JPS63128044A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To provide the titled halogen-free composition outstanding in flame- retardancy, mechanical strength, electrical properties, and deterioration resistance, generating no toxic gas even in case exposed to flame, comprising an olefin resin, hydrated alumina, etc., and ferrocene 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 ferrocene (e.g., ferrocene, tert-amylferrocene).

Description

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

As conventional flame-retardant resin compositions, those prepared by adding an organic halogen flame retardant to a halogen-containing polymer or a non-halogen polymer are known. 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 is continued, there are drawbacks such as excessive smoke generation and the generation of highly corrosive and toxic acid gas due to thermal decomposition.

The present invention is halogen-free, has excellent flame retardancy, mechanical strength, electrical properties, aging resistance, and is highly acidic and highly corrosive and toxic when exposed to flame. It is an object of the present invention to provide a flame-retardant resin composition having characteristics such as not generating gas and generating little smoke.

In other words, the present invention contains 100 parts by weight of an olefin resin, 50 to 250 parts by weight of hydrated alumina and/or hydrated magnesia, and 0.1 to 8 parts by weight of 7 erocenes. The present invention relates to a flame-retardant resin composition characterized by:

As the olefin resin used as the base 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 a catalyst using an olefin having 4 to 10 carbon atoms as a comonomer (q
essentially linear polyethylene with a density of 0
．． 91-0.96, melt index (MI) 0.1
-10 is preferred. Examples include Yucalon LL, F-30F, F-30H (all manufactured by Mitsubishi Yuka Co., Ltd.), Urtozex 2020m, 3520F, 3
021FC (all manufactured by Mikata Petrochemical Co., Ltd.), 0FOA-
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 A-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. The third component is dichloropentadiene (DCPD>, ethylidenenorbornene (ENB), 1,4-hexadiene (1,
An ethylene-propylene-diene terpolymer copolymerized with 4HD) etc., the amount of the third component represented by the 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, ■Spren 501
(all manufactured by Sumitomo Chemical), EPT4021, EPT1
045 (all manufactured by Mikata Petrochemical Co., Ltd.), etc.

Still other preferable olefin resins include copolymers of ethylene and vinyl acetate with a vinyl acetate content of 2 to 5.
0% by weight and MI in the range of 1 to 30. 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 A9203・nl-120(
(rl indicates 2.5 to 3.5), more specifically Hysilite 842M (manufactured by Showa Karukinbo Co., Ltd.), 81403, B
1403-D-18 (all manufactured by Nippon Light Metal Co., Ltd.), etc., and as the hydrated magnesia, a wide variety of conventionally known hydrated magnesias can be used.
2.5). Among the above hydrated magnesias, the specific surface area according to the BET method is 3 to 15 m2.
/(J, and 0% of particles of 5μ or more in the particle size distribution determined by the Luzetx method are suitable. Specific examples include Kis75B, Kisuma 5A, Kisuma 5
E (all manufactured by Kyowa Kagaku Kogyo Co., Ltd.), etc. can be exemplified. In the present invention, such hydrated alumina and/or hydrated magnesia is usually used in an amount of 50 to 250 parts, preferably 70 to 20 parts, per 100 parts by weight of polyolefin (hereinafter simply referred to as "parts").
It is preferable to mix 0 parts, more preferably 80 to 150 parts. The amount of hydrated alumina and/or hydrated magnesia is 2
If the amount exceeds 50 parts, there will be a disadvantage that the physical properties of the resulting composition will deteriorate.

Also, a combination of hydrated alumina and/or hydrated magnesia m
If it is less than 50 parts, flame retardant performance will not be exhibited.

A feature of the present invention is that in addition to the above hydrated alumina and/or hydrated magnesia, 0
．． It consists in adding 1 to 8 parts, preferably 0.5 to 5 parts of ferrocenes. Examples of the erocenes include ferrocene, monoalkyl derivatives of ferrocene, dialkyl derivatives of ferrocene, and acetyl derivatives of ferrocene. More specific examples include ferrocene, tert-amylferrocene, n-butylferrocene, acetylferrocene, 1,1'-dimethylferrocene, formylferrocene, N,N'-dimethylaminomethylferrocene, etc., each of which may be used singly. It can be used alone or in combination of two or more. As mentioned above, the addition of the 7 erocenes of the present invention can further improve the flame retardancy even if the amount of ω is relatively small, so that the same flame retardance can be obtained as compared to when these are not added. The amount of hydrated alumina and/or hydrated magnesia required for the composition can be reduced, resulting in improved mechanical properties, electrical properties, etc. of the composition, or the same amount of hydrated alumina and/or water can be reduced. The added amount of Japanese magnesia can exhibit the effect of imparting even higher degree of flame retardancy.

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 absorbent is 100 to
160cm3/100g and ASTM code is N5
Carbon black such as furnace black recognized as 30-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 H1 Diablack H3 (both manufactured by Mitsubishi Chemical Corporation), VuI Ca
n-3, Vul can-3t (all manufactured by Cabot), Geast H, Gyst 3 day (all manufactured by Tokai Electrode), Keratsuen Black HAF (manufactured by Keratsuen), etc. Among these, Diamond Black H and V
Lllcan-3 is particularly preferred.

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 resulting 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 amount of a 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 monoalkoxy type, neoalkoxy type, coordination type, chelate type titanate coupling agents and silane coupling agents. Among the titanate coupling agents mentioned above, those containing phosphorus are preferred. The coordination titanate coupling agent containing phosphorus 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).

As a chelate type titanate coupling agent, R represents an acyl group, a sulfonyl group, a phosphoryl group, or an aryl group in the general formula C. X represents /CH2 or \C=0. ] Preferred are organic titanates represented by the following, specifically diisostearoyloxyacetate titanate (
KR-101, manufactured by Kenrich], isostearoylmethacryloxyacetate titanate (KR-106,
], isostearoylacryloxyacetate titanate (KR-1108, made by the above 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-methoxyethoxysilane) (A172, manufactured by Nippon Unicar Co., Ltd.), γ-methacrylate Examples include roxypropyltrimethoxysilane (A174, manufactured by Nippon Unicar Co., Ltd.).

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. Furthermore, 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 blended is preferably 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 tert-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(tert-butylperoxy)hexyne-3,1,3-bis(tert-butylperoxy-isopropyl)benzene, etc. Crosslinking may be carried out by a method using a physical crosslinking agent, an irradiation crosslinking method using an electron beam or radiation, etc. In that case, a crosslinking aid commonly used in the above 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, etc. Nitrogen-containing polyfunctional cyclic compounds, especially triallylisocyanurate-1 (TAIC), trimetaallylisocyanurate (TMAIC), triallyl cyanurate (TAC), triacryloyl hexahydro-1,
Examples include 3,5-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 first mix the polymers uniformly 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 kneading machine such as a roll kneader, and then this is mixed according to the purpose. It may be molded into various shapes.

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.

EXAMPLES Examples will be given below to explain the present invention in more detail.

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, and then heated and press molded to create a sheet sample with a thickness of 3.5 mm. The oxygen index (LOI) is determined according to the following and the flame retardance is evaluated.

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, the sheet samples with a thickness of 11IIIl, and the compositions of Example 12 and Comparative Example 5, the sheet samples with a thickness of 2ml) were evaluated for each property by the following method. Find out.

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

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

(3) Tensile strength (kg/mm　2) 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 ferrocene were uniformly mixed in a roll mill, and then a sheet-like composition was prepared. The conditions at this time were 120 to 1 for Examples 1 to 6 and Comparative Examples 1 to 2.
40°C, 1 for Examples 7-12 and Comparative Examples 3-4
For Examples 13-16 and Comparative Examples 5-6, the temperature range was from room temperature to 80°C.

In addition, the above compositions were heated to 100 to 15
Sheets of each composition were prepared by molding or mold crosslinking under a pressure of 0 ka/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
For Examples 13 to 16 and Comparative Examples 5 to 6, the temperature was 165° C. for 30 minutes.

A-150-90100-50--50--Am2
-50--25----50-A-3--1---
10090--100A-4--------- A-5505010-5050--5050-A-6-
---25-------- A-7--------10--- C-112352----- C-2--23----- C-3- ------3----- C-4---------2--- 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----- --1----- F-13------1,52,0--F-14--
---111--- F-15--111-----F-161111110,30,3---A-1--1
0--1-----A-2--1-----A-31005090--100--A-4-5
0------1--- A-5--------- A-6--------- A-7--100----- 100-C-133--
35----- C-2---2--3---- C-3---2---3--- C-4---------- E- 15510---5-555 E-2---3101055--- F-i---t------F-2---
−−1−−−−− F−3−−−−1−−−−−− F−410, 51−−−−−−− 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 symbols in indicate the following.

<Base polymer> A-1...Low density polyethylene (manufactured by Mitsui Petrochemicals,
"Ultozex J 202DL, 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 (Mitsui Petrochemical Co., Ltd., Tafmer A4090, MI=4.0, density 0.89> A-6...Poly-α-olefin ( Manufactured by Mitsui 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 = ENB, iodine value = 19
) A-8...EVA (manufactured by Bayer, Levaprene 450
, VA included! =45wt%) <Flame retardant> B-1...MCI(OH)2 (manufactured by Kyowa Chemical Co., Ltd., Kisuma 5B) B-2...AQ(OH)3 (manufactured by Showa Light Metal Co., Ltd., Hisilite 842M> Ferrocene Type> C-1... Ferrocene C-2-tert-7) Ly ferrocene C-3...
n-Butylferrocene C-4...Acetylferrocene C-5...N,N'-dimethylaminomethylferrocene (flame retardant aid) D-1...Red phosphorus (manufactured by Rin Kagaku Co., Ltd., Tsuba Red) #120
><Carbonblack>, E-1...HAF carbon (manufactured by Mitsubishi Kasei Corporation, Dia Black H) E-2...HAF carbon (manufactured by Cabot Corporation, Vul
can-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 (manufactured by Kenrich Co., Ltd., KR46B, (tetraoctyl di(ditridecyl phosphite) titanate)> F-3... Chelate type titanium coupling agent (manufactured by Kenrich Co., Ltd., KRIOI, [diisostearoyloxyacetate titanate]) ) F-4... Chelate type titanium coupling agent (manufactured by Kenrich 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 (silicic acid Magnesium) F-8... Stearate 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 = 15-20C3t, 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-11...Irganox 1010' (manufactured by Ciba Geigy, tetrakis (5-di-tert-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 sheets obtained using the composition of the present invention have excellent properties, particularly in terms of flame retardancy and mechanical properties.

(that's all)

Claims (1)

[Claims] (1) A flame-retardant resin composition characterized by containing 100 parts by weight of an olefin resin, 50 to 250 parts by weight of hydrated alumina and/or hydrated magnesia, and 0.1 to 8 parts by weight of ferrocenes.