JPS63128039A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To provide the titled halogen-free composition outstanding in flame- retardancy, mechanical strength, electrical properties, etc., generating no toxic gas even in case exposed to flame, comprising an olefin resin, hydrated alumina, etc., and borate of specific metal element in specified proportions. CONSTITUTION:The objective composition comprising (A) 100pts.wt. of an olefin resin (pref., a straight chain polyethylene with a density 0.91-0.96 and melt index 0.1-10 prepared by polymerization of ethylene under reduced pressure using as the comonomer 4-10C olefin), (B) 50-250pts.wt. of hydrated alumina and/or hydrated magnesia, and (C) 0.1-8(pref., 0.5-5)pts.wt. of a borate of group VIII, IIa or IIb metal element (e.g., Mn, Zn, Mg).

Description

[Detailed description of the invention] Industrial applications The present invention relates to a flame retardant resin composition.

Conventional flame-retardant resin compositions include halogen-containing polymers or non-halogen-based polymers to which an organic halogen-based flame retardant is added. However, although all products obtained using such flame-retardant resin compositions self-extinguish when kept away from flames, they do not burn to the end when exposed to high-temperature flames such as during a fire. If the process continues, a large amount of smoke is generated, and the thermal decomposition generates highly corrosive and toxic acid gas.

'RBJI Stand' [1 The present invention is halogen-free, has excellent flame retardancy, mechanical strength, electrical properties, aging resistance, and generates corrosive and highly toxic acid gas even when exposed to flame. The purpose of the present invention is to provide a flame-retardant resin composition that has characteristics such as low flame resistance and low smoke generation.

Once tested, the present invention consists of 100 parts by weight of an olefinic resin, 50 to 250 parts by weight of hydrated alumina and/or hydrated magnesia, and elements from Group VIIa and Group [a] of the Periodic Table of Elements. and Article I
The present invention relates to a flame-retardant resin composition containing 0.1 to 8 parts by weight of borates of metal elements belonging to group Ib.

As the olefin resin used as the pace polymer in the present invention, a wide variety of conventionally known ones can be used, such as olefin homopolymers such as polyethylene, polypropylene, and polystyrene, ethylene-propylene rubber (EP
M), ethylene-propylene-diene rubber (EPDM)
Copolymers of olefins such as styrene-butadiene rubber (SBR), isobutylene-isoprene rubber (IIR)
, acrylonitrile-butadiene rubber (NBR>), ethylene-ethyl acrylate copolymer (EEA), ethylene-vinyl acetate copolymer (EVA), and other copolymers of vinyl monomers and olefins.

Among these, ethylene is polymerized under low pressure using an olefin having 4 to 10 carbon atoms as a comonomer and a catalyst.
essentially linear polyethylene with a density of 0
．． 91-0.96, melt index (MI) 0.1
-10 is preferred. Examples include Yucalon L-11F-30F, F-30H (all manufactured by Mitsubishi Yuka Co., Ltd.), Kur1-Zex 202OL, 3520F,
3021F (all manufactured by Mikata Petrochemical Co., Ltd.), DFDA
-7540 (manufactured by Union Carbide) and the like.

Another preferred olefin resin is a copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms, which is polymerized using a Ziegler catalyst, and has an Mi of 1 to 10. Density is 0.
Examples include those in the range of 85 to 0.90. Examples include Tafmar 8-4090, A-4085, P-01
80, P-0480 [all manufactured by Mitsubishi Yuka Co., Ltd.], and the like.

