JPS58194948A - Polyamide resin composition - Google Patents

Abstract

PURPOSE:To provide a polyamide resin compsn. having greatly improved thermal stability without detriment to flame retardance, by blending melamine cyanurate and a specified piperidine derivative with a polyamide resin. CONSTITUTION:Melamine cyanurate and a piperidine derivative of formula I (wherein R<1>-R<6> are each H, alkyl; R<7> is OH, amino, alkoxy, aryloxy, acyloxy, alkoxycarbonyl, substd. carbamoyloxy, substd. thiocarbamoyloxy, substd. sulfinyloxy, substd. sulfonyloxy) or formula II (wherein R<9>-R<14> are each H, alkyl; R<8> is O, carbonate, aliph., arom. or heterocyclic diacyloxy, dicarbamoyloxy, bisthiocarbamoyloxy, alkylenedioxy, arylenedioxy) are blended with a polyamide resin. Examples of the piperidine derivatives of formulas I and II are compds. of formulas III and IV.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyamide resin compositions. Specifically, the present invention relates to a polyamide resin composition with excellent flame retardancy and thermal stability.

As a flame-retardant polyamide resin composition, the polyamide resin composition made of polyamide resin and melamine cyanurate has sufficient flame resistance and is an extremely excellent resin composition without problems such as plate-out and blooming. The present inventors have conducted repeated studies in order to further improve the thermal stability of a flame-retardant polyamide resin composition containing melamine cyanurate. Resin compositions with poor thermal stability may, for example, be melt-molded at relatively high temperatures, or if the molten resin remains in a molding machine for a relatively long time, the resulting molding mechanical properties of the product.

For example, it is observed that tensile strength, elongation, and Izot impact strength are reduced.

As a result of extensive research in view of the above points, the present inventors found that
The present invention has been completed by showing that when a specific compound is blended with melamine cyanurate into a polyamide resin, thermal stability can be greatly improved without impairing flame retardancy.

In other words, this company aims to provide polyamide resin compositions with great industrial value, and its gist is to add melamine cyanurate and general formula or general formula to polyamide resin. This is a polyamide resin composition containing a piperidine derivative represented by:

The present invention will be explained in detail below.

The polyamide resin used in the present invention includes polymers such as lactams such as ε-caprolactam, and ε-amino acids such as aminocaproic acid.

Diamines such as hexamethylene diamine, nonamethylene diamine, metaxylylene, adipic acid, cepatine #, dodecane dibasic acid, terephthalic acid, isophthalic acid,
1 dicarboxylic acid such as cyclohexanedicarboxylic acid
One example is nylon 6.6.6.4.10.4T%&/6.
Examples include 6.6/6T.

The cyanuric acid melamine used in the present invention is a reaction product of cyanuric acid and melamine, for example, by mixing an aqueous solution of cyanuric acid and an aqueous solution of melaquin.
It can be obtained by carrying out the reaction under stirring at a temperature of about 0.degree. C., and then treating the resulting precipitate with P. This product is a white solid and is used after being ground into a fine powder. Of course, it is also possible to use a commercially available product by pulverizing it as it is. t+, some of the 7 amino acid hydroxyl groups in melamine cyanurate may be substituted with other substituents.

Usage amount Fi of cyanuric acid mela 2, polyamide resin 10
3 to -201 parts per 0g part, preferably 1 to 11 parts
If the amount is less than 1g, the flame retardant effect cannot be expected, and if it is too much, the mechanical properties will be adversely affected, which is not preferable.

Examples of the piperidine derivatives represented by the general formulas [1] and [1) include the piperidine derivatives described in Japanese Patent Publication No. 4T3304.

Typical examples include: 1, Kuhydroxyiko, J, 4,4-teto2methyl1piperidine lil□, :.

