JPH0647648B2 - Polyamide composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a transparent impact-resistant polyamide composition. More specifically, it relates to a polyamide composition having improved transparency and low temperature impact resistance by blending a specific metal salt and a specific quaternary ammonium salt.

[Conventional technology and problems]

Conventionally, transparent nylon is mainly produced by co-condensation polymerization of a nylon monomer and a cyclic monomer (for example, Japanese Patent Laid-Open No. 51-119794 and West German Laid-Open Publication No. 27).
4351), because it retains the excellent chemical resistance inherent to polyamide resins, ordinary transparent resins (for example, pormethylmethacrylate, polstyrene, acrylonitrile styrene resin, polycarbonate, etc.) devitrify with ordinary organic chemicals. It is also being used in fields that cannot be applied due to cracking or cracking. However, the cost was high because a special cyclic monomer was used, and because the cyclic monomer segment in the copolymer had a high melting temperature, the moldability of the obtained copolymer was poor and the field of use was limited. .

On the other hand, the polyamide resin itself has a certain degree of impact resistance, but in fields where higher impact resistance is required, it is known to blend rubber such as ethylene-propylene terpolymer (EPDM). (For example, U.S. Pat. No. 4.174,358 (1979)), they show a very high impact resistance at a temperature above room temperature, but at a low temperature, the value thereof drops sharply.

[Means for solving problems]

Therefore, as a result of diligent efforts to solve the above-mentioned drawbacks, the inventors of the present invention blended a polyamide resin with a combination of two or more specific additives, resulting in an inexpensive molding processability and a polyamide resin. The present inventors have found that it is possible to produce a high impact transparent polyamide resin composition which retains the original excellent mechanical and chemical properties and has no change in impact resistance from room temperature to low temperature, and has reached the present invention.

That is, the present invention relates to a combination of the general formula MX _n (where M is a monovalent to trivalent metal cation, X is a monovalent halogen or pseudohalogen), and a combination of M and X is 100 parts by weight of the polyamide resin. Is the following formula [I] However A: Maderungu constant n: valence of the metal cation N: number should bone r _+: ionic radius of M in MX _n in the crystal (pm) r _-: X ion radius at MX _n in the crystal (pm) It is selected from the ones that satisfy. ) 0.01% metal salt
And more than 50 parts by weight, the general formula [II] (However, in the formula, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen, an alkyl group,
A quaternary ammonium salt compound represented by an unsaturated aliphatic group, an aromatic group or the like, at least one of which is a group having 6 to 18 carbon atoms, and Y is an anion capable of forming a monobasic acid) The present invention provides a polyamide composition containing 0.1 part by weight or more and 50 parts by weight or less.

The anion X in the metal salt MX _n used here is
In addition to the usual halogens of fluorine, chlorine, bromine, and iodine, ions such as azide, cyanide, cyanic acid, thiocyanic acid, selenocyanic acid, and azidothiocarbonic acid, which are called pseudohalogens, are also included.

The combination of the metal cation M and the anion X in MX _n is selected from the combination of anions and cations having an ionic radius satisfying the above formula [I].

In the formula, the radii of cation and anion represented by r ₊ and r ₋ respectively represent the ionic radius in the crystal. Ions consisting of a single atom have been determined by boring (Boring, "Chemical bond theory", Kyoritsu Shuppan). The anion composed of multiple atoms can also be determined from its crystal structure.

The ionic radii of typical metal cations, halogens and pseudohalogens are shown below.

Metal cations Li ⁺ (60pm), Na ⁺ (95pm), Be ²⁺ (31p
m), Mg ²⁺ (65pm), Ca ²⁺ (99pm), Sr ²⁺ (113 pm), Ba ²⁺
(135 pm), Zn ²⁺ (74pm), Cd ²⁺ (97pm), Al ³⁺ (50p
^{m), La 3+ (115 pm} ) halogen ^{Cl - (181 pm), Br} - (195 pm), I - (216 p
m) pseudohalogen ^{SCN - (195 pm), ClO} 4 - (236 pm), ClO 3 - (2
^{_{00 pm), BO 3 - (}} 191 pm) Further, in Maderungu constant wherein A in the crystal of the metal salt, may be calculated from the crystal structure (D.Quane, JC
hem. Educ., 47 , 396 (1970)). N indicates the power of the bone. This value depends on the electronic configuration of the ion, and each value is determined by boring (Boring “Chemical bond theory”, Kyoritsu Shuppan).

The metal salts MX _n satisfying the above formula [I] are shown in Table 1 below.

Further, examples of the quaternary ammonium salt compound used in the present invention include the following compounds (wherein the anion Y capable of forming a monobasic acid is halogen, pseudohalogen, perhalogen, nitric acid). Residues, hydroxyl groups, dimethylsulfate residues, etc.).

That is, hexyl trimethyl ammonium chloride, hexyl ethyl dimethyl ammonium chloride,
Octyl trimethyl ammonium chloride, octyl trimethyl ammonium thiocyanate, decyl trimethyl ammonium chloride, decyl ethyl dimethyl ammonium chloride, decyl ethyl dimethyl ammonium chlorate, decyl trimethyl ammonium thiocyanate, lauryl trimethyl ammonium chloride, lauryl trimethyl ammonium thiocyanate, lauryl trimethyl ammonium thiocyanate,
Lauryl ethyl dimethyl ammonium chloride, lauryl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium berchlorate, cetyl trimethyl ammonium thiocyanate, cetyl ethyl dimethyl ammonium chloride,
Cetylethyldimethylammonium bromide, cetylethyldimethylammonium perchlorate, cetylethyldimethylammonium thiocyanate, octadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, octadecyltrimethylammonium perchlorate, octadecyltrimethylammonium thiocyanate, cetylbenzyldimethylammonium chloride, cetyltrimethylammonium hydroxy. And so on.

