JPH093327A - Polyarylene sulfide resin composition for low-temperature molding and its molding method - Google Patents

Abstract

PURPOSE: To obtain a polyarylene sulfide resin compsn. for low-temp. molding which exhibits a sufficient degree of crystallization even when molded at a low mold temp. by adding a specific piperidine compd. to a polyarylene sulfide resin. CONSTITUTION: This compsn. comprises a polyarylene sulfide resin and a solid or liq. piperidine compd. which has at least one tetramethylpiperidyl group represented by the formula I [R1 is H, an alkyl, or acyl; and X is a group represented by the formula II or III (R2 is a lower alkyl)] at the molecular end and has an m.p. of 100 deg.C or lower. Pref. this compsn. further contains a nucleating agent (e.g. talc or silica).

Description

Detailed Description of the Invention

[0001]

The present invention has a high crystallization rate,
A polyarylene sulfide resin composition suitable for low-temperature molding, which has a sufficient crystallinity even at a mold temperature as low as 0 ° C., and a resin for injection molding the composition at a mold temperature of less than 120 ° C. The present invention relates to a method for molding a composition.

[0002]

2. Description of the Related Art Polyphenylene sulfide (hereinafter referred to as PP)
Polyarylene sulfide (hereinafter abbreviated as PAS) resin represented by a resin (S) is excellent in heat resistance itself,
Molding materials, which have chemical resistance and are reinforced with reinforcing materials such as glass fiber, are being used as metal substitutes in the fields of automobile parts, electronics-related parts, etc. There is.

However, the PAS resin represented by the PPS resin is originally a crystalline resin, but it has a drawback that the crystallization rate is very slow. For this reason, other thermoplastic resins such as polyethylene, polypropylene, polyacetal, polybutylene terephthalate, and polyamide may be used at room temperature to 10
In contrast to molding at a mold temperature of 0 ° C, PAS resin cannot be molded into a sufficiently crystallized mold unless the mold temperature is 120 ° C or higher, generally 150 ° C or higher. Even if molding can be performed at a low mold temperature, the appearance of the molded product, the releasability from the mold itself, etc. are extremely poor, and the molded product can be obtained only when the molded product is deformed or cracked. It was often not possible. Further, the molded product obtained by molding at a low mold temperature has poor heat resistance, and it is necessary to perform heat treatment in an atmosphere having a glass transition temperature or higher in order to increase the crystallinity. However, when left in an atmosphere having a glass transition temperature or higher, it may be deformed depending on the shape of the molded product or the size of the molded product. In addition, since the mold temperature is high at 150 ° C or higher, workers are liable to be burned, especially during insert molding, and the mold temperature rise time is longer than usual, or the mold life is longer. There was also a problem of poor workability such as short length. Furthermore, for example, in precision moldings that extremely dislike the generation of burrs and require heat resistance such as solder heat resistance, burrs are suppressed and mold release is possible at a mold temperature of less than 90 ° C. After molding,
It was also necessary to perform post-treatment such as annealing at 120 ° C. or higher to sufficiently raise the crystallinity and use the PPS resin in a state where the original heat resistance was not lost.

In order to solve these problems, the following method has been proposed as a method for high speed crystallization using a die at a relatively low temperature. The method of adding an oligomeric ester described in JP-A-62-45654, the method of adding another thioether described in JP-A-62-230849, and the carboxylic acid ester described in JP-A-62-230848 Method of addition, JP-A-62-230850, JP-A 1-22
5660, a method of adding a phosphoric acid ester described in JP-A-3-91563, a method of adding a certain silicon compound containing a mercapto group described in JP-A-2-225565, JP-A-6-192473. 1, 2, 3, described in Japanese Patent Publication
A method of adding a 4-butanetetracarboxylic acid imide compound and the like.

[0005]

However, among these methods, ~ is not sufficient in the effect of promoting crystallization, or if a large amount is added to increase the effect, the compound or resin is generated during molding or use. There is a practical problem that gas or decomposed gas is generated to cause inconvenience such as adhesion to a mold or the like for contamination, deterioration of the environment, and adverse effects on physical properties. Although the method (1) is relatively effective, the compound has a large hygroscopicity, and if a large amount of this compound is added, the water absorption of the PPS molded article becomes large, and the physical properties such as electrical characteristics or mechanical characteristics in a high humidity atmosphere are increased. There was a drawback that lowered. Further, it cannot be said that the generated gas has been sufficiently improved, and there is a drawback that the crystallization promoting effect cannot be obtained when an epoxy compound such as epoxysilane is simultaneously mixed.

