JPH06184434A - Thermoplastic resin composition - Google Patents

Abstract

(57) [Summary] [Structure] Resin compositions 10 to 9 comprising 10 to 100% by weight of an epoxy-modified polyarylene sulfide resin and 90 to 0% by weight of an unmodified polyarylene sulfide resin.
A thermoplastic resin composition containing 0 parts by weight and 90 to 10 parts by weight of a thermoplastic polyamide (the total amount of the resin composition and the thermoplastic polyamide is 100 parts by weight) as essential components. [Effect] Impact resistance, mechanical strength and heat resistance are good and well balanced.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition comprising polyarylene sulfide and a thermoplastic polyamide, and more specifically to a thermoplastic resin composition containing an epoxy-modified polyarylene sulfide and a thermoplastic polyamide as essential components. INDUSTRIAL APPLICABILITY The thermoplastic polyarylene sulfide / polyamide resin composition of the present invention has an excellent balance of impact resistance, mechanical strength and heat resistance, and can be widely used as mechanical parts, automobile parts, electric / electronic parts, structural materials and the like.

[0002]

2. Description of the Related Art Polyphenylene sulfide (hereinafter referred to as
Polyarylene sulfide (hereinafter referred to as "PAS") represented by "PPS" has excellent heat resistance, chemical resistance, solvent resistance and flame retardancy, and is used as various molding materials. , Because it is inferior in impact resistance,
Its use is quite limited. Further, since PAS does not have a polar group, it has a problem of poor compatibility with other engineering plastics and other resins, and even when polymer alloying is performed for the purpose of improving impact resistance, Since the compatibility is poor, there is a problem that it is difficult to obtain a polymer alloy having excellent mechanical properties and well-balanced physical properties.

Many polymer blends with other engineering plastics have been proposed for the purpose of improving the impact resistance and other properties of PAS, and blends with polyamides have also been proposed (JP-A-53-6925).
5 and 59-155462). Further, it has been reported that an epoxy resin is mixed in the composition to enhance the compatibility between PAS and the other resin when blending the other resin (JP-A-59-64657 and 59-59). 155
461 and ibid. 59-155462). These blends are simple blends of unmodified PAS with other polymers, and in such blends the poor compatibility of PAS with other polymers results in satisfactory impact resistance and other properties. Has not been obtained.

[0004]

An object of the present invention is to provide a PAS resin composition having a good balance of impact resistance, mechanical strength and heat resistance by solving the above-mentioned drawbacks of the prior art. There is.

[0005]

The above object is to provide 10 to 90 parts by weight of a PAS resin composition consisting of 10 to 100% by weight of epoxy-modified PAS and 90 to 0% by weight of unmodified PAS and 90 to 10 parts by weight of a thermoplastic polyamide. Is included as an essential component (the total amount of the PAS resin composition and the thermoplastic polyamide is 100 parts by weight).
This is achieved by the AS / polyamide resin composition.

The PAS used for producing the unmodified PAS and the epoxy-modified PAS used in the present invention has a skeleton composed of an arylene sulfide bond represented by the following formula (I), or the arylene sulfide bond (I). As the main component,

[0007]

[Chemical 1]

An ether bond represented by the following formula (II), a sulfone bond represented by the following formula (III), a biphenyl bond represented by the following formula (IV), and a substituted phenyl represented by the following formula (V): Sulfide bond (provided that in the formula (V), R ¹ represents an alkyl, nitro, phenyl, alkoxy, or carboxyl group), and a copolymerization group exemplified by the trifunctional bond represented by the following formula (VI) It contains a bond derived from the combined component as a poor component. However, the copolymerization component is preferably less than 30 mol%.

[0009]

[Chemical 2] The PAS having the skeleton as described above is obtained, for example, by reacting an alkali metal sulfide (typically sodium sulfide) with a dihalide. here,
Examples of the dihalide used as a raw material include dihalogenated benzene represented by the following formula.

[0010]

[Chemical 3] (In the formula, R ² represents an alkyl or alkoxy group having 1 to 3 carbon atoms, n represents an integer of 0 to 3, and X represents a halogen atom).

Specific examples of the dihalogenated benzene include compounds represented by the following formula. However, in these formulas, X ₁ is a halogen atom, and examples thereof include Cl or Br. These dihalogenated benzenes are generally used in the form of a mixture,
It is preferable that the mixed dihalide is contained in the mixture in an amount of 85 mol% or more.

[0012]

[Chemical 4]

In the reaction of the alkali metal sulfide with the dihalide, if necessary, a trihalide such as tolchlorbenzene may be added to the reaction system within a range of 5 mol% or less based on the dihalide. The polymerization reaction may be carried out in a polar solvent, preferably an amide solvent such as N-methyl-2-pyrrolidone (NMP) or dimethylacetamide, or a sulfone solvent such as sulfolane. At this time, in order to control the degree of polymerization, it is desirable to add an alkali metal salt of carboxylic acid or sulfonic acid, alkali hydroxide or the like. The preferred polymerization reaction temperature and time are approximately 120 to 300 ° C. and 2 to 10 hours. It is desirable to carry out the reaction in an inert gas atmosphere. After completion of the reaction, the solid product is filtered off, washed thoroughly with deionized water and dried to obtain a PAS resin.

PAS can be used as an unmodified PAS after being crosslinked to have a high molecular weight by heating after polymerization in an oxygen atmosphere or by adding a crosslinking agent such as peroxide and heating. It is also possible to use it for reaction with an epoxy resin as a raw material for producing epoxy-modified PAS. As the PAS used in the present invention, various types can be widely used as described above, but PAS having a sodium content of 900 ppm or less obtained by deionization treatment can also be used. Examples of the deionization treatment include acid treatment.

A typical method of acid treatment is to immerse PAS in an acid or an aqueous solution thereof. It is also possible to appropriately stir or heat the acid treatment. A specific example of the acid treatment method is a method in which the PAS powder is immersed in an acetic acid aqueous solution having a pH of 4 and stirred for about 30 minutes. The acid-treated PAS needs to be washed several times with water or warm water to remove residual acid or salt. The water used for washing is preferably distilled water or deionized water so as not to impair the denaturing effect of the acid treatment. P
The acid used for the acid treatment of AS is not particularly limited as long as it has no action of decomposing PAS, and specific examples thereof include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid and propionic acid. Of these, acetic acid and hydrochloric acid are preferable, and nitric acid is not preferable because it decomposes and deteriorates PAS.

The epoxy resin used for the modification of PAS in the present invention is not particularly limited as long as it has at least two epoxy groups in the molecule, and specific examples thereof include conjugated or non-conjugated dienes. , Epoxidized compounds such as unsaturated carboxylic acid esters having conjugated or non-conjugated cyclic dienes and conjugated or non-conjugated dienes, aliphatic diols, aliphatic polyhydric alcohols, bisphenols, phenol novolacs and cresol novolacs and epichlorohydrin or β- Examples thereof include a polyglycidyl ether obtained by reacting with methyl epichlorohydrin, and a polyglycidyl ester obtained by reacting a dicarboxylic acid with epichlorohydrin or β-methylepichlorohydrin.

To prepare an epoxy-modified PAS by reacting PAS with an epoxy resin in a polar organic solvent, the PAS and epoxy resin synthesized and polymerized as described above are reacted in a polar organic solvent. Method or PAS
A method is used in which an epoxy resin is added to a solution-type or slurry-type reaction liquid generated during the synthesis (polymerization) of (1) to react.

When PAS obtained by synthesis (polymerization) and purification is reacted with an epoxy resin, the charging ratio of both reaction components is 0.1 parts by weight or more, preferably 1 to 100 parts by weight of PAS, preferably 1 to 100 parts by weight. If the amount of the epoxy resin is less than 0.1 part by weight, the object of the present invention cannot be achieved. When the epoxy resin is added to the solution or slurry reaction liquid generated during the synthesis of PAS and the reaction is performed,
0.01 part by weight or more, preferably 0.1 to 20 parts by weight of an epoxy resin is added to 100 parts by weight of the reaction solution.

In order to add the epoxy resin to the reaction solution formed during the PAS synthesis, the epoxy resin may be added immediately after the PAS synthesis (polymerization) is completed or while the temperature is high, or the synthesis (polymerization) may be performed.
After the completion, the reaction solution may be cooled after a sufficient time and then added. The epoxy resin may be added as it is to the reaction liquid, or may be dissolved in an organic solvent and added as a solution.

The polar organic solvent used as a reaction medium in the reaction between PAS and the epoxy resin is, for example, N-
Methyl-2-pyrrolidone (NMP), dimethylacetamide, dimethylformamide, dimethylsulfoxide may be mentioned. Reaction temperature and reaction time are generally room temperature to 3
00 ° C, preferably 100 ° C to 280 ° C and 10 minutes to
You can choose within a range of 20 hours.

After completion of the reaction, the slurry is filtered, and the obtained cake is washed with a solvent capable of dissolving the epoxy resin such as acetone and NMP to remove the unreacted epoxy resin.
Then it is dried. When the unreacted epoxy resin remains in the washing with the solvent, the dispersibility is deteriorated when melt-kneading with the polyamide resin and the melt fluidity is lowered depending on the epoxy resin used, which is not preferable. In such a case, the object of the present invention cannot be achieved because the impact strength is insufficiently improved, the strength is lowered, or the surface shape of the molded product is inferior. Also, NMP
In the case of washing with a high boiling point organic solvent as described above, it is desirable to further wash with ion-exchanged water or the like in order to facilitate drying.

When carrying out the reaction between PAS and the epoxy resin, if necessary, a curing agent for the epoxy resin or a curing agent for the epoxy resin may be added to the reaction system.
A catalyst that accelerates the reaction between PAS and the epoxy resin may be present. The curing agent is PA according to the reaction according to the invention.
Since it has a function of promoting the bonding between the epoxy resin bonded to S and another epoxy resin, it serves to increase the amount of the epoxy resin bonded to PAS. As a curing agent,
Amines, acid anhydrides, imidazoles, polysulfides, phenol resins and the like which are generally used as a curing agent for epoxy resins can be added. A curing accelerator may be used in combination with these curing agents. Tertiary amines and phosphines are preferably used as catalysts for promoting the reaction between PAS and epoxy resin. Specific examples thereof include triethylamine, tributylamine, dimethylbenzylamine, tris (dimethylaminomethyl) phenol, tributylphosphine, triphenylphosphine and the like.

The modified PAS obtained by the method of the present invention preferably has a weight average molecular weight of 5,000 to 100,000. When PAS is reacted with an epoxy resin according to the present invention, the terminal glycidyl group of the epoxy resin becomes PA.
It is considered that S reacts with -SH and / or -SNa of S to bond, and the hydroxyl group generated by this bond may react with a glycidyl group of another epoxy resin. Thus, the modified P having an epoxy resin addition rate of 0.1 to 10% by weight, preferably 2 to 8% by weight.
AS is obtained. If the addition rate is less than 0.1% by weight, the effect of the present invention cannot be obtained, and if it exceeds 10% by weight, the melt viscosity of PAS is remarkably increased, and it becomes difficult to knead with the polyamide resin, or the dispersibility is improved. It gets worse.

In the thermoplastic resin composition of the present invention,
As the PAS resin, a composition comprising 0 to 90% by weight of unmodified PAS and 100 to 10% by weight of epoxy modified PAS is used. If the proportion of unmodified PAS exceeds 90% by weight and the proportion of epoxy modified PAS is less than 10% by weight, PA
The affinity between the S resin and the thermoplastic polyamide becomes insufficient, and it becomes difficult to obtain high impact strength.

The thermoplastic polyamide used in the present invention is not particularly limited as long as it has a terminal amino group. Examples of the polyamide having an amino group at the terminal include aliphatic polyamide and aromatic polyamide, and aliphatic polyamide is preferable. Polyamide having an amino group at the terminal is, for example, terephthalic acid,
Dicarboxylic acids such as isophthalic acid, adipic acid, sebacic acid, and 1,4-cyclohexyldicarboxylic acid, and ethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine, 1,4-cyclohexyldiamine, and meta-xylylenediamine. Polycondensation with such diamines: Polymerization of cyclic lactams such as caprolactam, laurolactam: Polycondensation of aminocarboxylic acids such as aminoenanthic acid, aminononanoic acid, aminoundecanoic acid, or the above cyclic lactams, dicarboxylic acids and diamines It can be obtained by copolymerization of Specific examples of the polyamide having an amino group at the terminal include nylon 6, nylon 66, and aliphatic polyamide.
Examples thereof include nylon 610, nylon 612, nylon 11 and nylon 12, and those exemplified here are preferably used, but other amorphous nylon, copolymer nylon, etc. can also be used.

The ratio of the PAS resin composition consisting of unmodified PAS and epoxy modified PAS to the thermoplastic polyamide is 10 to 90% by weight for the former and 90 to 10% by weight for the latter. When the proportion of the PAS resin composition is less than 10% by weight, the high heat resistance, chemical resistance and rigidity inherent in the PAS resin are insufficient, and conversely, when the thermoplastic polyamide is less than 10% by weight, high impact resistance is obtained. Can't get

The PAS / polyamide resin composition of the present invention has various properties depending on its application.
An appropriate amount of fibrous or particulate filler can be blended. Examples of such fillers include glass fibers, carbon fibers, metal fibers, aramid fibers, fibrous potassium titanate, asbestos and fibrous inorganic and organic fillers such as various whiskers such as silicon carbide and silicon nitride. , Graphite, calcium carbonate, mica, silica,
Boron Nitride, Barium Sulfate, Calcium Sulfate, Kaolin, Clay, Vylophyllite, Bentonite, Sericite, Zeolite, Mica, Nepheline Cinite, Ferrite, Attapulgite, Wollastonite, Calcium Silicate, Magnesium Carbonate, Dolomite, Antimony Trioxide Inorganic particulate fillers such as magnesium oxide, zinc oxide, titanium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass powder, glass beads, quartz, quartz glass, iron, zinc, copper, aluminum and nickel. To be
These fillers may be used alone or in combination of two or more.

The thermoplastic PAS / polyamide resin composition of the present invention can be used as a blend with various resins and elastomers. Specific examples of the resin and elastomer to be blended include ethylene, propylene, butylene, pentene, butadiene, isoprene, chloroprene, styrene, α-methylstyrene, vinyl acetate, vinyl chloride, acrylic acid ester, and (meth) acrylonitrile alone. Polymer and copolymer, polyester, polyurethane, polyacetal, polycarbonate, polysulfone, polyallylsulfone, polyethersulfone, polyarylate, polyphenylene oxide,
Homopolymers such as polyether ether ketone, polyimide, silicone resin, phenoxy resin, fluororesin, polyaryl ether, and polysulfide, random copolymers, block copolymers, graft copolymers, and polyamides and elastomers other than the above. To be Also,
It is also possible to blend a polyamide elastomer.
To mix these resins and elastomers, use PA
A method of dissolving and mixing S in the same solvent common to S and these resins or elastomers, and a method of mixing using a melt kneader such as an extruder are adopted.

The resin composition of the present invention further includes a heat stabilizer, an ultraviolet absorber, a foaming agent, a flame retardant, a colorant, a release agent, a gas adsorbent, etc. within a range not hindering the achievement of the object of the present invention. Can be added.

The resin composition of the present invention is generally in the form of pellets and is mainly used as a molding raw material for injection molding and injection molding. The method for producing pellets is not particularly limited, but epoxy modified PAS, unmodified PAS, thermoplastic polyamide, and if necessary, other fillers, additives, etc. may be added to a tumbler mixer, ribbon blender, Henschel mixer, After dry blending using a V blender or the like, the mixture is melt-kneaded using a kneader, Banbury mixer, single-screw or twin-screw extruder, extruded, and cut into pellets. For melt kneading,
Particularly, single-screw and twin-screw extruders having a large kneading force are preferable.
In this case, the melt-kneading temperature is 275 ° C. or higher, preferably 2
85-340 degreeC.

[0031]

EXAMPLES Specific examples of the epoxy-modified PAS and examples of the resin composition of the present invention will be described below. Reference Example 1 (Preparation of epoxy-modified PPS) PPS (T-2 manufactured by Topren Co., Ltd.) was treated with an acid to obtain a Na ion content of 20.
8.0 ppm of 0 ppm PPS and 0.80 kg of epoxy resin (Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) were added to 2 kg in 72 kg of N-methyl-2-pyrrolidone (NMP).
The reaction was carried out at 40 ° C for 3 hours. After the reaction, it was cooled to 100 ° C. and then filtered. The obtained cake was washed with acetone and vacuum dried at 150 ° C to obtain an epoxy-modified PPS.

When the IR spectrum of the obtained product was measured by the film method, the absorption due to the epoxy resin was 2980, 1520, 1260, 960, 570 cm.
^It was found near ^-1 .

Addition rate of epoxy resin of the obtained product [(weight of combined epoxy resin / weight of PPS resin) × 1
00 (%)] was determined from the IR spectrum as follows. Using a calibration curve prepared in advance by blending PPS before reaction used for modification and epoxy resin used for modification at various ratios, the absorbance at 1520 cm ^-1 based on epoxy resin and 1580 cm ^-1 based on PPS was used. The addition rate was calculated from the ratio. The addition rate was 3.2%.

Examples 1 and 2 and Comparative Examples 1 and 2 The components shown below were uniformly premixed in the proportions (% by weight) shown in Table 1, and then 300 ° C. and 400 rpm using a counter-rotating 20 mmφ twin-screw extruder. Were melt-kneaded to obtain pellets. Epoxy-modified PPS: the one prepared in Reference Example 1. Unmodified PPS: T-4AG manufactured by Topren Co., Ltd. Thermoplastic polyamide: Nylon 6 (manufactured by EMS, trade name A28). The above pellets were injection molded and the mechanical properties were evaluated at 23 ° C according to the following method. The results are shown in Table 1. Tensile breaking strength, tensile breaking elongation JIS K7113 Flexural modulus, bending strength JIS K7203 Izod impact strength JIS K7110

[0035]

[Table 1]

[0036]

EFFECTS OF THE INVENTION The thermoplastic PAS / polyamide resin composition of the present invention has excellent impact resistance and mechanical properties while maintaining the good properties inherent to PAS resins such as heat resistance and chemical resistance. . Therefore, molded articles obtained from the resin composition of the present invention are particularly useful as automobile parts, electric / electronic parts, structural materials and the like.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tadao Ikeda 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Tonen Research Institute

Claims (1)

[Claims] 1. 10 to 90 parts by weight of a polyarylene sulfide composition consisting of 10 to 100% by weight of an epoxy-modified polyarylene sulfide and 90 to 0% by weight of an unmodified polyarylene sulfide, and a thermoplastic polyamide 90.
10 to 10 parts by weight as an essential component (the total of the polyarylene sulfide composition and the thermoplastic polyamide is 1
It is 00 parts by weight. ) The thermoplastic resin composition characterized by the above.