JPH07276414A - Molding method of polyarylene sulfide resin composite - Google Patents

Abstract

PURPOSE:To enable molding to be performed even in low temperature by injecting a resin composite containing an imide compound in a specific amount that is selected from a group consisting of bisimide or the like and the metallic salt thereof relative to polyarylene sulfide resin. CONSTITUTION:To polyarylene sulfide resin of 100 pts.wt. a resin composite is injection-molded which contains one or two or more imide compound of 0.1-100 pts.wt. selected from bisimide or the like and metallic salt thereof represented by following formula. In the formula, R<1>, R<2> represent 4-22C alkyl group or alkenyl group respectively, and 4-6C cycloalkyl group or the like and A<1>, A<2> represents a single bond or a phenylene group. The resin temperature in injection molding is preferred to be 280-400 deg.C, and the injection pressure is to be 500-1300kg/cm<2>, and the injection is carried out at high pressure and high speed, resulting in obtaining a molded item with uniformity and fine luster, on the contrary, at low pressure and low speed, resulting in obtaining a molded item with small warpages or flashes.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for molding a polyarylene sulfide (PAS) resin composition with a low temperature mold.

[0002]

2. Description of the Related Art In recent years, as the demand for higher performance of plastic materials has increased, PAS, which is excellent in heat resistance, mechanical characteristics and chemical resistance, has been attracting attention, and automobile parts, precision mechanical parts, electrical / electrical parts, etc.
Applications are expanding to electronic parts.

PAS is a crystalline engineering plastic, but since it has a slow crystallization rate, it requires a high mold temperature of about 130 ° C. and a long mold temperature to obtain a resin having practically sufficient mechanical strength in injection molding. Cooling time was required. This is a major problem in expanding the applications of PAS, and it is desired that molding can be performed in a short time at a mold temperature of 100 ° C. or less, which is a processing condition, by a general-purpose resin molding machine.

In order to solve this problem, for example, a fatty acid ester (JP-A-4-154867) or an aromatic sulfonamide (JP-A-5-59279) is added to improve the mold releasability from the mold. And a method of accelerating crystallization by adding a modified polyalkylene glycol (JP-A-3-250049) or an organic phosphate metal salt (JP-A-2-142854).

However, in these methods, since the heat resistance of the resin composition is insufficient, the desired effect cannot be obtained, and the mechanical strength and the heat resistance are improved even if the releasability and the appearance are improved. There are problems such as damage.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a novel and useful molding method of a polyarylene sulfide resin composition which can be used even at a low temperature without deteriorating the mechanical properties and heat resistance inherent to polyarylene sulfide. With the goal.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that by using a polyarylene sulfide resin composition containing a specific imide compound, the mold temperature It was found that a molded product having the original mechanical strength and heat resistance of polyarylene sulfide can be obtained even at 100 ° C or lower, and the present invention has been completed based on such findings.

That is, the molding method of the polyarylene sulfide resin composition according to the present invention is based on 100 parts by weight of the polyarylene sulfide resin, the bisimide represented by the general formula (1), the general formula (4) or the general formula (4). 1 selected from the group consisting of monoimides represented by 5) and their metal salts
It is characterized in that a resin composition containing 0.1 to 100 parts by weight of one kind or two or more kinds of imide compounds (hereinafter referred to as "this imide compound") is injection-molded.

[0009]

[Chemical 6] [In the formula, R ¹ and R ² are the same or different and have 4 to 22 carbon atoms.
Represents an alkyl group or an alkenyl group, a cycloalkyl group having 4 to 6 carbon atoms, or a group represented by the general formula (2) or the general formula (3). A ¹ and A ² are the same or different and each represents a single bond or a phenylene group. ]

[0010]

[Chemical 7] [In the formula, R ³ represents an alkyl group having 1 to 22 carbon atoms. R ⁴
Represents a single bond or an alkylene group having 1 to 2 carbon atoms. a represents the integer of 1-2. ]

[0011]

[Chemical 8] [In the formula, R ⁵ represents an alkyl group having 1 to 22 carbon atoms. R ⁶
Represents a single bond or an alkylene group having 1 to 2 carbon atoms. b represents an integer of 0 to 2. ]

[0012]

[Chemical 9] [In the formula, when X is NH-A ⁴ -R ⁸ , Y represents a hydroxyl group,
Y is X when the NH-A ⁴ -R ⁸ represents a hydroxyl group. R ⁷ , R ⁸
Are synonymous with R ¹ in the general formula (1) and may be the same or different. A ³ and A ⁴ are the same or different and each represents a single bond or a phenylene group. ]

[0013]

[Chemical 10] [In the formula, R ⁹ and R ¹⁰ are the same or different and have 4 to 2 carbon atoms.
2 represents an alkyl group or an alkenyl group. A ⁵ and A ⁶ are the same or different and each represents a single bond or a phenylene group. ]

The imide compound is, for example, 1, 2, 3,
4-butanetetracarboxylic acid (hereinafter abbreviated as "BTC") or its monoanhydride or dianhydride (hereinafter "BT")
Collectively referred to as "C type". ) And an aliphatic primary amine, alicyclic primary amine or aromatic primary amine having a predetermined structure by dehydration condensation or by a decarboxylation reaction of the amine with an isocyanate derivative.