[0006]

The present inventor has been
It eliminates the need for a high mold temperature, which has been a drawback of molding an S resin composition, particularly a defect in injection molding, and has a sufficient crystallinity even at a low mold temperature. In addition, low-priced PA that does not adversely affect physical properties
As a result of extensive studies to obtain an S resin molded product, a piperidine compound having a specific structure has a high crystallization rate when melted and solidified in a composition obtained by adding a small amount of this to a PAS resin,
The inventors have found that a PAS resin molded product that exhibits a high degree of crystallinity even at a mold temperature lower than that of a conventional one and has good heat resistance can be molded, and has completed the present invention.

That is, the present invention relates to a polyarylene sulfide resin (A) and the following general formula (1)

[0008]

Embedded image

(In the above formula, R 1 represents a hydrogen atom, an alkyl group or an acyl group, and X is

[0010]

Embedded image

Or

[0012]

[Chemical 6]

Wherein R2 represents a lower alkyl group. ) A compound having at least one tetramethylpiperidyl group represented by the formula (1) at the terminal of the molecule, and comprising a solid or liquid piperidine compound (B) having a melting point of 100 ° C. or lower. The present invention relates to a polyarylene sulfide resin composition for low temperature molding, and a method for molding the resin composition by injection molding the composition at a mold temperature of less than 120 ° C.

The above-mentioned general formula (1) used in the present invention
The piperidine compound (B) having a tetramethylpiperidyl group represented by
431, Japanese Patent Publication No. 57-26306, Japanese Patent Publication No. 60-2
No. 3716, Japanese Patent Publication No. 60-23717, Japanese Patent Publication No. 61-
16775, 61-58492, JP-A-3-
229748, JP-A-4-230364, JP-A-5
It is contained in a part of a large number of piperidine-based compounds described as a hindered amine-based light stabilizer in each publication such as -112686 and is a known compound. In addition, the same as the piperidine compound (B) used in the present invention may be included in many commercially available hindered amine-based light resistance stabilizers or ultraviolet absorbers.

An object of the present invention is to provide a PAS resin composition suitable for low-temperature molding, which enables molding at a low mold temperature, which has been difficult with conventional PAS resin compositions. And the object of the present invention is P
In a PAS resin composition containing a piperidine-based compound having a specific structure described above in an AS resin and having a melting point within a specific range, the crystallization rate of the PAS resin composition when melted and solidified is It has a high degree of crystallinity even at high speed and even at a lower mold temperature than before.
This was achieved by being able to manufacture a PAS resin molded product having excellent physical properties.

In the present invention, the base PAS resin is
A polymer containing 70 mol% or more of a repeating unit represented by the general formula [-Ar-S-] (wherein, -Ar- represents a divalent aromatic group containing at least one 6-carbon carbon ring). In the combination, the representative substance is structural formula [-φ-S-] (however,
-Φ- is a polymer containing 70 mol% or more of the repeating unit represented by p-phenylene group).

PAS resins are generally known to have a substantially linear molecular structure having no branched or crosslinked structure and one having a branched or crosslinked structure depending on the production method.
In the present invention, both types are effective. Further, the PPS resin used in the present invention is the one which is washed with hot water, organic solvent, acid or the like as described in JP-A-2-200415 at the time of its production. A more effective effect appears for achieving the object of the invention. Therefore, it is desirable to perform the above-mentioned cleaning treatment on the PAS resin before the molding process, for example, the PPS resin after the production, from the viewpoint of improving the crystallization characteristics. In addition, P with a sodium content of 2000 ppm or less
It is preferable to use PS resin.

PAS preferred for use in the present invention
The resin (a) has the repeating unit [-φ-S-] described above.
(However, -φ- is a p-phenylene group) is a PPS resin containing 70 mol% or more. This repeating unit is 70
When it is at least mol%, the crystallinity, which is a characteristic of the crystalline polymer, is high, sufficient strength is obtained, and the toughness and chemical resistance are excellent.

Such a PPS resin may contain less than 50 mol%, preferably less than 30 mol%, of the other copolymerization structural unit shown below.

