JPS62148546A - Flame retardant olefin polymer composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition with outstanding mechanical characteristics such as strength and processability and various properties such as heat resistance, by blending an ethylene-alpha-olefin copolymer of low crystallinity, high-density polyethylene and non-halogen type flame-retardant. CONSTITUTION:The objective composition can be obtained by blending (A) 100pts.wt. of an ethylene-alpha-olefin copolymer of low crystallinity with a density 0.87-0.91g/cm<3>, ethylene unit content pref. 75-95mol% and degree of crystallinity pref. 5-50%, (B) 10-100(pref. 20-80)pts.wt. of high-density polyethylene with a density 0.94-0.965g/cm<3> and MFR 0.01-5g/10min and (C) 50-200(pref. 70-150)pts.wt. per 100pts.wt. of the components A plus B, of a non-halogen type flame-retardant with an average particle size pref. 0.1-3mum and specific surface area pref. 2-12m<2>/g, which has pref. been surface-treated (pref. metal hydroxide, esp. magnesium hydroxide).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a flame-retardant first nofine polymer composition7, more specifically, it uses a non-halogen flame retardant and has flame retardancy as well as strength and The present invention relates to a polymer composition that has excellent mechanical properties such as processability and various properties such as heat resistance.

(Prior art) Conventionally, as a flame retardant composition, a composition consisting of polyethylene, an ethylene-α-olefin copolymer iyF, a 9-base elastomer, and a flame retardant has not been known (Haru (Unexamined Japanese Patent Publication No. 58-49739).

This composition is based on polyethylene,
For example, the thermoplastic elastomer is used in an amount of 5 to 150 parts by weight based on 100 parts by weight of poly-11 ethylene.

In addition, as a flame retardant, a methane containing norogen is indispensably used.

Such prior art attempts to improve the deterioration of the tensile properties and processability of polyethylene and the deterioration of the appearance of molded products due to the addition of flame retardants.

(Problems to be Solved by the Invention) However, in such conventional technology, since the flame retardant and the halogen-containing flame retardant are mixed together, halogen gas is generated in the event of a fire. 7) There is a problem that it has an adverse effect on the human body and various devices.

In this case, it is conceivable to use a non-halogen type flame retardant such as magnesium hydroxide or aluminum hydroxide as the flame retardant, but in such a case, the flame retardant is blended.
As a result, disadvantages such as deterioration of mechanical properties such as tensile properties and processability and deterioration of the appearance of the molded product are unavoidable.

Therefore, the present invention uses a non-halogen flame retardant as a flame retardant (
The present invention provides a flame-retardant polymer composition that can be used for a long time and effectively prevents deterioration of various properties of the polymer due to the addition of the flame retardant.

(Means for solving the problems) The present invention uses a non-halogen type flame retardant as a flame retardant and a low crystalline ethylene/α-olefin copolymer (
(hereinafter sometimes simply referred to as thermoplastic elastomer)10
It has a structural feature in that high density polyethylene is blended at a ratio of 10 to 100 parts by weight per 0 parts by weight.

(Operation of the invention) That is, by using a non-halogen type flame retardant as a flame retardant, no halogen gas is generated even in the event of a fire, so that no negative effects are exerted on the human body or various equipment.

Also, 10 parts by weight of the thermoplastic elastomer
By blending high-density polyethylene in a proportion of 100 parts by weight, deterioration of various properties such as mechanical strength and moldability can be effectively suppressed even when a non-halogen type female combustion agent is blended. 0 (Embodiment of the invention) Low crystalline copolymer The α-olefin and 17 constituting the low crystalline ethylene/α-olefin copolymer used in the present invention are α-olefins having 6 to 10 carbon atoms. Olefins, such as propylene,
1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-naphthene, 1-decene, etc. are used.

