JPS63128043A - Flame-retardant resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Good chestnut upper Yu and ■ top mutual The present invention relates to a flame retardant resin composition.

Moxibustion - Summer 151 Gen 1 Sumire Conventional flame-retardant resin compositions include halogen-containing polymers or non-halogen-based polymers to which organic halogen-based flame retardants are added. However, although all products obtained using such flame-retardant resin compositions self-extinguish when kept away from flames, they burn to the maximum extent when placed in high-temperature flames such as during a fire. However, there were disadvantages such as a large amount of smoke being generated due to continuous decomposition, and highly corrosive and toxic acid gas being generated due to thermal decomposition.

The present invention is halogen-free, has excellent flame retardancy, mechanical strength, electrical properties, aging resistance, and is free from highly corrosive and toxic acid gases even when exposed to flame. The purpose of the present invention is to provide a flame-retardant resin composition that has characteristics such as not generating any smoke and generating little smoke.

The present invention is based on a combination of 100 types of olefinic resin, 50 to 250 parts by weight of hydrated alumina and/or hydrated magnesia, and aliphatic primary diamines and element periodic compounds. Table of Laws 1b
Organometallic complexes with metal elements belonging to Groups and Groups 0.1
The present invention relates to a flame-retardant resin composition characterized in that it contains 8 to 8 double-layered resin compositions.

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 (SSR), 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
It is 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-308 (all manufactured by Mitsubishi Yuka Co., Ltd.), Urtozex 2020L13520F, 3
021F (all manufactured by Mitsui Petrochemicals), DFDA-7
540 (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 and a density of 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.), etc.

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 third component expressed 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, Nisprene 50
1 (all manufactured by Sumitomo Chemical), EPT4021, EPT
1045 (all manufactured by Mitsui Petrochemicals), 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,)
-12031, K2O10 (all manufactured by Sumitomo Chemical),
Examples include NtJC8450 and 3145 (both manufactured by Nippon Unicar).

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 ones can be used, such as AQ203.nH2O (n is 2.5 to 3.5), more specifically Hysilite 842M [Showa (manufactured by Light Metal Company), 81403, B140
3-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, such as MqO-mH20 (m is 1.5 to 2.
5), etc. Among the above-mentioned hydrated magnesias, those having a specific surface area of 3 to 15 m<2>/g by the BET method and 0% of particles of 5 microns or more in the particle size distribution determined by the Luzex method are particularly suitable. Specific examples thereof include Kiss 75B, Kisuma 5A, and Kiss 75E (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! It is preferable to mix 50 to 250 parts, preferably 70 to 200 parts, and more preferably 80 to 150 parts per part (hereinafter simply referred to as "parts"). 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 above hydrated alumina and/or hydrated magnesia, 0
．． 1 to 8 parts, preferably 0.5 to 5 parts, of an organometallic complex of an aliphatic primary diamine and a metal element belonging to Groups 1b and 2 of the Periodic Table of the Elements is added. Examples of aliphatic primary diamines include ethylenediamine,
Examples include propylene diamine. Moreover, as the above-mentioned metal element, Cu1CO1Ni etc. can be illustrated.

The above-mentioned mirrors may be used alone or in combination of two or more. As mentioned above, even if the complex of the present invention is added in a relatively small amount, the flame retardance can be further improved. The amount of hydrated alumina and/or hydrated magnesia required 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 reduced. The added amount of magnesia can exhibit the effect of imparting even higher flame retardancy.

In the present invention, as a flame retardant aid, the red phosphorus content is 80% or more, the drying loss is 0.8% or less, the 74 mesh sieve residue is 7% or less, and the surface is made of thermosetting resin. A red phosphorous coated with phosphorus 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 (both 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, conversely, the above flame retardant additive formulation] 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 carrier 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), VulCan
-3, vu I can-3t- (all manufactured by Cabot), G-E-ST H, G-E-ST 3-day (all manufactured by Tokai Electrode), Keratsuen Black HAF (manufactured by Keratsuen), etc. Among them, 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 content 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. 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) titamine (KR-4181 manufactured by Kenrich),
Examples include tetraoctyl di(ditridecyl phosphite) titanate (KR-4681, 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 is ':CH2 or ":;c=o
shows. ] Preferred are organic titanates represented by
Specifically, diisostearoyloxyacetate titanate (KR-101, manufactured by Kenrich Co., Ltd.), isostearoyl methacryloxyacetate titanate (KR-1)
06, manufactured by the same company], isostearoylacryloxyacetate titanate (KR-1103, manufactured by the same company), and di(dioctylpyrophosphate) ethylene titanate (KR-2388, 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, tris(β-methoxyethoxysilane) (A172, manufactured by Nippon Unicar Co., Ltd.), γ-methacryloxypropyltrimethoxysilane (A174,
manufactured by Nippon Unicar Co., Ltd.).

In the present invention, the amount of such a coupling agent is usually 0.1 to 5 parts, preferably 0.1 to 5 parts, preferably 0.1 to 5 parts, preferably 0.1 to 5 parts, preferably 0.1 to 5 parts, preferably 0.1 to 5 parts, preferably 0.1 to 5 parts, preferably 0.
2 to 3 parts, more preferably 0.3 to . It is recommended to mix 1.5 parts. In addition, when using hydrated alumina and/or hydrated magnesia whose surface has been treated with the above-mentioned coupling agent, it is preferable that the amount of the coupling agent used does not deviate from 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 mistron vapor talc, calcium carbonate, magnesium carbonate, pigments such as phthalocyanine blue, chrome yellow, red iron, lubricants such as stearic acid, oleic acid, higher fatty acid metal salts, etc. , processing aids, etc. The amounts of these various additives can be appropriately determined within a wide range, but usually 1 to 50 parts of plasticizer, 0.1 to 10 parts of antioxidant, and 0.1 to 10 parts of filler per 100 parts of polyolefin resin. 5
~200 parts, pigment 0.1-10 parts, lubricant 0.1-5 parts
It is preferable to mix 0.1 to 10 parts of a 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 filtrate such as rt-butylperoxy)hexane, 2゜5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,1,3-bis(tert-butylperoxy-isoprobyl)benzene, etc. Crosslinking may be carried out by a method using an oxide crosslinking agent, a method of irradiation crosslinking with 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), trimethallyl isocyanurate (TMAIC), triallyl cyanurate (TAC), triacryloylhexahydro-1,3
, 5-triazine (TAF), and the like.

The amount of the crosslinking agent and crosslinking aid used in the layer 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.

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 on each side were tested by the following method.

<Flame retardancy test> After uniformly kneading the composition of the present invention using a roll mill, a sheet sample with a thickness of 3.5 cm was prepared by hot press molding.
For this sample, the oxygen index (Lot) is determined according to JIS K7201 (oxygen index method) 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 1 mm, and the compositions of Example 12 and Comparative Example 5, the sheet samples with a thickness of 2 II 1 m) were tested for each property by the following method. Find out.

(1) 100% modulus (kg/m…2) 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, after uniformly mixing the pace polymer, the female fuel agent, and the complex in a roll mill, 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;
100-1 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 mold crosslinking under a pressure of 0 ku/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.

A-150-90100-50--50--A-2-5
0--25----50- to-3-------10090--100A-4---
---------- A-55050To -5050--5050-Am
5 ---1-25--1---A-7-----
--10--- C-1235-----1,5--- 〇-2---3--------- 〇-3---3--------- C-4 ------6------- C-5-------6----- E-110101010---------F-'l
-----10,50,5---F-2---2-
−−1−−− F−310,5−−−−−−−−− F−4−−1−−−−−−−− F−5−−−−−−−−−−− F− 6−−−−−−−−−−− F−7−−−−−−−−−−− F−822222−−−−−− F−9−Lee−−−11−= F−10− −−−−−−−−−− F−11−−−−−−−−−− F−12−−−−−−−−−−− F−13−−−−−−1,52゜〇 ---F-14-
------m----- F-15---------- F-181111110,30,3----F-17--
-----0,30,3----A-1--10----111- A-2-------A-31005090----100- -A-4-5
0-m------ A-5--------- A-6--------- A-7---100---- 100-3-i
100100120 70 - -100100100
120 -C-131,5---= 3 5- --
C-2--3--------- 〇-3---3------- C-4-1,5--3--------- C-5--- --3------ E-15510---5-555 F-1---1------ 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 Mikata Petrochemical Co., Ltd.,
[Ultozex J 202DL, Mr=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, containing VA = 25 wt%, M
I=3.0) A-5...Poly-α-olefin (manufactured by Mikata Petrochemical Co., Ltd., Tafmer A4090.MI″=4.01 density 0.89
> A-6...Poly-α-olefin (manufactured by Mikata Petrochemical Co., Ltd., Tafmer 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...M(J (OH)2 (manufactured by Kyowa Chemical Co., Ltd.,
Kisuma 5B) B-2...AQ (OH)3 (manufactured by Showa Light Metal Company,
Hysilite 842M) Complex> C-1...Ethylenediamine-copper complex C-2...Ethylenediamine-nickel complex C-3...Ethylenediamine-cobalt complex C-4...Propylenediamine-copper complex C-5 ...Propylene diamine-nickel complex C-6...Propylene diamine-cobalt complex (flame retardant aid) D-1...Red phosphorus (manufactured by Rin Kagaku Co., Ltd., Tsubared #120
) <Carbon black> 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 (Kenridge Co., Ltd., KR41B, [Tetraisoprovir di(dioctyl phosphite) titanate]) F-2... Coordination type titanium Coupling agent (manufactured by Kenrich Co., Ltd., KR46B1 (tetraoctyl di(ditridecyl phosphite) titanate)) F-3... Chelate type titanium coupling agent (manufactured by Kenrich Co., Ltd., KRlol, [diisostearyloxyacetate 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 (magnesium silicate ) F-8... Stearic acid F-9... Zinc stearate F-10... Zinc oxide F-11... Triallylisocyanurate 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 = 15-20 cst, specific gravity = 0.920
> F-15...Mercaptobenzimidazole F-16
...Anti-aging agent (Manufactured by Iriuchi Shinkosha, Tsukrank 300,
4,4'-dihydroxy-3.

3'-di-tert-butyl-5,5'-dimethyl-
diphenyl sulfide) F-11... Irganox 1010 (manufactured by Ciba Geigy, Tetrakis [methylene-3- (3.

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.

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Claims (1)

[Claims] (1) 100 parts by weight of olefinic resin, 50 to 250 parts by weight of hydrated alumina and/or hydrated magnesia, and aliphatic primary diamines and Group Ib and Group Ib of the Periodic Table of Elements
A flame-retardant resin composition containing 0.1 to 8 parts by weight of an organometallic complex with a metal element belonging to Group VII.