JPH072848B2 - Light-stabilized polyary lentithioether - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyarylene thioether having improved photostability, a composition thereof, and a method for producing the same.

[Prior Art] Polyarylene thioether is an engineering resin with excellent heat resistance, electrical insulation and flame retardancy, and can be applied to injection molded products, extruded products, films, sheets, fibers, wire coatings, etc. . In particular, the present inventors have developed a method for economically producing polyarylene thioether, which has very little coloration (Japanese Patent Laid-Open No. 61-7332). However, polyarylene thioethers generally have 38
Since it had a large absorption in the near-ultraviolet region of 0 nm or less, it was a beautiful molded product with excellent color tone at the beginning, but there was a problem that the color tone changed when exposed to ultraviolet rays and sunlight. .

Conventionally, benzophenone-based stabilizers, benzotriazole-based light stabilizers, etc. have been used as light stabilizers for general-purpose resins.

The benzophenone stabilizer is It has a chemical structural unit of (Ar; aryl residue). Basically, light energy is generated by the interaction between the carbonyl group bonded to the benzene ring and the hydroxy group at the position (2) of the benzene ring. It functions as a light stabilizer by absorbing it, converting it into heat energy and dissipating it. However, the benzophenone stabilizer shows strong absorption near 300 nm, but
Since the absorption around 50 nm is weak, it was found to be not very effective as a light stabilizer for polyarylene thioether.

The benzotriazole-based light stabilizer is It has a chemical structural unit of, and basically absorbs light energy and converts it into heat energy by the interaction between the triazole ring bonded to the benzene ring and the hydroxy group at the position (2) of the benzene ring. By escaping,
It is said to function as a light stabilizer (HO
DGEMAN, DC, GELLERT, E, P, J.of Polymer Sci., Polymer
Chem. Ed. 18 1105-1114 (1980)).

Stabilizers of this type begin to absorb from UV radiation near 400 nm 3
Since it has a maximum absorption around 50 nm, polyarylene thioene
Have been suggested to be effective as light stabilizers for ether
(CIBA-GEIGY company TINUVIN 234 Catalog March 1981
Edition).

However, the melt processing temperature of polyarylene thioether, which is a heat-resistant resin, is considerably higher than that of a general-purpose resin, and when a conventional benzotriazole-based light stabilizer for a general-purpose resin is mixed in, most of them are not sufficiently large in molecular weight. It volatilizes and disappears during melt processing, and the effective amount that can remain in the final molded product becomes very small, so it is necessary to add a large amount to avoid it, which is not industrially preferable, and when a large amount of light stabilizer is used There was also a problem that the physical properties of the molded product were affected.

For the purpose of reducing the volatilization of the above benzotriazole-based light stabilizer at high temperature, a method has been proposed in which the hydroxy group at the position (2) of the benzene ring is esterified to have a large molecular weight and mixed ( In JP-A-60-71663), this method has a problem that the hepatorenal hydroxy group disappears due to the action of the light stabilizer, so that the expected stabilizing effect against light cannot be obtained.

[Advantageous Effects of the Invention] The present inventors have found that a chemical structure having a photostabilizing effect by the benzotriazole group bonded to the benzene ring and the hydroxy group at the position (2) of the benzene ring. Is chemically bonded to the polyarylene thioether while holding it, resulting in a polyarylene thioether with improved photostability, and solving the problem of using a benzotriazole-based photostabilizer in the above polyarylene thioether. The inventors have also found that they can do so and have completed the present invention.

That is, since the light-stabilized polyarylene thioether of the present invention contains the chemical structural unit having the above-mentioned light-stabilizing effect by being chemically bonded in the molecule, it is exposed to the high melt molding temperature used for the polyarylene thioether. Light stability is not impaired even if it is done.

Therefore, the melt-molded product produced from the light-stabilized polyarylene thioether of the present invention has little change in color tone when exposed to ultraviolet rays and light, and various molded products, sealing materials, films, sheets, pipes, rods. ， Processed products such as fibers can be used for a long time without being colored or altered by light.
Further, the light-stabilized polyarylene thioether of the present invention or the composition thereof can be used as a coating which is free from coloring and deterioration due to light for a long period of time.