In compounding these with the polyamide resin, one kind or a mixture of two or more kinds may be used.

The polyamide resin used in the present invention includes homopolyamides and copolyamides containing lactam as a main component, represented by nylon 6 and nylon 12, and homopolyamides and copolyamides containing aminocarboxylic acid as a main component, represented by nylon 11. Examples thereof include homopolyamides containing diamine and dicarboxylic acid as the main components, such as polyamide, nylon 6.6, nylon 610, nylon 612, and the like, and copolyamides. At the same time, a polyether amide, which is a copolymer of nylon monomers and monomers other than nylon monomers,
Also included are polyesteramides, polyetheresteramides, and the like.

The addition amount of the metal salt in the present invention is 100% polyamide resin.
The amount is 0.01 part by weight or more and 50 parts by weight or less with respect to parts by weight.
The amount of the quaternary ammonium salt compound added is 0.1 part by weight or more and 50 parts by weight or less based on 100 parts by weight of the polyamide. If the amount of these additives to be added to the polyamide is less than the above amount, sufficient transparency and high impact cannot be obtained, and if the amount is more than the above amount, especially 50 parts by weight of the metal salt is added. If it exceeds the range, the metal salt itself will be dispersed as fixed particles in the poiamide, and the transparency and impact resistance will drop sharply.

As the method for adding the metal salt and the quaternary ammonium salt-based compound to the polyamide resin in the present invention, the method of adding during the polymerization of the polyamide, the polyamide and the metal salt, and the extruder after mechanically mixing the quaternary ammonium salt-based compound Various methods such as a method of melt-kneading can be carried out.

Further, the high impact transparent polyamide resin composition according to the present invention includes a conventional resin additive such as an oxidation stabilizer, a flameproofing agent,
You may mix | blend a ultraviolet stabilizer, a plasticizer, etc.

[Effect of the Invention] The transparent polyamide composition of the present invention thus obtained has very good low temperature impact resistance, transparency, good processability, and mechanical properties, and very good resistance to organic chemicals.

〔Example〕

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Examples 1 to 5 Nylon 12 (Daiamide L19 manufactured by Daicel-Hyurus)
01), magnesium chloride and cetyltrimethylammonium chloride were mixed in the amounts shown in Table 2, melt-kneaded in a usual extruder, and pelletized. Using this pellet, Izod test sample was prepared by injection molding and
The impact strength at 23 ° C, -20 ° C, and -40 ° C was measured according to TMD 256. The obtained results are shown in Table 2. The transparency of these molded samples is also shown in Table 2.

Example 6 In Example 2, instead of nylon 12, nylon 1
An Izod test piece was molded and an impact test was performed in exactly the same manner as in Example 2 except that 1 (BESN 40TL manufactured by Lilsan) was used. The results are shown in Table-2.

Example 7 In Example 2, instead of nylon 12, nylon 6 was used.
An Izod test piece was molded and subjected to an impact test in exactly the same manner as in Example 2 except that (CM-1021T manufactured by Toray) was used. The results are shown in Table 2.

Example 8 In Example 2, instead of Nylon 12, Nylon 6
An Izod test piece was molded and an impact test was conducted in the same manner as in Example 2 except that 6 (Toray CM-3001) was used. The results are shown in Table 2.

Example 9 I was carried out in the same manner as in Example 2 except that lithium chloride was used instead of magnesium chloride.
A zod test piece was molded and subjected to an impact test. The results are shown in Table 2.
Shown in.

Example 10 An Izod test piece was molded in the same manner as in Example 2 except that magnesium bromide was used instead of magnesium chloride, and an impact test was conducted. The results are shown in Table 2.

Example 11 An Izod test piece was molded and subjected to an impact test in the same manner as in Example 10 except that cetyltrimethylammonium bromide was used instead of cetyltrimethylammonium chloride. The results are shown in Table 2.

Example 12 I was carried out in the same manner as in Example 11 except that zinc iodide was used instead of magnesium bromide.
A zod test piece was molded and subjected to an impact test. The results are shown in Table 2.
Shown in.

Comparative Examples 1 to 5 Magnesium chloride and cetyltrimethylammonium chloride were mixed with nylon 12 in the amounts shown in Table 2, melted and kneaded in an ordinary extruder, and pelletized. Using this pellet, an Izod test piece was prepared by an injection molding method and subjected to an impact test. The obtained results are shown in Table 2.

Claims (1)

[Claims] 1. A general formula for 100 parts by weight of polyamide resin.
MXn (where M is a metal cation with a valence of 1 to 3)
X is a monovalent halogen or pseudohalogen, and the combination of M and X is represented by the following formula [I]. However A: Maderungu constant n: valence of the metal cation N: number should bone r _+: ionic radius of M at MXn crystal (pm) r _-: meet the X in MXn in the crystal ionic radius (pm) Chosen from the things. ) 0.01% metal salt
And more than 50 parts by weight, the general formula [II] (Wherein R ₁ , R ₂ , R ₃ and R ₄ are groups such as hydrogen, an alkyl group, an unsaturated aliphatic group and an aromatic group, and at least one of them is a group having 6 to 18 carbon atoms, Further, Y is a polyamide composition containing 0.1 to 50 parts by weight of a quaternary ammonium salt compound represented by (an anion capable of forming a monobasic acid).