not mixed (experiment number 1) was 2517 g, but for example,
Ca(OH)2 is 0.5! Based on the value of Δ(ΔHmc) of the blended tIk portion (experiment number 2), that is, the value of ΔHmc of powder polymer P1, Ca (OH)2 was set to 0.
PTK obtained by melt extruding a composition containing 5 parts by weight
The value after subtracting the ΔHmc of the pellet of the composition is 6
It was 17g. Therefore, the reduction in crystallinity of Ca (OH) 2 formulations is greatly improved.

PolyP-phenylenethioether (manufactured by Kureha Chemical Industry Co., Ltd., 1-ri c1) is a FATE that does not have a ketone group in the molecule.
20.5 parts of the basic compound Ca (OH) were added to 100 parts by weight of the basic compound Ca (OH).

Poly p-phenylenethioether and the above Ca (OH) 2 blend were melt-extruded in the same manner as for PTK to obtain pellets (however, the cylinder temperature was 320°C). Melt viscosities ηt, z, and η80t after holding at ℃ for 5 minutes, 30 minutes, and 60 minutes.

The result is a bow of extruded pellets without stabilizers. /
The bow is 0.8, the bow. /η5 was 0.6. On the other hand, the η;0/η5 of the pellet containing the stabilizer is 0.5. η80
/” 5 was 0.35.

That is, by blending the basic compound, the melt viscosity is drastically reduced, and the melt stability is not improved but rather deteriorated.

(Left below) Extrusion molding experiment example Polymer PIioo11, a PTK with good melt processability
1 part by weight of polyP-phenylenethioether, 1 part by weight of silica powder, and a predetermined amount of Ca(OH)2 powder were added to the mixture, and the mixture was dry mixed using a Henschel mixer, and then mixed using a 35 mmφ codirectional twin screw equipped with a 5 mmφ nozzle. The mixture was supplied to an extruder under a nitrogen gas flow, melted and kneaded at a cylinder temperature of 375°C and an average resin residence time in the cylinder of about 3 minutes, extruded into a strand, and rapidly cooled.
The pellets were cut to obtain respective composition pellets (Extrusion-1 and Extrusion-2).

Next, the nozzle of the extruder was replaced with a slit die, the pellets (extrusion-1 and extrusion-2) were supplied, and the cylinder temperature was 375°C, and the average residence time of the resin in the cylinder was about 3 minutes, and the pellets were shaped into a plate. Extrude, quench, cut,
A plate-shaped extrudate was obtained. The obtained rapidly cooled molded product was
The extruded product (
Anyl compound) was obtained.

The physical properties of the extruded products (annealed products) obtained from the pellets (Extrusion-1 and Extrusion-2) were as shown in Table 4.

The long run properties of the Ca(OH) blended pellets were good.

The deliverability improvement effect was determined by measuring ΔHmc and TmcIt after preparing the sample using the method described in the section ``Improvement of melt stability and crystallinity reduction by stabilizer fia''.
Δ(ΔHmc) and Δ(Tmc) were calculated and evaluated (
The same applies hereafter).

(Left below) Glass fiber #I (diameter 13 μm, length 3 mm, manufactured by Nippon Electric Glass Co., Ltd., #
EC303T-717K) 65 East amount part and specified amount of C
a (OH) 2 powder was added, triblended with a tumbler blender, and melt mixed and extruded in the same manner as the pellet preparation method of the extrusion molding experiment described above to obtain each composition pellet (injection 1 and injection 2). Ta.

The obtained pellets (injection 1 and injection 2) were each supplied to an injection molding machine under a nitrogen gas flow, and the cylinder temperature was 3.
75℃, mold temperature 200℃, resin residence time in cylinder within about 1.5 minutes, injection holding pressure 1000kg/crrf,
Injection molding was performed under molding conditions for an injection cycle of about 1 minute to obtain a molded product. It was annealed at 280°C for 5 hours. The physical properties of the annealed molded product are shown in Table 1.

The Ca (OH) 2 blended pellets had good long run properties.

Polymer Pl with good melt processability for fiber molding and Ca (OH) 2e
A predetermined amount of powder was added and tri-blended using a three-tumbler blender, and melt-kneaded and extruded in the same manner as the beret preparation method in the extrusion experiment described above to obtain each beret (spinning 1 and spinning 2). These berets are 0.5
The fibers were supplied to a melt-spinning test fi (manufactured by Fuji Filter Co., Ltd.) equipped with a nozzle having 18 mmφ holes, and melt-spun at R of about 70 times to obtain each undrawn yarn. This was stretched 3 times at 155°C using a jig, and then stretched at 280"C under tension.
-' Heat set for 2 seconds. The physical properties of the obtained yarn are as shown in Table 1-6 - The Ca(OH)2-containing pellet had good long-run properties.

