JPS61179259A - Polyamide resin composition - Google Patents

Abstract

PURPOSE:To improve resistance to metal halide so as to fit the use as automobile underhood parts, by blending a polyamide with a copolymer of ethylene or propylene and an olefinically unsaturated silane compd. CONSTITUTION:1-120pts.wt. copolymer of ethylene or propylene and an olefinically unsaturated silane compd. of the formula (wherein R is an olefinically unsaturated hydrocarbon group; R' is an aliph. satd. hydrocarbon group; Y is a hydrolyzable org. group; n is 0, 1, 2) is blended with 100pts.wt. polyamide. If desired, not more than 120pts.wt. at least one compd. selected from among modified ethylene/alpha-olefin copolymers (a) obtd. by grafting an alpha,beta-unsaturated carboxylic acid or its derivative onto an ethylene/alpha-olefin copolymer, products (b) obtd. by neutralizing component (a) with a metal ion and neutralized products (c) obtd. by neutralizing an ethylene/alpha,beta-unsaturated monocarboxylic copolymer with a metal ion, may be added thereto to further improve resistance to metal halide.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a polyamide resin composition, a polyamide resin composition used in automobile parts that is resistant to metal halogens such as TPFK calcium chloride.

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, the control cable tube, which is a type of underhood component, requires both calcium chloride resistance and high impact resistance, and the present invention is intended to provide improved both of these properties at the same time.

[Conventional technology]

A polyamide composition with excellent metal resistance and chemical properties is produced by adding and blending an ethylene-based ionomer resin and inorganic fine particles to a polyamide whose main constituents are caproamide and/or hexamethylene diadipamide. S7-/3/24t! issue) has been proposed.

Furthermore, it is known that impact resistance can be improved by blending a modified ethylene-α-olefin copolymer, but the effect of improving metal resistance is not clear, but it is presumed to be equivalent to that of an ionomer resin.

[Purpose of the invention]

The present invention provides a polyamide composition which has further improved metal/percentage resistance compared to the above compositions.

That is, the gist of the present invention is that (100 parts by weight of Al polyamide, (b) ethylene or propylene, and a compound of the general formula R8i
Wn Y@-n (wherein, R represents an olefinic unsaturated hydrocarbon group, y represents an aliphatic saturated hydrocarbon group, Y represents a hydrolyzable organic group, and n represents Q and/or -) A copolymer with an olefinic unsaturated silane compound represented by i-/JO and optionally (C1 (a) ethylene-α olefin copolymerization KKα1β unsaturated carboxylic acid or a derivative thereof is grafted to modify the copolymer Metal ion neutralized product (2) of ethylene-α-olefin copolymer (a) (1) At least one metal ion neutralized product of ethylene-α, β-unsaturated monocarboxylic acid copolymer (7) -0 parts by weight or less of the polyamide resin composition.
- [Structure of the Invention] To explain each of the above components, firstly, the polyamide used in the present invention includes lactam with three or more membered rings,
Polymerizable ω-amino acids.

A polyamide obtained by polycondensation of a dibasic acid and a diamine can be used. Specifically, C-caglolactam, aminocaproic acid, enantholactam, 7-
Polymers such as aminohebutanoic acid, l/-aminoundecanoic acid, 9-aminanoic acid, α-pyrrolidone, α-piperidone, hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, metaxylenediamine, etc. A polymer obtained by polycondensing a diamine with a dicarboxylic acid such as terephthalic acid, isophthalic acid, adipic acid, cepatic acid, dodecanibasic acid, or geltaric acid, or a copolymer thereof, for example.

Examples include nylon&, //, /ko, A, A, 6.10.1, /ko, AT, etc.

The content of olefinically unsaturated silane compound units in the copolymer of ethylene or propylene and the olefinically unsaturated silane compound represented by the general formula R8i&nYa-1 is 0.001-/! weight%
and preferably 0.0/-j times f times. R represents an olefinic unsaturated hydrocarbon or hydrocarbonoxy group, R' represents an aliphatic saturated hydrocarbon group, Y represents a hydrolyzable organic group, n FiO % 1 or -. Specific examples of this unsaturated silane compound include R being vinyl, allyl, isopropenyl, butenyl, cyclohexenyl, γ-(meth)acryloxyglobyl, and Y being methoxy, ethoxy, formyloxy, acetoxy, glopionoxy, alkyl or Arylamino, R/ is methyl, ethyl, propyl, decyl, phenyl. Particularly preferred unsaturated silane compounds are those represented by the following formula.

OH* = OHS i (OA) s (where A is a hydrocarbon group having 7 to 7 g, preferably 1 to 4 carbon atoms) The copolymerization method of ethylene or propylene with an unsaturated silane compound It may be carried out under any conditions that allow polymerization, and may be graft copolymerization or high-pressure radical copolymerization.

In addition, other ethylenically unsaturated compounds,
Vinyl esters, such as vinyl acetate, (meth)
Methyl acrylate% [Methacrylic esters such as butyl (meth)acrylate, (meth)acrylic acid, unsaturated carboxylic acids such as maleic acid, (meth)acrylonitrile, (meth)acrylamide, ) of acrylic acid derivatives, vinyl methyl ether, vinyl phenyl ether! 56 vinyl ethers may also be copolymerized.

Fi as a high-pressure radical copolymerization condition, for example, pressure! ;
00-4' 000kl/crl, preferably 1O
A radical polymerization initiator (e.g., an organic peroxide such as t-butylperoxyisobutyrate, benzoyl peroxide, oxides, azo compounds such as azobisisobutyronitrile) and, if necessary, chain transfer agents (paraffinic hydrocarbons such as methane, propane, butane; α-olefins such as propylene, butene-1; formaldehyde , aldehydes such as acetaldehyde;
The monomers are contacted simultaneously or stepwise in a seed or tube reactor, preferably a seed reactor, in the presence of a ketone such as methyl ethyl ketone.

As a graft copolymerization method, for example, the above-mentioned olefinically unsaturated silane compound is added to ethylene or propylene resin.
, /-/jtit part, the radical polymerization initiator is 0
．． About 0/-, O parts by weight and antioxidants (e.g.
6-di-tert-butyl-4-methylphenol, tetrakis-[methylene-3-(3,!;-di-tert-butyl-hydroxyphenyl)globionate] methane, and other diphenolic radical chain inhibitors. , dilauryl thiodiglopionate, trisnonylphenyl phosphite, thioether, phosphite-based peroxide decomposers, etc.) are added to the O-S in one part by weight - two-way extruder, Banbury mixer, etc. This can be carried out by a known method in which the reaction is carried out using a radical polymerization initiator at a temperature higher than the decomposition temperature of the radical polymerization initiator.

For details on these, please refer to Tokko Sho Qg-/7// issue, Tokko Sho! ! -91. // issue, Tokukai Showa 3 Day 361/! listed in the number.

The blending amount is 20 parts by weight, preferably 3 to 100 parts by weight, per 100 parts by weight of the polyamide resin. If the amount is small, the improvement effect will be small, and if the amount is too large, the properties of the polyamide resin will be impaired.

Of course, when compounding, it may be mixed alone with a polyamide resin, or it may be mixed with polyethylene, polypropylene, or a comonomer copolymerizable with ethylene, such as vinyl acetate, methyl acrylate, acrylic acid, propylene, butene, hexene, etc. Both! A masterbatch may be produced by combining and then blended.

Modified ethylene-α-olefin copolymer is a copolymer of ethylene and α-olefin (hereinafter referred to as unmodified ethylene copolymer) with α-olefin added to it.

It is obtained by graft polymerizing a β-unsaturated carboxylic acid or a derivative thereof to an unmodified ethylene copolymer at a ratio of 0.0r-jii.

