JPS6210253B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a flame-retardant resin composition, in particular, the main component is an ethylene-vinyl acetate copolymer having a vinyl acetate content within a specific range, and a hydrated metal oxide powder is blended therein to synergistically retard the flame-retardant resin composition. Resin composition with improved flammability Furthermore, by treating the surface of the hydrated metal oxide powder with a titanate-based coupling agent, physical and mechanical properties, especially tensile elongation, can be improved. The present invention relates to a flame-retardant resin composition that has improved processability by using a coupling agent and a saturated fatty acid compound in combination. Conventionally, methods for making synthetic resins flame retardant generally include (1) adding flame retardants, (2) highly filling inorganic substances, and (3) coating the surface with nonflammable substances such as inorganic substances. However, from the viewpoints of resource saving, non-pollution (low amount of smoke or harmful gas produced during combustion), economic efficiency, etc., method (2) is considered to be the best method to make synthetic resin flame retardant. I can say it. Based on this perspective, calcium carbonate, calcium sulfate, calcium sulfite, aluminum hydroxide, magnesium hydroxide,
Attempts have been made to highly fill polyolefin resins such as polyethylene and polypropylene with inorganic powders such as calcium hydroxide. However,
Among these inorganic powders, aluminum hydroxide,
Magnesium hydroxide etc. are inexpensive and easily available, and since they themselves dehydrate at temperatures around 200° to 250°C, they have the properties of a kind of flame retardant.
It is suitable as a filler for flame retardancy.
On the other hand, using these substances to make polyolefins,
In order to achieve a degree of flame retardancy that is approximately the same as that obtained by combining a synergistic flame retardant such as a halogen-containing compound and antimony trioxide, it is possible to use aluminum hydroxide, etc., which has a flame retardant effect. The resulting composition requires a high filling amount, and as a result, the resulting composition exhibits a significant decrease in physical and mechanical properties, especially tensile elongation. The above-mentioned attempts at high loading of inorganic substances have focused only on improving the elastic modulus or strength, or making flame retardant through specific formulations, and there has been no attempt at all to compensate for the deterioration in tensile elongation. It is. The present inventors have developed various types of polyolefins, including polymer blends, in order to achieve high flame retardancy by filling polyolefins with inorganic substances and to improve the resulting reduction in tensile elongation properties of the compositions. As a result of detailed research on the effects of hydrated metal oxide powder and various coupling agents or various lubricants, we found that among polyolefins, ethylene-vinyl acetate copolymer with a vinyl acetate content in a specific range It has been found that at a specific blending ratio with aluminum oxides, especially aluminum hydroxide and magnesium hydroxide, it is possible to achieve a significantly higher degree of flame retardancy than with other polyolefins at the same loading level. Furthermore, it was discovered that by combining these hydrated metal oxide powders whose surfaces were treated with a titanate coupling agent, the tensile elongation properties were highly improved. If saturated fatty acids or their esters, amides, metal salts, etc. are used in the system, this tensile elongation property can be further improved.
Furthermore, the inventors discovered that the kneading processability using a roll or Banbury mixer was significantly improved, leading to the present invention. That is, in the present invention, the decomposition initiation temperature is
Hydrated metal oxide powder, in particular 70 to 500 parts by weight of aluminum hydroxide or magnesium hydroxide, whose surface is optionally treated with a titanate coupling agent, in the range of 150° to 450°C, and optionally A resin composition with improved flame retardancy and mechanical properties characterized by the combined use of one or more compounds selected from the group consisting of saturated fatty acids having 4 to 22 carbon atoms, their esters, amides, and metal salts. It is. Among hydrated metal oxides, aluminum hydroxide,
It is a well-known fact that compounds such as magnesium hydroxide and tin hydroxide can be added alone to general-purpose polyolefin resins such as polyethylene and polypropylene to impart flame retardancy. The present inventors experimentally confirmed this fact using aluminum hydroxide as an example, and obtained the result shown in FIG. 1 (A). That is, low density, medium density, high density polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, ethylene-propylene copolymer, ethylene-butene-1 copolymer,
Polyolefins such as ethylene-hexene-1 copolymer, ethylene-ethyl acrylate copolymer, and ethylene-propylene rubber do not contain aluminum hydroxide, regardless of the type of resin, crystallinity or rubbery state, presence or absence of crosslinked structure, etc. (expressed in parts by weight of the filler relative to 100 parts by weight of polyolefin; hereinafter referred to as phr) and the oxygen fat number (JIS K7201-1976 "Polymer materials determined by the oxygen index method", which is one measure of flame retardancy). The larger the oxygen index is, the higher the flame retardancy is.) The relationship between the oxygen index and the flame retardance is approximately linear, and for any polyolefin, the value is the same as the aluminum hydroxide filling amount. If they are equal, they are substantially the same and are shown in FIG. 1 of the example below (A)
The value was within ±1 of the value read from the straight line. In contrast to these polyolefins, the oxygen index of ethylene-vinyl acetate copolymer increases almost exponentially as the aluminum hydroxide loading increases, as shown in Figure 1 (B). Straight line (A) showing the oxygen index of other polyolefins
It was found that there was a significant deviation from the This is truly surprising when it comes to flame retardant polyolefin resins, and has never been reported anywhere else. Furthermore, when the same ethylene-vinyl acetate copolymer is made flame retardant with a known synergistic flame retardant consisting of a halogen-containing compound and antimony trioxide, no such abnormal tendency is observed at all.