SUMMARY OF THE INVENTION The present invention relates to a chemical structural unit for a sulfur atom of a thioether bond in a molecule; Is a light-stabilized polyarylene thioether having 0.002 to 0.2 (mol / gram sulfur atom) chemically bonded thereto.

The present invention also relates to a chemical structural unit for a sulfur atom of a thioether bond in the molecule; A composition comprising a light-stabilized polyarylene thioether chemically bound to and a non-light-stabilized polyarylene thioether not bound to the chemical structural unit, wherein the chemical structural unit is all thioether bonds in the composition. The composition is characterized by containing 0.002 to 0.2 mol / g of sulfur atom with respect to sulfur atom.

The present invention also provides a method for producing the above light-stabilized polyarylene thioether.

That is, the first method for producing a light-stabilized polyarylene thioether of the present invention is to produce a polyarylene thioether by a dehalogenation / sulfurization reaction of an alkali metal sulfide and a dihalogenated aromatic compound in an organic polar solvent. A chemical structural unit; A halogenated organic compound containing 0.002 to 0.2 (mol / gram sulfur atom) during the polymerization, followed by pickling the reacted polymer.

The second method for producing the light-stabilized polyarylene thioether of the present invention is a polyarylene thioether polymer having an effective amount of a thiolate group or a thiol group at the molecular end in a strongly alkaline organic polar solvent, and a chemical structural unit; A halogenated organic compound containing 0.002 to 0.2 mol / gram of sulfur atom, a dehalogenation reaction, and a pickling of the reaction polymer.

DETAILED DESCRIPTION OF THE INVENTION Basic Structure of Polyarylene Thioether The main part of the polyarylene thioether of the present invention is Ar--
It has a structure of S _n (Ar: arylene group).
Those having a paraphenylene group as a main component as the arylene group are preferable from the viewpoint of heat resistance and moldability. In addition to para-phenylene group, m-phenylene group o-phenylene group Alkyl-substituted phenylene group R: alkyl group, n: 1 to 4), p, p'-diphenylene ketone group p, p'-diphenylene sulfone group p, p'-diphenylene group p, p'-diphenylene ether group Naphthylene group Those including etc. are used.

In terms of heat resistance of the molded product, Polyphenylene thioether consisting only of repeating units is preferred. In addition, a copolymer of polyphenylene thioether is preferable in terms of easiness of melt processing, that is, the processing temperature is lowered and pellets with little coloring are easily obtained. As a copolymer Unit or A unit containing 5 to 40 mol%, particularly 10 to 25 mol% of a unit is preferable. If the amount of these m- or o-phenylene thioether units is 5 mol% or more, the effect of improving melt processing can be exhibited, and if it is not more than 40 mol%, heat resistance and mechanical properties are not significantly deteriorated. The same again If it is a copolymer containing 60 to 95 mol% of units, rather than a random copolymer, With repeating units A block copolymer in which the repeating unit contains a continuous block-like bond as a block is preferred. This is because the block copolymer gives a final molded product having the same processability and excellent heat resistance and mechanical properties as compared with the random copolymer. Such a block copolymer and a method for producing the same are
It is described in JP-A-61-14228.

From the viewpoint of processing, it is desirable that the polyarylene thioether has an appropriate molecular weight or melt viscosity. That is, the melt viscosity (η ^* ) is 30,000 poise (temperature = 310 ° C, shear rate =
It is preferably 200 seconds- ¹ ) or less, particularly preferably 20000 poise or less.

If it exceeds 30,000 poise, it becomes difficult to produce a pellet-shaped molded product by melt extrusion, and the processing temperature becomes high, so that coloring easily occurs.

When the light-stabilized polyarylene thioether of the present invention is mixed with other light-unstabilized polyarylene thioether and used, the light-stabilized polyarylene thioether may have a low molecular weight.

When the light-stabilized polyarylene thioether of the present invention is used alone, it should be a polymer having a high molecular weight that does not require an increase in the molecular weight due to so-called "cure", and can be easily applied to films, sheets, fibers, etc. It should be a substantially linear polymer in order to be processable. Such a substantially linear, high molecular weight polyarylene thioether can be produced particularly economically by the water-added two-step polymerization method (JP-A-61-7332).