[0020]

[Chemical 7]

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image

[0024]

Embedded image

[0025]

[Chemical 12]

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

And the like. Of these, the trifunctional unit is 1
It is also preferable that the content is mol% or less from the viewpoint of not lowering the crystallinity.

On the other hand, the piperidine compound (B) used in the composition of the present invention is a compound having at least one tetramethylpiperidyl group represented by the general formula (1) at the molecular end, as described above. And a solid or liquid piperidine compound having a melting point of 100 ° C. or lower, preferably 90 ° C. or lower. If the melting point of the compound exceeds the above range, a molded product having sufficiently advanced crystallization cannot be obtained by molding at a low mold temperature of less than 120 ° C., and only a molded product having inferior performances can be obtained. The melting point of the piperidine compound used is the glass transition point (T) of the PAS resin (A) used.
Particularly preferably lower than g).

Examples of piperidine compounds having the tetramethylpiperdyl group represented by the general formula (A) at the molecular end and suitable for use in the present invention are shown below. The tetramethylpiperidyl group-containing organic compound represented by (2) may be used alone or as a mixture with the tetramethylpiperidyl group-containing organic compound represented by the general formula (3). The mixing ratio when these are mixed is from 10 to 100% by weight of the compound represented by the following general formula (2) and 0 to 90% by weight of the compound represented by the following general formula (3). Become.

[0032]

Embedded image

[0033]

Embedded image

In the above general formulas (2) and (3), R
1 and X have the same meanings as shown in the general formula (1), n is 3 to 6, m is 1 to 6, and n is
> M, R is a hydroxyl group, an acyloxy group, or an n-valent hydrocarbon group which may be substituted with a halogen atom, or

[0035]

Embedded image

Wherein p is 1 to 5, R3 is an alkyl or alkenyl group having 8 to 30 carbon atoms, Y is --O-- or

[0037]

Embedded image

And R4 represents a hydrogen atom or R3. )

In the tetramethylpiperidyl group represented by the general formula (1), or in the general formula (2),
In the compound represented by (3), the alkyl group represented by R1 is methyl, ethyl, propyl, isobutyl, sec-butyl, heptyl, octyl, dodecyl, benzyl, 2-hydroxyethyl, 2-hydroxypropyl, 2 -Hydroxybutyl, acetoxyethyl, propionylethyl, 2.3-epoxypropyl, etc., and the alkyl group preferably used among these includes methyl, ethyl, propyl and the like. Examples of the acyl group include acetyl, propionyl, methacryloyl, benzoyl and the like. R1 is preferably a hydrogen atom or a methyl group.

The lower alkyl group represented by R2 is
Methyl, propyl, ethyl, isopropyl, butyl and the like can be mentioned.

Examples of the alkyl group represented by R3 are octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, dodecyl, 2-methylundecyl, tridecyl, 2-methyldodecyl, tetradecyl, 2-methyl. Root lydecyl, hexadecyl, 2
-Hexyldecyl, octadecyl, eicosyl, docosyl, tetracosyl, 2-decyltetradecyl, 2-decylpentadecyl, 2-undecyltetradecyl, 2-undecylpentadecyl, triacontyl and the like, and the alkenyl group is decenyl. , Dodecenyl, tetradecenyl, hexadecenyl, octadecenyl and the like. Nonyl and isononyl are preferred.

In the compounds represented by the general formulas (2) and (3), the hydrocarbon group represented by R is

[0043]

Embedded image

(In the formula, n is the same as the above) and is the residue of the polycarboxylic acid. The carboxylic acid includes those shown below. Tricarballylic acid, citric acid, acetylcitric acid, butane-1,2,3-tricarboxylic acid, 3-butene-1,2,3-tricarboxylic acid, trimellitic acid, butane-1,2,3,4-tetracarboxylic acid, 1,1.2・ 2-Ethene tetracarboxylic acid, 7-bicyclo (2.2.2) octene-2,3,5,6-tetracarboxylic acid, 1,1,2,3-propanetetracarboxylic acid, pyromellitic acid, 1.6.7・ 8,9,14-tetradecanehexacarboxylic acid, 1,6,8,14-tetradecanetetracarboxylic acid, nitrotriacetic acid, nitrilotripropionic acid and the like can be mentioned, butane-1,2,3,4-tetracarboxylic acid is preferably used. To be

Specific examples of the compounds represented by the general formulas (1) and (2) include the following. In the following, Z1 is

[0046]

[Chemical 21] And Z2 is

[0047]

Embedded image

And RX is

[0049]

Embedded image

Is shown.