This unusually high flame retardance of the ethylene-vinyl acetate copolymer by aluminum hydroxide is influenced by the amount of vinyl acetate contained in the copolymer. In other words, as shown in Figure 2, aluminum hydroxide
100 phr of ethylene with different vinyl acetate contents
The oxygen index of the composition when blended with a vinyl acetate copolymer is saturated in the vinyl acetate content of 10% by weight or more and exhibits a substantially constant value. In other words, the above-mentioned abnormally high flame retardance can be achieved significantly with ethylene-vinyl acetate copolymers containing 10% by weight or more of vinyl acetate, which means that the aluminum hydroxide loading can be increased to 70 to 500 phr. They are exactly the same within the range. Although the above has been described using aluminum hydroxide as an example, the same holds true when other hydrated metal oxides such as magnesium hydroxide (decomposition initiation temperature ranges from 150° to 450°C) are charged. In the present invention, the abnormally high flame retardance for polyolefin resins of the ethylene-vinyl acetate copolymer due to the use of hydrated metal oxides is due to the fact that hydrated metal oxides such as aluminum hydroxide and magnesium hydroxide are generally used as bases. Because it is a chemical or Lewis basic substance, it participates in deacetic acid removal during the thermal decomposition and combustion process of ethylene-vinyl acetate, acts in some way on the hydroxyl groups pendant to the formed polymer main chain, and catalytically causes combustion. It is thought that this is due to a mechanism that promotes the formation of a carbon skeleton at the interface, but this is not clear. Incidentally, in the case of ethylene-acrylic acid ester copolymers which have a similar ester structure but form pendant carboxyl groups on the polymer main chain through saponification, the above-mentioned abnormality can be obtained by filling with the same hydrated metal oxide. Although high flame retardancy is not observed, a polymer obtained by partially saponifying the ethylene-vinyl acetate copolymer exhibits almost the same behavior as the polymer before saponification. Furthermore, in the present invention, carbon atoms having 8 to 22 carbon atoms such as isopropyl-tristearoyl-titanate are used.
By using hydrated metal oxide powder such as aluminum hydroxide or magnesium hydroxide whose surface has been treated with a titanate coupling agent containing long-chain aliphatic hydrocarbon groups, It is possible to obtain an ethylene-vinyl acetate copolymer-based flame-retardant composition that has improved tensile elongation properties while maintaining flammability. This improvement effect on tensile elongation properties is remarkable when the hydrated metal oxide loading is in the range of 100 to 500 phr and the vinyl acetate content of the ethylene-vinyl acetate copolymer used is in the range of 10 to 30% by weight. The retention rate is approx.
Showing an increase of over 60%. The cause of the above effect is not clear, but the long-chain aliphatic hydrocarbon groups such as isostearoyl groups contained in titanate coupling agents through chemical bonds are compatible with the ethylene-vinyl acetate copolymer matrix. In addition to being rich in aliphatic hydrocarbon groups, crystalline ethylene molecular chains or vinyl acetate groups in the copolymer, and aluminum hydroxide, which is basic or Lewis basic and has little reinforcing effect as a filler. It is thought that this is due to the fact that each interaction that occurs with the surface of the hydrated metal oxide powder is balanced in a state that is favorable for improving the tensile elongation properties. It is generally well known that an ethylene-vinyl acetate copolymer containing 10 to 75% by weight of vinyl acetate exhibits rubber-like properties and is highly adhesive. The composition of the present invention is a composition containing a large amount of hydrated metal oxide powder (70 to 500 parts by weight). Alternatively, the melt may stick to the inner surface of the mixer, which tends to reduce workability such as stripping from the roll or dumping out from the Banbury mixer.
