JPS61233057A - Polyamide resin composition - Google Patents

Abstract

PURPOSE:To provide the titled composition containing a specific amount of a specific metal salt and having improved moldability, low-temperature impact resistance and transparency while keeping the excellent mechanical and chemical properties of polyamide resin. CONSTITUTION:The objective resin composition can be produced by compounding (A) a polyamide resin containing >=30wt%, preferably >=50wt% nylon having <=14 amide groups per 100 carbon atoms with (B) a metal salt of formula MXn [M is 1-3-valent metal cation; X is univalent halogen or pseudohalogen; the salt satisfies the formula (A is Madelung constant; n is valence of metal cation; N is Bone's exponent; r+ is ionic radius of M; r- is ionic radius of X)]. The amount of the component B is 0.02-0.5 mol, preferably 0.02-0.2 mol per 1 mol of the amide group of the polyamide.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is a polyamide resin that can be produced easily and inexpensively, and has good moldability without impairing the excellent mechanical and chemical properties inherent to polyamide resin. The present invention relates to a high impact transparent polyamide resin composition having the following properties.

[Conventional technology and problems]

Hitherto, transparent nylon has been mainly produced by cocondensation polymerization of nylon monomers and cyclic monomers (for example, Japanese Patent Application Laid-Open No. 119794/1983, West German Publication No. 27).
No. 4551), it also maintains the excellent chemical resistance inherent to polyamide resins, making it difficult for common transparent resins (such as polymethyl methacrylate, polystyrene, acrylonitrile styrene resin, polycarbonate, etc.) to be devitrified by common organic chemicals. It is being used in fields where it cannot be applied due to the occurrence of cracks. However, since it uses a special cyclic monomer, the cost is high, and the cyclic monomer segment in the copolymer has a high melting temperature, so the molding processability of the obtained copolymer is poor, and the fields of use are limited. It was getting worse.

On the other hand, polyamide resin itself has a certain degree of impact resistance, but for fields that require higher impact resistance, polyamide resins containing rubber such as ethylene-propylene terpolymer (IPDM) are known. (for example, U.S. Pat. No. 4,174,558 (1979)), and they exhibit very high impact resistance at temperatures above room temperature, but this value decreases rapidly at low temperatures. I end up.

[Means for solving problems]

Therefore, the inventors of the present invention made earnest efforts to solve the above-mentioned drawbacks, and found that by blending specific additives into polyamide resin, it is possible to achieve a method that is inexpensive, has good molding processability, and has the excellent mechanical properties inherent to polyamide resin. The inventors have discovered that it is possible to produce a high-impact transparent polyamide resin composition that retains its physical and chemical properties and whose impact resistance does not change from room temperature to low temperature, and has thus arrived at the present invention.

That is, in the present invention, the number of diamide groups is 1 per 100 carbon atoms.
Polyamide resin whose main component is nylon, which has 4 or less amide groups, per 1 mol of amide groups,! 110.002 mol or more and 0.5 mol or less of metal salt MXn (However, M is a monovalent or more and trivalent or less metal cation, and X refers to a monovalent halogen or pseudohalogen. Also, the combination of M and X in MXnK is expressed by the following formula (1, Mathematics A: Madelung constant n: Valence of metal cation N: Bohn power number r+: Ionic radius of M in MXn crystal (pm) r-: Ionic radius of X in MXn crystal (p -) The purpose is to provide a polyamide resin composition formed by blending a compound that satisfies the following:
In addition to halogens such as fluorine, chlorine, bromine, and iodine,
It also includes ions called pseudohalogens such as azide, cyanide, cyanic acid, thiocyanic acid, selenocyanic acid, and azidothiocarbonate. In addition, the combination of M (metal cation) and X (anion) in MXn is represented by the above formula [''l]
selected from combinations of anions and cations that have an ionic radius that satisfies the In particular, M is divalent or higher (n≧2)
In the above formula (Ill), a combination of M and X such that the left side of Ill is 1350 or less is preferable. Indicates the ionic radius inside. Regarding ions other than monatomic atoms, it was determined by Pauling (Pauling's ``Chemical Bond Theory'' published by Bengata). Polyatomic anions can also be determined based on their crystal structures.

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

Metal cations Li” (60pm), Na” (
95pm).

Be” (31pm), Mg” (65pm).

Oa” (99pm), 8r” (113pm).

Ba” (135pm), zn” (74pm) 5O
(1” (97pm), AJ5+ (50pm).

La (115pm) Ha0gen (J-(IEN pm), Br'''
(195pm) *Knee (216pm) Pseudo Halogen: / Son'''' (195pm), O
A) q-(236pm).

CJO3'' (200pm), BO, - (191p
m) In addition, the middle part of the above formula (1) can be calculated from the crystal structure using Madelung's constant in the crystal of the metal salt.
D, Q, uane, J, Ohem, Ind.
ue, , 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 Pauling (Pauling's "Chemical Bond Theory", Bengata Publishing).

Metal salts MXn satisfying the above formula [Equation] are shown in Table 1 below.