[0051]

Embedded image

[0052]

Embedded image

[0053]

[Chemical formula 26]

[0054]

Embedded image

[0055]

Embedded image

[0056]

[Chemical 29]

[0057]

Embedded image

[0058]

[Chemical 31]

[0059]

Embedded image

And the like.

Of these, preferably

[0062]

[Chemical 33]

[0063]

Embedded image

And the like.

Piperidine compound (B) used in the present invention
As the next preferable examples, there are piperidine compounds represented by the following general formula (4).

[0066]

Embedded image

(In the formula, R5 represents a residue of a polycarboxylic acid having a valence of 3 to 6, a represents 1 to 4, and Y1 represents -O- or

[0068]

Embedded image

Wherein R7 represents a hydrogen atom, an alkyl group or an aryl group, in which two R7's may be bonded to each other to represent an alkylene group, and A represents the remaining divalent alcohol. Group or a divalent amine residue, and b is 1
-10, and R6 is

[0070]

Embedded image -Y1-A-Y1-H (wherein Y1 and A are the same as above) or

[0071]

Embedded image

And X, R1 and R2 have the same meanings as described above. In the compound represented by the general formula (4), the group represented by R5 is

[0073]

Embedded image

Residues of polycarboxylic acids having a valence of 3 to 6 represented by: carboxylic acids such as tricarballylic acid,
Citric acid, acetylcitric acid, butane-1,2,3-tricarboxylic acid, 3-butene-1,2,3-tricarboxylic acid, trimellitic acid, butane-1,2,3,4-tetracarboxylic acid, 1,1,2,2-ethene Tetracarboxylic acid, 7-bicyclo (2.2.2) octene-2.3.5
・ 6-Tetracarboxylic acid, 1,1.2,3-Propanetetracarboxylic acid, Pyromellitic acid, 1,6,7,8,9
・ 14-Tetradecane hexacarboxylic acid, 1 ・ 6 ・ 8 ・
14-tetradecanetetracarboxylic acid, nitrotriacetic acid, nitrilotripropionic acid and the like can be mentioned, and butane-1,2,3,4-tetracarboxylic acid is preferably used.

The alkyl group represented by R7 is methyl, ethyl, propyl, isopropyl, isobutyl, butyl, amyl, hexyl, cyclohexyl, 2-ethylhexyl, heptyl, octyl, isooctyl, nonyl, decyl, dodecyl, octadecyl, tetradecyl, etc. Can be given. Examples of the aryl group include phenyl, naphthyl, tolyl, xylyl, tert-butylphenyl, octylphenyl, 2,4-di-tert-butylphenyl, nonylphenyl and dinonylphenyl. When two R7's are bonded to each other to represent an alkylene group, they may be methylene, ethylene, 1,2-propylene or 1,3-propylene.

The group represented by A is a divalent alcohol residue or a divalent amine group. Examples of the divalent alcohol include ethylene glycol, diethylene glycol, triethylene glycol and 1,2-propylene glycol.
1,4-butylene glycol, 1,2-propylene glycol, thiodiether, 1.6-hexanediol, 3-methylpentane, neopentyl glycol,
1,10-decanediol, 1,12-dodecanediol, cyclohexanemethanol, hydrogenated bisphenol A, 2-butene, -1,4-diol, 3,9-bis (1,1-dimethyl-2-hydroxyl Ethyl-2,
Examples include 4,8,10-tetraoxaspiro (5,6) undecane. Examples of the divalent amine include ethylenediamine, 1,3-propylenediamine,
1,6-hexamethylenediamine, 1,10-decamethylenediamine, 1,11-undecanemethylenediamine, xylylenediamine, bis (amonomethyl) cyclohexane, isofluoronediamine, bis (aminocyclohexane) methane, 3,9-bis (3-Amonopropyl) -2,4,8,10-tetraoxaspiro (5,5
5) Examples include undecane, piperazine, and 2,5-dimethylpiperazine.

Specific examples of the piperidine compound represented by the general formula (4) used in the present invention are as follows. In the following, Z1, Z3 and RE are the same as the groups shown in the examples of the piperidine compounds represented by the general formulas (2) and (3). That is, what is Z1

[0078]

Embedded image

And Z2 is

[0080]

Embedded image

And RX is

[0082]

Embedded image

Is shown.