As will be explained later, this shows that even if other polyolefin resins are added up to 40% by weight, there is almost no change.
Moreover, this tendency for workability to decrease becomes more pronounced as the vinyl acetate content of the ethylene-vinyl acetate copolymer increases.
Even if the surface of the hydrated metal oxide powder such as aluminum hydroxide used in the present invention is treated with a titanate-based coupling agent, problems with kneading and blending due to excessive adhesion cannot be eliminated; It has been found that this problem can be solved very easily by adding and using saturated fatty acids, their esters, amides, metal salts, etc. Furthermore, the mechanical properties such as tensile elongation properties of the resulting composition were even more improved than when using a titanate coupling agent. Compounds such as saturated fatty acids having 4 to 22 carbon atoms, their esters, amides, and metal salts are known to be effective as lubricants for polyolefins, but when used alone, they are Since they do not show any effective effects, some kind of interaction occurs between the fatty acid groups contained in these compounds and the titanate coupling agent, leading to aggregation of the polymer phase at the hydrated metal oxide interface and the inner surface of the mixer. This is thought to be due to changes in the state. It is thought that the improvement in tensile elongation properties is also due to this. The ethylene-vinyl acetate copolymer used in the present invention has a comonomer vinyl acetate content of 10
The copolymer may be a random copolymer or a block copolymer in a range of 75% by weight. When the vinyl acetate content is below the lower limit of the above range, as already mentioned, the flame retardant behavior is similar to that of other polyolefin resins, making it difficult to achieve the abnormally high flame retardancy mentioned above. If the upper limit is exceeded, the compatibility with other polyolefin resins will decrease as described below, and therefore the ethylene-vinyl acetate copolymer-based high flame retardant composition of the present invention may be used as a flame retardant for other polyolefin resins. It becomes difficult to use it as In addition, when improving the tensile elongation properties by combining with a hydrated metal oxide surface-treated with a titanate coupling agent, the ethylene-vinyl acetate copolymer has a vinyl acetate content of 10 to 30%. A range of % by weight is desirable. If it is below the lower limit of this range, the crystallinity due to the molecular chain consisting of ethylene in the copolymer will become excessive, and the balance of interaction with the hydrated metal oxide and the titanate coupling agent will be disrupted. It becomes difficult to achieve the desired improvement in tensile elongation properties, and if the upper limit is exceeded, the effect of combining a titanate coupling agent becomes less noticeable. Furthermore, in the present invention, a partially saponified product of ethylene vinyl acetate copolymer having a vinyl acetate content within the range described above may be used. In the present invention, polyethylene, polypropylene, polybutene-1, ethylene-propylene rubber, ethylene-ethyl acrylate copolymer, acrylic acid graft-modified polyethylene, etc. are used as the base resin in place of a part of the above-mentioned ethylene-vinyl acetate copolymer. It is also possible to use a polyolefin resin. Furthermore, at least one of these may be used in combination. The purpose of blending these polyolefin resins is to improve various properties of the composition of the present invention, such as hardness, stress at yield, thermal deformability, etc., without significantly changing the oxygen index. The addition ratio of these polyolefin resins has a limit in terms of the small change in oxygen index, and is 40% by weight or less of the total resin component. The blending of the polyolefin resin with the ethylene-vinyl acetate copolymer depends on the molecular structure, density, crystallinity, melt index, etc. of the polyolefin, and the resulting composition has mechanical properties such as tensile elongation properties. is often affected. As mentioned above, tensile elongation properties etc. can be improved by using a titanate coupling agent or a titanate coupling agent in combination with a saturated fatty acid having 4 to 22 carbon atoms or a derivative thereof, but depending on the polyolefin used, this may not be possible. There are also limits. Therefore, for use in fields of application where tensile elongation characteristics are important, such as electric wires and cables, it is necessary to select the following. This choice was made entirely on an experimental basis, and the rationale is not clear. Furthermore, at least one of the polyolefin resins listed below can be used by blending them in any proportion. That is, as a polyolefin alone (including those containing a small amount of comonomer components such as medium and low pressure polyethylene and polypropylene), (1) medium and low pressure polyethylene with a density of 0.92 to 0.94 g/cm ³ , (2) as the X axis Display the melt index and press Y
Point A (0.01g/10 min, 0.97g/
cm ³ ), point B (0.7 g/10 min, 0.94 g/cm ³ ) and point C (0.01 g/10 min, 0.94 g/cm ³ ) △
(3) High-pressure polyethylene with a melt index of 0.05 to 1.0 g/10 minutes; (4) More preferable polyethylene is a density of 0.91 to 0.94 g/ ^cm3. , melt index 0.01
High-pressure polyethylene of ~1.0 g/10 minutes and medium-low pressure polyethylene, (5) polybutene-1 with a density of 0.90-0.92 g/cm ³ and the like, and crystalline polypropylene etc. are not preferred at all. In addition, as an ethylene copolymer and modified polyethylene, (1) Ethyl acrylate content as a comonomer
10 to 35% by weight ethylene-ethyl acrylate copolymer, (2) modified polyethylene such as acrylic acid graft modified polyethylene, (3) chlorinated polyethylene (chlorine content 45% or less), etc. Ethylene-propylene rubber and ethylene-propylene terpolymer are not particularly limited as mentioned above, and blending with them will not adversely affect the tensile elongation properties, but those with a propylene content of 10 to 50% by weight is desirable. In addition, only those containing dicyclopentadiene as the third component of ethylene-propylene terpolymers can be used in combination with hydrated metal oxides such as aluminum hydroxide and magnesium hydroxide.