The unmodified ethylene copolymer 1l-tl, for example, a Ziegler-Natsuta catalyst, especially vanadium oxytrichloride,
Using a vanadium compound such as vanadium tetrachloride and an organoaluminum compound, ethylene having a carbon number of 3 or more and 30 mol % or more, preferably θ to 93 mol, and 30 mol % or less, preferably 10 to S mol, Examples include those copolymerized with olefins.

The above-mentioned unmodified ethylene copolymer has an α-olefin having 3 to -0 carbon atoms, a crystallinity of 7 to 7S, and an M process of θ.
, 0/~! Particularly preferable are those in which the α-olefin is propylene or butene-1, the crystallinity is 0.01 to 0.01/10, and the crystallinity is 0.01 to 0.01 to 0.01 to 0.01.

Suitable such unmodified ethylene copolymers include the series of resins sold under the Tafmer trademark by Mitsui Petrochemical Industries ■, such as Tafmer AeOg! ;,
Toughmarm series such as Ari090%Akoθoqo (
(ethylene-butene l copolymer), Tafmer PO copolymer 10.
Pθ da go.

Examples include Tafmer P series (ethylene-propylene copolymer) such as Pobgo and Pogtro.

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 grafted onto the unmodified ethylene copolymer is 0. Or
-k 1tit part. If this amount is too small, the effect of modifying the 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 I don't like it.

On the other hand, too much content is not preferable because it causes discoloration. Preferably, it is in the range of O, L-co, and Rijukurabe.

Grafting is carried out by adding an unsaturated carboxylic acid to an unmodified ethylene copolymer according to a conventional method, usually at a rate of 1/s.

This is carried out by melting and kneading at ~aOO°C. During this grafting, α,
An organic peroxide such as .alpha.'-bis-t-butylperoxy-p-diisopropylbenzene may be used at an O2O3/-0, .theta.S weight ratio relative to the unmodified ethylene copolymer.

The modified ethylene-α-olefin copolymer used in the present invention has a crystallinity (Journal of Polymer Science,
Vol.
It is preferable that the melt index is Q, Q/~!
rO, preferably haO07 to -〇.

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

In order to neutralize the modified ethylene-α-olefin copolymer thus produced with metal ions, after blending the modified ethylene-α-olefin copolymer with a metal salt of acetic acid, etc.:
The melt reaction may be carried out in an extruder at a temperature of about 100°C.

Preferably, 5% or more of the carboxyl groups, particularly 10 qb or more, are neutralized with metal ions.

The ethylene content of metal ion neutralized ethylene-α,β-unsaturated monocarboxylic acid copolymers (commonly referred to as ionomer resins) is usually in the range of 70-99 moles. α
Specifically, as the β-unsaturated monocarboxylic acid, acrylic acid and methacrylic acid can be used. In addition, vinyl monomers include vinyl acetate, methyl (meth)acrylate, ethyl (meth)acrylate, isobutyl (
It is possible to open (meth)acrylates such as meth)acrylate.

Neutralized products of the above-mentioned modified polyolefin polymer grafted with ethylene-α olefin polymer and α,β unsaturated carboxylic acid and ethylene-α,β unsaturated monocarboxylic acid copolymer were prepared according to 1, n. 1%IVA and Vll group metal ions, specifically Na+, K+
, L1+%0 total, Ag+, Hg 10, otl+, Bo!
Ten, Mg! +, □ a t +, B r t +
, B a yi+Qut+, C6-*ten, Hgd\B
n * 10, Pb”, Fe * 10, CO! 10, N 1
t+%, z n4+%A1m+, S Q@ 10, F'e
Fist ten, Yl + sudo dl is thrown, but N”, Oa' ten, Z
n'10 is preferable, and a mixture of two or more species may be used.

Modified ethylene-α olefin copolymers (a) obtained by grafting α, β unsaturated carboxylic acids or derivatives thereof to these ethylene-α olefin copolymers (a), metal ion neutralized products thereof (b), or ethylene-α, Metal ion neutralized product of β-unsaturated monocarboxylic acid copolymer ← By further adding one of the following, metal halogen resistance can be further improved and impact resistance can be improved and controlled. It began to show excellent properties as a tube material for cables. The blending amount of these polymers is not more than /-0 parts by weight, preferably not more than lθO heavy parts; if the amount is more than this, the properties as a polyamide are significantly impaired.