Method for producing light-stabilized polyarylene thioether The method for producing the light-stabilized polyarylene thioether of the present invention comprises the following chemical structural units; Is introduced into the polyarylene thioether in the form of a chemical bond, and the following method described above is effective for this purpose.

That is, the first method is a method of producing a polyarylene thioether from a dihalogenated aromatic compound and an alkali metal sulfide by a dehalogenation / sulfurization reaction in a polar organic solvent, wherein the chemical structural unit is added during the reaction. In this method, a halogenated organic compound (hereinafter referred to as compound A), particularly a halogenated benzotriazole-based light stabilizer, is added to cause a dehalogenation / sulfurization reaction and the above-mentioned chemical structural unit is introduced into the polyarylene thioether.

This method is known in the prior art, as disclosed in JP-A-45-3368 and 52-1224.
Although it can be applied to the polymerization method described in No. 0, it is particularly disclosed in JP-A No. 61-7332, by applying to the water-added two-stage polymerization method, high molecular weight of excellent light stability. Linear polyarylene thioethers can be produced economically.

In these polymerization methods, during the polymerization or at the final stage of the polymerization, the compound A is added to the polymerization system to the alkali metal sulfide.
Is preferably added so that the amount of the chemical structural unit is 0.002 to 0.2 mol / mol, more preferably 0.01 to 0.1 mol / mol, and the reaction is carried out at a temperature of 200 ° C. to 290 ° C. for 20 minutes to 20 hours. If it is less than 0.002 (mol / mol), the light-stabilizing effect may be insufficient, and if it is more than 0.2 mol / mol, the increase in the effect tends to reach the ceiling, which is economically disadvantageous.

After completion of the reaction, the polymer is 0 to 200 ° C. in a solution of an acid having a pH of less than 2 in order to effectively activate the hydroxy group in the light stabilization.
It is preferable to treat at the temperature of 1 to 500 minutes.

An example of the bond between the polyarylene thioether and the triazole-based light stabilizer in this method is shown below by a chemical reaction formula.

[The triazole light stabilizer used above is CIBA-GEIGY
Commercially available TINUVIN 327 (-tBu is tertiary butyl
Group is shown). ] The second method is a polyaryle produced in advance and once collected.
Of the compound A,
In the case of, the polyarylene thioether used is compound A
It is not preferable for the one with poor reactivity with.

A polyarylene thioether having a terminal thiolate group or a thiol group of 2 μmol / g or more, more preferably 3 μmol / g or more is preferable (the amount of the terminal thiolate group and the thiol group was quantified by the iodoacetamide method. ).

The binding reaction is carried out in a strongly alkaline polar organic solvent at 200-290.
It is preferable to react at 20 ° C. for 20 minutes to 20 hours.

Organic amides are preferred as polar organic solvents. In particular, from the viewpoint of polymer stability, it is preferable that the water-containing organic amide is mixed with 2.5 to 25% by weight of water, and that the solvent is strongly alkaline. For example, it is desirable that the pH value of the aqueous solution when the solvent is diluted with 10 times the amount of water is such that the pH value is 9.5 or higher.

Polyarylene thioether and the chemical structural unit is 0.00 relative to the amount of thioether-bonded sulfur in the polymer molecule.
Compound A to be 2 to 0.2 (mol / gram sulfur atom)
Is charged in a solvent and reacted at a temperature of 200 to 290 ° C. for 20 minutes to 20 hours. As in the first method, the polymer after the reaction is preferably treated with an acid.

An example of the bond between the polyarylene thioether and the triazole-based light stabilizer in this method is shown below by a chemical reaction formula.

The polyarylene thioether of the present invention obtained by the above method has, for example, the general formula; Or Or [Wherein R is hydrogen or a C _{1 to} C ₁₄ hydrocarbon or halogenated hydrocarbon group, X ₁ and X ₂ are hydrogen, halogen, a thiol group (-SH), a thiolate group (-SM: M is an alkali metal Or C _{1 to} C ₁₄ hydrocarbon or halogenated hydrocarbon group, Y ₁ is hydrogen, halogen or C _{1 to} C ₁₄ hydrocarbon or halogenated hydrocarbon group, Y ₂ is C _{1 to} C ₁₄ Hydrocarbon or halogenated hydrocarbon group, Ar is an arylene group,
m and n are integers of 2 or more, provided that m + n is 5 to 50
Is in the range of 0].

