JPH08157712A - Flame-retardant polyamide resin composition - Google Patents

Abstract

PURPOSE: To obtain a flame-retardant polyamide resin composition which does not suffer from the deposition of flame retardant on the surface of the mold when injection-molded by mixing a polyamide resin with melamine cyanurate, a metal salt of an aliphatic carboxylic acid and a nonionic surfactant. CONSTITUTION: This resin composition is obtained by mixing 100 pts.wt. polyamide resin (A) with 2-20 pts.wt. melamine cyanurate (B), 0.01-5 pts.wt. metal salt (C) of an aliphatic carboxylic acid and 0.02-2 pts.wt. nonionic surfactant (D). Although it has heretofore been proposed that compound B is added to resin A to make it flame-retardant, there is a problem that compound B is separated from the molten resin and firmly fixed on the surface of the mold when the composition is injection-molded. By further adding agents C and D, a flame-retardant polyamide resin composition having high flame retardancy and not suffering from the deposition of the flame retardant on the surface of the mold in injection molding can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant polyamide resin composition, and more particularly to a flame-retardant material having a high degree of flame-retardant property, which is free from mold contamination by a flame-retardant agent during injection molding. -Related polyamide resin.

[0002]

2. Description of the Related Art In order to make a polyamide flame-retardant, it is known to blend melamine (Japanese Patent Publication No. 49-1714) and cyanuric acid (Japanese Patent Publication No. 50-105744). , These known flame retardants have excellent flame retardant effects,
The former has the problem that melamine sublimes during molding and clogs the degassing part of the mold, causing burns on the molded product, and melamine bleeds out from the resulting molded product. The compounded one had a defect that it foamed during molding. In order to improve these problems, both melamine and cyanuric acid are blended (JP-A-51-54655).
However, the sublimation of melamine and the foaming by cyanuric acid were improved but not satisfactory as compared with the single addition. In order to overcome such drawbacks, it has been proposed to use melamine cyanurate obtained from an equimolar amount of melamine and cyanuric acid (Japanese Patent Laid-open No. Sho-61-85).
53-31759 publication). With melamine cyanurate, sublimation of melamine was suppressed, foaming was small, and some improvement was achieved.

[0003]

However, the composition obtained by this technique has a new problem that the melamine cyanurate separates from the molten resin during injection molding and adheres to the mold surface. Since the melamine cyanurate fixed substance of is strong, it requires the work of periodically disassembling the mold and polishing the surface, so that there is a serious problem that productivity is unavoidably reduced. It was

[0004]

The inventors of the present invention provide a flame-retardant polyamide resin composition in which melamine cyanurate does not stick to the mold surface during molding of a polyamide resin containing melamine cyanurate. As a result of repeated intensive studies to solve the problem, melamine cyanurate in the polyamide resin, a polyamide resin composition comprising a metal salt of a specific aliphatic carboxylic acid and a specific nonionic surfactant can all solve the above problems. The present invention has been completed and the present invention has been completed.

That is, according to the present invention, a) polyamide resin 10 is used.
B) Melamine cyanurate 2 to 20 parts by weight relative to 0 part by weight
A gist is a polyamide resin composition containing 1 part by weight, c) 0.01 to 5 parts by weight of a metal salt of an aliphatic carboxylic acid, and d) 0.02 to 2 parts by weight of a nonionic surfactant. . Hereinafter, the present invention will be described in detail.

The a) polyamide resin used in the present invention is
Polylactams such as nylon 6, 11, 12 and the like, polyamides obtained by polycondensation of diamine and dicarboxylic acid such as nylon 66, 46, 610 and 612, nylon 6/66, 66 / 6T, 66 / 6I and the like. Examples of the copolymerized polyamides, a mixture of the above polyamides, etc., and use of nylon 66, nylon 6, and nylon 66/6 copolymers are expected to be more effective in terms of heat resistance, flame retardancy, and moldability. it can.

The b) melamine cyanurate used in the present invention is an equimolar reaction product of melamine and cyanuric acid,
For example, it is a product obtained by stirring melamine and an aqueous solution of cyanuric acid in water at about 90 to 100 ° C., filtering and drying the precipitate obtained by the reaction, and then pulverizing it into a fine powder. Since melamine cyanurate is commercially available, industrially available products can be used.

The blending amount of melamine cyanurate is 2 to 20 parts by weight, preferably 3 parts by weight with respect to 100 parts by weight of the polyamide resin.
15 to 15 parts by weight is suitable, and if it is less than 2 parts by weight, the flame retarding effect is small, and if it exceeds 20 parts by weight, no further effect is obtained with respect to flame retardancy, and rather physical properties are deteriorated, which is not preferable. . Metal salts of c) aliphatic carboxylic acids used in the present invention include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, cerotic acid, montanic acid, melissic acid, oleic acid and erucic acid. Examples thereof include sodium salts, lithium salts, calcium salts, magnesium salts, zinc salts, and aluminum salts of aliphatic carboxylic acids having 9 or more carbon atoms, which are industrially easily available and have particularly high action and effect. , Calcium montanate, sodium montanate, calcium stearate, and aluminum stearate are preferably used.

The metal salt of the aliphatic carboxylic acid is added in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the polyamide resin. The amount is preferably 0.02 to 3 parts by weight, and if less than 0.01 parts by weight, the effect of preventing the sticking of melamine cyanurate to the mold is small, and if it exceeds 5 parts by weight, a further effect on the sticking prevention of melamine cyanurate is obtained. Is not obtained, and rather gas is generated during molding, and new problems such as a decrease in flame retardancy occur, which is not preferable.

The nonionic surfactant d) used in the present invention is polyoxyethylene tridecyl ether, polyoxyethylene oleyl ether, polyethylene glycol, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene. Examples thereof include polyoxypropylene block polymer, sorbitan monolaurate, sorbitan monooleate, polyoxyethylene dodecylamine, and polyglycerin oleate. Among them, polyoxyethylene tridecyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene dodecylamine, polyethylene glycol, polypropylene glycol, etc., liquid at 1 atm and 30 ° C. But,
In particular, the effect of preventing melamine cyanurate from sticking to the mold is high, which is preferable.

The content of the nonionic surfactant is 0.02 to 2 parts by weight, preferably 0.03 to 1 part by weight, based on 100 parts by weight of the polyamide resin. The effect of preventing the sticking of melamine cyanurate is small, and if it exceeds 2 parts by weight, no further effect can be obtained with respect to the sticking prevention of melamine cyanurate, but rather, a new gas generation or a decrease in flame retardance is caused during molding. It is not preferable because it causes problems.

The polyamide resin composition of the present invention, that is, the polyamide resin containing melamine cyanurate, contains a melamine cyanurate containing a specific metal salt of an aliphatic carboxylic acid and a nonionic surfactant in combination. For the first time, the problem of the melamine cyanurate sticking to the mold, which the polyamide resin had, was solved and it became possible to obtain a highly flame-retardant polyamide resin composition.

The method for producing the composition of the present invention is not particularly limited, and for example, a melamine cyanurate-containing polyamide resin obtained by adding equimolar amounts of melamine and cyanuric acid during polymerization of polyamide is extruded. Method of melt kneading a metal salt of an aliphatic carboxylic acid and a nonionic surfactant with a machine, a method of adding a metal salt of a melamine cyanurate and an aliphatic carboxylic acid and a nonionic surfactant during polymerization of polyamide, melamine shear A method in which both or both components of a metal salt of an aliphatic carboxylic acid and a nonionic surfactant at the time of producing a nurate are added, and then added at the time of polymerizing a polyamide, or melt-kneaded by an extruder or the like. , For example, both components of a metal salt of melamine cyanurate and an aliphatic carboxylic acid and a nonionic surfactant, or either component There is a method of mixing and melt-kneading with an extruder or the like, and a method of melt-kneading a polyamide resin and melamine cyanurate, a metal salt of an aliphatic carboxylic acid, a nonionic surfactant with an extruder, a molding machine, or the like. Regarding the addition of the components, the order of addition is not particularly limited, and the product obtained by any method may be used.

With respect to the composition of the present invention, a heat stabilizer, an oxidative deterioration inhibitor, a weather resistance improver, an antistatic agent, a lubricant, a release agent, and a filler are provided so long as the intended effects are not significantly impaired. Other additives such as agents and other resins can be added at any stage.

[0015]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In Examples and Comparative Examples, melamine cyanurate fixation on the mold surface and UL94 flammability were measured by the following methods. 1) Melamine cyanurate adhesion to mold surface (molding condition); Injection molding machine: PS40E mold manufactured by Nissei Plastic Industry Co., Ltd .: Mold shown in FIG. 1 Cylinder temperature: 260 ° C. nozzle part, 265 ° C. front part ,
Middle part 265 ° C, rear part 265 ° C (resin temperature 272 to 276)
Mold temperature: 80 ° C setting (surface temperature 122 to 12)
8 ° C) Molding cycle: injection 1.2 sec, cooling 5.0 sec,
Intermediate 1.0 sec Injection speed: 99% Injection pressure: 43% (Measurement method): After 1,500 shots molding under the above-mentioned molding conditions, the mold was disassembled and the adhered matter was observed on the mold surface. The adhered matter is scraped off and a Fourier transform infrared spectrophotometer (FTIR-8500) manufactured by Shimadzu Corporation is used.
Was used to determine the sticking of melamine cyanurate by the presence or absence of the characteristic absorption band (1743 cm ⁻¹ ) of the melamine cyanurate.

(Criteria for Adherence): A: No adhesion is observed. ◯: A thin film of melamine cyanurate was slightly observed, but it could be easily removed by wiping. X: Melamine cyanurate firmly adhered to the mold surface,
It had to be strongly ground and removed with a metallic brush and thinner. 2) UL94 flammability (measurement method); the well-known method specified in UL94, 1
A combustion test was carried out using a / 16 inch thick test piece.

[0017]

Examples 1 to 11 JIS-K6810 relative viscosity (η
r) of 2.8, nylon 66 (Leona 1300) manufactured by Asahi Kasei Co., Ltd. was used as the polyamide resin, and MCA-CO manufactured by Mitsubishi Petrochemical Co., Ltd. was used as the melamine cyanurate. A metal salt of an aliphatic carboxylic acid and a nonionic surfactant are added, mixed with a Henschel mixer, and then melt-kneaded with a PCM45 extruder manufactured by Ikegai Tekko KK to obtain a composition, which is molded and measured by the above method. did.

[0018]

[Examples 12 to 13] As a polyamide resin, JIS-
Compositions were obtained in the same manner as in Examples 1 to 11 except that nylon 6 (Leona 2300) manufactured by Asahi Kasei Kogyo Co., Ltd. having a relative viscosity (ηr) of 2.3 of K6810 was used and molded by the above method. And measured. The results are shown in Table 1.

[0019]

Comparative Example 1 Only the polyamide resin used in Examples 1 to 11 was molded and measured by the above method. The results are shown in Table 2.

[0020]

Comparative Examples 2 to 7 The compositions shown in Table 2 were used in Examples 1 to 11.
A composition was obtained by the same method as described above, and molded and measured by the above method. The results are shown in Table 2. The types of components c) and d) used in the examples and comparative examples are shown. The following metal salts of aliphatic carboxylic acids were used.

* 1: Hostamont CaV102 of Hoechst Japan KK * 2: Hostamont NaV1 of Hoechst Japan KK
01 * 3: SA-1000 of Sakai Chemical Industry Co., Ltd. * 4: SC-100 of Sakai Chemical Industry Co., Ltd. The following nonionic surfactants were used.

* 5: Nonionic T-20 manufactured by NOF CORPORATION
8.5 (Liquid at 30 ° C under 1 atm) * 6: Nonion NS-202S of NOF Corporation (Liquid at 30 ° C under 1 atm) * 7: Nonion NS-240 of NOF Corporation ( Solid at 30 ° C under 1 atm) * 8: Pronone 102 from Nippon Oil & Fats Co., Ltd. (3 at 1 atm)
(Liquid at 0 ° C) * 9: Nymeen L-201 from NOF CORPORATION (1 atm, liquid at 30 ° C) * 10: PEG400 from Sanyo Kasei Co., Ltd. (at 1 atm,
Liquid at 30 ° C) * 11: PEG6000 from Sanyo Kasei Co., Ltd. (solid at 30 ° C under 1 atm)

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

EFFECTS OF THE INVENTION The composition of the present invention has a problem in the prior art, that is, melamine on a mold surface of a flame-retardant polyamide resin composition containing melamine cyanurate at the time of molding processing. I was able to solve the cyanurate sticking problem.

[Brief description of drawings]

FIG. 1 is a view of a mold for observing fixation of melamine cyanurate in the present invention.

Claims (5)

[Claims] 1. A) 100 parts by weight of a polyamide resin, b) 2 to 20 parts by weight of melamine cyanurate, c) 0.01 to 5 parts by weight of a metal salt of an aliphatic carboxylic acid, and d) a nonionic surfactant. A polyamide resin composition containing 0.02 to 2 parts by weight of the agent. 2. The polyamide resin is nylon 66,
The polyamide resin composition according to claim 1, which is a nylon 6 or nylon 66/6 copolymer, and the molded product obtained has a relative viscosity (ηr) of JIS-K6810 of 1.5 to 3.5. 3. The aliphatic carboxylic acid metal salt according to claim 1, wherein calcium montanate, sodium montanate,
Calcium stearate, aluminum stearate,
The polyamide resin composition according to claim 1 or 2, which is one or more selected from the above. 4. The polyamide resin composition according to claim 1, wherein the nonionic surfactant according to claim 1 is liquid at 30 ° C. under 1 atm. 5. The nonionic surfactant is selected from the group consisting of polyoxyethylene tridecyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene dodecylamine, polyethylene glycol and polypropylene glycol. It is 1 or more types selected.
The polyamide resin composition according to any one of 4 above.