Other preferable olefin resins include copolymers of ethylene and propylene with a propylene content of 15 to 70 mol%, preferably 20 to 50 mol%, and copolymers containing ethylene and propylene. Dichloropentadiene (DCPD), ethylidenenorbornene (ENB), 1,4-hexadiene (1,
An ethylene-propylene-diene terpolymer copolymerized with 4HD) etc., the third component expressed as an iodine value is 8 to 25, preferably 9 to 15, and the raw rubber Mooney viscosity is 30 to 70. I can list a range of things. Examples of the above resins include EP21, EP51 (all manufactured by Japan Synthetic Rubber Co., Ltd.), Nisprene 301, and Nisprene 50.
1 [all manufactured by Sumitomo Chemical Co., Ltd.], EPT4021, EPT
1045 (both manufactured by Mikata Petrochemical Co., Ltd.), etc. are included.

Still other preferable olefin resins include copolymers of ethylene and vinyl acetate with a vinyl acetate content of 2 to 5.
Those having a weight ratio of 1 to 30 are included. Examples include Levaprene 450, Levaprene 452 [
Both manufactured by Bayer], Evatate-D2021, H
2O31, K2O10 (all manufactured by Sumitomo Chemical), NU
Examples include C8450 and C3145 (both manufactured by Nippon Unicar Co., Ltd.).

In the present invention, the above-mentioned olefin resins may be used alone or in a mixture (blend) of two or more. The olefin resin may be crosslinked. As this cross-linked olefin resin, a wide variety of conventionally known ones can be used. Specifically, the above-mentioned olefin-based resin is added with an organic peroxide and cross-linked by heat treatment, and the above-mentioned olefin-based resin is applied with electron beams. Examples include crosslinked olefin resins obtained by irradiation with water, and crosslinked water-crosslinkable olefin resins.

The composition of the present invention contains hydrated alumina and/or as flame retardants.
Alternatively, it is necessary to incorporate hydrated magnesia. As the hydrated alumina used in the present invention, a wide variety of conventionally known hydrated aluminas can be used, such as AQ203.mH2O (n is 2
．． 5 to 3.5), more specifically Hysilite H42M (manufactured by Showa Light Metal Co., Ltd.), B1403, B1403
-D-18 (all manufactured by Nippon Light Metal Co., Ltd.) etc. can be exemplified,
Furthermore, as the hydrated magnesia, a wide range of conventionally known ones can be used, such as MgO-mH2O (m is 1.5 to 2.5
), etc. can be exemplified. Among the above-mentioned hydrated magnesias, those having a specific surface area of 3 to 15 m2/g by the BET method and having 0% of particles of 5 μ or more in the particle size distribution by the Luzex method are particularly suitable. Specific examples include Kisuma 75B, Kisuma 5A, and Kisuma 5E (all manufactured by Kyowa Chemical Industry Co., Ltd.). In the present invention, such hydrated alumina and/or hydrated magnesia is usually used as a polyolefin 100! The amount is preferably 50 to 250 parts, preferably 70 to 200 parts, and more preferably 80 to 150 parts per part li (hereinafter simply referred to as 1 part). If the amount of hydrated alumina and/or hydrated magnesia exceeds 250 parts, there will be a disadvantage that the physical properties of the resulting composition will deteriorate.

Furthermore, if the amount of hydrated alumina and/or hydrated magnesia is less than 50 parts, flame retardant performance will not be exhibited.

A feature of the present invention is that, in addition to the hydrated alumina and/or hydrated magnesia, per 100 parts of the polyolefin resin,
0.1 to 8 parts, preferably 0.5 to 5 parts of borates of metal elements belonging to Groups VIIaFA, Groups [A and UB of the Periodic Table of Elements] are added. Examples of such 1m salts include borates of metals such as 1vln, Zn, and Mg, and more specifically, manganese borate, zinc borate,
Examples include magnesium borate, which may be used singly or in combination of two or more. As mentioned above, even if the borate of the present invention is added in a relatively small amount, the flame retardancy can be further improved, so the amount required to obtain the same flame retardance is lower than when the borate is not added. The amount of hydrated alumina and/or hydrated magnesia can be reduced, resulting in improved mechanical properties, electrical properties, etc. of the composition, or the same amount of hydrated alumina and/or hydrated magnesia can be used. When added in an amount of , the effect of imparting even higher flame retardance can be achieved.

