JPH06207103A - Heat-resistant polyarylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To provide a composition comprising a polyarylene sulfide resin, a polyamide resin, a copper iodide, a specific compound, a fibrous filler. etc., in a specified ratio, excellent in mechanical physical properties, heat-resistant stability and useful for electric and electronic parts, etc. CONSTITUTION:The composition comprises (A) 97-50 pts.wt. of a polyarylene sulfide resin, (B) 3-50 pts.wt. of a polyamide, the total amount of the components A and B being 100 pts.wt., (C) 0.002-0.5 pt.wt. of a copper iodide, (D) 0.002-10 pts.wt. of a kind or more of compounds selected from an amino alkoxysilane compound of the formula (R is 1-8C alkylene; R<1>, R<2> are 1-6C alkyl; l is 1-2; n is 1-3; m is 0-2; l+m+n=4), (ii) a compound having two or more of epoxy groups in the molecule, and (iii) a compound having a carbon double bond and an epoxy group in the molecule, and (E) 0-400 pts.wt. of one kind or more of fillers selected from a fibrous filler, a particulate filler, a plate-like filler, and a hollow filler.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyarylene sulfide resin composition having improved thermal stability and a method for producing the same. More specifically, it relates to a polyarylene sulfide resin composition having excellent heat resistance stability, which is obtained by blending a copper iodide and a specific silane or epoxy compound with a resin composed of a polyarylene sulfide resin and a polyamide resin.

[0002]

2. Description of the Related Art In recent years,
Electrical and electronic equipment parts materials, automobile equipment parts materials, chemical equipment parts materials, etc. are required to have excellent mechanical properties, high heat resistance, chemical resistance, and flame-retardant thermoplastic resin. Is coming. Polyarylene sulfide resins typified by polyphenylene sulfide are also one of the resins that meet this demand, and the demand for them is growing because of their good cost-property ratio. However, the resin has a serious drawback that it is poor in toughness and fragile as compared with engineering plastics such as nylon, polycarbonate, polyacetal, polybutylene terephthalate and the like. As a means to solve this problem,
In general, many blends of various thermoplastic resins having excellent toughness have been proposed. Among them, polyamide resin is a promising blended resin for improving various physical properties, especially toughness, but polyarylene sulfide resin is a polyamide-based resin. The composition containing is not sufficiently stable against heat, and there is a drawback that the mechanical properties are greatly deteriorated especially when exposed to high temperature for a long time.
The improvement is an important issue.

[0003]

In view of the above-mentioned problems, the present inventors diligently studied a polyarylene sulfide resin composition having high toughness and good heat stability and a method for producing the same. As a result, a polyamide resin having high toughness is blended with the polyarylene sulfide resin, and further, a copper iodide and a specific silane compound or an epoxy compound are blended together, and by melt kneading, mechanical properties such as toughness are obtained. It was found that the present invention is excellent, and the heat resistance stability is remarkably improved, and the deterioration of physical properties due to deterioration at high temperature and for a long time is suppressed, and the present invention has been completed. That is, the present invention relates to a resin component comprising (A) 97 to 50 parts by weight of a polyarylene sulfide resin and (B) 3 to 50 parts by weight of a polyamide resin.
0.002 to 0.5 part by weight of (C) copper iodide to 0.00 part by weight of (D) 0.002 to 10 parts by weight of at least one compound selected from a), b), and c) below, a) Aminoalkoxysilane compound represented by the general formula (1)

[0004]

[Chemical 2]

(However, -R- is an alkylene group having 1 to 8 carbon atoms, -R ¹ and -R ² are alkyl groups having 1 to 6 carbon atoms, and l = 1 to 1
2, n = 1 to 3, m is 0 to 2, l + m + n = 4) b) A compound having two or more epoxy groups in the molecule c) A compound having a carbon double bond and an epoxy group in the molecule (E ) A heat-resistant polyarylene sulfide resin, characterized in that it contains 0 to 400 parts by weight of any one selected from fibrous fillers, particulate fillers, plate-shaped fillers and hollow fillers, or a mixture thereof. It is a composition.

The polyarylene sulfide (hereinafter referred to as PAS) resin as the component (A) in the composition of the present invention is composed mainly of repeating units-(-Ar-S-)-(where Ar is an arylene group). It is a thing. Arylene group (-Ar
-) Is, for example, p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group, p, p'-
Diphenylene sulfone group, p, p'-biphenylene group, p,
Examples thereof include p'-diphenylene ether group, p, p'-diphenylene carbonyl group and naphthalene group. In this case, in the arylene sulfide group composed of the above-mentioned arylene group, a polymer using the same repeating unit, that is, a homopolymer can be used, and in view of processability of the composition, different repeating units are used. In some cases, included copolymers are preferred. As the homopolymer, those having a p-phenylene sulfide group as a repeating unit, which uses a p-phenylene group as an arylene group, are particularly preferably used. Further, as the copolymer, a combination of two or more different arylene sulfide groups consisting of the above-mentioned arylene groups can be used, but among them, p-phenylene sulfide groups are 60 mol% or more, more preferably
Those containing 70 mol% or more are suitable from the viewpoint of physical properties such as heat resistance, moldability and mechanical properties. In this case, the repeating units of the components contained in the block form rather than the random form (for example, those described in JP-A-61-14228) have good processability, heat resistance and mechanical properties. It has excellent physical properties and can be preferably used. The PAS resin as the component (A) used in the present invention is preferably a high molecular weight polymer having a substantially linear molecular structure obtained by polycondensation from a monomer having a bifunctional monomer as a main component,
A polymer having a relatively low molecular weight linear polymer whose melt viscosity is increased by oxidative crosslinking or thermal crosslinking to improve molding processability can also be used. The PAS resin of the present invention may be a polyarylene sulfide resin having a branched or crosslinked structure obtained by polymerizing a small amount of a monomer having three or more functional groups as a part of the monomer, or a linear arylene sulfide resin having the above-mentioned linear structure. A compounded resin blended with a polymer can also be used and is preferable.

As the polyamide resin as the component (B) of the present invention, various well-known polyamide resins can be mentioned. For example, oxalic acid, adipic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dicarboxylic acids such as 1,4-cyclohexyldicarboxylic acid and ethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine, 1,4- Polyamide resin obtained by polycondensation with diamine such as cyclohexyldiamine and m-xylylenediamine; polyamide resin obtained by polymerizing cyclic lactam such as caprolactam and laurinlactam; or cyclic lactam, dicarboxylic acid and diamine Examples thereof include a polyamide resin obtained by copolymerizing a salt of Among these polyamide resins, 6 nylon, 66 nylon, 12 nylon, 46 nylon and copolymers thereof are preferable. Further, a polyamide elastomer resin can also be used as the polyamide resin of the component (B). The polyamide elastomer resin is a soft polyamide block copolymer in which a polyamide hard segment and another soft segment are bonded. Examples of the hard segment of the polyamide elastomer include polyamide 6, polyamide 66, polyamide 6,12, polyamide 11 and polyamide 1
2, polyamides such as polyamides 4 and 6, and polyalkylene oxides (having 2 to 6 carbon atoms in the alkylene group) are typical examples of the soft segment, such as polyoxyethylene glycol, polyoxypropylene glycol, and polyoxyethylene glycol. Examples thereof include oxytetramethylene glycol. Further, the polyamide resin as the component (B) is not limited to only one kind, and it is also possible to use two or more kinds, for example, the polyamide resin and the polyamide elastomer resin in combination in order to adjust the desired physical property values. is there. In the present invention, the blending ratio of the (B) polyamide resin is 3 to 50% by weight based on the total amount of the resin components (A) and (B). (B)
If the amount of the component is too small, the effect of improving the toughness is small, and if it is too large, the advantage of the polyarylene sulfide resin is impaired, which is not preferable.

Next, the present invention is characterized by blending copper iodide as the component (C). A typical substance as a copper iodide is copper iodide, or a compound containing another element may be used. Further, it may be a complex of copper iodide and an oxide, sulfide, hydroxide or salt of another metal. By incorporating such a copper iodide, the heat resistance stability of the resin composition, particularly the deterioration of mechanical properties due to deterioration at high temperature for a long time, is remarkably improved. The content of copper iodide is 0.0 based on 100 parts by weight of the total of component (A) and component (B).
The amount is 02 to 0.5 parts by weight, preferably 0.005 to 0.5 parts by weight. If this blending amount is too small, the heat stability improving effect is small, and if it is too large, it may cause problems such as deterioration of mechanical properties of the resin composition, which is not preferable.

Next, the composition of the present invention is characterized in that the component (C) is used in combination with at least one specific compound (D) selected from the following a), b) and c). a) Aminoalkoxysilane compound represented by the following general formula (1)

[0010]

[Chemical 3]

(However, -R- is an alkylene group having 1 to 8 carbon atoms, -R ¹ and -R ² are alkyl groups having 1 to 6 carbon atoms, and l = 1 to 1
2, n = 1 to 3, m is 0 to 2, l + m + n = 4) b) A compound having two or more epoxy groups in the molecule c) A compound having a carbon double bond and an epoxy group in the molecule The combined use of component D) improves the mutual compatibility and dispersibility of each component, and in particular synergistically works with the component (C) to remarkably improve the heat deterioration of the composition. It is extremely effective for maintaining mechanical properties when used for a long period of time. A kind of such (D) component a)
Is an aminoalkoxysilane represented by the general formula (1), and has 1 to 3 (preferably 2 to 3) silicon atoms.
Oxyalkyl group (each alkyl group has 1 to 6 carbon atoms, preferably 1 to 3) and an alkylene group on the silicon atom (the alkylene group has 1 to 8 carbon atoms, preferably 2 to 4 carbon atoms).
A specific aminoalkoxysilane compound having a structure bonded to at least one amino group via
-Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, etc. Can be mentioned. In addition, one of the specific compounds belonging to component (D) b) has two epoxy groups in the molecule.
Compounds having three or more, for example, bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, 1,3,5-trihydroxybenzene, bisphenol S, trihydroxydiphenyldimethylmethane, 4,4′-dihydroxybiphenyl, 1 Diglycidyl ether compounds of bisphenol such as 1,5-dihydroxynaphthalene and dihydroxydiphenyl sulfone, diglycidyl ether compounds such as halogenated bisphenol and diglycidyl ether of butanediol instead of bisphenol, diglycidyl ester such as diglycidyl phthalate Examples thereof include diglycidyl compounds such as system compounds, vinylcyclohexenedioxide, and dicyclopentadiene oxide. Also, component (D)
Another kind of specific compound belonging to c) is a compound having a carbon double bond and an epoxy group in the molecule, such as allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, vinyl benzoic acid glycidyl ester, and allyl benzoic acid glycidyl. Ester, N- [4
-(2,3-Epoxypropoxy) -3,5-dimethylbenzyl] acrylamide, N-diallylaminoepoxypropane, cinnamic acid glycidyl ester, cinnamylidene acetic acid glycidyl ester, chalcone glycidyl ether, epoxyhexene, dimer acid glycidyl ester, epoxy Examples thereof include esterified stearyl alcohol and an ester of acrylic acid or methacrylic acid, and two or more kinds can be used in combination. Particularly preferred are glycidyl methacrylate, vinyl benzoic acid glycidyl ester, allyl benzoic acid glycidyl ester, N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide, and N-diallylaminoepoxypropane. To be done. The amount of component (D) used is the same as resin components (A) and (B).
Is 0.002 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight. The amount of component (D) to be blended varies depending on the type and intended use of the composition, but if it is too small, the heat resistance and mechanical properties retention effect is small, and if it is too large, the melt viscosity increases too much and molding Processing inconvenience may occur.

When the alkali metal iodide (F) is used in combination with the stabilizers (C) and (D), the heat resistance stability improving effect is further improved. Examples of such alkali metal iodides include lithium iodide, potassium iodide, sodium iodide, and the like, with potassium iodide being preferred. When an alkali metal iodide is used in combination, its content is preferably 0.002 to 0.5 part by weight based on 100 parts by weight of the total of the component (A) and the component (B). If this amount is too large, it may cause inconvenience such as deterioration of mechanical properties of the resin composition.

Next, the filler as the component (E) used in the present invention is not always an essential component, but a molded article excellent in performance such as mechanical strength, heat resistance, dimensional stability, and electrical properties can be obtained. In order to obtain it, it is preferable to mix. A fibrous, powdery, plate-shaped or hollow filler is used for this purpose. As the fibrous filler, glass fiber, asbestos fiber, carbon fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, further stainless steel, aluminum, titanium, Inorganic fibrous substances such as metallic fibrous substances such as copper and brass can be used. A particularly representative fibrous filler is glass fiber or carbon fiber. Incidentally, a high melting point organic fibrous substance such as an aromatic polyamide resin, a fluororesin or an acrylic resin can also be used. On the other hand, as the particulate filler, carbon black, silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, silicates such as wollastonite, Iron oxide, titanium oxide, oxides of metals such as alumina, carbonates of metals such as calcium carbonate, magnesium carbonate, sulfates of metals such as calcium sulfate, barium sulfate, other silicon carbide, silicon nitride,
Examples thereof include boron nitride and various metal powders. Examples of the plate-like filler include mica, glass flakes, various metal foils and the like. As the hollow filler, shirasu balloon,
Examples thereof include metal balloons and glass balloons. The surface of these fillers is preferably surface-treated using organic silane, organic borane, organic titanate, urethane or the like. These inorganic fillers can be used alone or in combination of two or more. The combined use of a fibrous filler, particularly glass fiber or carbon fiber, with a granular or plate-like filler is a preferable combination particularly in terms of having both mechanical strength, dimensional accuracy, and electrical properties. The amount of inorganic filler added is the same as the resin component (A).
It is not more than 400 parts by weight based on 100 parts by weight of the total of (B), and if it is more than 400 parts by weight, moldability and toughness are impaired, which is not preferable. It is particularly preferably 250 parts by weight or less.

In the composition of the present invention, a small amount of other thermoplastic resin such as polyvinyl chloride resin, polyvinylidene chloride resin, polycarbonate resin, polyester resin, etc. may be supplementarily added within a range not departing from the purpose. A small amount of polyolefin resin, natural rubber, synthetic rubber, etc. may be supplementarily added. Further, depending on the purpose, known additives such as flame retardants, antioxidants, anti-UV agents, other stabilizers, lubricants, release agents, nucleating agents, foaming agents, cross-linking agents, and coloring agents can be added.

The method for preparing the composition of the present invention can be carried out by various known methods, but if necessary, in the presence of at least four components (A), (B), (C) and (D) ( It is necessary to add the components E) and (F), heat and melt, and knead for 30 seconds or more. Also, other components may be blended together at the same time. Specifically, for example, (A), (B), (C), (D) components,
The components (E) and (F) are mixed in advance with a mixer such as a tumbler or a Henschel mixer, and then fed into a single-screw or twin-screw extruder and melt-kneaded to produce pellets. The kneading temperature is 5 ° C. to 100 ° C. higher than the melting temperature of the resin component, and particularly preferably 10 ° C. to 60 ° C. higher than the melting point of the resin. If the temperature is too high, the resin is decomposed or an abnormal reaction occurs, which is not preferable. The kneading time varies depending on the processing temperature, the type of each component and the amount added, but is at least 30 seconds or more and 15 minutes or less, preferably 1 minute
10 minutes.

[0016]

INDUSTRIAL APPLICABILITY The polyarylene sulfide resin composition of the present invention has excellent mechanical properties and excellent heat resistance stability, and is suitable as a material to be used under severe conditions in which mechanical properties are not deteriorated particularly when used at high temperature for a long time. Is.

[0017]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Examples 1 to 6 and Comparative Examples 1 to 7 (A) Polyphenylene sulfide resin (melting point 285 ° C., 31
(B) Nylon 66 (30 parts by weight) is added to 70 parts by weight of melt viscosity (500 poise measured at a shear rate of 1200 sec ^-1 at 0 ° C), and (C) copper iodide and (D) -a) as γ components. -Aminopropyltriethoxysilane and optionally potassium iodide were added in the proportions shown in Table 1 and premixed in a Henschel mixer for 5 minutes. This was melt-kneaded with a twin-screw extruder having a cylinder temperature of 310 ° C. to prepare pellets of the polyphenylene sulfide resin composition. Then, an ASTM test piece was molded by an injection molding machine under conditions of a cylinder temperature of 310 ° C. and a mold temperature of 150 ° C., and a tensile test and an impact test were conducted. Also, set the tensile test piece to 1
After heat treatment in air at 80 ° C for 500 hours, a tensile test and an impact test were performed to evaluate the decrease in tensile strength due to this heat treatment. The results are summarized in Table 1. For comparison,
When at least one of the components (C) and (D) does not exist, and when a silane compound (γ-glycidoxypropyltrimethoxysilane) which does not belong to the present invention is used in place of the component (D) -a) Was similarly evaluated. The results are also shown in Table 1.

Examples 7 to 8 and Comparative Examples 8 to 11 In the above Examples and Comparative Examples, the ratio of the (A) polyphenylene sulfide polymer to the (B) nylon 66 was set to the ratio shown in Table 2 and the same procedure was followed. . The results are shown in Table 2.

Examples 9 to 11 and Comparative Examples 12 to 13 Table 3 shows the results of the same tests as in the above Examples and Comparative Examples in which glass fiber was further added.

Examples 12 to 13 and Comparative Examples 14 to 15 The nylon 66 resin used in the preceding examples was changed to nylon 6, and the same blending amounts as shown in Table 4 were used. The results are shown in Table 4.

Examples 14 to 16 and Comparative Examples 16 to 17 (D) -b) Two epoxies instead of γ-aminopropyltrimethoxysilane which is the component (D) -a) in the above Examples and Comparative Examples. Table 5 shows the results of the same tests and evaluations using a compound having a group (diglycidyl ether of bisphenol A).

Examples 17 to 19 and Comparative Examples 18 to 19 As component (D), N- [4- (2,3-
When epoxypropoxy) -3,5-dimethylbenzylacrylamide (AXE) was used, it was similarly tested and evaluated. The results are shown in Table 6.

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

[Table 3]

[0026]

[Table 4]

[0027]

[Table 5]

[0028]

[Table 6]

Claims (3)

[Claims] 1. A (A) polyarylene sulfide resin 97-
Resin component consisting of 50 parts by weight and (B) 3 to 50 parts by weight of polyamide resin 1
0.002 to 0.5 parts by weight of (C) copper iodide to 0.00 parts by weight of (D) 0.002 to 10 parts by weight of at least one compound selected from the following a), b), and c) a) Aminoalkoxysilane compound represented by the formula (1): (However, -R- is an alkylene group having 1 to 8 carbon atoms, -R ¹ , -R
² is an alkyl group having 1 to 6 carbon atoms, l = 1 to 2, n = 1 to 1
3, m is 0 to 2, l + m + n = 4) b) Compound having two or more epoxy groups in the molecule c) Compound having carbon double bond and epoxy group in the molecule (E) Fibrous filler, A heat-resistant polyarylene sulfide resin composition comprising 0 to 400 parts by weight of any one selected from a particulate filler, a plate-shaped filler and a hollow filler, or a mixture thereof. 2. The polyarylene according to claim 1, which further comprises, as the component (F), an iodide of an alkali metal together with 0.002 to 0.5 part by weight of an iodide of an alkali metal based on 100 parts by weight of the resin component (A + B). Sulfide resin composition. 3. At least (A) according to claim 1 or 2,
(B), (C), (D) component and optionally (E), a method for producing a polyarylene sulfide resin composition, which comprises heat kneading for 30 seconds or more in the coexistence of the (F) component .