The above-mentioned additives can be blended into the polyamide by various means at any stage up to just before molding the final molded product. The simplest method is to tri-blend polyamide and additives, but this tri-blend may also be melt-mixed and extruded to form pellets.

Alternatively, a master pellet kneaded with a predetermined amount or more of the additive may be prepared, and this may be blended with polyamide pellets for dilution.

In order to obtain the final molded product, the above-mentioned blend or pellet may be subjected to injection, extrusion, blowing, compression, etc.

The composition of the present invention may also contain reinforcing agents such as glass fibers and carbon fibers, fillers such as clay, silica, alumina, silica alumina, glass peas, asbestos, graphite, and gypsum, dyes and pigments, and hindered materials. Known additives such as phenol, hindered amine, stabilizers such as copper salts, antistatic agents, etc. may be used in combination.

〔Example〕

The present invention will be specifically explained below with reference to Examples.
The invention is not limited to the following examples unless it goes beyond the gist of the invention.

In the examples, "part" and "part" indicate "part by weight" and "part by weight," respectively.

Powdered high-density polyethylene (density 0.96 ta, il/
ac, M engineering q, o 17cc) / o o part and dicumyl peroxide (NOF) θ, LA, vinyltriethoxysilane (Nippon Uni: 1ffA-/g/) 3
After mixing with a high-speed stirrer for λ minutes,
Ethylene-vinylsilane copolymer (7) grafted with a silane compound was produced by melt-kneading at 190° C. in a coaxial extruder (manufactured by Nakatani Kikai) with OL/D = −g. MI of this 1. The core is 7/10 minutes, and the content of silane compounds is subject to fluorescent X-ray analysis.

Yoriko was in charge of S.

A mixture of ethylene, 7217/hr, vinyltrimethoxysilane (KBM1003, manufactured by Shin-Etsu Chemical Co., Ltd.), 2 kli/hr, and vinyl acetate, θkvhr, and propylene g 073/hr as chain transfer MIJ was placed in a stirred autoclave with an internal volume of JIJ liter. send the
As a polymerization initiator, t-butyloxyisobutyrate (NOF M) o, g Iyhr was added and the pressure was increased to 00 Yu/7. Ethylene-vinyltrimethoxylane-vinyl acetate copolymer (a) was continuously synthesized at a temperature of 1j°C. MI of the product is 3.19719 min, vinyl acetate content ft/g%, vinylsilanno content -1.O
, was in charge of S.

(1) Production bed for propylene-vinylsilane copolymer Powdered isotactic polypropylene loop part r Benzoyl peroxide (manufactured by NOF Corporation) 0-! ; Part - 3 parts of vinyltrimethoxysilane! A propylene-vinylsilane copolymer (2) was prepared by melt-kneading at 10 DEG C. in the same manner as in the case of the ethylene-vinylsilane copolymer.

MI of this produced copolymer! rl//10 minutes,
The content of the silane compound was in the order of magnitude.

2) Production of modified ethylene-α-olefin copolymer and its metal ion neutralized product” Ethylene-butene-1 copolymer (crystallinity - ○, M grade 3.6, butene-7 metal lid l damol grade) ) 7 o θ part α, α l-bis-t-butylperoxy-p-diimpurpylbenzene (dissolved in acetone with a small amount of f) 0.0 co! Maleic anhydride. - Part g The above mixture was blended in a Henschel mixer.

This blend is aowl, L/D = J g (7
) Using a bent tie extruder (manufactured by Isuzu Kakoki),
It was extruded at 0°C and pelletized to obtain modified ethylene-α-olefin copolymer K (-C1).

The crystallinity of this product was 20%, and the M finish was /, &.