In the present invention, as a flame retardant aid, the red phosphorus content is 80% or more, the loss on drying is 0.8% or less, the 74 mesh sieve residue is 7% or less, and the surface is made of thermosetting resin. The coated red phosphorous may be incorporated into the composition of the present invention. Examples of the thermosetting resin include phenol resin, phenol-formalin resin, and the like. A specific example of such red phosphorus is No Bullet #12.
0, No Bullet #120uF (all manufactured by Rin Kagaku Kogyo Co., Ltd.), and the like.

In this case, such red phosphorus is usually 100% olefin resin.
3 to 40 parts, preferably 5 to 15 parts, more preferably 5 to 12 parts. Its blending amount is 4
If the amount exceeds 0 parts, there will be a disadvantage that the physical properties of the resulting composition will deteriorate. In addition, on the contrary, the amount of the flame retardant aid added is 3
If the amount is less than 10%, the flame retardant effect of the resulting composition will be difficult to exhibit.

Furthermore, in the composition of the present invention, the DBP oil absorption is 100 to
160cm3/100g and ASTM code is N3
Carbon black such as furnace black recognized as 30 to N351 may be blended, and in this case, the flame retardance of the resulting composition can be further improved. Such carbon blacks include, for example, HAF or HAF.
- What is called HS carbon can be preferably exemplified,
Specific examples include Diablack H, Diablack H3 (both manufactured by Mitsubishi Kasei Corporation), and yulcan.
-3, Vul can-3H' (all manufactured by Cabot), Giest H1 Giest 3 days (both manufactured by Tokai Electrode), Keratsuen Black HAF (manufactured by Keratsuen)
etc. Among these, Diamond Black H and Vu
Particularly preferred is lCan-3.

In the present invention, such carbon black is usually used in an amount of 3 to 50 parts, preferably 5 to 2 parts, per 100 parts of olefin resin.
It is preferable to mix 0 parts, more preferably 5 to 15 parts. If the amount exceeds 50 parts, the composition tends to harden and its mechanical properties are impaired. On the other hand, if the amount of the flame retardant aid is less than 3 parts, the effect of the addition will be lost, which is not preferable.

In the composition of the present invention, a coupling agent may be added as necessary. Alternatively, hydrated alumina and/or hydrated magnesia may be surface-treated in advance with a predetermined old coupling agent and used in the present invention. As the coupling agent, a wide variety of conventionally known coupling agents can be used, and examples include titanate coupling agents such as monoalkoxy type, neoalkoxy type, coordination type, and Kir-1 type, and silane coupling agents. Among the titanate coupling agents mentioned above, those containing phosphorus are preferred. This phosphorus-containing coordination type titanate coupling agent has the general formula % (%) [wherein R represents an alkyl group having 1 to 12 carbon atoms].

R' represents an alkyl group having 3 to 30 carbon atoms. Preferred examples include organic titanates represented by the following. Specific examples include tetraisoprovir di(dioctyl phosphite) titanate (KR-41B, manufactured by Kenrich),
Examples include tetraoctyl di(ditridecyl phosphite) titanate (KR-46B, manufactured by the same company).

The chelate-type titanate coupling agent has the general formula [wherein R represents an acyl group, a sulfonyl group, a phosphoryl group, or an aryl group]. X represents; CH2 or /C=0. ] Preferred are organic titanates represented by the following, specifically diisostearoyloxyacetate titanate (
KR-101, manufactured by Kenrich), isostearylmethacryloxyacetate titanate (KR-106,
Isostearoylacryloxyacetate titanate (KR-11O3, manufactured by the same company), di(dioctyl pyrophosphate) ethylene titanate (KR
-2383, manufactured by the same company].

