JPH03247656A - Impact-resistant polyarylene sulfide resin composition and production thereof - Google Patents

Abstract

PURPOSE:To obtain the title resin composition having improved impact resistance and ductility and improved appearance of molded article by blending a polyarylene sulfide resin with a polyamide elastomer and an alkoxysilane in a molten state under heating. CONSTITUTION:100 pts.wt. total amounts of (A) 99-20 pts.wt. polyarylene sulfide resin (e.g. polyphenylene sulfide polymer), (B) 1-8C pts.wt. polymide elastomer and optionally (C) 0-79 pts.wt. polyamide are blended with (D) 0.01-5 pts.wt. one or more silane compounds selected from vinylalkoxysilane, epoxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane and allylalkoxysilane and optionally (E) 0-400 pts.wt. one ore more fillers of fibrous, powdery or granular and lamellar fillers in a molten state under heating for >=30 seconds to give a composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an improved polyarylene sulfide resin composition and a method for producing the same.

More specifically, the present invention relates to a polyarylene sulfide resin composition with improved impact resistance and ductility and a good appearance on the surface of a molded product, and a method for producing the same.

[Conventional technology and its issues]

In recent years, electric/electronic equipment parts materials, automobile equipment parts materials,
Thermoplastic resins that have high heat resistance, chemical resistance, and flame retardancy are increasingly required for chemical equipment component materials.

Polyarylene sulfide resin, typified by polyphenylene sulfide, is one of the resins that meet this demand, and demand is increasing due in part to its good cost-property ratio.

However, this resin has serious drawbacks such as poor ductility and brittleness. Therefore, it is known that the properties required for engineering plastics, such as strength, rigidity, toughness, and heat resistance, can be significantly improved by adding fibrous reinforcing materials such as glass fiber and carbon fiber to the resin. ing.

However, even with the addition of the fibrous reinforcement,
It is more brittle than other engineering plastics such as nylon and polyacetal, and despite its excellent properties, its lack of toughness limits its application to many uses.

The following techniques have been proposed to solve this problem.

(1) An α-olefin copolymer obtained by graft copolymerizing 10% by weight or less of an unsaturated carboxylic acid or its anhydride with an epoxy resin is blended (JP-A-59207921).

(2) Blending an olefin copolymer consisting of an α-olefin and a glycidyl ester of an α,β-unsaturated acid (Japanese Patent Application Laid-open No. 189166/1983).

(3) Blending polyamide resin and epoxy resin (Japanese Unexamined Patent Publication No. 155462/1983).

However, each of these methods has its own problems and is not a sufficient solution.

That is, in the additional tests conducted by the present inventors, methods (1) and (2) aim to improve toughness by combining an olefin copolymer having an ester bond with a polyarylene sulfide resin. If the molding temperature is as high as 300 to 320°C, the olefin copolymer will decompose during the molding process, resulting in insufficient toughness of the molded product.

Regarding the method [3], the inventors' additional tests revealed that bleeding to the surface of the molded product occurred due to poor dispersion state,
It was observed that peeling occurred, the surface condition was poor, and the melt flow stability of the composition was extremely poor, so that it was still not sufficient for practical use.

[Means to solve the problem]

The present inventors have made extensive studies to improve the toughness of polyarylene sulfide resin compositions and to improve the appearance of the molded product surface, and have found that the reactive terminals of polyarylene sulfide and highly tough polyamide resins We focused on reactive substances that react with both resins under conditions that do not cleave the main chain.

As a result, by kneading a silane compound having an alkoxy group in its molecule in the coexistence of polyarylene sulfide resin and polyamide elastomer resin at a specific temperature and for a specific time, The present inventors have discovered that it is possible to provide a practical molding material that has high toughness and a good appearance on the surface of a molded product, and has completed the present invention.