It has been discovered in the process leading up to the present invention that it has the effect of preventing drips during vertical combustion as stipulated in UL-94. It is preferred to use this ethylene-propylene terpolymer in the composition. The hydrated metal oxide used in the present invention has a decomposition initiation temperature in the range of 150° to 450°C, and has a general formula of
A compound represented by MmOn・xH ₂ O (where M is a metal, m and n are integers of 1 or more determined by the valence of the metal, and x is a number indicating the amount of bound water contained) or a double salt containing this compound. be. The compound may be, for example,
Aluminum hydroxide (Al ₂ O ₃・3H ₂ O; or Al
(OH) ₃ ), magnesium hydroxide (MgO・H ₂ O; or Mg(OH) ₂ ), calcium hydroxide (CaO・
H ₂ O, or Ca(OH) ₂ ), barium hydroxide (BaO・H ₂ O or BaO・9H ₂ O), zirconium oxide hydrate (ZrO・nH ₂ O), tin oxide hydrate (SnO・_nH2O ), basic magnesium carbonate ( _3MgCO3・Mg(OH) ₂・_3H2O ), hydrotalcite (6MgO_{・ Al2O3}・_H2O ), dawsonite ( _NaCO3・_{Al2O3 ・}nH ₂ O), borax (Na ₂ O・B ₂ O ₃・
5H ₂ O) etc. Ethylene used in the present invention
Since the thermal decomposition temperature of vinyl acetate copolymer and polyolefin is in the range of 150° to 450°C, the decomposition starting temperature of the hydrated metal oxide should be within this temperature range, so that the bound water can be removed. Detachment, dilution due to heat of vaporization, and endothermic effects appear most efficiently and contribute to flame retardancy. Two or more of the above hydrated metal oxides may be used in combination so that decomposition and dehydration can be carried out in multiple stages. Note that it is preferable to use aluminum hydroxide, magnesium hydroxide, etc. because they are easily available and inexpensive. The above-mentioned hydrated metal oxides are used as powders, the average particle size of which is usually in the range from 0.01 to 60 μm, preferably from 0.01 to 30 μm. If the particle size exceeds the upper limit of this range,
This is undesirable because it not only causes rough skin and a decrease in mechanical strength of the molded product, but also lowers flame retardancy.If the particle size is less than this lower limit, tensile elongation may be reduced due to the combination with titanate coupling agents, etc. The effect of improving characteristics becomes smaller. Note that fibrous materials such as dawsonite may also be used. In the present invention, the amount of the hydrated metal oxide charged is in the range of 70 to 500 parts by weight based on 100 parts by weight of the ethylene-vinyl acetate copolymer. If the filling amount is below the lower limit of this range, it will be difficult to achieve the extraordinary high flame retardancy of the present invention, and if the filling amount exceeds the upper limit, the mechanical properties will deteriorate significantly, resulting in great practical difficulties. When using a surface-treated hydrated metal oxide as a titanate coupling agent, the loading amount is in the range of 100 to 500 parts by weight per 100 parts by weight of the ethylene-vinyl acetate copolymer. It is preferable. When in this filling amount range,
The reason for this is that the tensile elongation properties are characteristically improved. In the present invention, the titanate coupling agent used for the surface treatment of the hydrated metal oxide powder is a monoalkoxy organic titanate, which has a small number of aliphatic hydrocarbon groups having 8 to 22 carbon atoms as organic groups in the molecule. Both contain one piece. For example, isopropyl-triisostearoyl-titanate, isopropyl-isostearoyl-dimethacryl-titanate, isopropyl-isostearoyl diallyl-titanate, isopropyl-tri(dioctylphosphate)-titanate, isopropyl-tri(dioctyl-pyrophosphate) )--like titanates, etc. Among these, isopropyl-triisostearoyl-titanate is preferably used because it is easy to handle and generally has good compatibility with synthetic resins such as polyolefins. The effective amount of the titanate coupling agent used is 0.1 to 10 parts by weight, preferably 0.5 to 7 parts by weight, based on 100 parts by weight of the hydrated metal oxide powder. Since it is efficient and economical to pre-treat the surface of the hydrated metal oxide with the titanate-based coupling agent described above, pre-treatment is preferable. The hydrated metal oxide powder may be added at the same time as the hydrated metal oxide powder is added and kneaded. The saturated fatty acids having 4 to 22 carbon atoms and their metal salts, esters, and amides used in the present invention are the following compounds. As fatty acids and their metal salts,