Although the light-stabilized polyarylene thioether as described above can be used as it is as a molding material, the light-stabilized polymer is not particularly stabilized against other light having the same or different main structure. A composition mixed with polyarylene thioether can also be used for molding, painting and the like.

Even in this case, the amount of the above chemical structural unit is 0.002 to the total amount of thioether-bonded sulfur contained in the composition.
It is preferable to mix so as to be 0.2 (mol / gram atom).

Benzotriazole-based Light Stabilizer (Compound) A The benzotriazole-based light stabilizer that can be chemically bonded to the polyarylene thioether of the present invention is, for example, a compound represented by the general formula; [R is hydrogen or a C ₁ -C ₁₄ hydrocarbon or halogenated hydrocarbon group, X is halogen, Y is hydrogen, halogen or C ₁
To C ₁₄ hydrocarbon or halogenated hydrocarbon group], and specifically include the following.

Light-stabilized polyarylene thioether composition <Composition containing a filler> The above-mentioned light-stabilized polyarylene thioether or a composition obtained by mixing the light-stabilized polyarylene thioether with a non-light-stabilized polyarylene thioether Can be used as it is, but in order to improve physical properties such as dimensional stability, heat distortion temperature, flame retardancy, mechanical strength and hardness, as long as it does not hinder molding,
Alternatively, in order to reduce the cost, an inorganic filler can be mixed into the above-mentioned base resin, if necessary.

The inorganic filler can be roughly classified into powdery or particulate ones and fibrous ones. The former is generally a low-cost filler, and the latter is generally high in cost but characterized by a large effect of improving physical properties.

Such powdery or particulate fillers include calcium carbonate, calcium silicate, talc, silica, mica,
Titanium oxide, carbon or graphite, alumina, silica-alumina, clay, glass, red iron oxide, gypsum, sand, cement, calcium silicate, calcium sulfate and various metal powders or fine particles are used.

As the fibrous filler, glass, carbon or graphite,
Fibers or whiskers such as potassium titanate, silica, calcium silicate, and calcium sulfate can be used.

The amount of the filler mixed is preferably in the range of 0 to 70% by weight. If the content is 70% by weight or more, melt processing of the composition becomes difficult, such being undesirable.

<Composition of Thermoplastic Resin Mixture> The light-stabilized polyarylene thioether of the present invention can be used by blending with another thermoplastic resin as long as it does not hinder the extrusion molding process. It has been described above that polyarylene thioethers having the same or different chemical structures can be mixed. The mixing of the thermoplastic resin is intended to improve physical properties such as lubricity, heat distortion temperature, weather resistance and impact resistance, or to reduce cost.

It is desirable that the resin that can be mixed does not decompose or deteriorate at the melt processing temperature (usually in the range of 200 to 380 ° C).
Examples of such resins include polyamide, polyether ether ketone, polysulfone, polyether sulfone, polyphenylene ether, polycarbonate, polyalkylene terephthalate (polyethylene terephthalate, polybutylene terephthalate, etc.), polyolefin (polyethylene, polypropylene, etc.), ABS, polystyrene and Examples thereof include fluororesins such as polyvinylidene fluoride, polytetrafluoroethylene and tetrafluoroethylene copolymer, and elastomers such as PE rubber, hydrogenated SBR, silicone rubber and fluororubber.

The amount of these thermoplastic resins mixed is 0 to 40% by weight of the composition.
Is preferred. If it exceeds 40%, the physical properties of the molded article (physical properties such as heat resistance and corrosion resistance) may change significantly, which is not preferable.

<Other additives> Alkali metal, alkaline earth metal salts, hydroxides as necessary for the purpose of improving color tone, improving thermal stability, rust prevention, imparting lubricity, adjusting crystallization speed, coloring, etc. It is also possible to add auxiliaries such as oxides, hydrocarbyl oxides, stabilizers, lubricants, release agents and pigments.

[Examples] Hereinafter, the present invention will be further described with reference to Examples.

Example 1 Preparation of a light-stabilized polyarylene thioether by the first method A 20 l autoclave was charged with N-methyl-2-pyrrolidone (NM
P) Charge 3.51 kg (21.0 mol as Na ₂ S) of Na ₂ S ・ 5 hydrate salt crystal (manufactured by Sankyo Kasei Co., Ltd.) containing 8.01 kg and 46.0 wt% Na ₂ S, and gradually stir it while stirring under nitrogen atmosphere. The temperature was raised to 203 ° C. and 1.40 kg of water, 0.81 kg of NMP, and 0.98 mol of H ₂ S were distilled out.

Paradichlorobenzene (P-DCB) 2.97 kg (20.2 mol, P
-DCB / Na ₂ S = 1.01 mol equivalent) and NMP2.81 kg
Polymerization was performed at 5 ° C. for 5 hours to obtain a polymerized slurry.

Part of this slurry 753.5 g (containing 1.01 mol of P-DCB)
And 54 g of water were charged into one autoclave and replaced with nitrogen.
After that, the temperature was raised and the reaction was carried out at 260 ° C. for 5 hours. Cool to 50 ° C
After rejection TINUVIN Add 327 (manufactured by CIBA-GEIGY) 0.01 mol
Then, the atmosphere was replaced with nitrogen again, the temperature was raised, and the mixture was reacted at 255 ° C for 3 hours.
I have After cooling as a post-treatment, polymer with a 150 mesh screen
Separated and collected, and put into hydrochloric acid of pH 1 for about 30 minutes at 50-70 ℃
After pickling, the polymer is deionized and then washed with water.
After repeated washing with seton, vacuum drying at 80 ° C
Was collected.

310 ° C using Koka type flow tester (Shimadzu)
When the melt viscosity of the polymer was measured by (preheating 5 minutes),
The shear rate was 3000 poise when converted into 200 sec- ¹ .

Example 2 Production of light-stabilized polyarylene thioether by the second method <Production of polyarylene thioether> Part of 7535 g (containing 10.1 mol of P-DCB) of the slurry of Example 1 and 540 g of water were charged in a 10 l autoclave and nitrogen. After substituting, the temperature was raised and the reaction was carried out at 260 ° C. for 5 hours. After the reaction, a part of the post-reaction slurry was sampled and the terminal thiolate group or thiol group was quantified. The total amount of terminal thiolate groups or thiol groups was 20.3 (micromoles / gram sulfur atom).

The remaining slurry was post-treated in the same manner as in Polymerization Example 1 to recover the polymer. The melt viscosity of the polymer was 3200 poise.

<Analysis of Polymer End Group> In this example, the analytical quantification of the terminal thiolate group or thiol group was carried out as follows.

Immediately after the completion of the polymerization reaction, a part of the reaction solution is sampled and put into water to precipitate the polymer, which is then washed in pure water. Then, the terminal thiolate group was changed to a thiol group by treatment with dilute hydrochloric acid, washed with pure water for 30 minutes, further washed with acetone for 30 minutes, and then dried under reduced pressure with a vacuum dryer (room temperature) to obtain a polymer sample. About 10 mg to 1 g of a polymer sample is precisely weighed and placed in a tightly stoppered test tube, and acetone 2.5 ml and iodoacetamide 50 mmol /
2.5 ml of acetone solution (1) is added and the container is tightly closed, heated at 100 ° C for 60 minutes and cooled with water. Then, the tube was opened to separate the liquid phase portion, and the absorbance at 460 nm (absorption of I ₂ ) was measured using an ultraviolet absorptiometer.

The chemistry in the above operation is as follows when the reaction is represented by a formula.

I. Conversion of thiolate groups to thiol groups by acidification B. Release of I ₂ (iodo-acetamide method) Model thiol compound in advance The concentration of the thiol group at the terminal was calculated from the absorbance using the calibration curve prepared for (the sample amount should be selected so that the concentration of the thiol group in the acetone slurry is in the range of 0.1 to 0.3 mmol). Is preferred).

The same dried sample was analyzed three times to obtain the average value of the terminal thiol group concentration.

