JPH03146551A - Reinforced polyamide-polyolefin resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having the merits of constituent resins and excellent paintability by compounding a modified polyolefin and a fibrous reinforcing material and/or an inorganic filler to a polyamide resin and a polypropylene resin having melt-viscosity ratio satisfying a specific formu la. CONSTITUTION:The objective composition is produced by compounding (A) 100 pts.wt. of a mixture composed of (a) 80-40wt.% of a polyamide resin (prefer ably a polyamide having high amino-terminal content). (b) 1-40wt.% of a modi fied polyolefin having a melt index of 0.01-100g/10min (e.g. polypropylene grafted with maleic anhydride) and (c) 20-60wt.% of a polypropylene resin having an MFR of preferably 1-50g/10min with (B) 1-200 pts.wt. of a fibrous reinforcing material and/or an inorganic filler. The ratio of the melt-viscosity of the compo nent (a) etaPA to that of the component (c) etaPP at the molding temperature and a shear rate of 3,500/sec satisfies the formula I, preferably formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a reinforced polyamide/polyolefin resin composition. This invention relates to a reinforced polyamide/polyolefin resin composition.

[Prior art and problems to be solved by the invention] In general, various reinforced polyamide resins have high mechanical strength, heat resistance (
It has excellent properties such as heat aging resistance, heat deformation resistance), chemical resistance, electrical properties, and friction and abrasion properties, so it is widely used as an engineering resin for various mechanical parts materials. On the other hand, it has some problems due to its water absorption properties due to the amide group (-CONH-). In particular, reinforced boria resins that have absorbed water tend to contain bubbles and cause whitening or hydrolysis when molded, which poses many practical problems. Moreover, water absorption not only causes a significant decrease in mechanical strength, but also causes problems such as dimensional changes and deformation.

Since the reinforced polyamide resin has the above-mentioned drawbacks, its use as an engineering resin is limited, and the excellent properties inherent to the polyamide resin itself cannot often be utilized.

On the other hand, polypropylene resin is relatively inexpensive and has good properties such as exhibiting almost no water absorption, but has the drawback of being soft and having poor physical properties at high temperatures. Therefore, attempts have been made to use polyamide resins and polypropylene resins in combination in order to complement and improve their respective drawbacks. However, simply melt-kneading polyamide resin and polypropylene resin results in poor compatibility and peeling between them, so even if they are reinforced with fibrous reinforcing materials or inorganic fillers, compositions with excellent properties still remain. The problem is that it cannot become a thing.

For this reason, we have traditionally developed resin compositions that combine the excellent properties of boria straw resin and polypropylene resin, that is, the excellent mechanical strength, heat deformation resistance, abrasion resistance, oil resistance, etc. of polyamide resin, and the excellent properties of polypropylene resin. Various studies have been carried out with the aim of obtaining a resin composition that has excellent low water absorption, hot water resistance, resistance to metal halides, and low-temperature impact resistance. (Japanese Patent Publication No. 42-12546, Japanese Patent Publication No. 50-7636, etc.).

In the case of these various reinforced resin compositions, mechanical strength, heat deformation resistance, oil resistance, and metal halide resistance are required.

Although some improvements in physical properties such as low water absorption have been achieved, there is currently little research into improving paintability. In other words, these resin compositions (polymer alloy compositions) contain polypropylene resin, which has poor paintability compared to polyamide resins, so they have insufficient paintability overall, and as a result, their applications are quite limited. The current situation is that

The present inventors have completed the present invention as a result of extensive research aimed at improving the paintability, especially while maintaining the excellent properties of polyamide resins and polypropylene resins.

[Means to solve the problem]

That is, the present invention comprises (A) 80 to 40% by weight of polyamide resin, (B) 1 to 40% by weight of modified polyolefin, and (
C) 1-200 parts by weight of (D) a fibrous reinforcing material and/or inorganic filler is blended with 100 parts by weight of a mixture consisting of 20-60% by weight of polypropylene resin, and the molding temperature.

The ratio of the melt viscosity ηrA (poise) of the polyamide resin (A) and the melt viscosity ηrr (poise) of the polypropylene resin (C) at a shear rate of 35005 ec-' is expressed by the formula η1. /ηps＞0.75 ・ ・
- Provides a reinforced polyamide/polyolefin resin composition that satisfies (1).

Various types of polyamide resin (A) can be used in the present invention, and specifically, nylon 6, nylon 11. Polylactams such as nylon 12; nylon 66, nylon 610. Nylon 612. nylon 46
Polyamides obtained from dicarboxylic acids and diamines such as nylon 6/66, nylon 6/12. nylon 6
/667610 and other copolymer polyamides; nylon 6
/6T (T: terephthalic acid component), semi-aromatic polyamides obtained from aromatic dicarboxylic acids such as isophthalic acid and metaxylene carbonate or alicyclic diamine; polyesteramide, polyetherade and polyesteretheramide. can be mentioned. In addition, (A)
As the component polyamide resin, the above-mentioned various polyamides may be used alone, or two or more types of polyamides may be used in combination.

Furthermore, the polyamide resin that can be used in the present invention is
As long as it is selected from the above-mentioned polyamides, various polyamides can be used without being limited by the type, concentration, molecular weight, etc. of the terminal groups of these polyamides, but highly amino-terminated polyamides are particularly preferred.

Furthermore, it is also possible to use polyamide in which low molecular weight substances such as monomers and oligomers that remain or are generated during polymerization of polyamide are mixed.

Next, the modified polyolefin (B) of the present invention includes carboxylic acid groups (acetic acid groups, acrylic acid groups, methacrylic acid groups,
fumaric acid group, itaconic acid group, etc.), carboxylic acid metal bases (sodium salt, calcium salt, magnesium salt, zinc salt, etc.), carboxylic acid ester group (methyl ester group,
Ethyl ester group.

A polyolefin having at least one functional group selected from a propyl ester group, a butyl ester group, a vinyl ester group, etc.), an acid anhydride group (maleic anhydride group, etc.), and an epoxy group.

Also, this polyolefin is polyethylene.

Examples include polypropylene, polybutene, ethylene/propylene copolymers, ethylene/butene copolymers, ethylene/hexene copolymers, and copolymers containing a small amount of diene.

Specific examples of such modified polyolefins include ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, ethylene/fumaric acid copolymer, ethylene/methacrylic acid/zinc methacrylate copolymer, and ethylene/acrylic acid copolymer. Acid/sodium methacrylate copolymer, ethylene/
Isobutyl acrylate/methacrylic acid/zinc methacrylate copolymer, ethylene/methyl methacrylate/methacrylic acid/magnesium methacrylate copolymer, ethylene/
Ethyl acrylate copolymer, ethylene/vinyl acetate copolymer, ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, maleic anhydride grafted polyethylene, acrylic acid grafted polyethylene, maleic anhydride Grafted polypropylene.

Maleic anhydride grafted ethylene/propylene copolymer, acrylic acid grafted ethylene/propylene copolymer,
Fumaric acid grafted ethylene/l-butene copolymer, ethylene/1-hexene-itaconic acid copolymer, ethylene/
Propylene-endobicyclo(2,2,11-5-heptene-2,3-dicarboxylic anhydride copolymer, ethylene/
Propylene-grafted glycidyl methacrylate copolymer.

Maleic anhydride grafted ethylene/propylene/1.4
-Hexadiene copolymer, fumaric acid grafted ethylene/
These modified polyolefins include propylene/dicyclopentadiene copolymer, maleic acid grafted ethylene/propylene/norbornadiene copolymer, and acrylic acid grafted ethylene/vinyl acetate copolymer, and these modified polyolefins may be used alone, or It is also possible to use two or more types together.