These include stearic acid, isostearic acid, butyric acid, capric acid, caproic acid, lauric acid, oleic acid, etc., and their metal salts such as Na, Ca, Al, Zn, and Sn. Examples of fatty acid esters include vinyl stearate and n-butyl stearate, and examples of fatty acid amides include stearic acid amide, oxystearic acid amide, oleic acid amide, and ricinoleic acid amide. The amount used is 0.5 to 10 parts by weight based on 100 parts by weight of the total resin components. If the usage ratio is below the lower limit, the effect of the present invention, that is, the effect of preventing tackiness during compounding, will not be obtained, and if it exceeds the upper limit, excessive lubricity will result, and the filler will become weaker. This results in a decrease in uniform dispersibility in the resin. When blending the composition of the present invention, a kneading machine such as an open roll, Banbury mixer, calender roll, or extruder is usually used as appropriate. Depending on the application, the composition of the present invention may include ultraviolet absorbers, antioxidants, copper inhibitors, antistatic agents, colorants, plasticizers, dispersants, crosslinking agents, crosslinking aids, blowing agents, Flame retardants and the like may be added as appropriate. Furthermore, it is also possible to crosslink by irradiating with ionizing radiation. If no improvement in tensile properties is expected, the surface of the hydrated metal oxide may be treated with a coupling agent other than the titanate coupling agent, such as a silane coupling agent. The composition of the present invention can be processed into a film, sheet, board, pipe, or specific product form by general synthetic resin molding methods such as extrusion molding, calendar molding, and injection molding. can be easily done. As will be clear from the examples below, the composition of the present invention exhibits high flame retardancy, saves resources,
It meets the social demand for pollution-free and has high industrial value. The embodiments of the present invention will be explained in more detail with reference to Examples below. Example 1 100 parts by weight of ethylene-vinyl acetate copolymer containing 19% by weight of vinyl acetate (Evaflex EV460, Melt Index 2.5, product of Mitsui Polychemical Co., Ltd.) and aluminum hydroxide powder (Hygilite H-42, Average particle size approximately 0.9 μm, Showa Denko Co., Ltd. product), 70, 100, 150, respectively.
200, 233, and 300 parts by weight were thoroughly kneaded in a two-roll mill whose temperature was adjusted so that the roll surface temperature was 145°C for 20 minutes, and this composition was heated and pressed. A sheet with a thickness of 3 mm was obtained by press molding at 140°C. About the sample cut from this sample JISK7201-
The oxygen index was measured by the method specified in the 1976 "Flammation Test Method for Polymer Materials Using Oxygen Index Method," and the results shown in Table 1 and Figure 1B were obtained. For comparison, instead of the above ethylene-vinyl acetate, low-density polyethylene (Yukalon HE-
30, density 0.920g/cm ³ , melt index 0.5,
Mitsubishi Yuka Co., Ltd. product), medium density polyethylene (Neosex 2015M, density 0.920g/cm ³ , melt index 1.5, Mitsui Petrochemical Co., Ltd. product), high density polyethylene (Shiorex
4002B, density 0.94g/cm ³ , melt index
0.2, product of Showa Yuka Co., Ltd.), polypropylene (Noblen BC-8, density 0.910 g/cm ³ , melt index 1.2, product of Mitsubishi Yuka Co., Ltd.), polybutene-1 (Witsutron 0100, density 0.915 g/cm 3 ),
cm ³ , melt index 0.4, product of U.S. Witco Chemical Co., Ltd.), the oxygen index measured by the above method on a sample of the composition obtained in the same manner as above is also listed in Table 1, Illustrated in FIG. 1A. As is clear from Table 1 and FIG. 1, the composition of the present invention exhibits extremely high flame retardancy compared to other polyolefin resins.