<Bonding of benzotriazole type light stabilizer> 2g of lithium hydroxide was added to 600g of water-containing NMP (water content 11% by weight).
It was made strongly alkaline (pH of 10 times diluted with water = 13). This
108g of polymer (1 mol of sulfur atom) and TINUVI
N 327 0.01 mol was added and reacted at 255 ° C. for 3 hours.
After the reaction, post treatment was carried out in the same manner as in Example 1 to obtain a polymer.
It was Also, blend the polymer with the polymer 1: 1 and
Got a limmer.

Example 3 Light stability test <Comparative light stabilizer> 71.58 g (0.2 mol) of TINUVIN 327 and terephthalic acid
Dissolve 20.30 g (0.1 mol) of loride in anhydrous pyridine and prepare 1
The reaction was conducted at 20 ° C. for 5 hours in a reflux state. White solid
The product was separated, washed with acetone, and dried under reduced pressure at room temperature.
The white solid obtained was analyzed by infrared absorption spectrum (IR),
Identified by spectral analysis (MS) and nuclear magnetic resonance (NMR)
As a result, as shown below, without hydroxy group (-OH)
It was found that the ester of the structure is the main component (light stabilizer
I).

Light stabilizer I: In addition, the following commercially available light stabilizers were used.

Light stabilizer II: TINUVIN  327 (manufactured by CIBA-GEIGY)[TBu represents a tertiary butyl group. ] Light stabilizer III: TINUVIN  P (manufactured by CIBA-GEIGY)<Sample preparation> Stabilizer I, Stabilizer II or Stabilizer for polymer
Extruder with vents containing 0.5% by weight of III respectively
Then, the mixture was heated to 330 ° C. and melt-kneaded.

The pellets thus obtained are hot-pressed under a nitrogen atmosphere, preheated at 320 ° C. for 1 minute and then pressed at 320 ° C. for 30 seconds,
It was rapidly cooled to prepare a sheet having a thickness of about 0.3 mm and subjected to a light resistance test (shown in order as execution numbers 5, 6, and 7).

Polymers were also prepared into sheet samples in the same manner as above (Run Nos. 1, 2, 3, 4).

<Light resistance test> As a light stability evaluation method, each sheet-shaped sample was exposed to light, and the degree of coloring of the exposed sample was evaluated by the Yellowness Index. As the colored light source, an indoor light accelerated deterioration tester INDOOR ACTINIC EXPOSURE SYSTEM HP-UV (light source; 11 fluorescent lamps, 2 UV lamps through glass) manufactured by Atlas was used, and a 120-hour exposure test was performed. Equivalent to a month).

After the exposure test, a color difference meter (Tokyo Denshoku KK COLOR ACE TCA-
The Yellowness Index was measured using 1). The results are shown in Table-1.

According to Table-1, it was found that a chemical structural unit having an OH group at the 2-position of the benzotriazole-bonded benzene ring bonded to a polyarylene thioether, or a compound containing it, exhibits excellent light resistance. did.

Claims (4)