That is, the present invention comprises (A) 99 to 20 parts by weight of polyarylene sulfide resin, (B) 1 to 80 parts by weight of polyamide elastomer resin, (
C) For a total of 100 parts by weight of the resin component consisting of 0 to 79 parts by weight of polyamide resin, (D) 0.01 to 5 parts by weight of alkoxysilane and (E) fibrous filler, powdery filler, plate-shaped A polyarylene sulfide resin composition, as well as (A) and (B), characterized in that 0 to 400 parts by weight of any one filler selected from fillers or a mixture thereof is added and blended.

The method for producing the polyarylene sulfide resin composition is characterized in that component (D) and optionally components ([:) and (E) are added and blended, and the mixture is heated and melted and kneaded for at least 30 seconds.

The polyarylene sulfide resin as component (A) in the composition of the present invention mainly consists of repeating units → Ar
-5÷ (where Ar is an arylene group).

Examples of the arylene group (-Ar-) include p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group (however, the substituent is an alkyl group, preferably 0
1-C5 alkyl group, or haphenyl group), p, p'
-diphenylene sulfone group, p,p'-biphenylene group, p,p'-diphenylene ether group, p,p'-diphenylenecarbonyl group, naphthalene group, etc. can be used.

In this case, among the arylene sulfide groups composed of the above-mentioned arylene groups, a polymer using the same repeating unit, that is, a homopolymer, can be used, and from the viewpoint of processability of the composition, different repeating units can be used. Copolymers containing copolymers may be preferred.

As the homopolymer, a substantially linear homopolymer using a p-phenylene group as the arylene group and having a p-phenylene sulfide group as a repeating unit is particularly preferably used.

Further, as a copolymer, a combination of two or more different types of arylene sulfide groups consisting of the above-mentioned arylene groups can be used, but among them, a combination mainly consisting of p-phenylene sulfide groups and containing m-phenylene sulfide groups is used. It is particularly preferably used. In this p
A substantially linear material containing 60 mol % or more, more preferably 70 mol % or more of -phenylene sulfide groups is suitable from the viewpoint of physical properties such as heat resistance, moldability, and mechanical properties.

In addition, m-phenylene sulfide group is 5 to 40 mol%,
In particular, a copolymer containing 10 to 25 mol% is preferable.

In this case, components whose repeating units are contained in blocks (for example, Japanese Patent Laid-Open No. 61-1989-1) rather than random repeating units
14228) has good processability and excellent heat resistance and mechanical properties, and can be preferably used.

For the polyarylene sulfide resin used as component (A) in the present invention, polymers obtained by increasing the melt viscosity and improving moldability by oxidative crosslinking or thermal crosslinking of the above-mentioned polymers can also be used, but bifunctional monomers can also be used. It is also possible to use polymers having a substantially linear structure obtained by condensation polymerization from a polymer based on a polymer. The latter, substantially linear structured polymer, is often preferable because the physical properties of the obtained molded product are higher.

In addition, the polyarylene sulfide resin of the present invention is polymerized using a mixture of Chitsumar having three or more functional groups as a part of Chitsumar in addition to the above-mentioned polymers, and exhibits a gel-like state when melted. A blended resin in which a crosslinked polyarylene sulfide resin is blended with the linear polymer described above can also be suitably used.

The polyamide elastomer resin as component (B) of the present invention is:
The flexural modulus of the combined polyamide hard segment and other soft segments is 100100O0/cm2 or less (
It is a polyamide-based block copolymer (50% relative humidity, 23°C). The soft segments of such elastomers include polyalkylene oxides, especially polyalkylene oxides with a molecular weight of 400.
~60,000 polyalkylene oxide (arylene group having 2 to 6 carbon atoms) is a typical example. There are many reports on methods for synthesizing such polyamide elastomers, but they are usually carried out in two steps: generation of nylon oligomers and increase in molecular weight by esterification.

Here, as the polyamide component as the hard segment, polyamide 6, polyamide 66, polyamide 6.
Examples of the polyether component as a soft segment include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, and the like.

The polyamide elastomer resin (B) used preferably has a water content below a certain limit, and is desirably dried before use.