The above-mentioned modified polyolefin can be produced by known methods, for example, Japanese Patent Publication No. 39-6810, Japanese Patent Publication No. 46-27527, Japanese Patent Publication No. 50-2630, Japanese Patent Publication No. 52-43.
Publication No. 677, Special Publication No. 53-5716, Special Publication No. 577
It can be produced according to the methods disclosed in Japanese Patent Publication No. 3-19037, Japanese Patent Publication No. 53-41173, Japanese Patent Publication No. 56-9925, and the like. Regarding ethylene ionomers, generally "Surlyn", Hymirampa,
Various grades commercially available under the trade name "Corpolene" can be used. Further, the degree of polymerization of the modified polyolefin used in the present invention is not particularly limited, but it can be selected arbitrarily from one having a melt index usually in the range of 0.01 to 100 g/10 minutes.

Subsequently, as the (C) polypropylene resin of the present invention,
Propylene homopolymers and/or propylene copolymers are used. Examples of propylene copolymers include propylene-ethylene copolymers, propylene-butene-1 copolymers, and block copolymers and random copolymers of these copolymers. In addition, for this polypropylene resin, a propylene homopolymer or a propylene copolymer may be used alone, or two or more types may be used in combination. At this time, the molecular weight of the propylene homopolymer or propylene copolymer is not particularly limited, but those having a VFR of 1 to 50 g/10 minutes are generally preferably used.

Furthermore, in the present invention, (D) a fibrous reinforcing material and/or an inorganic filler is used. That is, as component (D), one or both of a fibrous reinforcing material and an inorganic filler are used.

Examples of the fibrous reinforcing material include glass fiber, potassium titanate fiber, and metal-coated glass fiber.

Ceramic fiber, wollastonite, carbon fiber.

Examples include aramid fibers, metal carbide fibers, and ultra-high modulus polyethylene fibers.

Examples of inorganic fillers include oxides such as iron oxide, alumina, magnesium oxide, calcium oxide, and zinc white, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, calcium hydroxide, tin oxide hydrate,
Hydrated metal oxides, such as zirconium oxide hydrate, etc.
Carbonates such as calcium carbonate, magnesium carbonate etc., silicates such as talc, clay, bentonite, attapulgite etc., borates such as barium borate, zinc borate etc., aluminum phosphate.

Examples include phosphates such as sodium tripolyphosphate, sulfates such as gypsum, and sulfites. Other materials that can be used include spherical objects such as glass peas, glass balloons, and glass balloons, glass powder, glass flakes, and mica.

The type of these fibrous reinforcing materials or inorganic fillers can be selected as appropriate depending on the purpose. When using a mixture of various fibrous reinforcing materials and inorganic fillers, multiple fibrous reinforcing materials may be used. In some cases, multiple inorganic fillers may be used.

In the composition of the present invention, various components as described above can be used as components (A) to (D), but among these,
Between component (A) and component (C), the melt viscosity η of component (A) and the melt viscosity 7 of component A (poise) and component (C) at a molding temperature and a shear rate of 35005 ec-'
7 The ratio of rp (poise) is expressed by the formula η, 2/ηPA>
0.75...(1) It is necessary to select a combination of those that preferably satisfy the formula ηPF/ηPA>1.00...[I''].Here, η
If the value of 22/η is less than 0.75, the polyamide resin will form a dispersed phase, making it impossible to impart desired paintability to the resulting resin composition, which is not preferable. The term "molding temperature" as used herein refers to the temperature at which various molded products are produced by molding the composition of the present invention, and is generally in the range of 180 to 350''C.

The blending ratio of each component in the resin composition of the present invention is based on the total amount of the components (A), (B), and (C).
) component 80-40% by weight, preferably 80-45% by weight
, component (B) 1 to 40% by weight, preferably 3 to 30TJ
, amount%, and component (C) is selected within the range of 20 to 60% by weight, preferably 20 to 50% by weight. The amount of component (D) is in the range of 1 to 200 parts by weight, preferably 5 to 180 parts by weight, based on a total of 100 parts by weight of components (A), (B), and (C).

