JPH03177454A - Glass-fiber reinforced polyamide resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent heat-resistance, impact resistance, low moisture absorbence, calcium chloride resistance, etc., and suitable as a material for radiator tank of automobile by compounding a polyamide with specific amounts of a polyphenylene ether resin, a styrene- maleic anhydride copolymer, etc. CONSTITUTION:The objective composition can be produced by compounding (A) 100 pts.wt. of one or more kinds of polyamides selected from nylon 66, nylon 6-66 and nylon 6 with (B) 5-100 pts.wt. of a polyphenylene ether resin [e.g. poly(2,6-dimethyl-1,4-phenylene) ether], (C) 5-100 pts.wt. of a styrene-maleic anhydride copolymer, (D) 0.5-100 pts.wt. of a modified polyolefin, (E) 0-150 pts.wt. of a propylene homopolymer and/or propylene copolymer and (F) 10-180 pts.wt. of glass fiber.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a glass fiber reinforced polyamide resin composition,
Specifically, the present invention relates to a glass fiber-reinforced polyamide resin composition that has both the excellent properties of polyamide and polypropylene and is particularly suitable as a material for automobile radiator tanks.

[Prior art and problems to be solved by the invention] In general, glass fiber-reinforced boria main cells have high mechanical strength, heat resistance (
Due to its excellent properties such as heat aging resistance, heat deformation resistance), electrical properties, and friction and abrasion properties, it is widely used as an engineering resin for various mechanical parts materials, but it has various problems due to its high water absorption rate.

In particular, glass fiber-reinforced polyamide that has absorbed water is undesirable because it tends to contain air bubbles and cause whitening or hydrolysis when molded, and its mechanical strength decreases significantly due to water absorption. In addition, problems such as dimensional changes and deformation also occur.

Because glass fiber reinforced polyamide has such drawbacks, its use as an engineering resin is limited.
In many cases, it is not possible to take advantage of the excellent properties inherent to polyamide itself.

On the other hand, propylene-based polymers such as polypropylene are inexpensive and exhibit almost no water absorption, but have the disadvantage of being soft and having poor physical properties at high temperatures.

Therefore, attempts have been made to use polyamides and propylene polymers in combination in order to complement and improve their respective drawbacks. However, simply melt-kneading polyamide and a propylene polymer such as polypropylene results in poor compatibility and mutual peeling.
Even if it is reinforced with glass fiber, there is a problem in that the composition cannot have excellent properties.

In recent years, plastics, which are lighter and easier to mold than metals, have come to be used for various parts of automobiles from the viewpoint of resource and energy conservation.

In particular, polyamides such as nylon 66, which have excellent strength and heat resistance, are widely used in automobile parts as the above-mentioned glass fiber-reinforced polyamides, which are reinforced with glass fibers. However, automotive parts made from glass fiber reinforced boria, especially parts such as radiators that come in contact with moisture on one side and outside air on the other and are repeatedly exposed to high temperatures, are used for road maintenance in the winter. Road surface antifreeze agents, which are mainly composed of calcium chloride and are used in road vehicles, have the disadvantage of causing cracks if they adhere to them. Therefore, recently, if low water absorption polyamide is used as polyamide,
It has been reported that such drawbacks can be improved to some extent (Japanese Patent Laid-Open No. 168654/1983). It has also been reported that a composition of nylon 66 and modified polyolefin has resistance to calcium chloride (Japanese Patent Application Laid-open No. 58
-21445, Japanese Patent Application Laid-open No. 61-76540)
.

However, although these techniques can be expected to improve to some extent, they are still not satisfactory in practical terms, and in particular, the mechanical strength of compositions of nylon 66 and modified polyolefin is significantly reduced. However, it has a fatal drawback of low high temperature rigidity.

In view of the above-mentioned circumstances, the present inventors have discovered the excellent properties of polyamide, such as mechanical strength and heat resistance (heat deformation resistance), as well as the excellent properties of propylene-based polymers, such as low water absorption and resistance to calcium chloride. We conducted intensive research to develop a glass fiber-reinforced resin composition that has an excellent synergistic effect while maintaining the same properties, and is particularly useful as a molding material for automobile parts such as radiators.

(Means for solving the problem) As a result, in order to improve the compatibility between polyamide and propylene-based polymer, glass fiber and modified polyolefin were blended, and at the same time, polyphenylene ether-based resin It has been found that a resin composition having desired physical properties can be obtained by blending a styrene-maleic anhydride copolymer and a styrene-maleic anhydride copolymer. Additionally, when these components are blended, a resin composition with the desired physical properties can be obtained by adjusting the blending amount of each component, even without blending the propylene polymer. I found it.

The present invention was completed based on this knowledge. That is, the present invention provides: (A) at least one borian compound selected from nylon 66, nylon 6/66, and nylon 6;
100 parts by weight.

(B) Polyphenylene ether resin 5-100 parts by weight.

(C) 5 to 100 parts by weight of styrene-maleic anhydride copolymer.

(D) Modified polyolefin 0.5 to 100 parts by weight.

The present invention provides a glass fiber-reinforced boriacamedo resin composition containing as main components (E) 0 to 150 parts by weight of a propylene homopolymer and/or propylene copolymer and (F) 10 to 180 parts by weight of glass fiber. .

Component (A) of the composition of the present invention is a polyamide made of either nylon 66°, nylon 6.66, or nylon 6. Here, nylon 6.66 is a copolymer of nylon 6 and nylon 66. Note that these nylons may be used alone or in combination of two or more. In addition, the polyamide that is the component (A) can be any of the above-mentioned nylons without being limited by the type, concentration, or molecular weight of the terminal groups, but the is preferred. Furthermore, it is also possible to use polyamide (nylon) in which low molecular weight substances such as hetamine and oligomers that remain or are generated during polymerization of polyamide are mixed.

Next, component (B) of the composition of the present invention is a polyphenylene ether resin, and has the following general formula: an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, and a haloalkyl group having 1 to 4 carbon atoms.

Indicates a monovalent residue such as an aryl group having 6 to 10 carbon atoms. However, R5 and R6 are not hydrogen at the same time. ] It is a polymer consisting of at least one type of repeating unit represented by the following. In particular, homopolymers consisting of repeating units of general formula [I] or repeating units of general formula (1) and general formula (I
A copolymer consisting of repeating units of I) can be preferably used.

Typical examples of homopolymers of polyphenylene ether resins include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1
,4-phenylene〉ether.

Poly(2,6-danityl-1,4-phenylene) ether, poly(2-ethyl-6-n-propyl-1,4-phenylene) ether, poly(2,6-d-n-propyl-1,4) -phenylene) ether.

Poly(2-methyl-6-n-butyl-1,4-phenylene) ether, poly(2-ethyl-6-isopropyl-
1,4-phenylene)ether, poly(2-methyl-6)
-chloro-1,4-phenylene)ether, poly(2-
methyl-6-hydroxyethyl-1,4-phenylene)
ether, poly(2-methyl-6-chloroethyl-1,
4-phenylene) ether and the like.

On the other hand, as a typical example of a copolymer of polyphenylene ether resin, [wherein R3-R6 are the same as above]. ] (For example, an alkyl-substituted phenol such as 2.3.6-drimethylphenol) and [wherein R1 and Rz are the same as above. Examples include polyphenylene ether copolymers mainly having a polyphenylene ether structure obtained by copolymerizing phenol represented by the following formula or a substituted phenol (for example, 0-cresol, etc.).

The blending ratio of component (B) in the composition of the present invention is (A
) to 1100 parts by weight of the boria main component, 5 to 1
00 parts by weight. Here, if the amount of component (B) is less than 5 parts by weight, the desired chemical resistance such as CaC1z resistance cannot be imparted to the resulting composition, and heat resistance cannot be imparted either. Moreover, even if it exceeds 100 parts by weight, the effect corresponding to the amount blended will be small, and there is a possibility that the various physical properties of the resulting resin composition may be deteriorated.

Next, component (C) of the composition of the present invention is a styrene-maleic anhydride copolymer, and there are various types.
- For boat fishing, a copolymer of styrene mixed with maleic anhydride in an amount of several to 30% is used.

The blending ratio of component (C) in the composition of the present invention is (A
) per 100 parts by weight of the polyamide component.
00 parts by weight. Here, if component (C) is less than 5 parts by weight, (A) polyamide with tc content and (B)
Compatibility of the component polyphenylene ether resin cannot be imparted. Moreover, even if it exceeds 100 parts by weight, the effect corresponding to the amount blended is small, and there is a risk that the various physical properties of the resulting resin composition may be deteriorated.

Next, component (D) of the U acid product of the present invention is a modified polyolefin, and there are various types, but in the present invention, it can be mainly classified into the following two types.

In other words, (1) a graft-modified polyolefin in which an α,β-unsaturated carboxylic acid or its derivative is grafted onto a polyolefin in the presence of a radical generator, and (2) a graft-modified polyolefin in which an α,β-unsaturated It is a ternary modified polyolefin obtained by copolymerizing a carboxylic acid or its derivative, and a methacrylic acid ester or an acrylic acid ester.

Among these, for the graft-modified polyolefin mentioned above, various polyolefins can be used as the base, but preferably low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, polybutene- 1, Polymethylpentene-1゜Copolymers of ethylene and α-olefins (ethylene-propylene copolymers, ethylene-propylene-diene ternary copolymers, ethylene-butene-1 copolymers, etc.), ethylene and Copolymers with vinyl compounds (ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic ester copolymers, ethylene-methacrylic acid copolymers, ethylene-methacrylic ester copolymers).

Ethylene-(meth)acrylic acid (ester)-α, β-
Unsaturated carboxylic acid (derivative) terpolymer, ethylene-
vinyl chloride copolymers, etc.) or mixtures thereof.

Further, as the α,β-unsaturated carboxylic acid or its derivative used for graft modification, acrylic acid is used.

Maleic acid, fumaric acid, itaconic acid, 3.6-nindomethylene-1.2.3.6-titrahydrosis-phthalic acid or their anhydrides and esters, alkylaminomethacrylates such as 2-dimethylaminoethyl methacrylate, and glycidyl Examples thereof include methacrylate, and among these, acrylic acid, maleic acid, maleic anhydride, and the anhydride of 3°6-endomethylene-1,2,3,6-titrahydrosis-phthalic acid are preferred. In addition,
These may be used alone or in combination of two or more.

Furthermore, as radical generators used for graft modification, dicumyl peroxide; benzoyl peroxide; di-t-butyl peroxide; 2,5-dimethyl-
2,5-di(L-butylperoxy)hexane; 2,5
Organic peroxides such as -dimethyl-2,5-di(t-butylperoxy)hexene-3; lauroyl peroxide; t-butylperoxybenzoate are preferably used.

To produce the graft-modified polyolefin described in (1) above, the polyolefin described above is suspended or dissolved in an appropriate solvent, the above α, β-unsaturated carboxylic acid or its derivative, and a radical generator are added thereto, and the mixture is heated and stirred. There are two methods: a method in which polyolefin is mixed with an α,β-unsaturated carboxylic acid or a derivative thereof, and a radical generator, and the mixture is melt-kneaded using an extruder, a Banbury mixer, a kneader, etc. The method is preferably adopted. The amount of each compound used in this case is not particularly limited as long as it can be selected appropriately depending on various situations, but usually α,
β-unsaturated carboxylic acid or its derivative 0.1-5.0
Parts by weight and 0.1 to 5.0 parts by weight of the radical generator may be used as a guide.

Such a graft-modified polyolefin has a structure in which an α,β-unsaturated carboxylic acid or a derivative thereof is grafted onto a polyolefin. In other words, it may have a constant number (concentration) of carboxyl groups (such as carboxyl groups derived from α, β-unsaturated carboxylic acids or derivatives thereof), but it may also have various numbers of functional groups or a mixture of different types of polyolefins to be grafted. It is preferable that In particular, it is preferable to select the amount of graft addition within the range of 0.05 to 5% by weight. By providing a range or distribution in the number of functional groups and the type of polyolefin in this way, the particle size distribution of the propylene homopolymer and/or propylene copolymer, which is the dispersed phase in the polyamide, is expanded, and the resulting polyamide composition is Improvements in impact resistance, heat resistance, peeling resistance, and other physical properties become even more remarkable.

On the other hand, for the above ternary modified polyolefin (2), various olefin monomers can be used, but ethylene, propylene, butene-1, methylpentene-2, etc. are preferred, and ethylene is particularly preferred. Further, the α,β-unsaturated carboxylic acid or its derivative is the same as described above.

This ternary modified polyolefin can be produced using a conventional polymerization method. The amount of each compound used in this case is not particularly limited as long as it can be selected appropriately depending on various situations, but usually 1 to 5 parts of α,β-unsaturated carboxylic acid or its derivatives are used per 100 parts by weight of olefin. Such ternary modified polyolefins, which may be used in amounts of 8 to 25 parts by weight and methacrylic ester or acrylic ester, contain olefin units, units of α, β-unsaturated carboxylic acid or its derivatives, and methacrylic acid esters or acrylic esters. The ternary modified polyolefin used as component (D) of the present invention has a structure in which acid ester or acrylic acid ester units are randomly or block copolymerized.
, β-unsaturated carboxylic acids or their derivatives, and carboxyl groups derived from methacrylic esters or acrylic esters), the number (concentration) of the functional groups may be constant, but the number (concentration) of olefin units may vary. It is preferable to use a mixture of different types for the same reason as in the case of the graft-modified polyolefin described above. In this case, it is particularly preferable that the content of α,β-unsaturated carboxylic acid or derivative units thereof in the ternary modified polyolefin be set at 0.05 to 10% by weight.

Component (D) of the composition of the present invention is a modified polyolefin,
In particular, the above-mentioned (1) graft-modified polyolefin and/or (3) ternary modified polyolefin are preferably used, and the blending amount thereof is 0.5 to 100 parts by weight per 100 parts by weight of the polyamide as component (A). It is.

If the amount of modified polyolefin (D) is less than 0.5 parts by weight, the compatibility between the polyamide as component (A) and the propylene homopolymer and/or propylene copolymer as component (E) may be affected. Therefore, desired physical properties cannot be imparted to the resulting composition. On the other hand, the blending amount of (D) modified polyolefin is 10
Even if it exceeds 0 parts by weight, there will be no effect corresponding to the amount blended, but rather there is a risk that the various physical properties of the resulting composition will be deteriorated.

Next, (E")I'li, of the composition of the present invention is a propylene homopolymer and/or a propylene copolymer, and here the propylene copolymer is a propylene-ethylene copolymer, There are propylene-butene-1 copolymers, etc., and there are block copolymers and random copolymers of these.As this component (E), one type of propylene homopolymer or propylene copolymer is used. Alternatively, two or more types can be used in combination.

The molecular weight of this propylene homopolymer and propylene copolymer is not particularly limited, but -g has an MFR of 0.
．． 1 to 40 g/10 minutes is used.

The amount of component (E) to be blended should be 0 to 150 parts by weight based on 100 parts by weight of the polyamide (A). That is, in the composition of the present invention, the component (E) is not an essential component and may be omitted.

However, preferably polyamide 10 as component (A)
It is blended in an amount of 5 to 100 parts by weight relative to 0 parts by weight. Incidentally, if the blending ratio exceeds 150 parts by weight, the resulting composition will be unsatisfactory in physical properties such as heat resistance and mechanical strength.

In addition, among the physical properties required for the composition of the present invention, when reducing water absorption and calcium chloride resistance are important, (B
) Polyphenyl ether resin 1 (C) styrene-maleic anhydride copolymer, (D) modified polyolefin and (E
) It is effective to make the total blending amount of the propylene homopolymer and/or propylene copolymer larger than the blending amount of (A) polyamide. In addition, when particularly heat resistance is expected from the composition of the present invention, (A) polyamide 1 (
It is preferable that the amount of B) polyphenyl ether resin and (C) styrene-maleic anhydride copolymer be greater than the total amount of components (D) and (E).

Furthermore, although the component (F) of the present invention is glass fiber, it may be any fiber that has been conventionally blended into polyamide as a reinforcing material and is not particularly limited. Further, the blending amount of the glass fiber (F) may be 10 to 180 parts by weight based on 100 parts by weight of the polyamide (A).

When producing the glass fiber reinforced polyamide resin assembly of the present invention, (A), (B), (C), and (D) are used.

Components (E) and (F) can be melt-kneaded in various conditions. For example, (A) polyamide, which is still in a molten state after the polymerization reaction, is mixed with (B) polyphenyl ether resin, (C) styrene-maleic anhydride copolymer, (D) modified polyolefin, and (E) propylene alone. A polymer and/or a propylene copolymer and (F) glass fiber may be added and melt-kneaded.

The temperature when melting and kneading each component is usually 220 to 35
0"C1 is preferably selected from the range of 220 to 300°C. If the temperature is too low, each component will be insufficiently melted, making complete melting and kneading difficult; if the temperature is too high, the decomposition reaction will proceed. There is a risk that this is not desirable.

The above-mentioned melt-kneading operation may be performed using a known melt-kneading device such as a single-screw or twin-screw extruder.

The composition of the present invention can be prepared as described above (A), (B), (C).
The main components are components (D), (E), and (F), but depending on the purpose, dyes, pigments, and fillers may be added.

Nucleating agent, other fibrous materials, plasticizer, lubricant, coupling agent 1
Appropriate amounts of foaming agents, heat-resistant agents, weather-resistant agents, flame retardants, etc. may also be added.

The composition of the present invention can also be used in pipes and tubes.

It can be processed into rods, injection molded products, etc., and can also be plated, painted, etc. as post-processing.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

The various physical properties of the glass fiber reinforced polyamide resin compositions obtained on each side below were measured based on the following test methods.

The left standing charcoal wide test piece was prepared by molding the bottom of the composition using a screw in-line injection molding machine. The cylinder temperature at this time is (
A) Nylon 66° Nylon 6.66 as polyamide
Alternatively, when nylon 6 was used, the temperature was all set at 280°C. Moreover, the mold temperature was 80°C.

1l-4 (4 years old (1) Izot impact strength test (notched)) Izot impact strength test (notched) was conducted at 23°C on a 1/6 inch wide test piece according to ASTM-D-256. The measured values are given in kg f -cta 10.

Measurement of water absorption rate Using a tensile test specimen specified in ASTM-D-638, this test specimen was immersed in boiling water at 100°C for 1 hour to determine the weight of the molding machine when it was absolutely dry and when it absorbed water. It was calculated according to the following formula.

(3) Heat distortion temperature In accordance with the provisions of ASTM-D-648, Measured at 18.6 kgf/d.

(4) Peelability test Bending stress Regarding the glass fiber reinforced polyamide resin composite acid after melt-kneading, strand bending test (extrude a strand with a diameter of 5IIIN11, bend it 90' at room temperature after cooling, and then fold it back 180' to the opposite side) Perform back and forth bending 3 times,
The peeling (separation) state between the polyamide and the propylene polymer at the cut surface or the bent portion is visually observed. ) to evaluate the releasability.

(5) Calcium chloride resistance (CaCfz) resistance test First, ■
The tension dumbbells were saturated with distilled water. Next, ■ apply a 5% CaC1z aqueous solution to this dumbbell with a brush, and then ■ apply it in an atmosphere of 100°C for 2 hours, and then at room temperature for 1 hour.
A time load of 200 kgf/d (tensile creep) was applied to confirm cracks.

These operations ① and ② were considered as one cycle, and these were repeated for 20 cycles and 60 cycles.

(6) Bending test A bending test was conducted in accordance with ASTM D790.

Also used on each side was (A) polyamide.

(B) Polyphenylene ether? ? 'l Resin, (C
) Styrene-maleic anhydride copolymer, (D) modified polyolefin, (E) propylene polymer, and (F) glass fiber are as follows.

-Shiku L cliff'Lar Lヱ(1) Nylon 66 Relative viscosity: 2.85 Amino terminal group concentration: 5.0XlO-' equivalent/g (2) Nylon 6.66 Copolymerization ratio: Nylon 6/Nylon 66 = 10 /9 Relative viscosity: 2.90 Amino end group concentration: 4.5X10-S equivalent 7g (3) Nylon 6 Relative viscosity: 3.10 Amino end group concentration: 4.5X10-' equivalent/gB in polyphenylene ether 30'C Poly(2,6-cymethyl-l) with an intrinsic viscosity of 0.58 a/g in chloroform solution (5-t%),
4-Phenylene) Ether C Styrene-Whale Malein Ushijyuto Dai-Lark #232 Sekisui Chemical Co., Ltd. D Polyolefin (1) Graft-modified polypropylene I Aitsu Tactical with an MFR of 1.0 g/10 min at 230°C 0.3 maleic anhydride in polypropylene
Graft-modified polypropylene with 5 weight addition ■.

(2) Graft-modified polypropylene ■ Maleic anhydride added to tactical polypropylene having an MFR of 1.0 g/10 min at 230°C with 0.7 g of maleic anhydride.
Graft-modified polypropylene with added weight%■.

(3) Ternary modified polyethylene I A ternary modified polyethylene (■) obtained by copolymerizing 7 parts by weight of methyl methacrylate and 1 part by weight of maleic anhydride to 100 parts by weight of ethylene.

(4) Ternary modified polyethylene ■ Ternary modified polyethylene ■ which is obtained by copolymerizing 9 parts by weight of methyl methacrylate and 3 parts by weight of maleic anhydride to 100 parts by weight of ethylene.

E Propylene 28(1) Propylene homopolymer A propylene homopolymer with an MFR of 10 g/10 min according to JIS K 6758 (manufactured by Showa Denko ■, Showaromer)
MA510).

(2) Propylene block copolymer A propylene-ethylene block copolymer with an MFR of 16 g/10 min according to JIS K 6758 (manufactured by Showa Denko ■,
Show Aroma-MK511).

Chopped strand fiber with a length of 3mm and a diameter of 10μ, the surface of which has been treated with an aminosilane coupling agent.

Examples 1 to 10 and Comparative Examples 1 to 3 The above (A) polyamide, (B) polyphenylene ether resin, (C) styrene-maleic anhydride copolymer,
(D) modified polyolefin and (E) propylene polymer were dry blended in advance for 5 minutes using a Henschel mixer in the amounts (parts by weight) shown in Table 1.

Each of the obtained mixtures was transferred to a vented co-directional twin screw extruder (diameter 30
m) to form pellets.

The glass fibers were introduced through the vent hole of the extruder to prevent breakage. The temperature when making these pellets is also all 2.
I set it to 80″C.

Samples for measuring physical properties were made from each pellet using an injection molding machine, and each physical property was measured. The results are shown in Table 2.

(Blank below C) [Effects of the Invention] The glass fiber-reinforced polyamide resin composition of the present invention, as shown in the picture above, uses a common polyamide such as nylon 66, a polyphenylene ether resin, and a styrene-maleic anhydride copolymer in combination. In addition, a propylene polymer (propylene, homopolymer and/or propylene copolymer) and modified polyolefin are melt-kneaded, and glass fiber is added, resulting in a high level of heat resistance and excellent impact resistance. , low water absorption, resistance to calcium chloride, etc.

Therefore, the glass fiber-reinforced polyamide resin composition of the present invention can be used as engineering plastics, specifically in various machines such as automobile parts (especially radiator tanks, etc.), pump housings, electrical or electronic parts, and connectors thereof. It is expected to be widely and effectively used as a material for parts and industrial parts.

Claims (1)

[Claims] (1) (A) At least one type of polyamide 10 selected from nylon 66, nylon 6/66, and nylon 6
0 parts by weight, (B) 5 to 100 parts by weight of polyphenylene ether resin, (C) 5 to 100 parts by weight of styrene-maleic anhydride copolymer, (D) 0.5 to 100 parts by weight of modified polyolefin, (E
) A glass fiber reinforced polyamide resin composition containing 0 to 150 parts by weight of a propylene homopolymer and/or propylene copolymer and (F) 10 to 180 parts by weight of glass fibers.