[Claims] 1. A compound represented by the general formula (I): [R is hydrogen or a C ₁ -C ₁₄ hydrocarbon or halogenated hydrocarbon group, X is halogen, Y is hydrogen, halogen or C ₁
~ C ₁₄ hydrocarbon or halogenated hydrocarbon group] is chemically bonded at a ratio of 0.002 to 0.2 mol to 1 gram atom of sulfur. )-(IV); Or Or [Wherein R is hydrogen or a C _{1 to} C ₁₄ hydrocarbon or halogenated hydrocarbon group, X ₁ and X ₂ are hydrogen, halogen, a thiol group (-SH), a thiolate group (-SM: M is an alkali metal Or C _{1 to} C ₁₄ hydrocarbon or halogenated hydrocarbon group, Y ₁ is hydrogen, halogen or C _{1 to} C ₁₄ hydrocarbon or halogenated hydrocarbon group, Y ₂ is C _{1 to} C ₁₄ Hydrocarbon or halogenated hydrocarbon group, Ar is an arylene group,
m and n are integers of 2 or more, provided that m + n is 5 to 50
Is in the range of 0]. The light-stabilized polyarylene thioether represented by 2. General formula (I); [R is hydrogen or a C ₁ -C ₁₄ hydrocarbon or halogenated hydrocarbon group, X is halogen, Y is hydrogen, halogen or C ₁
~ C ₁₄ hydrocarbon or halogenated hydrocarbon group] is chemically bonded to a halogenated organic compound represented by the general formulas (II) to (IV); Or Or [Wherein R is hydrogen or a C _{1 to} C ₁₄ hydrocarbon or halogenated hydrocarbon group, X ₁ and X ₂ are hydrogen, halogen, a thiol group (-SH), a thiolate group (-SM: M is an alkali metal Or C _{1 to} C ₁₄ hydrocarbon or halogenated hydrocarbon group, Y ₁ is hydrogen, halogen or C _{1 to} C ₁₄ hydrocarbon or halogenated hydrocarbon group, Y ₂ is C _{1 to} C ₁₄ Hydrocarbon or halogenated hydrocarbon group, Ar is an arylene group,
m and n are integers of 2 or more, provided that m + n is 5 to 50
A range of 0]], a light-stabilized polyarylene thioether chemically bound to a halogenated organic compound,
A composition comprising the halogenated organic compound and a non-light-stabilized polyarylene thioether which is not chemically bonded, wherein the halogenated organic compound is present in an amount of 0.002 to 0.2 mol per 1 gram atom of sulfur in the composition. A light-stabilized polyarylene thioether composition, which is chemically bonded. 3. When a polyarylene thioether is produced from an alkali metal sulfide and a dihalogenated aromatic compound by a dehalogenation / sulfurization reaction in an organic polar solvent, a compound represented by the general formula (I); [R is hydrogen or a C ₁ -C ₁₄ hydrocarbon or halogenated hydrocarbon group, X is halogen, Y is hydrogen, halogen or C ₁
~ C ₁₄ hydrocarbon or halogenated hydrocarbon group] is added during the polymerization at a rate of 0.002 to 0.2 mol / g sulfur atom, and then the reaction product polymer is pickled. Characteristic general formula (II) ~
(IV); Or Or [Wherein R is hydrogen or a C _{1 to} C ₁₄ hydrocarbon or halogenated hydrocarbon group, X ₁ and X ₂ are hydrogen, halogen, a thiol group (-SH), a thiolate group (-SM: M is an alkali metal Or C _{1 to} C ₁₄ hydrocarbon or halogenated hydrocarbon group, Y ₁ is hydrogen, halogen or C _{1 to} C ₁₄ hydrocarbon or halogenated hydrocarbon group, Y ₂ is C _{1 to} C ₁₄ Hydrocarbon or halogenated hydrocarbon group, Ar is an arylene group,
m and n are integers of 2 or more, provided that m + n is 5 to 50
The range is 0], and the method for producing the light-stabilized polyarylene thioether. 4. A polyarylene thioether polymer having an effective amount of a thiolate group or a thiol group at the terminal of a molecule thereof in a strongly alkaline organic polar solvent, which has the general formula (I); [R is hydrogen or a C ₁ -C ₁₄ hydrocarbon or halogenated hydrocarbon group, X is halogen, Y is hydrogen, halogen or C ₁
~ C ₁₄ hydrocarbon or halogenated hydrocarbon group] is added at a rate of 0.002 to 0.2 mol / g of sulfur atom to cause dehalogenation reaction, and then the reaction product polymer is pickled. General formulas (II) to (IV) characterized by Or Or [Wherein R is hydrogen or a C _{1 to} C ₁₄ hydrocarbon or halogenated hydrocarbon group, X ₁ and X ₂ are hydrogen, halogen, a thiol group (-SH), a thiolate group (-SM: M is an alkali metal Or C _{1 to} C ₁₄ hydrocarbon or halogenated hydrocarbon group, Y ₁ is hydrogen, halogen or C _{1 to} C ₁₄ hydrocarbon or halogenated hydrocarbon group, Y ₂ is C _{1 to} C ₁₄ Hydrocarbon or halogenated hydrocarbon group, Ar is an arylene group,
m and n are integers of 2 or more, provided that m + n is 5 to 50
The range is 0], and the method for producing the light-stabilized polyarylene thioether.