(Left below) Preparation of the film-like molded pellets (Spinning 1 and Spinning 2) were fed into a 35 mm diameter single screw extruder equipped with a small T-die under a nitrogen gas flow, and the resin was retained in the cylinder at a cylinder temperature of 375°C. Amorphous films each having an average thickness of 15071 m were prepared by melt extrusion under extrusion conditions for about 3 minutes and quenching with four cooling rolls.

A part of the obtained 'IP-product film was inserted with a polyimide film (Kapton ■, manufactured by DuPont).

Heat setting was performed at 310° C. for 5 minutes under pressure using a hot press, and heat relaxation was further performed at 290° C. for 5 minutes without applying pressure.

The physical properties of the obtained unstretched film were as shown in Table 7.

(Left below) Preparation of stretched film A portion of the amorphous film obtained from pellets, spinning 1 and spinning 2 during the preparation of unstretched film was tested using a biaxial stretching tester (manufactured by Toyo Mki Co., Ltd.). 3.0 times in the longitudinal direction at 155°C, then 2.9 times in the transverse direction at 157°C.
Biaxially stretched films were prepared by stretching the film twice, heat setting it at 310° C. for 5 minutes under constant length, and then heat relaxing it at 290° C. for 5 minutes without stress. The physical properties of the obtained stretched film are as shown in Table 8.

(Margin below)

Claims (5)

[Claims] (1) [A] Repeating unit ▲ There are mathematical formulas, chemical formulas, tables, etc. (a) to (c) 100 parts by weight of a thermally stable polyarylene thioetherketone (component A) having the physical properties described in each item, and [B] hydration of a Group IIA metal of the periodic table (excluding magnesium) compounds, oxides, aromatic carboxylates, and hydrocarbyl oxides of Group IA metals of the periodic table;
At least one basic compound (component B) selected from the group consisting of aromatic carboxylates, carbonates, hydroxides, phosphates (including condensates), and borates (including condensates)
A polyarylene thioetherketone composition having improved melt stability and crystallinity, containing 0.1 to 30 parts by weight. (a) The melting point Tm is 310 to 380°C. (b) Melt crystallization temperature Tmc (420°C/10 minutes) is 2
10°C or higher, and the residual melt crystallization enthalpy ΔHm
c (420℃/10 minutes) is 10J/g or more [
However, Tmc (420℃/10 minutes) and ΔHmc (
420°C/10 minutes) is a differential scanning calorimeter in which polyarylene thioetherketone is held at 50°C for 5 minutes in an inert gas atmosphere, then heated to 420°C at a rate of 75°C/min, and then heated to 420°C. These are the melt crystallization peak temperature and melt crystallization enthalpy when the temperature was lowered at a rate of 10° C./min after holding for 10 minutes]. (c) Reduced viscosity (in 98% sulfuric acid, concentration 0.5 g/dl,
25°C) is 0.2 to 2 dl/g. (2) Melt viscosity η^*_5 (shear rate: 1200 se
c^-^1) and melt viscosity after holding at 385°C for 60 minutes η^*_6_0 (shear rate: 1200 sec^-
The ratio of ^1) η^*_6_0/η^*_5 is 0.5 or more 1
2. The polyarylene thioetherketone composition according to claim 1, which has a molecular weight of 0 or less. (3) The thermostable polyarylene thioether ketone is
The density (25℃) of the crystallized product (assumed to be annealed at 280℃/30 minutes) is 1.34g/cm^3
The polyarylene thioether ketone composition according to claim 1, which has the above properties. (4) The thermostable polyarylene thioether ketone is
The polyarylene thioetherketone composition according to claim 1, which is an uncured polymer. (5) The composition contains 0 to 400 parts by weight of a thermoplastic resin (component C), which is optionally miscible with a thermostable polyarylene thioetherketone, per 100 parts by weight of component A, and optionally an inorganic filler (with the exception of components (other than B) and/or fibrous filler (component D) in an amount of 0 to 400 per 100 parts by weight of the total amount of resin components (component A + component C).
The polyarylene thioetherketone composition according to claim 1, which contains the polyarylene thioetherketone composition in the proportion of parts by weight.