[0084]

Embedded image

[0085]

Embedded image

[0086]

Embedded image

[0087]

Embedded image

[0088]

Embedded image

[0089]

Embedded image

[0090]

Embedded image

[0091]

Embedded image

Further, in addition to the above-mentioned piperidine compounds, compounds which can be preferably used as the piperidine compound (B) in the present invention include, for example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate,

[0093]

[Chemical 51]

Bis (2,2,6,6-pentamethyl-4
-Piperidyl) sebacate,

[0095]

Embedded image

4-benzoyloxy-2,2,6,6-tetramethylpiperidine,

[0097]

Embedded image

1,2,2,6,6-pentamethyl-4-piperidyl methacrylate,

[0099]

Embedded image

2,2,6,6-tetramethyl-4-piperidyl methacrylate

[0101]

Embedded image

In addition, 8-acetyl-3-dodecyl-7,7,9,9 in which a tetramethylpiperidyl group represented by the general formula (1) forms a spiro ring between adjacent groups.
-Tetramethyl-1,3,8-triazaspiro (4.
5) Decane-2,4-dione,

[0103]

Embedded image

And the like.

The method for obtaining the piperidine compound (B) used in the present invention is described in JP-B-56-5431.
Japanese Patent Publication No. 60-23716, Japanese Patent Publication No. 61-16775
Known methods described in Japanese Patent Publication No. 61-58492 and Japanese Patent Publication No. 61-58492 can be exemplified, but the present invention is not limited thereto.

The amount of the piperidine compound (B) used is P
The amount is 0.1 to 5 parts by weight, preferably 0.3 to 2 parts by weight, based on 100 parts by weight of the AS resin. If it is less than 0.1 part by weight, the effect is not obtained, and if it exceeds 5 parts by weight, the physical properties tend to be extremely deteriorated.

In the composition of the present invention, the PAS described above is used.
If necessary, a crystal nucleating agent (C) may be added to the composition system comprising the resin (A) and the piperidine compound (B) to give a resin composition suitable for lower temperature molding. Examples of the crystal nucleating agent (C) that can be used as necessary include commonly known crystal nucleating agents. Specifically, talc, mica, silica, kaolin, clay,
Attapulgite, romite powder, quartz powder, zinc white, diatomaceous earth, montmorillonite, verculite, amorphous silica, crystalline silica, glass powder, alumina silica, wollastonite, hytron, boron nitrite, carbon black, pyro Inorganic nucleating agents such as ferrite, graphite, zinc sulfide, boron nitride, silicon resin powder, calcium, magnesium, aluminum, lithium, barium, titanium silicates, sulfates, phosphates, aluminates, oxides, etc., fats Aromatic carboxylic acid, benzoic acid, terephthalic acid and other aromatic carboxylic acid metal salts, aromatic phosphonic acid and its metal salts, aromatic phosphoric acid ester metal salts, benzene sulfonic acid, naphthalene sulfonic acid and other aromatic sulfonic acid metals Salt, metal salt of β-diketones, metal salt of carboxyl group Molecular compound, 4,6 nylon, polyether ether ketone, polyether ketone, polysulfide polymer compound having a melting point higher than the melting point of the PAS resin, such as sulfide ketones and these powdery substance, and the like.
Among these, preferable crystal nucleating agents include talc, silica, boron nitride, and aromatic phosphoric acid ester metal salts.

The amount of the crystal nucleating agent used in the present invention is PAS resin 1
The amount is 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 00 parts by weight. Addition of a small amount is not very effective, and addition of a larger amount than necessary tends to extremely deteriorate the physical properties.

The composition of the present invention may optionally contain
It is also possible to blend the reinforcing material and / or the filler material shown below. Examples of these reinforcing materials and / or fillers include powdery, flat, scale-like, needle-like, spherical or hollow and fibrous forms. Specifically, calcium sulfate, calcium silicate, clay, talc, alumina, silica sand, glass powder, metal powder, graphite, silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride,
Granular filler such as carbon black, mica, glass plate, sericite, metal foil such as aluminum flake, flat or scale-like filler such as graphite, shirasu balloon, metal balloon, hollow filler such as glass balloon, Examples thereof include organic fibrous fillers such as glass fibers, carbon fibers, graphite fibers, whiskers, metal fibers, asbestos, wosnite, fibrous fillers and aromatic polyamide fibers.