If the content of component (A) is less than 40% by weight, sufficient paintability cannot be imparted to the resulting composition. 8 again
If it exceeds 0% by weight, the properties of the polypropylene resin will be lost. On the other hand, if the blending ratio of component (B) is less than 1% by weight, it is difficult to improve the compatibility between the polyamide resin as component (A) and the polypropylene resin as component (C). Desired physical properties cannot be imparted to the composition, and even if component (B) exceeds 40% by weight, there is little effect corresponding to the amount blended, and there is a risk that the various physical properties of the resulting composition may be deteriorated. Furthermore (C)
7i! If the content is less than 20% by weight, the original properties of the polypropylene resin cannot be brought out; conversely, if the content is less than 20% by weight,
If the amount exceeds 100%, it becomes difficult to impart sufficient paintability to the composition.

In addition, the blending amount of component (D) is the above (A), (B) and (
C) With respect to the total 100 parts by weight of the ingredients, if it is less than 1% by weight, physical properties such as mechanical strength cannot be imparted to the &tI treasure, and on the other hand, even if it exceeds 200 parts by weight, it is equivalent to the amount blended. The effect is small, and there is a risk that the various physical properties of the resulting composition may be deteriorated.

The resin composition of the present invention includes the above (A) and (B).

Although the four components (C) and (D) are the main components, other additives may be added as necessary to the extent that the properties of the above components are not impaired. Additives that can be blended here include dyes, pigments, nucleating agents, plasticizers, lubricant 2M type agents, coupling agents 2 blowing agents, heat resistant agents, weathering agents, flame retardants, antistatic agents, sliding agents, etc. It will be done.

The resin composition of the present invention is a resin composition formed by blending the above four components and additives added as necessary in predetermined amounts. There is no particular restriction on the order of blending, and each component may be blended sequentially or simultaneously. Also, after the completion of the polymerization reaction, CB), (C), and (D)rj are added to the powdered or pelleted component (A). ;c component may be added. Alternatively, component (A) that is still in a molten state after the polymerization reaction is
(C) and (D) Ift may be blended and melt-kneaded.

As described above, the resin composition of the present invention is prepared by mixing or kneading each component at the above-mentioned mixing ratio, and a conventionally known melt-kneading method is preferable. Mixing is carried out using a Banbury mixer, a Henschel mixer, etc., and a single-screw or twin-screw extruder is generally used as the kneader. The temperature during melt-kneading is based on the ingredients,
The temperature at which melting of each component sufficiently progresses and does not decompose may be appropriately selected depending on the blending amount and the like. Usually 180-350
°C, preferably in the range of 200 to 300 °C.

The obtained resin composition may be molded into any desired shape by extrusion molding, compression molding, injection molding, etc. to produce desired resin products such as pipes, tubes, rods, and blow molded products. Furthermore, processing such as plating and painting can be applied afterwards.

〔Example〕

Next, the present invention will be explained in more detail based on Examples and Comparative Examples.

The various physical properties of the reinforced polyamide polyolefin resin &Il obtained on each side below were measured based on the following test methods.

The 00XOOX three cabinet plates were molded from the composition using a screw in-line injection molding machine. The cylinder temperature at this time was 280°C regardless of the type of polyamide resin (A). Moreover, the mold temperature was 80°C.

Using a cavilograph manufactured by Nosha Nasho Toyo Seiki ■, the temperature is set at 280.
The melt viscosity was measured at a C1 shear rate of 35005 ec-'.

A two-component polyurethane resin paint (Stron Ace #680, manufactured by Cashew ■) was used as the paintable paint and was applied to the flat plate by spraying, and the drying conditions were 100°C for 40 minutes. After the sample was left at room temperature for one day, a base peel test and a measurement of the adhesion strength of the coating film were performed.