After pulverizing a portion of the pellets, unreacted maleic anhydride was extracted with acetone using a Soxhlet extractor for 1 hour. After drying, this product was press-molded and the amount of maleic anhydride was determined by infrared spectroscopy, and it was found that θJ/% of maleic anhydride had been graft-polymerized.

After blending the ioo part of the above modified ethylene-α olefin copolymer with acetic acid and the S part with zinc powder in a Henschel mixer, extrusion with the above extruder under the same conditions to form pellets, and zinc ion of the modified ethylene-α olefin copolymer. A neutralized product was obtained. The crystallinity of this product was 10% M/f. After pulverizing a portion of this pellet, unreacted zinc acetate was thermally extracted with a water:ethanol-l neutral solvent, and the zinc content was determined by atomic absorption spectroscopy to find that θ was /6 excellent.

Examples 1-3. Comparative example 7-ri Assuming 6-nylon on each side, ηrθ1=Jj.

After melt-mixing the ingredients listed in Table 1 below to this nylon lOO portion using a λ-axis extruder, 3. A OZ injection molding machine (Toshiba Machine Works 57jS
), samples for physical property tests were made at a molding temperature of -60°C and a mold temperature of pro°C.

In Table 1 below, the ionomer resins of Comparative Examples are as follows.

Ethylene content g A, j % Methacrylic acid content 6.4qb Zinc methacrylate content Ru, Techi M Engineering
−,0! l/10 minwc1 In the physical property test shown in the table, the IzOd impact value was ASTM DJjA,
The bending properties were measured according to A8TMD-90.

For calcium chloride resistance, we tested the A8TMD test piece using a test piece in which a notch with a radius of O and 5R was cut at a depth of 4txm from both sides of the parallel part of an ASTM No. 1 dumbbell piece.
50 Lander stress cracking tests according to
Calcium chloride at °C! Testing was carried out in a θ-related aqueous solution under the condition of a load of 10 kg, and the rupture time of the test piece was measured. The longer the rupture time, the better the resistance to calcium chloride. Examples 1 to 3 and comparative examples were the same as Examples 1 to 3, except that two types of compounded ingredients were used ('bl and (ol). The ionomer resin used in the example was the same as that used in the comparative example.The results are shown in Table 1.

Example g, Comparative Example 6 Using 66 nylon with ηrel = 0g, the nylon ioo portion was molded at the same molding temperature as in the previous example with the ingredients shown in Table 3 below.

It was carried out in the V external gyrus at ℃.

Table 3 [Effects of the Invention] The composition of the present invention has excellent metal halogen resistance, impact resistance, oil resistance, and heat resistance, so it can be used in underhood parts of automobiles, such as cooling fans, gears, pulp, and brake piping. , fuel piping tubes, control cable tubes, other exhaust gas system parts, electrical system parts such as connectors, and products containing reinforcing agents such as glass fibers for various functional parts such as radiator tank tops and bases, cylinder head covers, etc. Applications are attracting attention.

Sender: Mitsubishi Chemical Industries, Ltd. Representative patent attorney - 1 other person

Claims (2)

[Claims] (1) (a) 100 parts by weight of polyamide, (b) ethylene or propylene, and general formula RSiR'nY_3_-_
Represented by n (wherein, R is an olefinic unsaturated hydrocarbon group, R' is an aliphatic saturated hydrocarbon group, Y is a hydrolyzable organic group, and n is 0, 1 or 2). A polyamide resin composition comprising 1 to 120 parts by weight of a copolymer with an olefinically unsaturated silane compound. (2) In the composition according to claim 1, (
In addition to a) and (b), (c) (a) the ethylene-α-olefin copolymer also contains α,
Modified ethylene-α olefin copolymer grafted with β-unsaturated carboxylic acid or its derivative (b) Metal ion neutralized product of (a) (c) Metal ion of ethylene-α, β-unsaturated monocarboxylic acid copolymer A polyamide resin composition containing 120 parts by weight or less of at least one selected from neutralized products.