[Table] Example 2 100 parts by weight of ethylene-vinyl acetate copolymer with a vinyl acetate content of 25% (Evaflex EV360, Melt Index 2.0, product of Mitsui Polychemical Co., Ltd.) and magnesium hydroxide (Reagent 1)
70, 100, and average particle size of approximately 0.1 μm), respectively
150, 200, and 300 parts by weight were kneaded and molded in the same manner as in Example 1 to obtain a sheet with a thickness of 3 mm. Table 2 shows the oxygen index measured for samples cut from this sheet according to the measurement method described in Example 1. For comparison, low-density polyethylene (Yukalon)
HE-30, density 0.920g/cm ³ , melt index
0.5, Mitsubishi Yuka Co., Ltd. product), polypropylene (Noblen BC-8, density 0.910 g/cm ³ , melt index 1.2, Mitsubishi Yuka Co., Ltd. product), ethylene-ethyl acrylate copolymer (EEADPDJ-
6169, ethyl acrylate content 18% by weight, melt index 1.5, Nippon Unicar Co., Ltd. product),
Ethylene-propylene rubber (JSR EP81X, dicyclopentadiene content as iodine number 12, propylene content 28% by weight, product of Japan Synthetic Rubber Co., Ltd.) was used in place of the ethylene-vinyl acetate copolymer, and the above Table 2 also shows the oxygen index measured according to the above measurement method for samples cut from sheets kneaded and molded in the same manner as above.

[Table] As is clear from Table 2, the composition of the present invention:
It exhibits extremely high flame retardancy compared to similar compositions made of other polyolefins. Example 3 100 parts by weight of ethylene-vinyl acetate copolymer containing 19% by weight of vinyl acetate (Evaflex EV460, Melt Index 2.5, product of Mitsui Polychemical Co., Ltd.) and aluminum hydroxide powder (Hygilite H-32, After kneading 100 parts by weight of magnesium hydroxide powder (1st class reagent, average particle size of about 0.1 μm) in the same manner as in Example 1, , to obtain a sheet with a thickness of 3 mm. A sample cut from this sheet had an oxygen index of 36, measured according to the measuring method described in Example 1. Example 4 In Example 1, the ethylene-vinyl acetate copolymer was modified to have a vinyl acetate content of 25% by weight (Evaflex).
The same composition as in Example 1, except that the aluminum hydroxide powder was Hygilite H-32 (average particle size 3 μm, manufactured by Showa Denko Co., Ltd.). was prepared according to the same method as Example 1,
A sheet with a thickness of 1 mm was obtained. JISC3005-1977 regarding the dumbbell-shaped test piece cut out from this sample
The tensile strength and elongation at break were measured according to the test method specified in Section 16 of the "Plastic Insulated Wire Test Method", and the results are shown in Table 3. In addition, in the above, the surface of the aluminum hydroxide powder is
Table 3 also shows the results for test pieces obtained in exactly the same manner as above, except that the specimens were pretreated with isopropyl tris isostearoyl titanate at a ratio of 5 parts by weight per 100 parts by weight. Furthermore, in addition to pretreating the surface of the aluminum hydroxide powder with isopropyl tris isostearoyl titanate as described above, the same procedure was applied to a composition example in which 5 parts by weight of zinc stearate was added per 100 parts by weight of the ethylene-vinyl acetate copolymer. conduct a test,
The results obtained are shown in Table 3.

【table】

[Table] As is clear from Table 3, the composition example in which the surface of the aluminum hydroxide powder was pretreated with isopropyl tris isostearoi titanate had an extremely large tensile elongation at break compared to the untreated composition example.
Furthermore, composition examples containing zinc stearate show even better results. In addition, in the above composition example containing zinc stearate, there was very little adhesion on the roll surface during roll kneading, and not only was it easy to cut back, but it was also easy to remove the band from the roll surface. In addition, the same composition example was added to the resin temperature using a Banbury mixer.