H 2 teramino-λ, J, 4,4-tetramethylpiperidine 3 teracetoxyco, 2. t,6-Titramethylbiperidine 1 4 Dasearo,, Iloxico, J, G, 4-Tetramethylpiperidine 01'! 11□ 54t-acryloyloxy-,2,J,4.4-tetramethylpiperidine 1 6 Z-(phenylacetoxy)-1,co,6.4-tetramethylpiperidine 7 ter(phenoxyacetoxy)-J,,2 ,6.
-tetramethylpiperidine 8 g-cyclohexanoyloxy-J, 2. Is, -tetramethylpiperidine94t-benzoyloxy-J, J, 4. +4-Tetramethylpiperidine 1041-(p-chlorobenzoyloxy)-1, -2
゜) Shi6.6-Titrame4-Naviveridine 114t-(0-)luoyloxy)-, Tip 6.6-
Chitramethylpiveridine 124t-(β-naphthoyloxy) '+'
e'#6-tetramethylpiperidine fertilizer coomethoxy2. Co,6,6-titramethylbiveridine144t-stearyloxy-,2Ico,6,6-tetramethylpiperidine15cucyclohexyloxy-J,2. IIG, 6
-tetramethylpiperidine 164t-penzyloxyco,co,6,6-titramethylpiperidine 1 also17 Q-phenokidi-,co,6,6-titramethylpiperidinexsg-(ethylcarbamoyloxy) -J,, 2゜6.6-Tetramethylpiperidine 1 194t-(cyclohexylcarbamoyloxy)-,
2,2,6,6-tetramethylpiperidine 204t-(
phenylcarbamoyloxy)-a.

2.6.4-Tetramethylpiperidinezly-(p-/lorphenylcarpamoyloxy)
-J, J, d, 4-tetramethylpiperidine 22 4t
-(,0-toIJcarbamoyloxy)-J,2,6
．． 4-Tetramethylbiperidine 23 <t-(α-naphthylcarbamoyloxy)-,2,,,2,6,t-tetramethylpiperidine Zaa-(ethyl 1,000 mecarbamoyloxy)-2,2,t,4 -Tetramethylpiperidine 1 254t-(cyclohexylthiocarbamoyloxy)
-, 2, J4. ．． 4-Tetramethylpiperidine 8
, :.

a64t-(phenylthiocarbamoyloxy)-1,
Ko, 6. futetramethylbiperidine 274t-benzenesulfinyloxy-,2,J,4゜6-tetramethylpiperidine 284t-benzenesulfinyloxy-,2,Z,6.
-tetramethyl, piperidine・'1 □ z94t-(p-)luenesulfonyloxy)-1,,
2,4.4-tetramethylpiperidine 30 ¥-(p
-n-)"7'silbenzenesulfonyloxy)-co,
, 2, 6. t-Tetramethylpiperidine 314t-methanesulfonyloxy-,2,J4. d
-tetramethylpiperidine 32 bis(,2,co,6,6-titramethylpiperidyl)carbonate I 33 bis(,2,J,4.!;-tetramethylpiperidyl)oxalate 34 bis(J,J , 4.6-nitramethyl-goubiperidyl) malonate 35 Bis(-, co, 6,6-nitramethyl-goubiperidyl) adipate 36 Bis(-, 6,6-nitramethyl-gubiperidyl) sebacate 3 bis(co, 2,6.6-te, tramethylda-piperidyl) fumarate (3 days bis(j, J, G, 4-tetrametyl-piperidyl) hexahydroterephthalate 39 bis(λ, co, 6 , 6-titrame, thyl-goupiperidyl) terephthalate 40 /, , 2-bis('*'e'e≦-tetotsumethyl-derpiperidyl:, oxy)-emene 41 α, α'-bis(a, a, t , 4-tetramethyl-derhyhericyloxy)-p-xylene 42 bis(22,2,t,4-tetramethyl-
piperidyl) tolylene-J, 4t-cica-bamate 43
bis(,2,,2,6,/s-tetramethylda-
piperidyl)hexamethylene-/,4-cica-bamate0 0 44 bis(,!,co,6.O-tetramethylterpiperidyl)diphenylmethane-P,P'-sif)
-Amate 45 Bis(J,J,6,6-titramethyl-goupiperidyl)diphenyl ether-P,P/-dicarbamate 46 Bis(2,,2,t,t-tetramethylda-
(piperidyl)benzene-/, 3-disulfonate, etc.

The amount of the piperidine derivative is 0.07 to 1 part by weight, preferably 0.0-1 part by weight, based on the polyamide resin/θθ heavy part.
~/parts by weight. If it is too small, the effect of improving thermal stability cannot be expected, and on the other hand, if it is too large, it will reduce flammability, which is undesirable. Method (1) of blending can be carried out by various means at any stage immediately before producing the final molded product. For example, a method of tri-blending polyamide resin and additives, a method of melt-mixing and extruding a tri-blend material to pelletize it, and a method of preparing master pellets kneaded with more than a predetermined amount of additives and using this as diluting pellets. Examples include a method of blending, and a method of adding additives in a molding machine that produces the final molded product. It is also possible to mix the piperidine derivative with melamine cyanurate in advance and add it to the polyamide resin. , silica-alumina, silica-magnesia.

Fillers such as glass peas, asbestos, graphite, and gypsum, paraffins, fatty acid esters, fatty acid metal rings, lubricants such as bisuoxides, heat-resistant additives such as copper salts, and other well-known additives. □mL? 4 pieces 1 shi 7, eh. stomach.

The polyamide resin composition of the present invention can be made into various flame-retardant molded products by various molding methods such as injection, extrusion, blowing, and pressure m. When molding is performed at a relatively high temperature using hardened resin, when producing large molded products, the residence time in the molding machine and cooling of the molded product are long, or when molding is performed at high temperatures for a long time. Even if it takes a long time, it is possible to obtain a molded product with poor mechanical properties, so its industrial value is extremely large.

Hereinafter, the present invention will be explained in detail with reference to Examples, but this book is not limited to the following practical examples unless it goes beyond the gist of the present invention.

In addition, "parts" in the examples indicate "parts by weight."

It was. Flammability //iUI, -241 (Underwr1
ter'5 Laboratory, Inc.) The results of the standard vertical combustion test are shown, and the tensile strength and elongation rate are A8TMD4J/.

Izod impact strength shows the results measured according to AEITM D, 2jd K.

Examples/- and Comparative Example 1 Relative viscosity -0? Nylon 6.6 (manufactured by Asahi Kasei Kogyo ■, Leona/300B)/00@), melamine cyanurate (manufactured by Nippon Carbide ■) in the amount shown in Table 7 below, and piperidine derivatives shown in Table 7 below were mixed, <tOWρ The mixture was extruded into pellets at 2J°C using a pent extruder.

The pellets were molded using a 3 oz injection molding machine (manufactured by Nippon Seikyo Gosho ■), a 31X//ko'
Resin temperature -2? θ℃, mold temperature ♂θ℃, injection time 70
Flammability, tensile strength, and elongation of the obtained test specimens were injection molded under 28I conditions: a molding cycle with a cooling time of 7θ seconds and an injection time of IO seconds and a cooling time of 7θ seconds. The ratio and Izot impact strength were as shown in the M/Table below.

For comparison, the results obtained when no piperidine derivative was used are also shown.

Claims (2)

[Claims] (1) A polyamide resin composition comprising polyamide resin, melamine cyanurate, and a piperidine derivative represented by the general formula. (2) The polyamide resin composition 6 according to claim (1), wherein the blending amount of melamine cyanurate is 3 to -201 parts by weight based on the weight of the polyamide resin 10θ. The blending amount is polyamide resin i
The boria-containing F resin composition according to claim (1) or (2), wherein the amount is O0θl to - parts by weight relative to oo parts by weight.