Further, other thermoplastic resins may be added to the composition of the present invention within a range not departing from the gist of the present invention. Other thermoplastic resins include polyethylene, polypropylene, polystyrene, imide-modified polystyrene, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyamide, polycarbonate, ABS resin. , Imide-modified ABS resin, AES resin,
Polysulfone, polyphenylene ether, copolymer and / or mixture of polyphenylene ether and polystyrene, thermoplastic resin such as polyethersulfone, polysulfide ketone, polysulfide sulfone, polyetheretherketone, polyamideimide, polyester system, Polyamide-based, polyurethane-based, polyolefin-based, polystyrene-based, etc. thermoplastic elastomers, and these thermoplastic elastomers, glycidyl groups, carboxylic acids and acid anhydrides thereof, amino groups, isocyanate groups, mercapto groups, oxazoline groups and other organic functional Examples include modified products modified with an organic compound containing a group. Preferably, polypropylene, polybutylene terephthalate,
Polyamide, polyphenylene ether, copolymer and / or mixture of polyphenylene ether and polystyrene.

In the present invention, the imide group-containing organic compound and / or another piperidine compound having a crystallization promoting effect on the PAS resin may be used together with the present invention.

In the present invention, an inorganic flame retardant such as magnesium hydroxide, aluminum hydroxide or antimony trioxide, a halogen-based compound, a halogen-based compound,
Add additives such as phosphorus-based organic flame retardants, antioxidants, UV inhibitors, lubricants, dispersants, silane coupling agents, titanium coupling agents, foaming agents, crosslinking agents, colorants, plasticizers, etc. You can

As a method for producing a molded article from the PAS resin composition of the present invention, a general production method is used. The most common method is to uniformly mix the blend with a suitable mixer such as a tumbler, a Henschel mixer, a tumbler, etc., supply to an extruder, melt-knead, and extrude into a strand, cool and cut, After forming a product for molding material (for example, pellets), the mold surface temperature is 120 ° C.
Below 90 ° C, preferably below 120 ° C, and the cylinder temperature is -30 ° C to 100 ° C with respect to the melting point of the PAS resin.
There is a method of supplying to a molding machine set in the above range, melt-kneading, and injection molding. Briefly, omitting the extrusion step, the formulation of the present invention has a mold surface temperature of less than 120 ° C, preferably 90 ° C or more and less than 120 ° C and a cylinder temperature of PAS.
A method in which the resin is supplied to an injection molding machine set in the range of −30 ° C. to 100 ° C. with respect to the melting point of the resin, melt-kneaded, and injection-molded may be used, but is not particularly limited thereto.

As described above, in the composition of the present invention, 90
It is not necessary to anneal at 120 ° C. or more after molding even at a relatively low mold surface temperature of ℃ or more and less than 120 ° C., and a molded product in which crystallization is sufficiently advanced can be obtained as it is.

The composition of the present invention can be molded at a mold temperature lower than that of the conventional PAS resin composition and does not impair mechanical properties and heat resistance. Therefore, it can be used for various functional parts like conventional PAS resins. For example, injection molded products are generally used as automobile parts, electric machines, electronic parts, sealing materials, and extrusion molded products. It is useful as a profile extrusion, tube, hose, pipe, fiber, film, extrusion material such as wire coating, blow molding, and rotational molding material.

[0116]

The present invention will be further described with reference to examples.

(1) Melt index of PAS resin
(MI) Measurement After drying about 6 g of the sample at 120 ° C. for 3 hours, the melt indexer () was set to a predetermined temperature (315.6 ° C.) using an orifice having a diameter of 2.096 mm and a length of 8.001 mm. Toyo Seiki Co., Ltd. T01 type), after removing air bubbles, applying a predetermined load (5000 g) and preheating for 5 minutes, and then measuring.

