JPS61211363A - Polyamide resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent resistance to impact and metal halide, consisting of a polyamide resin and a modified ethylene/alpha- olefin copolymer. CONSTITUTION:0.05-5wt% alpha,beta-unsaturated carboxylic acid (derivative) and 0.01-5wt% olefinally unsaturated silane compd. of the formula (wherein R is an olefinically unsaturated hydrocarbon group; R<1> is an aliph. satd. hydrocarbon group; Y is a hydrolyzable org. group; n is 0-2) are grafted onto an ethylene/(3C or higher) alpha-olefin copolymer having an ethylene content of 50mol% or above, a crystallinity of 1-75% and an MI of 0.05-40g/10min at 150-300 deg.C to obtain a modified ethylene/alpha-olefin copolymer (A) having a crystallinity of 75% or below and an MI of 0.01-50dl/10min. 1-120pts.wt. component A and 0.1-120pts.wt. inorg. filler (e.g. talc) having a particle size of 1-100mu are blended with 100pts.wt. polyamide resin having a relative viscosity of 2-6.

Description

DETAILED DESCRIPTION OF THE INVENTION C. Industrial Application Field This invention relates to a polyamide resin composition, which is resistant to metal halogens such as calcium chloride and has excellent impact resistance.

Polyamide resin is widely used as a material for automobile parts because of its high resistance to gasoline and the like. However, its field of use is limited because it is not resistant to calcium chloride, which is sprayed on roads as an antifreeze agent. The present invention provides a material that has improved metal halogen resistance and is suitable for automobile underhood parts.

Furthermore, materials made of polyamide resin mixed with inorganic fillers such as glass fibers are widely used in the fields of vehicles, electrical/electronic, and machinery due to their excellent mechanical strength and heat resistance.

However, for example, bicycle wheels, gears for office automation equipment, and the like require extremely high impact resistance, and reinforced polyamide resins with ordinary fillers are insufficient. The present invention can satisfy both of these requirements.

Method of blending ethylene-α-olefin copolymer grafted with Japanese carboxylic acid into polyamide (JP-A-Sho!!-9
4A/publication) has been proposed. On the other hand, as a method of improving metal halogen resistance, a method of blending ethylene-based ionomer resin with polyamide (Japanese Patent Application Laid-open No. 3'7-/3/21
7! R publication) has been proposed.

Furthermore, as a method for improving the pavement impact resistance of non-reinforced resins, a polyamide resin blended with a random copolymer having a functional group capable of adhering to a matrix resin has been reported (Japanese Unexamined Patent Publication No. 5T-TA30B/). .

However, when a filler is added, the adhesion between the random copolymer and the filler is insufficient, so a resin containing an impact-resistant filler and a resin containing a random copolymer are manufactured separately. An unproductive method is used in which a resin containing both a filler and a random copolymer is produced by passing it through an extruder.

[Purpose of the invention]

The present invention has the following configuration to solve the above problem.

That is, a polyamide resin composition consisting of a polyamide resin composition consisting of a polyamide resin and a modified ethylene copolymer obtained by grafting an α, β unsaturated carboxylic acid or a derivative thereof and an olefinically unsaturated silane compound to an ethylene-α olefin copolymer. or a polyamide resin composition further comprising an inorganic filler in the above composition.

[Structure of the invention]

To explain each of the above components, first, the polyamide used in the present invention includes lactam having three or more membered rings,
Polyamides obtained by polycondensation of polymerizable ω-amino acids, dibasic acids, and diamines can also be used. Specifically, polymers such as ε-caprolactam, aminocaproic acid, α-pyrrolidone, α-piperidone, hexamethylene diamine, nonamethylene diamine,
' Polymers obtained by polycondensing diamines such as undecamethylene diamine, dodecamethylene diamine, and metaxylene diamine with dicarboxylic acids such as terephthalic acid, inphthalic acid, adipic acid, cepatic acid, dodecane dibasic acid, and geltaric acid; These copolymers, such as nylon, l/, l, 6.6, b
, io, le, /2.6T, etc.