In addition, this ethylene/α-olefin copolymer
The ene component may be further copolymerized. Examples of such polyene components include 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene,
5-vinylnorbornene and the like are used alone or in combination. These polyene components can be copolymerized in a range of 0 or less, which is generally expressed in terms of the cholesterol value of the resulting copolymer.

The ethylene unit content of such a low-crystalline ethylene/α-olefin copolymer is desirably in the range of 75 to 95 molar ratios. It is preferable that the crystallinity is in the range of 50% to 50%.In particular, if the crystallinity is lower than 5%, the obtained polymer composition will have unsatisfactory moldability. %, mechanical properties such as tensile properties tend to deteriorate when a non-halogen flame retardant, which will be described later, is blended.

In addition, this low crystalline ethylene/α-olefin copolymer generally has a density of 0.87 to 0.91? /'Cr1rs
within the range of

High-density polyethylene In the present invention, high-density polyethylene is used together with the above-mentioned low-crystalline ethylene/α-olefin copolymer.

In other words, by using this high-density polyethylene in combination with a non-halogen flame retardant described below, various mechanical properties such as tensile properties, hardness, rigidity, low-temperature brittleness, etc., and properties such as heat resistance may be reduced. can be effectively prevented.

This high-density polyethylene has a density of 0.940 to 0.940.
965t 7cm”, and melt flow rate (MF
R, 190C) is 0.01 to 5. Oy/10m
It is in the range of tn.

Such high-density polyethylene is the low-crystalline ethylene.
10 to 1 per 100 parts by weight of α-olefin copolymer
00 parts by weight, in particular from 20 to 80 parts by weight. If the amount is less than 10 parts by weight, the object of the present invention will not be achieved, and if it is more than 100 parts by weight, it will be difficult to effectively prevent deterioration of various properties.

Non-halogen type flame retardant In the present invention, a non-halogen type flame retardant is used. Therefore, even in the event of a fire or the like, halogen gas is not generated, so there is no risk of adverse effects on the human body or various devices.

Such non-halogen flame retardants include antimony oxide <
s b, o, ), barium metaborate (Bα (
BOs)2), aluminum hydroxide CAt(OH)s),
Non-halogenic flame retardants known per se such as magnesium hydroxide (Aff (QH)2) may be used, but metal hydroxides such as aluminum hydroxide and magnesium hydroxide are preferably used. Most preferably magnesium hydroxide is used.

In addition, it is preferable to use these non-halogen flame retardants that have been surface-treated with an unsaturated acid or the like in order to improve their affinity with the polymer components and to effectively and uniformly disperse them in the polymer. It is preferable that the specific surface edge falls within the range of 01 to 3μtnt7)@ and that the specific surface edge falls within the range of 2 to 12i/S'.

Kone, the non-halogen type flame retardant is M2O to 200 parts by weight per 100 parts by weight of the total amount of the low crystalline ethylene/α-olefin copolymer and high-density +1 ethylene;
In particular, it is used at a rate of 70 to 150 leaflets.

If the amount used is less than 50 parts by weight, the flammability will be insufficient, and if more than 200 parts by weight is used, mechanical strength, heat resistance, and other properties will deteriorate. .

Other Compounding Components In addition to the above-mentioned polymer components, the hemolytic composition of the present invention may appropriately contain boj1 olefins such as low-density polyethylene and so-called linear low-density polyethylene, depending on its use. can.

The polyolefins that may be blended as optional components are within a range that does not impair the characteristics of the present invention described above, such as the sum of a low crystalline ethylene/α-olefin copolymer and a high density polyethylene! It is used in a range of 300 parts by weight or less per 100 parts by weight.

Further, the polymer composition of the present invention may contain various compounding agents known per se, such as various reinforcing agents, antioxidants, colorants, etc., in known amounts.

For example, carbon black such as furnace black having an average particle size of 1 to 10 μm is preferably used as the reinforcing agent.

Antioxidants and 1. Teba 2,6-di-t-butyl-p-cresol, 2,6-di-butyl-4-ethylphenol, stearyl-β-(3,5-di-t-butyl-4
Monophenolic antioxidants such as -hydroxyphenyl)propionate, 4,4'-thiobis-(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol) , 2.2
Bisphenol antioxidants such as '-methylenebis(4-methyl-6-t-butylphenol), tetrakis [
Methylene-6-(ro',5'-di-t-butyl-4-hydroxyphenyl)propionate comethane, 1,3.
5-trimethyl-2,4,6-tris(6,5-di-bev-1,4-hydroxybenzyl)benzene, toco2
Polymeric phenolic antioxidants such as Erol, sulfur-based antioxidants such as dilauryl-ro,ro'-thiodipropionic acid ester, distea 11-6゜6'-thiodipropionic acid ester, misoxed, mono- and di-nonylphenyl) phosphite, tris(2,4-
Phosphorous antioxidants such as di-t-butylphenyl) phosphite are used alone or in combination with Vi, and polymeric phenolic antioxidants are preferably used.

The polymer composition of the present invention as prepared is a conventional 7J! , line method,
i.e. single screw extruder, twin screw extruder, roll mill, banha II
It is obtained by kneading the various ingredients described above using a kneader such as a mixer.

When using a roll mill, the polymer composition of the present invention can be obtained by kneading for 10 to 120 minutes at a temperature change of 120 to 1 BDC.

Knead. You may prepare a master patch from A beforehand and blend it, or you may mix everything together and blend it.

(Effects of the Invention) The polymer composition of the present invention has the following properties:
In addition to flame retardancy, it has excellent properties such as tensile strength, hardness, rigidity, low-temperature brittleness, workability, and heat resistance, making it suitable for buildings, vehicles,
It is effectively used in various types of piping, guardrails, handrails, etc. in ships, etc., and as various molded products that require flame retardancy.

The composition of the present invention also has excellent adhesion to 1l-tt wires, making it very useful for coating electric wires.

(Example) The physical properties shown in the Examples and Comparative Examples were measured as follows.

1. Melt flow rate (tWFR) JISK676
It was measured under a 190C1216Of load according to the method according to 0.

2. Create a 1WIM thick sheet from the sample using the tensile property press method, and
IS K 6301 A method according to JIS K6760 (pulling speed 200 m7H) by punching out 3 bone dumbbells.
/mtn) and then subjected to a tensile tester to determine the stress at break and the bending at break.

6. Hardness Shore D hardness was measured according to the method according to ASTM D 2240 (7).

4. Olzen rigidity It was measured according to the method according to ASTM D747.

5, embrittlement temperature Jl, 5 K OC~-5 according to the method according to 6760
The half-break temperature of the sample was determined in a temperature range of 5tZ'.06, and the limiting oxygen index of the sample was determined according to the method according to oxygen index JIS K 7201.

Z Extrusion Processability A sample was extruded into a tape using a 30-tone extrusion@, and the appearance of the tape and motor load were observed. Those with no problems in both were evaluated as ○, those with problems in either or both of them with no aggressiveness were evaluated as ×, and those in between were evaluated as Δ.

Example: The above-mentioned 1-butene random was combined (melt flow 17-3.6?/10 min, ethylene content 90 molt, density 0.88-7 cm3, crystallinity 15%) 80 weight part, high density polyethylene (melt flow rate 0.04?/10 ruin, density 0.
94 weight M/ayt3) 20 parts by weight, 120 parts by weight of magnesium hydroxide with an average particle size of 0.7 μm surface-treated with an organic fatty acid as a non-halogen flame retardant, and tetrakis[methylene-ro-(3', 5) as an antioxidant. '-di monobutyl-4-hydroxyphenyl)propionate] o, i, tt parts of methane were kneaded using a roll mill (140
C, 30 minutes) and then press molded and the physical properties were evaluated. As shown in the table, the resulting mixture has sufficient tensile properties, mechanical properties such as hardness and rigidity, flame retardancy as expressed by oxygen index, and extrudability.

Examples 2 and 3゜The high-density polyethylene used in Example 1 had a melt flow rate of 0.1117'/10 min and a density of 0.952.
S' 7cm3 and melt flow rate 0.11
As shown in the table, the results obtained by changing to the one with r/10 m1n and density 0.960 have sufficient mechanical properties, flame retardancy, and extrusion processability.

Examples 4 and 5゜The blending ratio of the ethylene-1-butene random copolymer and high-density polyethylene used in Example 1 was 70:30.65:
35 (weight ratio).

All have good mechanical properties, flame retardancy, and extrusion processability, and although the hardness and rigidity are increased compared to Example 1, the degree of increase in the embrittlement temperature is also small, which is preferable.

Example 6゜A part of the high-density polyethylene used in Example 5 was converted into a low a[vol.J ethylene (melt flow rate 0.23?/10 m
1n, density 0.924? /Crn”).

Example Z The formulation of Example 6 was followed by adding carbon black.

Comparative Example 1 The formulation of Example 1 was carried out using 100 parts by weight of ethylene-1-butene random copolymer without using high-density polyethylene.

The results are shown in the table.
It is clear that the extrusion processability is also poor.

Comparative Example 2゜The high-density polyethylene, magnesium hydroxide and antioxidant used in Example 1 were added to ioo:so:0.1 (weight ratio)
The mixture was carried out in the same manner as in Example 1 using the following ratios.

It is clear that the obtained sample is inferior in tensile elongation and extrusion processability compared to the examples.

Comparative Example 6 The low-density polyethylene used in Example 6, magnesium hydroxide, and antioxidant fr were mixed in the same ratio as in Example 1 at a ratio of 100:50:0.1 (weight ratio).

It is clear that the obtained sample is inferior in tensile elongation and extrusion processability compared to the examples.

Ethylene-1-putene fupolymer: Special 1 High density 11 ethylene-1 = 'fFRQ, 04'r/710m1n, density 0.945
97cm" ・High-density polyethylene-2: MF RC1, 11f/10m1n, density 0.952
W/crr? 2゜High density polyethylene-3: W F R0,11? /10m1n, density 0.960
W/cm33゜Low density 4 degree polyethylene: ,'+IF RO,23S'/ 10m1n, density 0
．． 924 y/, "Linear low density polyethylene: , VF R2, 19/1 [3-..., density 0.920
Y/crrr”.

Antioxidant: Patent applicant Mitsui Petrochemical Industries Co., Ltd. 6. Hand 1 ('? Yu T1 3 - Rest (voluntary) ■ (March 6, 1961 Director-General Uga Michibu 111 Displays Showa 1960 Patent Application No. 287922 Name of the invention Flame-retardant olefin polymer composition Relationship with the case of the person making the amendment No date of notice of reasons for refusal by the patent applicant Subject of amendment (1) Specification Hot water temperature Page 12, 5 from the bottom In lines 4 to 4, the words ``restricted solute index'' should be corrected to read ``f-drinke prime index''.

(2) In Table 1 on page 17, "oxidation index" in the physical properties column is corrected to read foxygen index j.

(3) On page 18, lines 13 to 14, [Linear low density......0.9
Delete 20 g/Cm3J.

Below

Claims (3)

[Claims] (1) Consisting of a low-crystalline ethylene/α-olefin copolymer, high-density polyethylene, and a non-halogen flame retardant; 100 parts by weight, and the non-halogen flame retardant is low crystalline ethylene α-
A flame-retardant olefin polymer composition, characterized in that it is contained in a proportion of 50 to 200 parts by weight per 100 parts by weight of the total amount of the olefin copolymer and high-density polyethylene. (2) The flame-retardant olefin polymer composition according to claim 1, wherein the non-halogen flame retardant is a metal hydroxide. (3) The flame-retardant olefin polymer composition according to claim 2, wherein the non-halogen flame retardant is magnesium hydroxide.