The dehydration reaction is most preferably industrially carried out by heating, but a dehydrating reagent such as acetic anhydride-pyridine or carbodiimide may be used if necessary.

Examples of the aliphatic primary amine include saturated and unsaturated linear and branched aliphatic amines.
This thing may have an aromatic ring.

Examples of the aliphatic amine include butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecyl. Examples include amines, hexadecylamine, heptadecylamine, octadecylamine, octadecenylamine, nonadecylamine, eicosylamine, henecoicylamine, docosylamine, benzylamine, among which decylamine, dodecylamine, tetradecylamine, hexadecylamine. , Octadecylamine is recommended.

Further, it is possible to use a mixture containing substantially these amines, that is, a natural amine such as palm amine, tallow amine, fish oil amine, hydrogenated palm amine, hydrogenated tallow amine, and hydrogenated fish oil amine. It is economically meaningful.

Specific examples of the alicyclic primary amine include cyclobutylamine, cyclopentylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexylethylamine, methylcyclohexylamine, dimethimecyclohexylamine and the like.

Specific examples of aromatic primary amines include allylaniline, butylaniline, pentylaniline, hexylaniline, heptylaniline, octylaniline, nonylaniline, decylaniline, undecylaniline, dodecylaniline, tridecylaniline, tetra. Decylaniline, pentadecylaniline, hexadecylaniline, heptadecylaniline, octadecylaniline, nonadecylaniline, eicosylaniline, heneicosylaniline, docosylaniline, and the like, among which decylaniline, dodecylaniline, tetradecylaniline, Hexadecylaniline and octadecylaniline are recommended.

The imide compound of the present invention is an intermediate partial ester or total ester of BTC and a lower alcohol (methyl alcohol, butyl alcohol, etc.), or an acid chloride with a chlorinating reagent such as thionyl chloride, phosgene and chlorine. It is also prepared by reacting the amine in a substantially dehydrated form of BTC such as.

Among the present imide compounds, the imide compound containing a carboxyl group has an increased affinity with the mold and an increased external lubricity. Specifically, a carboxyl group formed by an amic acid of BTCs and an aliphatic amine is effective. Therefore, the dehydration reaction between the BTCs and the aliphatic amine may be suppressed and the carboxyl group may remain if necessary.
The remaining carboxyl group may be used as it is, or may be in the form of a metallic soap such as sodium, potassium, calcium, magnesium, barium, zinc or aluminum. It is also possible to add an excess of an aliphatic amine to dehydrate amidate and block the carboxyl group.

In using the imide compound, the chain length of the alkyl group or alkenyl group is appropriately selected according to the intended effect. That is, the carbon number is generally 4 to 1
The present imide compound having a group having a chain length of 8 is often effective in reducing melt viscosity and promoting nucleation, and has 1 carbon atom.
The imide compound of 8 to 28 often functions as an external lubricant.

These imide compounds of the present invention may be used alone or may be appropriately mixed depending on desired physical properties. In some cases, it may be added in the form of a mixed imide compound.

The PAS used in the present invention is mainly (-
A polymer containing a repeating unit represented by Ph-S-) in an amount of 70 mol% or more, more preferably 90 mol% or more,
Particularly, polyphenylene sulfide (PPS) is preferably used.

The PPS is not particularly limited as long as it is produced by a generally known method. For example, a relatively low molecular weight polymer disclosed in JP-A-45-3368, which is prepared in an oxygen atmosphere, is used. And a polymer which has been made into a high-molecular-weight polymer by heating it at room temperature or by crosslinking with a peroxide.
The essentially linear, relatively high molecular weight polymers obtained by the method of 40 can be used.

Further, 30 mol% or less as a copolymerization component,
If it is preferably 10 mol% or less, a copolymer with another repeating unit can be used.