The amount of polyamide elastomer resin (8) used varies depending on the application, but polyarylene sulfide resin 99
~20 parts by weight of polyamide elastomer resin 1-8
It is preferably 0 parts by weight, and more preferably 5 to 80 parts by weight based on 95 to 20 parts by weight of the polyarylene sulfide resin. When the amount is less than 1 part by weight, the toughness of the resin composition cannot be sufficiently improved.

In the present invention, although it is not necessarily an essential component, (
The polyamide resin of component C) can be used in combination. (C) Polyamide resin has a flexural modulus of 1001
0000/cm" (50% relative humidity, 23°C) or higher, which has good affinity with polyamide elastomers and adjusts the mechanical properties of the entire composition, especially elasticity, etc.
In addition, since it is cheaper than polyamide elastomer resin, it is preferable to use it together in order to obtain molded products with excellent performance such as mechanical strength and heat resistance at low cost, but if it is used in excess, it may impair hygroscopicity etc. Undesirable.

As this polyamide resin ([''), various well-known ones can be mentioned. For example, oxalic acid, adipic acid,
Dicarboxylic acids such as superic acid, sebacic acid, terephthalic acid, isophthalic acid, 1,4-cyclohexyldicarboxylic acid and ethylenediamine, pentamethylenediamine,
Hexamethylenediamine, Camethylenediamine, 1
, 4-cyclohexyl diamine, m-xylylene diamine, and other diamines; polyamide resins obtained by polymerizing current lactams such as caprolactam and laurin lactam; or cyclic lactams. Examples include polyamide resins obtained by copolymerizing salts of dicarboxylic acids and diamines.

Of these polyamide resins, preferably 6 nylon, 66 nylon, 1
2 nylon, etc.

The polyamide resin (C) used also preferably has a water content below a certain limit, similar to the component (B), and therefore it is desirable to dry it before use.

Next, the present invention is characterized in that (D) an alkoxysilane compound is added and blended together with the above resin component.

The alkoxysilane (D) used in the present invention is one or more of vinylalkoxysilane, epoxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane, and allylalkoxysilane. Ethoxysilane, vinyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane, etc. Epoxyalkoxysilanes include, for example, T-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, T
Examples of aminoalkoxysilanes include T-aminopropyltrimethoxysilane, T-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, and T-7minopropylmethyldimethoxysilane. Ethoxysilane, N
-(β-T-minoethyl)-di-aminopropyltrimethoxysilane, N-phenyl-T-aminopropyltrimethoxysilane, etc. Examples of the mercaptoalkoxysilane include γ-mercaptopropyltrimethoxysilane, T-mercaptopropyltriethoxysilane, etc. Examples of allyl alkoxysilanes such as silane include T-diallylaminopropyltrimethoxysilane, T-allylaminopropyltrimethoxysilane, and T-allylthiopropyltrimethoxysilane.

The amount of the alkoxysilane compound used as component (D) is 100 parts by weight in total of polyarylene sulfide resin [component (A)], polyamide elastomer resin [component (B)], and polyamide resin [component (C)]. Against 0.
The amount is preferably 0.1 to 5 parts by weight, preferably 0.1 to 3 parts by weight.

The amount of the alkoxysilane compound added varies depending on its type and the intended use of the composition, but if it is too little, the effect of improving toughness will be small, and if it is too much, the melt viscosity will rise too much, causing problems in molding processing. There is.

Next, although the filler component (E) used in the present invention is not necessarily an essential component, it is necessary to obtain a molded product with excellent performance such as mechanical strength, heat resistance, dimensional stability, and electrical properties. is preferably blended. Fibrous, powdery or plate-like fillers are used depending on the purpose.

Fibrous fillers include glass fiber, asbestos fiber,
Carbon fiber, silica fiber, silica/alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, stainless steel, aluminum,
Examples include inorganic fibrous materials such as fibrous materials of metals such as titanium, copper, and brass. Particularly typical fibrous fillers are glass fibers or carbon fibers. Note that high melting point organic fibrous substances such as polyamide, fluororesin, and acrylic resin can also be used.

On the other hand, the powdery fillers include carbon black, silica, quartz powder, glass peas, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, silicates such as wollastonite, Metal oxides such as iron oxide, titanium oxide, alumina, calcium carbonate,
Metal carbonates such as magnesium carbonate, metal sulfates such as calcium sulfate, barium sulfate, other silicon carbide,
Examples include silicon nitride, boron nitride, and various metal powders.

Further, examples of the plate-like filler include mica, glass flakes, and various metal foils.

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, and a granular or plate-like filler is a particularly preferable combination in terms of achieving both mechanical strength, dimensional accuracy, electrical properties, and the like.

The amount of the inorganic filler added is 400 parts by weight or less per 100 parts by weight of the resin components (A), (B) and (C), and if it is more than this, the moldability and toughness will be impaired, which is not preferable. Particularly preferably 250 parts by weight or less.

The composition of the present invention can be prepared by various known methods, but at least the three components (^), (B), and (D), and if component (C) is used in combination, are also added. At the same time, it is necessary to knead the mixture in a molten state for 30 seconds or more. Specifically, for example (A) and (B).

Components (D) and (C), as well as component (E) and others are uniformly mixed in advance in a mixer such as a tumbler or Henschel mixer, and then fed into a single or twin screw extruder for melt kneading. , producing pellets.

At this time, some or all of the components (^), (B), and (C) are powdered, and after a part of this resin and the component (D) are mixed uniformly in a blender, the remaining required amount is further mixed. Preferably, it is mixed with the components and subjected to melt processing. Also (E)
Components may be added during or after melt processing. In particular, it is preferable to add the polymer component after it has been melt-kneaded and reacted with component (D), as the effect on toughness tends to be more pronounced7.
Delicious.

The processing temperature is 5℃ to 10℃ higher than the temperature at which the resin component melts.
The temperature is 0°C higher, particularly preferably 10°C to 60°C higher than the melting point. If the temperature is too high, decomposition or abnormal reactions may occur, which is undesirable.

Further, the melting treatment time varies depending on the treatment temperature and the type and amount of the silane compound added, but is at least 30 seconds or more and 15 minutes or less, preferably 1 to 10 minutes.

Although the detailed mechanism of the action and effect of the alkoxysilane compound of the present invention has not been sufficiently clarified,
Polyarylene sulfide molecules and polyamide polymer molecules are bonded by these silane compounds, (A),
This is understood to be due to improved compatibility between component (B) and component (C).

This has been confirmed by the fact that the viscosity increases due to melt treatment in the presence of component (D), and by observing the phase structure of a cross section of a molded product using an electron microscope. (D
) When the silane compound of ) is not present, the dispersion state of the polyamide resin is extremely large and coarse particles (10 mm or more) are formed.
However, according to the method of the present invention, it is possible to disperse them as extremely fine particles (less than 1 particle).

The composition of the present invention may contain antioxidants, heat stabilizers, lubricants, crystal nucleating agents, ultraviolet absorbers, colorants, mold release agents, and other conventional additives within the scope of the purpose of the present invention. can do.

These additives can be added and blended into the resin composition simultaneously with the above-mentioned melt-kneading treatment or separately.

〔Effect of the invention〕

As is clear from the above description and Examples, the polyarylene sulfide resin composition of the present invention exhibits an extremely good dispersion state of the resin components, and has the following effects.

(1) Mechanical properties such as tensile elongation and impact resistance of molded products are significantly improved.

(2) Good balance between mechanical properties and heat resistance.

(3) The appearance of the molded product is good.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to this.

Examples 1-5. Comparative Example 1.2 Polyphenylene sulfide polymer (melting point 285°C) 8
0 parts by weight of polyamide elastomer (trade name Diaamide E62: manufactured by Daicel Huls 1) (see Properties-1 below)
20 parts by weight of r-aminopropyltriethoxysilane and optionally glass fiber (diameter LOt-1
Chopped strands of length 3 east) were added in the amounts shown in Table 1 and premixed for 5 minutes in a Henschel mixer. This was melt-kneaded in an extruder with a cylinder temperature of 310°C to produce pellets of polyphenylene sulfide resin composition.

Next, an ASTM test piece was molded using an injection molding machine under conditions of a cylinder temperature of 310° C. and a mold temperature of 150° C., and a tensile test, an impact test, and a thermal deformation test were conducted.

In addition, the appearance of the molded product surface was visually determined.

The results are summarized in Table 1.

(Note-1) *Polyamide elastomer with nylon 12 as a hard segment and polyoxybutylene as a soft segment (flexural modulus 3500 kgf/cd) Examples 6 to 9.
Comparative Example 3.4 Diamide E62 was added to the same polyphenylene sulfide polymer as in the above Examples and Comparative Examples in the proportions shown in Table 2,
Further, T-aminopropyl 2-ethoxysilane and glass fiber were added in the proportions shown in Table 2, and the same procedures as in Examples 1 to 5 were carried out.

The results are shown in Table 2.

Examples 10 to 17 20 parts by weight of polyamide elastomer (Diamide ε62) was added to 80 parts by weight of the above polyphenylene sulfide polymer, and further γ-glycidoxypropyltrimethoxysilane, T-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane or T-diallylaminopropyltrimethoxysilane and glass fiber were added in the amounts shown in Table 3. The following steps were carried out in the same manner as in Examples 1 to 5.

The results are shown in Table 3.

Examples 18-22. Comparative Example 5.6 Polyamide elastomer (Diamide B62) and polyamide (FA) 66 were added in the amounts shown in Table 4 to 60 parts by weight of the above polyphenylene sulfide polymer, and the total amount was 100 parts by weight.
2 parts by weight of T-aminopropyltriethoxysilane and optionally glass fibers were added in amounts shown in Table 4 based on parts by weight. The following steps were carried out in the same manner as in Examples 1 to 5.

The results are shown in Table 4.

Examples 23 to 32, Comparative Example 7.8 To 80 parts by weight of the above polyphenylene sulfide polymer, 20 parts by weight of polyamide elastomer (trade name DIAMIDRO 40: 0 manufactured by Daicel Hyulus) (see property = 2 below) was added, and further, T- aminopropyltriethoxysilane,
T-glycidoxypropyltrimethoxysilane, T-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, T-diallylaminopropyltrimethoxysilane, and optionally glass fiber were added in the amounts shown in Table 5. The following steps were carried out in the same manner as in Examples 1 to 5. The results are shown in Table 5.

(Note-1) *Polyamide elastomer with nylon 12 as a hard segment and polyoxybutylene as a soft segment (flexural modulus of elasticity 900 kgf/Cn)

Claims (1)

[Scope of Claims] 1 (A) 99 to 20 parts by weight of polyarylene sulfide resin, (B) 1 to 80 parts by weight of polyamide elastomer resin, and (C) 0 to 79 parts by weight of polyamide resin, totaling 100 parts by weight. to (D) 0.01 to 5 parts by weight of alkoxysilane and (E) 0 to 400 parts by weight of any one selected from fibrous fillers, powdery fillers, plate-like fillers, or mixtures thereof. A polyarylene sulfide resin composition characterized in that it is made by adding and blending. 2(D) alkoxysilane is vinylalkoxysilane,
Epoxyalkoxysilane, aminoalkoxysilane,
The polyarylene sulfide resin composition according to claim 1, which is at least one silane compound selected from the group consisting of mercaptoalkoxysilane and allyl alkoxysilane. 3. Components (A), (B), and (D) according to claim 1 or 2 and optionally components (C) and (E) are added and blended, and then heated and melt-kneaded for at least 30 seconds or more. A method for producing a polyarylene sulfide resin composition.