Although the mixture was kneaded and blended at 155°C, there was little adhesion to the inner surface of the Banbury mixer, and the entire blended amount could be dumped out at once. In addition to this composition example, in the composition example shown in this example, there is significant adhesion to the roll surface or the inner surface of the Banbury mixer during kneading with the roll, and there is significant adhesion to the inner surface of the Banbury mixer during stripping work from the roll. Stripping from the rolls and dumping out from the Banbury mixer were difficult, and several pull-outs were required to remove the entire blend. Furthermore, the oxygen index of each composition in this example was measured, and the results were approximately the same as those obtained in Example 1. Example 5 Ethylene-vinyl acetate copolymer with a vinyl acetate content of 25% by weight (Evaflex EV360, Melt Index 2.0, Mitsui Polychemical Co., Ltd. product) and high-pressure polyethylene (Yukalon HE-
30, density 0.920g/cm ³ , melt index 0.5,
Mitsubishi Yuka Co., Ltd. product), medium-low pressure polyethylene (Shorex 4002E, density 0.935 g/cm ³ , melt index 0.20, Showa Denko K.K. product: and Neozex 2006H, density 0.922 g/cm ³ , melt index 0.7, Mitsui Petrochemical Industries Co., Ltd. products: and Hi-Zex 2100J, density 0.96g/
^cm3 , melt index 6.5, Mitsui Petrochemical Industries Co., Ltd. product), polybutene-1 (Uitron
0100, density 0.915g/cm ³ , product of Witco Chemical Company, USA), ethylene-propylene rubber (EPO7P,
Propylene content 26% by weight, manufactured by Japan Synthetic Rubber Co., Ltd.), or polypropylene (Mitsubishi Noblen EC-9, density g/cm ³ , melt index
0.4, Mitsubishi Yuka Co., Ltd. product), and aluminum hydroxide powder (Hygilite H-32, average particle size 3μ
The oxygen index of a composition prepared by blending the following compounds (m, product of Showa Denko K.K.) in the proportions shown in Table 4 was measured according to the method described in Example 1, and the obtained results are shown in Table 4. . As is clear from Table 4, the oxygen index was very close to the oxygen index of the composition containing the ethylene-vinyl acetate copolymer alone.

【table】

[Table] Example 6 The same composition as described in Example 5, that is, a part of the composition example shown in Table 4, and the aluminum hydroxide powder surface with the same blending ratio.
Regarding a composition example using aluminum hydroxide pretreated with isopropyl triisostearoyl titanate at a ratio of 5 parts by weight per 100 parts by weight, and a composition example using 3 parts by weight of sodium stearate per 100 parts by weight of the total resin components. Table 5 shows the results of a tensile test conducted according to the method described in Example 5. As is clear from Table 5, the same composition as described in Example 5, in which polypropylene EC-9 and polyolefin resins other than medium-low pressure polyethylene Hi-Zex 2100J are blended, gives a considerable tensile elongation at break. When the surface of the aluminum hydroxide powder, which is a filler, is treated with a titanate coupling agent, the value is markedly improved, and an example of a composition containing sodium stearate shows an even better value. Polypropylene EC
-9 or medium-low pressure polyethylene high-speed
In the composition example containing 2100J, the tensile elongation was small, and no improvement was seen even when combined with a titanate coupling agent or sodium stearate. This is an example of leaving the group of advantageous polyolefin resins. Note that the sodium stearate blending composition example had extremely good kneading workability with a roll and a Banbury mixer, similar to the zinc stearate blending composition example described in Example 5, but the other composition examples shown in this example In this case, the adhesion to the roll surface or the inner surface of the Banbury mixer was significant, and it was difficult to take it out from the roll or Banbury mixer.

【table】

[Table] Example 7 Ethylene-vinyl acetate copolymer with vinyl acetate content of 19% by weight (Elvax EV460, Melt Index 2.5, product of Mitsui Polychemical Co., Ltd.)
65 parts by weight and dicyclopentadiene as the third component (JSR
EP84X, third component content as iodine number 12, propylene content 32% by weight, Nippon Gosei Rubber Co., Ltd. product) 35 parts by weight, magnesium hydroxide powder (reagent grade 1 average particle size 0.2 μm) 150 parts by weight. The oxygen index and tensile properties of the composition (6-1) prepared as described in Example 1 were measured according to the methods described in Example 1 and Example 4. Also
Vertical flammability specified by UL-94 was measured. The results obtained are shown in Table 6.

[Table] In addition, in the above composition, the total amount of ethylene-propylene terpolymer containing dicyclopentadiene as the third component was replaced with the total amount of ethylene-propylene terpolymer containing ethylidene norbornene as the third component (JSREP-21, iodine number). The composition (6-
2) and the composition (6-3) in which the entire resin component was an ethylene-vinyl acetate copolymer were subjected to similar measurements, and the results are shown in Table 6. Example 8 Ethylene-vinyl acetate copolymer with a vinyl acetate content of 25% by weight (Elvax EV360, Melt Index 2.0, Mitsui Polychemical Co., Ltd. product)
Ethylene-propylene terpolymer containing 65 parts by weight and dicyclopentadiene as the third component (JSREP84X, third component content as iodine number)
12. 20 parts by weight of propylene content 32% by weight, manufactured by Japan Synthetic Rubber Co., Ltd.) and 15 parts by weight of medium-low pressure polyethylene (Shorex 4002B, density 0.94 g/cm ³ , melt index 0.2, manufactured by Showa Denko K.K.) and aluminum hydroxide powder (Higilite H-42, average particle size 1 μm, manufactured by Showa Denko K.K.)
The oxygen index and tensile properties of the composition (7-1) prepared by blending 150 parts by weight as described in Example 1 were measured according to the methods described in Examples 1 and 4. We also measured the vertical flammability specified by UL-94. In addition, a composition (7-2) with the same blending ratio as above except that the surface of the aluminum hydroxide powder in the above composition was treated with 5 parts by weight of isopropyltriisostearoyl titanate per 100 parts by weight of the same powder was used. ) and a composition (7-3) in which oleic acid amide was further blended in an amount of 5 parts by weight per 100 parts by weight of the total resin components. Furthermore, for comparison, in composition (7-1),
Only a combustion test was conducted on a composition (7-4) having the same formulation as composition (A) except that the ethylene-propylene terpolymer containing dicyclopentadiene as the third component was completely replaced with medium-low pressure polyethylene. The above results are shown in Table 7. As is clear from Table 7, the composition containing the ethylene-propylene terpolymer containing dicyclopentadiene as the third component has a drip prevention effect in the UL-94 vertical combustion test. Composition (7-2) in which the surface of aluminum hydroxide powder is treated with isopropyl tristearoyl titanate
It can be seen that the composition (7-1) has excellent tensile elongation properties compared to the untreated composition (7-1), and the composition (7-3) containing olefinic acid amide is even better than this. In addition, the above compositions (7-1) to (7-
Regarding 3), when we investigated the kneading and blending properties using a banbal mixer, we found that compositions (7-1) and (7-
With 2), the molten material adhered to the inner surface of the Banbury mixer significantly and was difficult to dump out after kneading, but this did not occur with composition (7-3) and it was easily dumped out. I was able to do that.

【table】 [Brief explanation of the drawing]

Figure 1 is a curve diagram plotting the amount of aluminum hydroxide loaded and the oxygen index of the resulting composition for various polymers in Example 1. It is a curve diagram plotting the oxygen index of a composition obtained when 100 phr of aluminum is blended.

Claims (1)

[Claims] 1. Ethylene containing 10 to 75% by weight of vinyl acetate.
Base resin 100 whose main component is vinyl acetate copolymer
70 to 500 parts by weight of hydrated metal oxide powder with a decomposition start temperature in the range of 150° to 450°C.
However, this surface is 0.5 to 10 parts by weight per 100 parts by weight of the powder.
parts by weight of a titanate coupling agent, and further treated with at least one compound selected from the group consisting of saturated fatty acids having 4 to 22 carbon atoms, their esters, amides, and metal salts.
1. A flame-retardant resin composition characterized by adding 0.5 to 10 parts by weight to 100 parts by weight of all resin components and uniformly mixing and blending. 2 The base resin is 60% by weight of an ethylene-vinyl acetate copolymer with a vinyl acetate content of 10 to 75% by weight.
The flame-retardant resin composition according to claim 1, which is a mixture of the above and 40% by weight or less of a polyolefin resin excluding ethylene-vinyl acetate copolymer. 3 The polyolefin resin has a density of 0.91 to
0.94g/ ^cm3 , melt index 0.01~1.0g/10
3. The flame-retardant resin composition according to claim 2, wherein the flame-retardant resin composition is polyethylene. 4. The flame-retardant resin composition according to claim 2, wherein the polyolefin resin is ethylene-propylene rubber. 5. Claim 2, wherein the polyosaphin-based resin is composed of ethylene-propylene rubber and polyethylene having a density of 0.91 to 0.94 g/cm ³ and a melt index of 0.01 to 1.0 g/min.
The flame-retardant resin composition described in . 6 The polyolefin resin is polybutene-1
The flame-retardant resin composition according to claim 2, characterized in that: