JPS60192742A - Flame-retardant polyolefin resin composition - Google Patents

Abstract

PURPOSE:A flame-retardant resin composition improved in dripping and generation of organic gases on burning, by the incorporation of a specified quantity of zeolite powders into a polyolefin resin. CONSTITUTION:A resin composition obtained by incorporating 5-150pts.wt. powders of natural and/or synthetic zeolites (A) with an average particle diameter of 30mum or less, shown by the formula [where M is K, Na, Ca, Fe or Zn; a is the valence of the cation; X is 0.1-20; Y is 0-20 (the number of moles of water of crystallization)]; 0-30pts.wt. halogenated organic flame retardant and/ or halogenated organophosphorus flame retardant (B); and 0-15pts.wt. antimony and/or boron flame-retarding assistant (C) into 100pts.wt. olefin resin. Examples of the natural zeolites include chabazite and clinoptilolite, and examples of the synthetic zeolites include zeolite A and zeolite Z.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyolefin resin composition having flame retardancy.

In recent years, attempts have been made to mix relatively large amounts of inorganic fillers primarily to make plastics flame retardant, but also to reduce toxic gases generated during combustion, prevent fire glare, and lower prices. There is. For example, t is known to have a composition in which a large amount of calcium carbonate is mixed in polypropylene, and in Japanese Patent Publication No. 46-29577 and Japanese Patent Publication No. 46-29613, 30 to 90 weight of gypsum, an inorganic filler, is added to polyethylene or polypropylene. %, optionally with a rubber-based thickener.

However, in these compositions, the effect is simply to increase or dilute the resin with a nonflammable inorganic substance, and the added inorganic substance does not essentially have the function of making IJ sock fat flame retardant. do not have.

On the other hand, among inorganic substances, aluminum hydroxide.

Magnesium hydroxide and the like are known to have a flame retardant effect. It is generally believed that when these inorganic substances are added, flame retardancy is developed because the inorganic substances are dehydrated when the matrix resin is ignited.

However, even if these inorganic substances are mixed with resins that have relatively high molding temperatures, such as high-density polyethylene, crystalline polypropylene, or rigid polyvinyl chloride, the moisture contained in the inorganic substances will evaporate at the molding temperature. Some dehydration occurs.

Therefore, the flame retardancy of the molded article inevitably decreases as the function of the added inorganic substance decreases. Moreover, bubbles are generated in the molded product due to dehydration, resulting in a rough surface and other defects such as a significant decrease in strength. Furthermore, these inorganic substances generally have inferior flame retardant functions compared to other flame retardants, such as organic no-logides, organosun compounds, and halogenated organophosphorus compounds, so they should be added in larger amounts than the latter. I have no choice but to do it. For this reason, the original physical properties of the resin,
In particular, there was a problem in that the field of application was limited because the mechanical properties were impaired.

The inventors have conducted extensive studies aimed at developing an excellent flame-retardant polyolefin composition that can solve all of the above-mentioned problems, and as a result have completed this invention.

That is, in this invention, the general formula M, 0 # A40. @X810. Fist YH, 0 (in the formula, M: K, Na, Oa, Fe
, one or more metal elements consisting of Zn, a: valence of cation, x: (value of Li-20, Y: number of moles of crystal water indicated by a value of 0 to 20), 30 microns 5 to 150 parts by weight of naturally produced and/or synthetic zeolite powder with an average particle size of 0.05 to 1.5 liters, 0 to 30 parts by weight of a halogenated organic flame retardant and/or a halogenated organophosphorus flame retardant, and antimony. system and/
Alternatively, it is a flame-retardant polyolefin resin composition characterized in that it contains 0 to 15 parts by weight of a boron-based flame retardant aid.

The composition of the present invention has the advantages of conventional compositions containing inorganic flame retardants, such as reduction in toxic gases generated during combustion, prevention of flame sag, and low cost.

Furthermore, the composition of the present invention not only has significantly higher flame retardancy than compositions containing conventional inorganic flame retardants, but also has foaming during molding and the resulting rough surface of the molded product. No decrease in physical strength was observed.

The polyolefin resin used in the present invention has low density,
Medium or high density polyethylene.

Polypropylene, polybutylene, polypentene, copolymers thereof, modified polymers mainly composed of these, or mixtures thereof.

The modified polymer referred to herein is, for example, a polyolefin copolymerized with another α-olefin or a vinyl compound, or a polyolefin to which another polymer is added. Specific examples of the copolymer or modified polymer include ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer.

Ethylene-propylene copolymer, ethylene-propylene/
-Diene terpolymer, chlorinated polyethylene, etc.

Zeolite, which is one of the elements constituting the present invention, has the general formula M
51p-A40. -XSiO! -YH, O. However, M in the formula is Na, Oa,
A cation of one or more metal elements consisting of Fe, Zn, a is the valence of the cation, or 11 to 2
The value is 0, and Ly is the number of moles of water of crystallization expressed as a value from 0 to 20. Any zeolite, whether naturally produced or synthesized, can be used as long as it has the general formula. Chapavite is a natural zeolite. Examples of the synthetic zeolites include clinoptilolite, erionite 9 mordenite, and so-called zeolite A, zeolite 2, zeolite Y, zeolite L, and chapasite.

Examples include mordenite.

The zeolite powder in the present invention is a powder having an average particle size of 50 micrometers (μm) or less. If the average particle diameter is larger than 50 μm, the surface of the resin-processed product will become rough, and at the same time, the mechanical properties of the product will deteriorate significantly, which is not preferable.

The amount of zeolite required to obtain the effects of the present invention is 5 to 150 parts by weight per 100 parts by weight of the polyolefin resin. If it is less than 5 parts by weight, flame retardancy is poor;
If the amount exceeds parts by weight, it becomes difficult to mold the product.

Examples of the halogen flame retardant of the present invention include hexabromobenzene, decabromo biphenyl, tecaprom diphenyl ether, tetrabromo bis-phenol A, 4.4'-
Aromatic bromine compounds or aromatic chlorine compounds such as bis(2,5-dibromopropoxy)-tetrabromobisphenol A, 2,5-dibromopropoxytribromophenol, yohyperchlorocyclodecane, hexabromocyclo Alicyclic bromine compounds or alicyclic chlorine compounds represented by dodecane, dodecachloropentacyclodecane, etc., and tris (chloroethyl) phosphate.

Tris(2,!l-sifuromeglovir) phosphate.

These include halides such as tris(2-chloropropyl) phosphate and aliphatic chlorine compounds or aliphatic bromine compounds such as chlorinated paraffin and chlorinated polyethylene.

The amount of halogen flame retardant necessary to obtain the effects of the present invention is 0 to 30 parts by weight per 100 parts by weight of the polyolefin resin.
Parts by weight. It is possible to increase the amount of halogenated flame retardant added to the composition of the present invention depending on the moldability and flame retardance required, but if it exceeds 30 parts by weight, halogenation occurs during combustion. This is undesirable as the generation of toxic gases such as hydrogen and carbon oxide becomes intense. When the amount is 30 parts by weight or less, generation of the above-mentioned toxic gas is hardly observed. Although the reason for this is not clear, it may be due to the unique adsorption ability of the zeolite particles blended into the resin for polar molecules.

Representative antimony-based flame retardant aids of the present invention include antimony trioxide, potassium antimonate, diantimony tetroxide, and the like. A representative example of the boron-based flame retardant aid is zinc borate.

The amount of the flame retardant aid required to obtain the effects of the present invention is 0 to 15 parts by weight per 100 parts by weight of the olefin resin. Even if more needles than 15 parts by weight are blended, no improvement in the effect of addition can be expected.

The flame-retardant polyolefin composition of the present invention may optionally contain organic and inorganic substances such as coloring agents such as dyes and pigments, lubricants, heat stabilizers, ultraviolet absorbers, and mold release agents. Can be blended.

The components of the compositions of the present invention can be combined in a variety of well-known steps. For example, an olefin resin can be melted on a heated roll, and then zeolite, a halogen flame retardant, a flame retardant aid, and other additives mentioned above can be mixed as appropriate into the molten resin.

When molding the flame-retardant polyolefin resin composition according to the present invention, conventional molding methods such as extrusion molding, injection molding, compression molding, and film molding can be applied.

The effects of the present invention will be explained below with reference to Examples, but the present invention is not limited by these in any way.

Example 1 500g of low-density polyethylene (PB172 manufactured by Toyo Soda Kogyo Co., Ltd.) and 500g on a 155±5”C hot roll
was mixed with synthetic type A zeolite (TOYOBUILDER manufactured by Toyo Soda Kogyo Co., Ltd., average particle size: 1.6 μm), and the mixed material was taken out in a sheet with a thickness of 3 mm. The sheet was run through a pelletizer to obtain a zeolite concentrate (master patch). The master patch and low density polyethylene (
pK170 (manufactured by Toyo Soda Kogyo Co., Ltd.) at a weight ratio of 20/100 using a ribbon blender.

A film with a thickness of 80 μm was obtained from the mixed pellet using a 501111 inflation processing machine. The surface of the film was very smooth, the film had high transparency, the zeolite was well dispersed in the resin matrix, and no bubbles or "spots" caused by zeolite aggregates were observed. The flame retardancy of the film was measured using an MVBB flame retardant tester manufactured by Suga Test Instruments. The flame retardancy of this film is a
It was very high at 55 El/1 nch. Also, the flame sag during combustion was extremely low. The results are shown in Table 1.

Comparative Example 1 A film with a thickness of 80 μm was obtained using the same recipe, procedure, and operation as in Example 1, except that aluminum hydroxide was used instead of the zeolite used in Example 1. The surface of the film was rough, had almost no transparency, and many "pops" caused by air bubbles and/or aggregates were observed in the film.

The flame retardancy of this film was 2.638/1 nch, which was very inferior to the result of Example 1. Furthermore, the fire resistance was extremely high. The results are shown in Table 1.

Comparative Example 2 Example 1 and 0.
A film with a thickness of 80 μm was obtained using the same recipe and one procedure.

The surface of this film was smooth, the transparency was high, and no "poop" was observed in the film. This is thought to be due to the surface treatment of the magnesium hydroxide used. How flame retardant is this film? h 01 e/1
The results were very inferior to those of nch and Example 1. Furthermore, the fire resistance was extremely high. The results are shown in Table 1.

Example 2 500 gr of low density polyethylene (manufactured by Toyo Soda Kogyo Co., Ltd., pH 72) and 500 gr of synthetic type A zeolite (
(same as in Example 1), 50 gr of an aromatic bromine compound flame retardant (B Tq s, manufactured by Seitec), and 15 i of antimony trioxide/(ATOX-8, manufactured by Nippon Seiko Co., Ltd.) at 155 ± 5 °C17) The mixture was kneaded on a heated roll and taken out as a 3 m thick sheet. Thereafter, a film with a thickness of 80 μm was obtained using the same recipe 2 procedure and operation as in Example 1.

The surface of this film is very smooth and transparent, and the film is made of zeolite and organic flame retardants.

Antimony trioxide and the like were well dispersed in the resin matrix, and no "poop" caused by bubbles and/or aggregates was observed. The flame retardance of this film was extremely high, and it was so self-extinguishing that the burning rate of pMVss could not be measured. Furthermore, no fire sagging was observed, and no toxic gases such as hydrogen halides were generated. The results are shown in Table 1.

Comparative Example 3 A film with a thickness of 80 μm was obtained using the same recipe and procedure as in Example 2 except that aluminum hydroxide was used in place of the zeolite used in Example 2. The surface of the film was rough and had almost no transparency, and many "pops" caused by air bubbles and/or aggregates were observed in the film. The flame retardancy of this film is 4.80 s/1n
It was ch. During combustion, there was a strong hydrogen halide odor.

The results are shown in Table 1.

Example 5 200g of ethylene-vinyl acetate co-op resin (UE535 manufactured by Toyo Soda Kogyo Co., Ltd.) and 160gT of zeolite (same as Example 1) were kneaded using a heated roll at 130 to 155°C. . The obtained mixed wire sheet was molded using a compression molding machine under molding conditions such as a molding temperature of 150°C, a molding resin pressure of 100°C, and a cooling time of 5 minutes.
A mm thick plate was obtained. A test piece was obtained from the No. 2 plate using a No. 65Q15 da/pel, and a tensile test (tensile speed 200 am/m1n) according to K 7210 from J was conducted. Further, the oxygen index, which is an indicator of flame retardancy, was measured using a 3U plate according to J.E. El K 7201. It exhibited high mechanical strength with a tensile yield strength of 85/9/Cdt and an elongation of 220 inches.

The results are shown in Table 1.

Moreover, the oxygen index was 259, and the flame retardance was also excellent. 3
When the cut surface of the seaweed plate was observed under a microscope, no air bubbles or aggregates were observed.

Comparative Example 4 Instead of the zeolite used in Example 3, an average particle size of 4 μm was used.
A test piece was obtained using the same recipe 9 procedure and operation as in Example 3, except that aluminum hydroxide was used, and mechanical strength and flame retardancy tests were conducted. This composition was significantly inferior to the composition of Example 3 in both mechanical strength and flame retardancy. Traces of air bubbles and some aggregates were observed on the cut surface of the third plate. The results are shown in Table 1.

Example 4 After mixing the following powders with a ribbon blender,
Dry for CXa time. The dried product was molded into test pieces (thickness 1
A No. 5 dumbbell and a No. 4 thick plate) were molded.

Measurement of mechanical strength of Gumpel (tensile speed 50 threads/m1n)
), and the plates were also subjected to flame retardancy tests. Each test is J Engineering 8K 7210. Compliant with JI8 K7201. As shown in Table 1, this composition has a yield strength of 565
It had excellent physical properties with ki/cdt and oxygen index of 24.5. There was no odor of hydrogen bromide during combustion. When the cut surface of the freight was observed under a microscope, no traces of air bubbles or aggregates were observed.

Comparative Example 5 A test piece was obtained using the same recipe 1 procedure and operation as in Example 4, except that aluminum hydroxide with an average particle diameter of 4 μm was used in place of zeolite. As shown in Table 1, both mechanical strength and flame retardancy were inferior to Example 4. The smell of hydrogen bromide during combustion was strong. Considerable air bubble traces were observed on the cross section of the plate.

Claims (1)

[Claims] Based on 100 parts by weight of polyolefin resin ←) General formula
MjfO-A40. -XSiO, -YH,0 in the formula, M
: One or more metal elements consisting of K, Na, Oa, Fe, and Zn a: Valence of cation 5 to 150 parts by weight of naturally occurring and/or synthetic zeolite powder with an average particle size of 50 microns or less (b) halogenated organic flame retardant and/or halogenated organophosphorus flame retardant. 0 to 30 parts by weight (c) A flame-retardant polyolefin resin composition containing 0 to 15 parts by weight of an antimony-based and/or boron-based flame retardant aid.