As the silane coupling agent, trialkoxysilane having a carbon-carbon double bond or an epoxy group is preferable, and specifically, vinyl-tris (β-methoxy silane)
xysilane) (A172, manufactured by Nippon Unicar Co., Ltd.), γ-methacryloxypropyltrimethoxysilane (A174,
(manufactured by Nippon Unicar Co., Ltd.), etc.

In the present invention, such a coupling agent is usually used in an amount of 0.1 to 5 parts, preferably 0.2 parts, per 100 parts of olefin resin.
It is preferable to add 3 parts, more preferably 0.3 to 1.5 parts. In addition, when using hydrated alumina and/or hydrated magnesia whose surface has been treated with the above-mentioned coupling agent, the amount of the coupling agent used should preferably be within the above-mentioned range. By incorporating a coupling agent into the composition of the present invention, the mechanical strength of the resulting composition is improved, and the processability is improved.

In addition to the above-mentioned various components, various known additives may be added to the composition of the present invention. Examples of such additives include naphthenic, aromatic, process oils, phthalic acid, esters, trimellitic acid, plasticizers such as epoxy resins, hindered phenols, aromatic amines,
Antioxidants such as thiopropionates, fillers such as Mystron paper talc, calcium carbonate, magnesium carbonate, pigments such as phthalocyanine blue, chrome yellow, red iron oxide, lubricants such as stearic acid, oleic acid, higher fatty acid metal salts, etc. , processing aids, etc. The amounts of these various additives can be determined as appropriate within a wide range, but
Normally, 1 part of plasticizer is added to 100 parts of polyolefin resin.
~50 parts, antioxidant 0.1~10 parts, filler 5~
200 parts, 0.1 to 10 parts of pigment, 0.1 to 5 parts of lubricant, and 0.1 to 10 parts of processing aid.

The composition of the present invention comprises (e'(-butylcumyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2°5-di(te)
Organic peroxides such as rt-butylperoxy)hexane, 2゜5-dimethyl-2,5-di(tertL-butylperoxy)hexyne-3,1,3-bis(tert-butylperoxy-isopropyl)benzene, etc. Crosslinking may be carried out by a method using a crosslinking agent, a method of irradiation crosslinking using an electron beam, radiation, or the like. In that case, as a crosslinking aid, a crosslinking aid commonly used in the above-mentioned crosslinking method may be used in combination. Preferred crosslinking aids include aliphatic and aromatic polyfunctional compounds, aliphatic polyfunctional cyclic compounds, nitrogen-containing polyfunctional cyclic compounds, metal-containing polyfunctional compounds, and especially nitrogen-containing polyfunctional compounds. Functional cyclic compounds, especially triallyl isocyanurate (TAIC), trimetaallylisocyanurate (TMAIC), triallyl cyanurate (TAC), triacryloyl hexagonal draw 1.3
．． Examples include 5-triazine (TAF).

The amount of the crosslinking agent and crosslinking aid used is preferably 0.1 to 5 parts, preferably 0.3 to 2 parts, per 100 parts of the polyolefin resin.

The composition of the present invention can be obtained by suitably blending predetermined amounts of the above-mentioned various components and uniformly mixing them using a Banbury mixer, Henschel mixer, etc. according to a conventionally known method. In addition, in a polymer blend system, it is preferable to mix the polymer uniformly first and then mix the other components.

When using the composition of the present invention, various conventionally known molding methods can be widely adopted. For example, the composition of the present invention is kneaded using a mixing machine such as a roll kneader, and then this is mixed according to the purpose. It may be molded into various shapes.

-1-1 Since the composition of the present invention is halogen-free, even if it is left in a high-temperature flame such as during a fire, it will not emit a large amount of smoke or cause thermal decomposition. It does not generate corrosive gas or acidic gas, and has excellent flame retardancy, mechanical strength, electrical properties, aging resistance, etc. Therefore, the composition of the present invention is suitable as a coating material for building materials, pipes, hoses, sheets, seat covers, wall materials, electric wires and cables (internal insulators, external sheaths, etc.), and the like.

X-111 Hereinafter, in order to explain the present invention in more detail, examples will be given.

The characteristics of the samples obtained in the 8 cases were tested by the following method.

Flame retardancy test> The composition of the present invention was uniformly kneaded using a roll mill, then hot press molded to prepare a sheet sample with a thickness of 3.5 mm. The flame retardancy is evaluated by determining the index (LOI).

<Mechanical properties> Sample sheets similar to the above (Examples 1 to 11 and 13 described later)
~16 and Comparative Examples 1 to 4 and 6, sheet samples with a thickness of '1 mm, and compositions of Example 12 and Comparative Example 5, sheet samples with a thickness of 2 mm) were prepared by the following method. Examine the characteristics.

(1) 100% modulus (kg/mm2) ASTM
According to D882.

(2) 200% modulus (kg/mm2) ASTM
According to D882.

(3) Tensile strength (kg/mm”) According to ASTM D882.

(4) Elongation (%) According to ASTM D882.

Examples 1 to 16 and Comparative Examples 1 to 6 Predetermined amounts (parts by weight) of each component shown in Table 1 below were mixed by the following method to obtain compositions of the present invention. That is, a base polymer, a flame retardant, and a borate were uniformly mixed in a roll mill, and then a sheet-like composition was prepared. The conditions at this time were 120 to 140°C for Examples 1 to 6 and Comparative Examples 1 to 2.
, 100-100 for Examples 7-12 and Comparative Examples 3-4
For Examples 13 to 16 and Comparative Examples 5 to 6, the temperature range was from room temperature to 80°C.

In addition, the above compositions were heated to 100 to 15
A sheet of each composition was prepared by molding or crosslinking under a pressure of 0 kg/cm2. The conditions at this time are from Example 1 to
6 and Comparative Examples 1-2 at 150°C for 5 minutes, Examples 7-12 and Comparative Examples 3-4 at 170°C, 45
1 minute for Examples 13-16 and Comparative Examples 5-6
The temperature was 65°C for 30 minutes.

8-'l 50-90100-50-
- 50 - -A-2-50--25----50- A-3-------10090--100A-4---
---------- A-5505010-5050--5050-A-6-
---25-------- A-7--------10--- B-11001001201301501301001
30100100100G-12--31,51-3-
-- C-2-3--1゜5-------- E-110101010--------F-1-----
10,50,5---F-2---2---1---- F-310,5------F-4--1--------- − F-5−−−−−−−−−− F−6−−−−−−−−−− F−7−−−−−−−−−−− F−822222−−−− -- F-9---------11--- F-10-------------- F-11------1------ F-12--- --------- F-13----1,52,0-m-F-14--
------------- F-15---------- F-161111110,30,3---A-1--1
0---------A-2---------A-31005090---100--A-4-5
0------------ A-5--------- A-6--------- A-7---100---- 100-B-11001
0012070--100100100120-C-1
23----23--- C-2--3------ E-15510--5-555 F-1--1--------- F-2- -----1----- F-3-----1------ F-410,51--1----- F-5--1---1---- - F-6-0,1------1--- F-7---30--- F-8-1-1-121--- F-9212-- 1---F-10---105101010---F-11---
-11111--- F-12---0,50,50,50,50,5---
F-132,02,02,02,72,72,72,7
2,7---F-14---5551010---F-15---11111---F-160,30,50,5---Each component in Table 1 The symbol in indicates the following: <Base polymer> A-1...Low density polyethylene (manufactured by Mikata Petrochemical Co., Ltd.,
[Ultozex J 2020m, MI=2.1, Density=0.920> A-2...Low density polyethylene (manufactured by Mitsubishi Yuka Co., Ltd., [Yukalon J LLF30F, MI=1.0.Density=0.920) A-3... Ethylene vinyl acetate copolymer (manufactured by Nippon Unicar Co., Ltd., NUC8450, VA content = 15 wt%, MI
=2.0> A-4... Ethylene vinyl acetate copolymer manufactured by Sumitomo Chemical Co., Ltd., evatate 2010, VA content = 25 wt%, M
I=3.0) A-5...Poly-α-olefin (manufactured by Mikata Petrochemical Co., Ltd., Tafmer A4090.MI=4.0, density 0.89> A-6...Poly-α-olefin (manufactured by Mikata Petrochemical Co., Ltd., Tafmar AO480, MI=1.2, density 0.88> A-7...EPDM (manufactured by Japan Synthetic Rubber Co., Ltd., EP21,
Mooney viscosity = 38, 3rd component = EN8, iodine value = 19
) A-8...EVA (manufactured by Bayer, Levaprene 450
, VA content = 45 wt%) <Flame retardant> B-1...M(J(OH)2 (manufactured by Kyowa Chemical Co., Ltd., Kisuma 5B> B-2...A Q (OH) 3 (manufactured by Showa Light Metal Co., Ltd.) , Hisilite 842M) Borate> C-1... Manganese borate C-2... Zinc I acid C-3... Magnesium WA acid (flame retardant aid) [)-1... Red phosphorus ( Manufactured by Rinkagaku Co., Ltd., Tsuba Red #12
0) Carbon black> E-1...HAF carbon (manufactured by Mitsubishi Kasei Corporation, Dia Black H) E-2...HAF carbon (manufactured by Cabot Corporation, ULC
an-3><Additives> F-1... Coordination type titanium coupling agent (manufactured by Kenrich Co., Ltd., KR41B, [Tetraisoprovir di(dioctyl phosphite) titanate]) F-2... Coordination type titanium coupling agent Tank coupling agent (manufactured by Kenrich Co., Ltd., KR46B, (tetraoctyl di(ditridecyl phosphite) titanate)) F-3... Chelate type titanium coupling agent (manufactured by Kenrich Co., Ltd., KRlol, [diisostearoyloxyacetate) titanate]) F-4... Chelate type titanium coupling agent (manufactured by Kenridge Co., Ltd., KR201, [diisostearoyl ethylene titanate]) F-5... Silane coupling agent (manufactured by Nippon Unicar Co., Ltd., A172, (vinyl - Tris (β-methoxyethoxysilane) F-6... Silane coupling agent (manufactured by Nippon Unicar Co., Ltd., A174, [γ-methacryloxypropyltrimethoxysilane]) F-7... Mistron paper talc ( Magnesium silicate) F-8... Stearic acid F-9... Zinc stearate F-10... Zinc oxide F-11... Triallyl isocyanurate F-12.
...N,N'-m-phenylene bismaleimide F-13...dicumyl peroxide F-14...
Process oil (naphthenic, manufactured by Nippon Sun Oil Co., Ltd., Sansen 4240, viscosity -15 to 2Qcst, specific gravity = 0.920
) F-15...Mercaptobenzimidazole F-16
...Anti-aging agent (manufactured by Iriuchi Shinkosha, Tsukurak 300.
4.4'-dihydroxy-3,.

3'-di-tert-butyl-5,5'-dimethyl-diphenyl sulfide) F-17... Irganox 1010 (Ciba Geigy, Tetrakis
ert-butyl-4-hydroxyphenyl)propionate comethane) The properties of the molded sheet samples of the compositions of the present invention obtained from each of the above are shown in Table 2 below.

From Table 2 above, it can be seen that the rate obtained using the composition of the present invention has excellent properties, particularly in terms of flame retardancy and mechanical properties.

(that's all)

Claims (1)

[Claims] (1) 100 parts by weight of an olefinic resin, 50 to 250 parts by weight of hydrated alumina and/or hydrated magnesia, and 0.0 borates of metal elements belonging to Group VIIa, Group IIa, and Group IIb of the Periodic Table of Elements. A flame-retardant resin composition containing 1 to 8 parts by weight.