Examples of the above-mentioned other repeating units include orthophenylene sulfide, metaphenylene sulfide, diphenyl sulfide ether, diphenyl sulfide sulfone, diphenylene sulfide ketone, biphenylene sulfide, naphthalene sulfide, diphenylene sulfide methane, diphenylene sulfide propane. Examples thereof include trifunctional phenylene sulfide and substituted phenylene sulfide (as a substituent, an alkyl group, a nitro group, a phenyl group, a carboxylic acid group, an alkoxy group, an amino group, etc.) and the like.

The melt viscosity of PPS is not particularly limited as long as it can be injection-molded, but is usually 10 to 1
00000 poise (300 ° C., shear rate 10 ³ / sec),
It is preferably about 100 to 50,000 poise.

The amount of the imide compound to be mixed with PAS is 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight, based on 100 parts by weight of PAS. Further, in order to use it as a low viscosity agent or a crystallization accelerator, it is desirable to add it in an amount of 1 to 20 parts by weight. If the addition amount is 0.1 parts by weight or less, the characteristics are not improved so much, and if the addition amount is 100 parts by weight or more, the heat resistance required for the resin may be impaired.

In the resin composition used in the present invention, if necessary, a crystal nucleating agent, a reinforcing agent, a filler, an antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant, a modifier, and the like. Lubricants and the like can also be added.

When a crystal nucleating agent is used in combination, the crystallization speed is further increased, so that favorable results are often obtained. As such a crystal nucleating agent, a known inorganic nucleating agent or organic nucleating agent can be used.

As the inorganic nucleating agent, talc, mica, silica, kaolin, clay, attapulcite, romite powder, quartz powder, zinc white, diatomaceous earth, montmorillonite,
Permiculite, amorphous silica, glass powder, silica-alumina, wollastonite, hytron, boron,
Silicates such as nitrite, carbon black, pyroferrite, graphite, zinc sulfide, boron nitride, silicon resin powder, calcium, magnesium, aluminum, lithium, barium, titanium, sulfates, carbonates, phosphates, aluminates , Oxides, and the like.

Examples of the organic nucleating agent include aliphatic carboxylic acid metal salts, aromatic carboxylic acid metal salts such as benzoic acid and terephthalic acid, aromatic phosphonic acid and metal salts, aromatic phosphoric acid metal salts, benzenesulfonic acid, Crystallinity of aromatic sulfonic acid metal salt such as naphthalene sulfonic acid, β-diketone metal salt, polymer compound having carboxyl group metal salt, parahydroxyl benzoate ester, 4,6 nylon, polyphenylene sulfide ketone, etc. Polymer fine powder and the like are exemplified.

A filler may be added as a reinforcing agent or for increasing the volume.

The filler is not particularly limited, and as filler for reinforcement, carbon black, calcium carbonate, magnesium carbonate, barium sulfate, kaolin, calcined clay, talc, aluminum silicate, calcium silicate, silica. Acid, carbon fiber, glass fiber, asbestos fiber, carbon fiber, silica fiber, zirconia fiber,
Examples include aramid fiber, potassium titanate fiber and metal fiber.

When using these fillers, it is desirable to use a surface treatment agent and a sizing agent if necessary. As such a surface treating agent and a sizing agent, a silane compound, an epoxy compound, an isocyanate compound or the like is used.

In addition, antioxidants such as hindered amine compounds, benzophenone compounds and benzotriazole compounds, and additives such as pigments, dyes, antistatic agents, lubricants and release agents can be optionally contained.

Further, within a range not impairing the object of the present invention,
Other thermoplastic resins such as polyethylene, polypropylene, polybutene, polystyrene, polyphenylene ether, polyether sulfone, polyether ether ketone, polyphenylene oxide, polyoxymethylene,
Aromatic polyamides such as PTFE, maleimide-modified ABS, chlorinated PVC, terephthalic acid and aliphatic diamines or xylylenediamine and aliphatic dicarboxylic acids, 6 nylon, 6,6 nylon, 4,6 nylon, 11 nylon,
It is also possible to add aliphatic polyamide such as 12 nylon, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyarylate, liquid crystal polymer, polyamide imide, polyether imide, and polyimide.

The PAS resin composition according to the present invention can be prepared by a known method. For example, a method of directly adding the imide compound to PAS resin powder, a method of dissolving in xylene, dimethylformamide or the like and mixing with PAS resin powder and drying, a method of adding to a slurry after polymerization of PAS, a glass fiber, etc. A reinforcing agent, a filler such as calcium carbonate, and other various additives used as necessary are uniformly mixed with a V-blender, a ribbon blender, a Henschel mixer, a tumbler blender, and the like, and then a Banbury mixer, a kneader, an oven roll, a single mixer. There is a method of heating, melting and kneading with a single screw extruder, a twin screw extruder, a single reciprocating screw and the like to obtain pellets, and the method of melt kneading into pellets is recommended. At this time, there is also a method of kneading only the necessary components into a masterbatch.

The kneading temperature is equal to or higher than the melting point of the target PAS resin. For example, in the case of PPS resin, it is usually 280 to 280.
It is preferable to carry out at 400 ° C., and if the temperature is 280 ° C. or lower, the dissolution of the resin becomes insufficient, and if it is 400 ° C. or higher, smoke is generated due to decomposition of the additive, which is not preferable.

A method for obtaining a molded article from the resin composition obtained by the above method can be carried out by a known method.

The injection molding machine is a screw in-line type,
Any plunger type is possible, and it is preferable that the molding machine capacity and the injection amount are the same in order to avoid excessive heat history. The screw is preferably a wear resistant material.

The resin pellets used for molding are 120 to 1
Preliminary drying at 60 ° C. for 2 to 6 hours is desirable, and appearance defects such as silver streaks and cloudiness are less likely to occur.

The resin temperature during injection molding is 280 to 40.
0 degreeC, especially about 290-360 degreeC are preferable.

The mold temperature is, for example, 0 to 100 ° C., and particularly 40 to 80 ° C. is recommended. However, injection molding can also be performed at a mold temperature of 100 ° C. or higher. When the heat resistance of the molded product is important, the mold temperature is high, and when the dimensional accuracy is important, the mold temperature is low.

The injection pressure is preferably 500~1300kg / cm ^2, high pressure, easier gloss good molded article with uniform can be obtained is performed at a high speed, low pressure, performed at a low speed when the low molding of warpage or burrs Easy to get goods.

The rotation speed of the screw is about 10 to 300 rotations, preferably about 40 to 200 rotations.

When it is desired to increase the molding cycle, it is preferable to increase the rotation speed, but it is not preferable to increase the rotation speed more than necessary because it causes cutting of the glass fiber and heat generation of the resin.

The PAS resin composition according to the present invention has a high crystallization rate and can be molded at a wide mold temperature from low temperature to high temperature, and the obtained molded product has a good appearance and less burr. Because of its small dimensional shrinkage and excellent mechanical strength, it can be used as a material for various molded products, such as electrical and electronic equipment parts,
Suitable for automotive parts and chemical parts materials.

[0051]

EXAMPLES The present invention is described in detail below with reference to examples. The mechanical properties of the PPS resin composition were evaluated by the following methods.

A composition prepared by preliminarily mixing predetermined resin composition components with a Henschel mixer and further mixing 65 parts by weight of commercially available glass fiber is melt-kneaded with an extruder having a cylinder temperature of 310 ° C. to obtain a PPS resin composition. Get a pellet of the product.
Next, injection molding is performed at a cylinder temperature of 310 ° C. and a mold temperature of 70 ° C. The tensile strength, bending strength and Izod impact strength of the test piece thus obtained are measured by the following methods.

Tensile Strength According to ASTM-D68.

Bending Strength of Molded Article According to ASTM-D790.

Izod impact strength of molded product According to ASTM-D256.

Production Example 1 650 g of sodium sulfide 2.9 hydrate in an autoclave
(5.0 mol) and N-methylpyrrolidone (NMP) 18
Charge 00g, raise the temperature to 205 ° C, distillate water approx. 150
g was removed. Next, 720 g of p-dichlorobenzene
(4.85 mol) and 400 g of NMP are added, and 250 degreeC is added.
And reacted for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, the product was filtered off, and the washing with warm water was repeated.
After drying at 0 ° C for one day, a PPS resin (PPS-1) having a melt viscosity of 300 poise was obtained.

Production Example 2 PPS-1 having a melt viscosity of 2500 poise was thermally crosslinked by treating "PPS-1" in air at 260 ° C for 5 hours.
Resin (PPS-2) was obtained.

Production Example 3 Sodium sulfide 2.9 hydrate 650 was placed in an autoclave.
g (5.0 mol), 210 g (5.0 mol) of lithium chloride and 1800 g of NMP were charged and the temperature was raised to 205 ° C. to remove about 140 g of distilled water. Next, 720 g (4.85 mol) of p-dichlorobenzene and 400 g of NMP.
Was added and reacted at 250 ° C. for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, the product was separated by filtration, washed with warm water repeatedly, and then dried at 100 ° C. for one day and a melt viscosity of 1800.
A Poise PPS resin (PPS-3) was obtained.

Production Example 4 19.8 g (0.1 mol) of BTC dianhydride and 53.8 g (0.2 mol) of tallow amine were mixed and stirred in xylene, and the temperature was raised. Xylene was also removed while separating and removing the produced water, and finally heated to 260 ° C., and the reaction was continued until the produced water reached 3.6 g. After the reaction was completed, the mixture was neutralized with an aqueous potassium hydroxide solution, treated with clay and filtered, and the remaining xylene was topped to prepare an imide compound (this imide A).

Production Example 5 Using 19.8 g (0.1 mol) of BTC dianhydride, 34.0 g (0.2 mol) of laurylamine and xylene, 3.0 g of produced water was distilled off to complete the reaction. did. After completion of the reaction, a monoimide compound (present imide B) in which xylene is topped as it is to partially leave a carboxyl group.
It was created.

Production Example 6 23.4 g (0.1 mol) of BTC and laurylamine 3
The reaction was terminated by using 4.0 g (0.2 mol) and xylene and distilling 5.4 g of produced water. After completion of the reaction, it is neutralized with sodium hydroxide, and xylene is topped as it is to form an imide compound containing a carboxylate (this imide C).
It was created.

Production Example 7 Using 23.4 g (0.1 mol) of BTC, 52.2 g (0.2 mol) of paradodecylaniline and xylene, 7.2 g of produced water was distilled off to complete the reaction. After the reaction,
It was neutralized with calcium hydroxide, and xylene was topped as it was to prepare a diimide compound (present imide D).

Examples 1 to 5 PPS resin compositions were prepared by blending the specified PPS resin, the present imide compound and, if necessary, talc, and the tensile strength, bending strength and Izod impact strength of the molded products were measured. did. The results obtained are shown in Table 1.

Comparative Example 1 The tensile strength, bending strength and Izod impact strength of a molded product of "PPS-1" itself were measured. The results obtained are shown in Table 1.

Comparative Example 2 PPS was prepared in the same manner as in Example 2 except that ethylene bis-stearamide (EBS) was used in place of the “present imide B”.
A resin composition was prepared, and the tensile strength, bending strength and Izod impact strength of the molded product were measured. The results obtained are shown in Table 1.

Comparative Example 3 A PPS resin composition was prepared in the same manner as in Example 3 except that "this imide A" was not used, and the tensile strength, bending strength and Izod impact strength of the molded product were measured. The results obtained are shown in Table 1.

[0067]

By applying the method according to the present invention, molding can be carried out at low temperature without impairing the mechanical properties and heat resistance inherent to polyarylene sulfide.

[Table 1]

Claims (3)

[Claims] 1. A group consisting of a bisimide represented by the general formula (1), a monoimide represented by the general formula (4) or the general formula (5), and a metal salt thereof based on 100 parts by weight of a polyarylene sulfide resin. A method for molding a polyarylene sulfide resin composition, which comprises subjecting a resin composition containing 0.1 to 100 parts by weight of one or more imide compounds selected from the following to injection molding. [Chemical 1] [In the formula, R ¹ and R ² are the same or different and have 4 to 22 carbon atoms.
Represents an alkyl group or an alkenyl group, a cycloalkyl group having 4 to 6 carbon atoms, or a group represented by the general formula (2) or the general formula (3). A ¹ and A ² are the same or different and each represents a single bond or a phenylene group. ] [Chemical 2] [In the formula, R ³ represents an alkyl group having 1 to 22 carbon atoms. R ⁴
Represents a single bond or an alkylene group having 1 to 2 carbon atoms. a represents the integer of 1-2. ] [Chemical 3] [In the formula, R ⁵ represents an alkyl group having 1 to 22 carbon atoms. R ⁶
Represents a single bond or an alkylene group having 1 to 2 carbon atoms. b represents an integer of 0 to 2. ] [Chemical 4] [In the formula, when X is NH-A ⁴ -R ⁸ , Y represents a hydroxyl group,
Y is X when the NH-A ⁴ -R ⁸ represents a hydroxyl group. R ⁷ , R ⁸
Are synonymous with R ¹ in the general formula (1) and may be the same or different. A ³ and A ⁴ are the same or different and each represents a single bond or a phenylene group. ] [Chemical 5] [In the formula, R ⁹ and R ¹⁰ are the same or different and have 4 to 2 carbon atoms.
2 represents an alkyl group or an alkenyl group. A ⁵ and A ⁶ are the same or different and each represents a single bond or a phenylene group. ] 2. The method for molding a polyarylene sulfide resin composition according to claim 1, wherein the mold temperature is 0 to 100 ° C. 3. The method for molding a polyarylene sulfide resin composition according to claim 1, wherein the polyarylene sulfide resin composition is a polyphenylene sulfide resin composition.