In particular, nylon 6.66 is preferred in terms of cost and heat resistance.

Also, relative viscosity (9 based on JIS K-t, gto)
The value measured in 1% concentrated sulfuric acid) is ~6, especially ~5.
5 is preferred.

A modified ethylene copolymer is a copolymer of ethylene and an α-olefin (hereinafter referred to as an unmodified ethylene copolymer), an α-, β-unsaturated carboxylic acid, a derivative thereof, and the general formula R8IRAYj-Y ( Here, R is an olefinically unsaturated hydrocarbon group, R1 is an aliphatic saturated hydrocarbon group, Y is a hydrolyzable organic group, and n is an integer of O-co). There are advantages and disadvantages in grafting the compounds to unmodified ethylene copolymers, respectively.

The above-mentioned unmodified ethylene copolymer can be produced by using, for example, a Ziegler-Natsuta catalyst, especially a vanadium compound such as vanadium oxytrichloride or vanadium tetrachloride, and an organoaluminum compound. More than θ mole, preferably go ~ 95 mole and less than 0 mole, preferably coO
Examples include those copolymerized with an α-olefin having 3 or more carbon atoms and a molar coefficient of ~S.

The above-mentioned unmodified ethylene copolymer has an α-olefin with a carbon number of 3 to θ, and a crystallinity of 1 to 3!壬、Melt index (MI) o, o t~5θt17to, especially α-olefin is propylene or butene-1 with crystallinity l~3! H, M I O, 0, t −
10y-//0 minutes is preferable.

Suitable such unmodified ethylene copolymers include the series of resins sold under the trademark Tamashi Petrochemical Industry Co., Ltd. under the trademark Yoshitatsumar, such as Tough? -A 4! θg
s, haoqo, haooq.

Tafmer series (ethylene-butene l copolymer) such as Tafmer PO Koto, popza 0゜pobto, p
Tough like orto? -P series (ethylene-propylene copolymer) and the like.

The α,β unsaturated carboxylic acids or derivatives thereof (hereinafter simply referred to as unsaturated carboxylic acids) to be grafted onto the unmodified ethylene copolymer include acrylic acid, methacrylic acid,
Examples include ethacrylic acid, maleic acid, fumaric acid, and anhydrides or esters of these acids.

Among these, maleic anhydride is particularly preferred.

The amount of unsaturated carboxylic acid to be grafted to the unmodified ethylene copolymer is o, or-
s parts by weight. If this amount is too small, the effect of improving impact resistance will be small, only molded products with low tensile elongation will be obtained, and surface peeling of molded products will occur due to poor compatibility with polyamide, so this is not preferred. do not have. On the other hand, too much content is not preferable because it causes discoloration. Preferably 0. /-2.5 parts by weight.

The olefinically unsaturated silane compound to be grafted onto the unmodified ethylene copolymer has the general formula R3I R"
Y, -n (where R is an olefinic unsaturated hydrocarbon group, R1 is an aliphatic saturated hydrocarbon group, Y is a hydrolyzable organic group, and n is an integer from θ to Y) Refers to a silane compound, specifically, for example, R is vinyl,
Allyl, impropenyl, butenyl, cyclohexenyl, r-(meth)acryloisooxypropyl, etc., R'
Camethyl, ethyl, propyl, decyl, phenyl, etc.
Y is methoxy, ethoxy, formyloxy, acetoxy, propionyloxy, altriethoxysilane, vinyltriacetoxysilane, r-methacryloyloxypropyltrimethoxysilane. The amount of grafting is o, oi-r parts by weight, preferably O, os- to ko2
There are parts by weight, and if it is small, the effect of improving physical properties of metal halogen resistance will be small. On the other hand, if the amount is too large, physical properties such as elongation will deteriorate.

Grafting is carried out by adding an unsaturated carboxylic acid and a silane compound to an unmodified ethylene copolymer according to a conventional method.
．． This is done by melting and kneading at yoo°C. In this grafting, 1-JJ-d 7 t in the grafting reaction 6 m
J-24u If /V /V/ t/ -F
An organic peroxide such as A-7'' tilperoxy-p-diisopropylbenzene may be used in an amount of about 0.007 to 0.05 weight percent based on the unmodified ethylene copolymer.

The modified ethylene-α-olefin copolymer used in the present invention has a crystallinity (Journal of Polymer Science,
According to the description in Volume X (lqrs)lili~λ6 page
The melt index (measured by line method) is preferably 75% or less, preferably 1 to 3'5%, and the melt index (MI
, ASO01 to YUO are preferable.

In order to prepare a modified ethylene-α olefin copolymer having such a crystallinity and melt index, an unmodified ethylene copolymer having a crystallinity and melt index within the above ranges may be used.

Grafting α, β-unsaturated carboxylic acid and olefinically unsaturated silane inclusion 1. The blending amount of the non-alpha olefin copolymer is 7 to 120 parts by weight, preferably 3 to 100 parts by weight, based on 100 parts by weight of the polyamide resin.
If it is too low, the effect of improving impact resistance and metal halogen resistance will be reduced, and if it is too high, heat resistance will be impaired, which is not preferable.

Inorganic fillers used include inorganic fibers, metal powders, metal oxides, metal carbonates, metal sulfates, clay minerals, carbon powder, etc. Specifically, glass fibers, carbon fibers, metal Whiskers, aluminum powder, zinc powder, silica, alumina, silica-alumina, titania, magnesia, zinc white, calcium carbonate, barium carbonate, aluminum sulfate, barium sulfate, calci sulfate sand, quartz powder, pumice, asbestos, feldspar powder, Examples include carbon black, graphite powder, glass powder, etc. Silicate-based inorganic fillers are preferred, and glass fibers, glass fibers, etc. are preferred for improving heat resistance.
If appearance is important, use wollastonite, talc,
Average particle size of kaolin, mica, glass powder, etc.
μ particles are preferred.

The blending amount of the inorganic filler is polyamide resin io.

0.1-720 parts by weight, preferably /
'-700 parts by weight. In a very small amount, a modified ethylene-α olefin copolymer or an inorganic filler may be blended with a polyamide resin at any stage immediately before molding the final molded product by any means. Can be done. The simplest method is to tri-blend the resin and additives, but this tri-blend may be melt-mixed and extruded to form pellets. Alternatively, master pellets kneaded with a predetermined amount or more of additives may be prepared and blended with diluent resin pellets.

In order to obtain the final molded product, the blend or pellets may be fed into various molding machines such as injection, extrusion, blowing, and compression, and molded according to conventional methods.

The composition of the present invention contains well-known additives such as hindered phenols, stabilizers such as copper salt compounds, flame retardants such as bromine compounds, antistatic agents, ultraviolet absorbers/stabilizers, dyes/pigments, etc. You may.

Furthermore, in order to improve the adhesion between the nylon resin and the inorganic filler, an amino-based or epoxy-based silane treatment agent, an epoxy compound, a urethane compound, or the like may be added.

[Example] The present invention will be specifically explained below with reference to Examples.
The present invention is not limited to the following examples unless it exceeds the gist thereof.

In the examples, "parts" and "chi" indicate "parts by weight" and "wt%", respectively.〇Ethylene-butene-7 copolymer (crystallinity: 1,4
To1 ILlu Rika, aLX
thaha snake α, α'-bis-1-butylperoxy-p
-Diisopropylbenzene.

(Dissolved in a small amount of acetone) 0.02!
r parts maleic anhydride o parts The above mixture was blended in a Henschel mixer.

The cono-blend product was processed into 2JOC using a Uormφ, L/D-2K vent type extruder (Isuzu Kako Yokozaki).
It was extruded and pelletized. The crystallinity of this product is
%, M! was 86.

After pulverizing a portion of the pellets, unreacted maleic anhydride was extracted with acetone using a Soxhlet extractor for 11 hours. After drying, this product was press-molded and the amount of maleic anhydride was determined by infrared spectroscopy, and it was found that 0.37% of maleic anhydride had been graft-polymerized.

IqO part Dicumyl peroxide O-12 parts Vinyltriethoxysilane 3 parts After mixing the above mixture in a Henschel mixer for 1 minute, J
OM4φL / D = J g coaxial extruder (manufactured by Nakatani Kikai) /? (By melting and kneading at 7C,
A modified ethylene-butene-1 copolymer grafted with maleic anhydride and a silane compound was produced. This thing M
1 is 8 l/io, and the content of maleic anhydride is 0. Unfortunately, the content of silane compounds was determined by fluorescent X-ray analysis.

Example 1, Comparative Examples 1 to 3 Nylon 6 on each side was ηrel m J, j, and the ingredients shown in Table 1 below were added to 100 parts of this nylon in the above-mentioned Yu-screw extruder. After melting and mixing,
, using an AOZ injection molding machine (Toshiba Machine xsqss),
Samples for physical property tests were prepared at a molding temperature of Y boc and a mold temperature of Oo.

The ionomer resins in Table 1 below are as follows.

Ethylene-containing Il-za6. ! Thimethacrylic acid content 6.6% Zinc methacrylate content Le. 9% MI 2. Of/10 minutes Table 1 Part 1 test The Izod impact value was measured according to ASTM D-56, and the bending properties were measured according to ASTM D-9θ.

For calcium chloride resistance, we used a test piece in which notches with a radius of O and SSR were cut at a depth of GaI from both sides of the parallel part of an ASTM No. 1 dumbbell piece.
! ! 2, a random-stress two-tracking test was carried out with SOC in an aqueous solution of calcium chloride SO%.
The test was carried out under the condition of a kg load, and the time to break of the test piece was measured. The longer the breaking time, the better the resistance to calcium chloride.Example and Comparative Examples Glunylon with ηrel m J, 0 100
As for the glass fiber, Asahi Fiberglass Co., Ltd.
Samples for physical property tests were prepared using so, yMhaii and the ingredients shown in Table 2 below in the same manner as in Example 1. The results are shown in Table 1.

Note that the tensile strength and elongation rate were measured in accordance with ASTM D&, 3g, and other tests were performed in the same manner as in Example 1.

Example 3 and comparative example! The same procedure as in Example 4 was carried out using the ingredients shown in Table 3, except that wollastonite (Nagase Sangyo Wolast Cup) was used for 700 parts of 6N oy (ηre+3.0). The results are shown in Table 1.

〔Effect of the invention〕

As is clear from the above description, the polyamide resin composition of the present invention has excellent metal halogen resistance and impact resistance, and is an extremely useful resin as an industrial material.

Applicant: Mitsubishi Chemical Industries, Ltd. Agent: Patent Attorney Hase - 1 other person

Claims (4)

[Claims] (1) Polyamide resin, ethylene-α olefin copolymer, α, β unsaturated carboxylic acid, or a derivative thereof,
A polyamide resin composition comprising a modified ethylene-α olefin copolymer grafted with an olefinically unsaturated silane compound. (2) The polyamide resin composition according to claim 1, which comprises 1 to 120 parts by weight of the modified ethylene-α olefin copolymer per 100 parts by weight of the polyamide resin. (3) A polyamide resin composition which further contains an inorganic filler in the polyamide resin composition according to claim 1. (4) The polyamide resin according to claim 3, which comprises 1 to 120 parts by weight of a modified ethylene-α olefin copolymer and 0.1 to 120 parts by weight of an inorganic filler based on 100 parts by weight of the polyamide resin. Composition.