Examples 1 to 11 and Comparative Examples 1 to 4 (A) polyamide resin, (B) modified polyolefin, (C) polypropylene resin, and (D) various reinforcing materials (fibrous reinforcing material, inorganic filler) shown in Table 1 were mixed in a predetermined amount and dry-mixed for 5 minutes using a Henschel mixer.
L/D=17) was melt-kneaded to create a pellet. The heating temperature when making pellets is all 280°.
It was set as C.

After drying this pellet by heating under reduced pressure, a flat plate was formed by injection molding, and a coating test was conducted. The results are shown in Table 1.

In addition, this Table 1 shows 280°C1 shear rate 3500
The melt viscosity ratio (ηpp/η,) of (A) polyamide resin and (C) polypropylene resin at 5ec-' is also shown.

*1 : *2 : *3 : *4 : *5 : *6 : To P66, relative viscosity 2.30AQ/terminal group concentration 5. lX10-'it/gPA6. Relative viscosity 2.52 Amino end group concentration 4.9X10
-' equivalent/gPA66, relative viscosity 2.85, terminal group concentration 5.2X10-' equivalent/gPA6.
Relative viscosity 3.20 ξ terminal group concentration 4.
9X10-' equivalents/g graft-modified polypropylene, 2
MFR at 30°C is 1. Maleic anhydride was added to isotactic polypropylene having a
Graft-modified polypropylene glycidyl methacrylate grafted ethylene-vinyl acetate copolymer with weight percent addition was produced with reference to the method described in Japanese Patent Publication No. 12449/1983. That is, ethylene-vinyl acetate copolymer pellets,
Glycidyl methacrylate with dicumyl peroxide dissolved in advance was mixed and infiltrated at room temperature. It was extruded using an extruder at a tip temperature of 170° C. to obtain graft-polymerized epoxy group-containing copolymer pellets (glycidyl methacrylate content: 2 wt%).

Propylene homopolymer, M in JIS K 6758
Propylene homopolymer/propylene block copolymer with FR of 0.5 g/10 min, JIS K 675B
"i" (7) Propylene block copolymer propylene homopolymer with MFR of 0.8 g/10 min, M in JIS K 6758
Propylene homopolymer with FR of 3g/10min, M in JIS K 6758
Propylene homopolymer with FR of 30 g/l 0 minutes *11: *12: * a : * b : Micron White 5000A Hayashi Kasei ■ Chopped strand fiber with length of 3 am and diameter of 10 μ, the surface of which is coated with aminosilane Coupling agent-treated product Percentage relative to the total amount of components (A), (B), and (C) (Parts by weight relative to 100 parts by weight of the total amount of components A), (B), and (C) [Effects of the invention] As explained, according to the present invention, it is possible to produce various reinforced polypropylene resin compositions that have both the excellent properties of polyamide resin and polypropylene resin and have particularly excellent paintability. A resin composition suitable for applications requiring paintability can be easily obtained.

Therefore, the reinforced polyamide/polyolefin resin composition of the present invention is suitably used for automobile parts (outer panels, exteriors, etc.), mechanical parts, industrial parts, etc. that require paintability.

Claims (1)

[Claims] (1) (A) Polyamide resin 80-40% by weight, (B)
(D) 1 to 200 parts by weight of a fibrous reinforcing material and/or inorganic filler is blended with 100 parts by weight of a mixture consisting of 1 to 40% by weight of modified polyolefin and (C) 20 to 60% by weight of polypropylene resin. and molding temperature and shear rate 3
The ratio of the melt viscosity η_P_A (poise) of the polyamide resin (A) and the melt viscosity η_P_P (poise) of the polypropylene resin (C) at 500 sec^-^1 is expressed by the formula η_P_P/η_P_A>0.75...[I
A reinforced polyamide/polyolefin resin composition that satisfies the following: