JPH01193347A - Flame-retardant polypropylene resin composition - Google Patents

Abstract

PURPOSE:To obtain a flame-retardant polypropylene resin composition having excellent flame-retardancy, by compounding a polypropylene resin with specific amounts of a polyethylene resin, ammonium polyphosphate or polyphosphoric acid amide and a 1,3,5-triazine derivative. CONSTITUTION:The objective flame-retardant polypropylene resin composition is composed of (A) 5-25wt.%, preferably 7-20wt.% of a polyethylene resin, preferably high-density polyethylene, (B) 12-25wt.% of ammonium polyphosphate or polyphosphoric acid amide, (C) 5-10wt.% of a 1,3,5-triazine derivative of formula (X is morpholino or piperidino; Y is bivalent residue of piperazine; n is 2-50) (e.g., 2-piperazinylene-4-morpholino-1,3,5-triazine oligomer or polymer) and (D) the remaining part of crystalline propylene homopolymer or copolymer, preferably crystalline ethylene-propylene block copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a flame-retardant polypropylene resin composition. In more detail, it is mainly composed of polypropylene resin, does not generate corrosive gas or toxic gas, has no deterioration in molding processability, and when made into a molded product (the mechanical strength of the molded product decreases little, and has a high degree of The present invention relates to a flame-retardant polypropylene resin composition from which a molded article having flame-retardant properties can be obtained.

Conventionally, polypropylene resin has excellent processability, chemical resistance,
Because of its good weather resistance, electrical properties, and mechanical strength, it is widely used in various fields such as household electrical products, vat dyes, interior decorations, and automobile parts.

(Prior art) Polypropylene resin is originally a resin that easily burns, but as the applications for which it is used expand, polypropylene resin is also required to have performance as a flame retardant material, and the performance requirements are becoming stricter year by year. There is. Various flame-retardant polypropylene resin compositions have been proposed to meet these demands.

For example, JP-A-53-92855, JP-A-54-2
Hydrous inorganic compounds as disclosed in JP-A No. 9350, JP-A-54-77658, JP-A-56-26954, JP-A-57-87462, JP-A-60-110738, etc. Compositions in which (e.g. magnesium hydroxide, aluminum hydroxide, barium sulfate, magnesium oxide, antimony oxide, hydrotalcite, etc.) are added to polypropylene resin, e.g.
As disclosed in Japanese Patent No. 5-30739, polyethylene with a melt index of 0.01 to 2.0, decabromo diphenyl ether (or dodecachlorododecahydromethanodibenzocyclooctene), powdered talc, and kaoli Composition in which one or more inorganic fillers selected from night, sericite, silica, and diatomaceous earth are added to polypropylene resin, JP-A-59-147050
As disclosed in the above publication, a composition in which an oligomer (or polymer) of ammonium phosphate (or phosphoric acid amide) and a 1,3,5-triazine derivative is added to a polypropylene resin has been proposed.

However, in a composition in which a hydrous inorganic compound is added to a polypropylene resin, for example, a composition in which magnesium hydroxide is added, it is necessary to add a large amount of the hydrous inorganic compound in order to impart a high degree of flame retardance. As a result, the composition causes a decrease in moldability and a decrease in the mechanical strength of the molded article.

In addition, compositions containing halogen compounds have relatively little reduction in molding processability or mechanical strength of molded products, and molded products with a high degree of flame retardancy can be obtained. The drawback is that corrosive and toxic gases are generated during processing and combustion.

In addition, the flame-retardant polypropylene resin composition disclosed in JP-A-59-147050 has relatively little deterioration in molding processability and mechanical strength of the molded product when it is made into a molded product. Although corrosive and toxic gases are rarely generated during combustion or combustion, UL Subject 94
(Underwriter Laboratories, Inc.) "Flammability test of plastic materials for equipment parts"
In a test based on the vertical combustion test of UL94 (hereinafter referred to as UL94 combustion test), the flammability rank was V-2 at 1/32 inch wall thickness, and the 1/32 inch wall thickness was highly flame retardant. It is difficult to achieve the flame retardancy of ■-O.

(Problems to be Solved by the Invention) The present inventors have discovered that the present invention has a high degree of flame retardancy, that is, a flame retardance of V-0 at 1/32 inch wall thickness in the UL94 flame test, and is corrosive during processing and combustion. does not generate any gas or toxic gas,
In addition, intensive research has been carried out to obtain a flame-retardant polypropylene resin composition that can produce molded articles with less deterioration in molding processability and less deterioration in mechanical strength of the molded article.

As a result, 1,3.5-17 having polypropylene resin, polyethylene resin, ammonium polyphosphate or polyphosphoric acid amide and a structure represented by the following general formula [I]
The inventors have discovered that a composition containing a specific amount of a gin derivative can solve the above-mentioned problems, and have completed the present invention based on this knowledge.

(wherein, An object of the present invention is to provide a flame-retardant polypropylene resin composition from which a molded article having a high degree of flame retardancy can be obtained.

(Means for solving problems) The present invention has the following configuration.

Assuming that the total weight of the following substances to (D) is 100 weight 2, Polyethylene resin 5 to 25 weight Z (B) Ammonium polyphosphate or polyphosphoric acid amide 12 to 25 weight 1z (C1 Represented by the following general formula [I] 1, which has a structure;
3.5-triazine derivative 5-10 weight 2 [wherein, X is a morpholino group or a piperidino group, Y is a divalent group of piperazine, and n is an integer of 2-50. (D) Remaining polypropylene resin The polypropylene resin used in the present invention is a crystalline propylene homopolymer, propylene as the main component, propylene and ethylene, butene-1, pentene-1, hexene-1,4-methylpentene-1. , heptene-1, octene-1, and decene-1, or a mixture of two or more of these. In particular, crystalline ethylene-propylene block copolymers are preferred.

The polyethylene resin used in the present invention can be high density polyethylene, medium density polyethylene, or low density polyethylene, but it is desirable to use high density polyethylene in order to prevent a decrease in the rigidity of the molded product.

The blending ratio of the polyethylene resin to the composition is 5 to 2.
5 weight ratio, preferably 7 to 20 weight ratio, preferably 10 to 20 weight ratio. If the blending ratio is less than 5% by weight, V-0 flame retardance cannot be achieved in a UL94 flame test with a wall thickness of 1/32 inches, and even if it exceeds 25% by weight, a flame retardance of 1/32 inches may not be achieved. This is not preferred because it becomes impossible to achieve the flame retardancy of v-O.

As ammonium polyphosphate or polyphosphoric acid amide used in the present invention, commercially available products may be used as they are. Examples of the commercially available ammonium polyphosphate include Sumisaf P (trade name, manufactured by Susumu Kagaku Kogyo ■); Sumisaf PM (trade name, manufactured by Sumima Kagaku Kogyo ■) can be mentioned.

The ammonium polyphosphate or polyphosphoric acid amide is blended in an amount of 12 to 25% by weight of the composition. If the blending ratio is less than 12% by weight, a composition that achieves V-0 flame retardancy at a wall thickness of 1/32 inch in the UL94 flammability test cannot be obtained, and even if the blending ratio exceeds 25% by weight, Not only is the above effect of improving flame retardancy not obtained, but also the hygroscopicity increases due to the ammonium polyphosphate or polyphosphoric acid amide, which is not preferable.

The 1,3,5-triazine derivative used in the present invention includes 2-piperadiene-4-morpholino-1°3.5-
Examples include oligomers or polymers of 1-riazine and oligomers or polymers of 2-piperadiene-4-piperidino-1,3,5-triazine. The proportion of the 1,3.5-triazine derivative in the composition is 5 to 10% by weight. The blending ratio is 5% by weight
Less than 1/3 of the UL94 flammability test, which is highly flame retardant.
I couldn't achieve V-0 with 2 inch wall thickness, and it was 10 again! Even if the amount is blended in excess of this amount, no further flame retardant improvement effect can be obtained.

Furthermore, the above-mentioned 2-piperadiene-4-morpholino-1°3.
A 5-triazine oligomer or polymer can be obtained, for example, by the following method.

That is, equimolar 2,6-cyhalo4-morpholino-
1,3,5-triazine (e.g. 2,6-dichloro-4
-morpholino-1,3,5-triazine or 2.6
-dipromo-4-morpholino-1,3,5-triazine) and piperazine with an organic or inorganic base (e.g. triethylamine, tributylamine, sodium hydroxide,
(potassium hydroxide, sodium carbonate, etc.) in an inert solvent such as xylene under heating, preferably at the boiling point of the inert solvent.

In addition, the above-mentioned 2-piperadiene-4-piperidino-1
, 3,5-triazine oligomers or polymers can also be obtained, for example, by the following method. That is, equimolar amounts of 2,6-cyhalo4-piperidino-1,3,
5-triazine (e.g. 2,6-dichloro-4-piperidino-1,3,5-triazine or 2,6-dipromo-4-piperidino-1,3°5-triazine) and piperazine are combined with an organic or inorganic base (e.g. Using an inert solvent such as triisopropylbenzene in the presence of triethylamine, tributylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, etc., the reaction is carried out under heating, preferably below the boiling point of the inert solvent, and the reaction is completed. After that, the reaction mixture was filtered to separate and remove by-product salts, and then
It can be obtained by washing with boiling water and drying.

In the composition of the present invention, various additives that are normally added to polypropylene resins, such as antioxidants, antistatic agents, lubricants, and pigments, can be used in combination.

The flame-retardant polypropylene resin composition of the present invention can be produced, for example, by the following method.

That is, predetermined amounts of the above-mentioned polyethylene resin, ammonium polyphosphate or polyphosphoric acid amide, the 1,3,5-triazine derivative having the structure represented by the general formula [I], and the various additives mentioned above are added to the polypropylene resin in a stirring and mixing device. , for example, in a Hensel mixer (trade name), super mixer, or tumbler mixer, and stirred and mixed for 1 to 10 minutes. It can be obtained by melt-kneading and pelletizing.

(Examples) Hereinafter, the present invention will be specifically explained using Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation method used in Examples and Comparative Examples was as follows.

1) Conforms to the vertical combustion test of Flame Retardant UL Subject 94 (Underwriter Laboratories Inc.) "Flammation Test of Plastic Materials for Equipment Parts". The wall thickness of the test piece is 1/32 inch.

2) Flexural modulus Compliant with JIS K 7203.

3) Izotsu impact strength Compliant with JIS K 7110.

Example 1, Comparative Example 1 As a polypropylene resin, ethylene content was 8.5% by weight, melt flow rate (temperature 230°C, load 2.16%).
Discharge amount of molten resin in 10 minutes when adding kg)2
0.9/10 minute crystalline ethylene-propylene block copolymer 6.3 kg, melt index as polyethylene resin (discharge amount of molten resin in 10 minutes when temperature 190°C and load 2.16 kg is applied) 6 .5.9/1
0 minute ethylene homopolymer (Tissopolyethylene (trademark)
M 680, manufactured by Chisso ■) 700 g, ammonium polyphosphate (Sumisafe P (trademark) manufactured by Sumitomo Chemical ■) 2.
1 kg, 800 g of a polymer of 2-piperadiene-4-morpholino-1,3,5-triazine (n=11, molecular weight 2770) as a 1.3.5-triazine derivative
, 20 g of 2,6-di-t-butyl-p-cresol 15y1 di-myristyl-β,β-thiodipropionate and 10y of calcium stearate as various additives were placed in a Hensel mixer (trade name) and mixed with stirring for 3 minutes. did. The resulting mixture was melt-kneaded and extruded using an extruder with a diameter of 45 mm at a melt mixing temperature of 200° C. to form pellets.

In addition, as Comparative Example 1, each compounded component was put into a Hensel mixer (trade name) at the compounding ratio according to Example 1, except that the polyethylene resin was not compounded, and the mixture was stirred and mixed according to Example 1, and melt-kneaded and extruded 1. , pelletized.

After drying the pellets obtained in Examples and Comparative Examples at a temperature of 100'C for 3 hours, the pellets were used to mold flame retardant,
Predetermined test pieces for measuring flexural modulus and Izod impact strength were molded.

Flame retardancy, flexural modulus, and Izot impact strength were measured using the test piece. The results are shown in Table 1.

Examples 2 to 4, Comparative Examples 2 to 4 Each compounded component was placed in a Hensel mixer (trade name) according to Example IK, except that the polypropylene resin and polyethylene resin were changed to the blending ratios listed in Table 1. According to Example 1, the mixture was stirred and mixed, melt-kneaded and extruded, and pelletized.

In addition, as Comparative Examples 2 to 4, each was carried out in accordance with Example 1, except that the polyethylene resin, ammonium polyphosphate, 1.3.5-triazine derivative, and polypropylene resin were changed to the blending ratios listed in Table 1. The ingredients were put into a Hensel mixer (trade name), mixed by stirring, melt-cross-extruded, and pelletized in accordance with Example 1.

A test piece for flame retardancy evaluation was prepared according to Example 1 using pellets obtained in each of the implementation and comparison sides, and the flame retardance was evaluated. The results are shown in Table 1.

Example 5 The procedure was carried out according to Example 1 except that a polymer of 2-piperadiene-4-piperidino-1,3,5-triazine (n==11, molecular weight 2800) was used as the 1.3.5-triazine derivative. Mix each ingredient in a Hensel mixer (
(trade name), stirred and mixed, melted and cross-extruded, and pelletized. Using the obtained pellets, a test piece for flame retardancy evaluation was prepared according to Example IK, and flame retardancy was evaluated. The results are shown in Table 1.

(Effects of the Invention) The composition of the present invention has a high degree of flame retardancy, that is, it has a flame retardance of -0 at 1/32 inch wall thickness in the UL94 flame test, and is free from corrosive gases and gases during processing and combustion. A flame-retardant polypropylene resin composition that does not generate toxic gases and can provide molded products with less deterioration in molding processability and less deterioration in the mechanical strength of the molded product when made into a molded product. It can be suitably used in the production of buildings, interior decorations, parts for household electrical appliances, parts for automobiles, and the like.

that's all

Claims (2)

[Claims] (1) The total of the following (A) to (D) is 100% by weight.
(A) 5 to 25% by weight of polyethylene resin (B) Ammonium polyphosphate or polyphosphoric acid amide 12
~25% by weight (C) 1 having the structure represented by the following general formula [I]
, 3,5-triazine derivative 5-10% by weight ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [I] [In the formula, X is a morpholino group or piperidino group, Y is a divalent group of piperazine, and n is 2- It is an integer of 50. (D) A flame-retardant polypropylene resin composition, which is the remaining polypropylene resin. (2) As polypropylene resin, crystalline propylene homopolymer, propylene as main component, propylene and ethylene, butene-1, pentene-1, hexene-1, 4-
The flame-retardant polypropylene resin according to claim 1, wherein a crystalline copolymer with one or more selected from methylpentene-1, heptene-1, octene-1, and decene-1 or a mixture of two or more of these is used. Composition.