(2) HDT (Heat Strain Temperature) Measuring Method The measurement is carried out according to ASTM D648. Test piece: length 125 mm x width 12.5 mm x thickness 3.0 mm (injection molded product) Measuring instrument: HDT tester S3FH manufactured by Toyo Seiki Co., Ltd.
Mold load: 4.6kgf / cm ²

[0119](3) Glass transition temperature and crystal of PAS resin
Temperature (T _C1 , T _C2 ) and melting point The composition of the present invention was set to a mold surface temperature of 30 ° C. ± 10 ° C.
However, the cylinder temperature is -30 with respect to the melting point of the PAS resin.
Supply to the injection molding machine set to ℃ ~ 100 ℃, thickness
A 0.5 mm sheet is molded. This sheet is almost amorphous
It has transparency in the state. Glass transition temperature, crystallization temperature,
And the melting point is about 6 mg of this sheet by DSC at 50 ° C.
To 20 ° C / min to 350 ° C,
After holding at 350 ° C for 3 minutes, cooling rate of 20 ° C / min
Cool down to 150 ° C. Journal of Polymer Scien
nce; Part B; Polymer Physics, Vol.30, 163-176 (1992)
Therefore, the glass transition temperature (Tg) that appears when the temperature rises,
And the peak temperature of the crystallization exothermic peak is raised.
(T_C1), And the endothermic peak as the melting point (Tm)
Measured. Also, the exothermic peak that appears during cooling is reduced.
Warm crystallization temperature (T _C2) Was measured.

Usually, JP-A-55-139448,
Plastic Age Vol.28, No.9, 106-113 (1982), Jour
nal of Polymer Sciennce; Part B; Polymer Physics, Vo
As described in l.30, 163-176 (1992), Tg
It is said that a mold having a low T _{c1 and a} low T _c1 can be molded by a relatively low temperature mold, and a mold having a high T _c2 has a faster molding cycle. Therefore, it is necessary for injection molding to satisfy both T _c1 and t _c2. is there.

Measuring instrument: Perkin-Elmer DSC7 atmosphere: In nitrogen atmosphere

(4) Melting Point of Organic Compound (B) The melting point of the piperidine compound (B) referred to in the present invention is measured by using an optical microscope, and specifically, it is a solid piperidine compound (B). 0.5 to 10 mg was taken on a commercially available slide glass and set on a commercially available cover glass heating stage (FP82 manufactured by METTLER CORPORATION), which was directly used as an optical microscope (manufactured by Nikon, Microphoto-F).
X) on the stage. The magnification of the microscope is set to 100 times, and observation is performed by a transmission method using white light. From the heating stage from 30 ℃ to temperature controller (FP800 manufactured by METTLER CORPORATION)
0) was used to raise the temperature at a rate of 20 ° C./min, and the temperature at which white light was completely transmitted was taken as the melting point.

Examples 1 to 3 and Comparative Example 1 As the PPS resin (A), linear type PP washed with hot water having MI of 300 g / 10 min and sodium content of 356 ppm.
S resin as a piperidine compound (B), the following structural formula

[0124]

Embedded image

J = 0: 29 wt%, j =
1:58 wt%, j = 2: 13 wt%, j = 3: 0 wt
% Of each of the piperidine compounds (B) which are liquid at 23 ° C. and blended by using a tumbler with the composition shown in Table 1 and a barrel temperature of 290 ° C.
After kneading with a twin-screw extruder (TEM-35B made by Toshiba Machine) set to, the extruded strand is cooled and solidified,
Pelletized. After drying the obtained pellets at 120 ° C. for 4 hours, the cylinder temperature was 290 ° C. and the mold surface temperature was 10 ° C. with an injection molding machine (IS-50AM: manufactured by Toshiba Machine).
Molding was performed at 0 ° C. and 150 ° C. to obtain HDT measurement test pieces. In addition, according to the method described above, Tg, T _{C 1} ,
T _C2 and Tm were measured.

As a comparative example, the PPS resin alone (Comparative Example 1) was similarly tested (mold surface temperature: 100 ° C. and 150 ° C.). The results are shown in Table 1.

[0127]

[Table 1]

As is clear from the results, in the present invention, the crystallization rate is increased without lowering the melting point, and
Molding is possible at the following mold temperatures, and a molded product having heat resistance equivalent to that of a molded product using a high temperature mold is obtained.

Examples 4 to 6 and Comparative Example 2 As the PPS resin (A), linear type PP washed with hot water having an MI of 160 g / 10 min and a sodium content of 450 ppm.
S resin as a piperidine compound (B), the following structural formula

[0130]

Embedded image

Each of the piperidine-based compounds (B) having the melting point of 50 ° C. and the blending ratio shown in Table 2 was blended using a tumbler, and a twin-screw extruder (TEM) set at a barrel temperature of 290 ° C. -35B made by Toshiba Machine)
Was kneaded, and the extruded strand was cooled and solidified, and then pelletized. After drying the obtained pellets at 120 ° C. for 4 hours, the pellets were molded with an injection molding machine (IS-50AM: manufactured by Toshiba Machine) at a cylinder temperature of 290 ° C., a mold surface temperature of 100 ° C. and 150 ° C., and an HDT measurement test. Got a piece.
Also, Tg, T _C1 , T _C2 , and Tm were measured according to the method described above.