The polyamide resin used in the present invention is mainly composed of nylon having 100 carbon atoms and 14 or less diamide groups.

Specifically, nylon 11. Nylon 12. Nylon 6-
10. There are nylon 6, 12, etc.

There are also copolymerized nylons containing nylon heptamers such as nylon 6 and nylon 6.6 other than these main components.

Also included are copolymers other than nylon monomers, such as polytetramethylene glycol, which are copolymerizable with nylon, such as polyether ester amide.

The content of nylon, which is the main component, is 50 wt% or more, preferably 50 wt% or more, more preferably 70 wt%.
% or more.

The amount of the metal salt added in the present invention is 0.002 mob or more and 0.5 m per 1 mol of amide group of the polyamide resin.
ob or less, preferably 0.02m0:1 or more 0.2rr
D1 or less. If it is less than 0.002 mol', sufficient transparency and high impact properties cannot be obtained, and if it exceeds 0.5 mol', the metal salt itself will be dispersed in the polyamide as solid particles, and both transparency and impact properties will deteriorate rapidly. It will drop.

Methods for adding the metal salt to the polyamide resin in the present invention include immersing the polyamide in an aqueous metal salt solution, mechanically mixing the metal salt and polyamide and then melt-kneading them using an extruder, and adding the metal salt during polymerization of the polyamide. Various methods can be used, such as adding.

The high-impact transparent polyamide resin composition containing the metal salt of the present invention is put into practical use after being molded into an arbitrary shape by a method such as press molding, extrusion molding, or injection molding.

The high impact transparent polyamide resin composition of the present invention may also contain conventional resin additives such as oxidation stabilizers, flame retardants,
Ultraviolet stabilizers, plasticizers, etc. may be added.

〔Effect of the invention〕

The thus obtained transparent polyamide resin composition of the present invention has extremely good low-temperature impact resistance, transparency, good processability, and mechanical properties, as well as extremely good organic chemical resistance.

A composition in which a metal salt MXn is blended with nylon 6 or nylon 6Φ6 will whiten due to moisture in water or in air containing moisture, and the impact resistance will also decrease. Whitening does not occur in compositions using nylon with a low

〔Example〕

The present invention will be described in detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Example 1c.

Example 1 Zinc chloride (special grade reagent manufactured by Gyudon Pharmaceutical Co., Ltd.) was added to a nylon 12 (Daicel Huels [11901) pellet] with 1 m of amide groups.
0.0029 mol of ol Todoroki was added, mixed using a Henschel mixer, melt-kneaded using an extruder, and then pelletized using a pelletizer. Using this beret,
A sample for the ZOEL test was created using the injection molding method, and the ASTM
D25611C Therefore, 23℃, -40℃, -76℃
The impact strength was measured. The results obtained are shown in Table 2.

This molded sample also showed good transparency.

Example 2 In Example 1, the amount of zinc chloride added was 1 mo
An impact piece was produced in exactly the same manner as in Example 1 except that the amount of F) was 0.044 mol. It shows good transparency. In addition, 23 of this molded sample
Table 2 shows the measurement results of the impact strength at -40°C, -40°C, and -76°C.

Example 3 In Example I, the amount of zinc chloride added was changed to 1 mo of amide group.
Right! A ZOD impact piece was produced in exactly the same manner as in Example 1 except that the amount was 0.15 mol. Table 2 shows the engineering zod impact strength of this material at 23°C, -40°C, and -76°C. Moreover, this molded piece showed good transparency.

Example 4 Continuing from Example 1, the amount of zinc chloride added was changed to amide group j m
Example 1 except that ol/p was 0.48 mol
A ZOA impact piece was produced in exactly the same manner as described above. The impact strength of this product at 25°C, -40°C, and -76°C is shown in Table 2. Also, this molded piece showed good transparency.

Example 5 In Example 1, magnesium chloride (Gyudon Yakuhin Exhibition Reagent Special Grade) was added to the zinc chloride paste (1 mol of amide group per F)
An XzOeL impact piece was produced in exactly the same manner as in Example 1 except for adding 0.05 mob. This product showed good transparency.
The engineering zod impact strength at -76°C is shown in Table 2.

Example 6 In Example 1, 1 mol of amide group of magnesium thiocyanate (special grade reagent made by Gyudon Pharmaceutical Co., Ltd.) was added to zinc chloride.
A zod test piece was prepared in exactly the same manner as in Example 1 except that m ly O,02mox was added. Table 2 shows the OD impact strength at 23°C, -40°C, and -76°C. In addition, these exhibited good transparency.Example 7 In Example 1, aluminum chloride (a reagent made by Semi-Yakuhin) was added to the zinc chloride sieve with an amide group of 1mox'A F).
A test piece for impact of ZOd was prepared in exactly the same manner as in Example 1 except that 0.04 mo1 was added. Table 2 shows the zO6 impact strength of these samples at 23°C, -40°C, and -76°C. They also showed good transparency.

Example 8 In Example 1, 1 mol of amide group was added to magnesium chloride (a reagent manufactured by Semi-Yakuhin Co., Ltd.) to the zinc chloride sieve.
A test piece of ZOa was prepared in the same manner as in Example 1 except that 0.46 mol was added.

These exhibited a unique blue color but good transparency. In addition, the engineering zod impact strength at 23°C, -40°C, and -76°C is shown in Table 2.Example 9 In Example 1, lithium chloride (
Gyudon Pharmaceutical reagent special grade) at 0.02 per 1 mol of amide group.
A zOd test piece was prepared in exactly the same manner as in Example 1, except that mol was added.

Although this product was colored brown, it showed good transparency. Table 2 shows the impact strength of this material at 23°C, -40'C, and -76°C.

Example 10 0.04 mob of zinc chloride per mol of amide group was added to Nylon 6-10 (CM-2001 manufactured by Toshi), mixed using a Henschel mixer, and pelletized using a pelletizer. Using this pellet, a ZOD test piece was produced by injection molding.

This one showed good transparency. Also, these 23
Table 2 shows the ZOD impact strength at -40°C, -76°C.

Example 11 In Example 10, z0 was manufactured in exactly the same manner as in Example 10, except that nylon 6-12 (D1700 manufactured by Daicel Huls) was used for the nylon 6-10.
d test piece was obtained. These products showed good transparency.
The Od impact strength is shown in Table 2.

Example 12 To nylon 11 (BKEINO manufactured by Rilsan), zinc bromide (reagent special grade manufactured by Hanka Pharmaceutical Co., Ltd.) was added in an amount equivalent to 1 mol of amide group.
) 0.10 mob was added, mixed with a Henschel mixer, melt-kneaded with an extruder, and pelletized with a pelletizer.Using this pellet, a test piece of ZOd was produced by an injection molding method. This one showed good transparency. Also,
These 23 degrees Celsius, -40 degrees Celsius, -76 degrees Celsius god
The impact strength is shown in Table 2.

Example 15 Polyamide elastomer (laurolactam 54.4 mol%, dodecanedioic acid 2.8 mol%, polytetramethylene glycol (number average molecular weight 1000) 24.7 mol%) was mixed with zinc iodide (Hanka Yakuhin reagent special grade). ) as an amide group 1
Addition of 0.05 mob per mol After mixing with a Henschel mixer, melt-kneading with an extruder and pelletizing with a pelletizer.
An L test piece was prepared. This one showed good transparency. Table 2 shows the IzO6 impact strength at 23°C, -40°C, and -76°C.

Comparative Example 1 In Example 1, the amount of zinc chloride added was changed to 1 mo of amide group.
A ZOa test piece was prepared in exactly the same manner as in Example 1 except that the concentration was 0.001 mob per liter, and it was opaque. These 25℃, -40℃, -76
The God impact strength at ℃ is shown in Table 2.

Comparative Example 2 In Example 1, the amount of zinc chloride added was changed to 1 mol of amide group.
A Z+)L impact piece was prepared in exactly the same manner as in Example 1, except for using 0.54 mob per block.In this piece, white particles thought to be zinc chloride were dispersed all over, and the transparency was significantly reduced. was. Table 2 shows the mechanical impact strength at 25°C, -40°C, and -76°C.

Comparative Example 3 In Example 1, sodium chloride (Gyudon Yakuhin reagent) was added to zinc chloride at a concentration of p 0.05 per mol of amide group.
A ZO test piece was prepared in the same manner as in Example 1 except that mol was added, and it was opaque. Comparative Example 4 In Example 1, potassium iodide (Gyudon Yakuhin reagent) was added per 1 mol of amide groups (F) to the zinc chloride paste.
A zod test piece was obtained in exactly the same manner as in Example 1 except that 05 mob was added. The appearance of this product was opaque. Also, 23℃, -40℃, -76℃ of this
Comparative Example 5 Example 15 was the same as Example 13 except that 0.05 mob of cuprous bromide per mol of amide group was added to the zinc iodide glue. When a ZOA test piece was prepared in exactly the same manner as above, it was green and opaque. The Xzod impact strength of this product at 23°C, -40°C, and -76°C is shown in Table 2. A test piece was prepared. This product exhibited a milky white appearance typical of nylon. These processing ZO at 23℃, -40℃, -76℃
Table 2 shows the impact strength.

Procedural master's letter (spontaneous) September 30, 1985

Claims (1)

[Claims] A polyamide resin whose main component is nylon having 14 or less amide groups per 100 carbon atoms, and 1 mo of amide groups.
0.002 mol or more and 0.5 mol or less of metal salt MXn per liter (where M is a monovalent or more and trivalent or less metal cation,
X refers to a monovalent halogen or pseudohalogen. Also MX
The combination of M and
/N)-64400[n^2/(r_++60)+n/
(r_-+25)]≦0[I] where A: Madelung's constant n: Valency of metal cation N: Bohn's power r_+: Ionic radius of M in MXn crystal (pm) r_-: In MXn crystal A polyamide resin composition, which is selected from those satisfying the ionic radius (pm) of X.