As a comparative example, the PPS resin alone (Comparative Example 2) was similarly tested (mold surface temperature: 100 ° C. and 150 ° C.). Table 2 shows the results.

[0133]

[Table 2]

As is apparent from the results, in the present invention, the crystallization rate is increased without lowering the melting point, and
Molding is possible at the following mold temperatures, and a molded product having heat resistance equivalent to that of a molded product using a high temperature mold is obtained.

Examples 7 to 9 Linear PPS resins solvent-washed with N-methylpyrrolidone having an MI of 450 g / 10 minutes and a sodium content of 650 ppm as PPS resins (A) were used as piperidine-based compounds (B) and had the following structures. formula

[0136]

Embedded image

And j = 0: 29 wt%, j
= 1: 58 wt%, j = 2: 13 wt%, j = 3: 0w
a mixture of t% and a liquid of piperidine compound (B) at 23 ° C., talc (Micron White 5000 Hayashi Kasei) as a crystal nucleating agent, sodium salt of aromatic phosphorus compound (NA-11 Asahi Denka Co., Ltd.) (Manufactured by Kogyo Co., Ltd.) and blended by using a tumbler with the composition shown in Table 3, and kneaded by a twin-screw extruder (TEM-35B manufactured by Toshiba Machine Co., Ltd.) having a barrel temperature of 290 ° C. After solidification, it was pelletized. After drying the obtained pellets at 120 ° C. for 4 hours, the cylinder temperature was 2 using an injection molding machine (IS-50AM: manufactured by Toshiba Machine).
Molding was performed at 90 ° C., mold surface temperature of 100 ° C. and 150 ° C. to obtain a HDT measurement test piece. Also, Tg, T _C1 , T _C2 , and Tm were measured according to the method described above. The results are shown in Table-3.

[0138]

[Table 3]

As is clear from the results, in the present invention, the crystallization rate is increased without lowering the melting point, and
Molding is possible at the following mold temperatures, and a molded product having heat resistance equivalent to that of a molded product using a high temperature mold is obtained.

Examples 10 to 14 PPS resins were used in the same manner as in Example 1 except that the following compounds were used as the piperidine compound (B).
An experiment was conducted in the same manner as in Example 1 with the formulation shown in. The results are shown in Table-4.

Piperidine compound (B-1) 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, piperidine compound (B-2) 8-acetyl-3dodecyl-7,7,9,9-tetramethyl-1 , 3,8-Triazaspiro (4.5) decane-2,4-dione, piperidine compound (B-3) 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, piperidine compound (B-4) 2 , 2,6,6-Tetramethyl-4-piperidyl methacrylate

[0142]

[Table 4]

As is clear from the results, the composition of the present invention was 1
It can be sufficiently molded at a mold temperature of 00 ° C.

[0144]

The crystallization rate is high and the mold temperature is 120 ° C.
Mold temperature is less than 1
It has the same heat resistance and molded product appearance as a molded product molded by a molding machine at 50 ° C. Therefore, when the composition of the present invention is used, low-temperature molding can be performed, the molding workability is improved, and it is advantageous for the safety of workers.

Claims (4)

[Claims] 1. A polyarylene sulfide resin (A)
And a compound having at least one tetramethylpiperidyl group represented by the following general formula (1) at the molecular end and having a melting point of 100 ° C. or lower, which is a solid or liquid piperidine compound (B) A polyarylene sulfide resin composition for low-temperature molding, comprising: Embedded image (In the above formula, R 1 represents a hydrogen atom, an alkyl group or an acyl group, and X represents Or Wherein R2 represents a lower alkyl group. ) 2. A polyarylene sulfide for low-temperature molding, which further comprises a crystal nucleating agent (C) in addition to the polyarylene sulfide resin (A) and the piperidine compound (B) according to claim 1. Resin composition. 3. A method for molding a polyarylene sulfide resin composition, which comprises subjecting the polyarylene sulfide resin composition according to claim 1 or 2 to injection molding at a mold temperature of less than 120 ° C. 4. A polyarylene sulfide resin molded product obtained by the molding method according to claim 3.