JPH0643531B2 - Flame-retardant composition of polyolefin resin - Google Patents

Description

TECHNICAL FIELD The present invention relates to a flame-retardant composition of a polyolefin resin.
Specifically, it is a composition containing a polyolefin resin, particularly a polypropylene resin as a main component, and hardly generating a corrosive gas or a toxic gas during thermal decomposition of the composition, and a molded article obtained from the composition has high temperature and high humidity conditions. And a flame-retardant composition of a polyolefin resin that hardly causes bleeding of the flame-retardant on the surface of the molded article.

Conventionally, polyolefin resin has been hygienic, processable,
Utilizing its superiority in chemical resistance, weather resistance, electrical characteristics, mechanical strength, etc., it is widely used in various fields such as industrial and household electric appliances, as well as buildings, upholstery and automobile parts. Has been done.

[Prior Art] Originally, a polyolefin resin is a resin that easily burns. However, with the expansion of the applications in which it is used, the performance as a flame-retardant material has begun to be demanded for the polyolefin resin, and the required performance has become stricter year by year. In particular, recently, in the compounding of a halogen compound or the compounding of a combination of a halogen compound and antimony oxide, which is the mainstream of conventional flame retardant technology, the toxicity of the halogen-based gas generated during combustion or molding of the flame-retardant composition is It is regarded as a problem.

Therefore, it has begun to be demanded for flame-retardant polyolefin resins not to generate these halogen-based gases either during combustion or during molding. In order to meet this demand, various flame-retardant polyolefin resin compositions have been proposed.

For example, JP-A-53-92855, JP-A-54-29350, JP-A-54-77658, JP-A-56-26954, JP-A-57-87462 and JP-A-60. -110738 and the like, a composition obtained by adding a water-containing inorganic compound (eg, magnesium hydroxide, aluminum hydroxide, hydrotalcite, etc.) to a polypropylene resin, or JP-A-52-146452. As disclosed in JP-A-59-147050, a nitrogen-containing compound containing ammonium phosphate (or amine phosphate) and a group> C = O (or> C = S or> NH) inserted in a cyclic structure; A composition in which a reaction product with an aldehyde or an oligomer (or polymer) of a 1,3,5-triazine derivative is added to a polypropylene resin has been proposed.

However, in order to exhibit a high degree of flame retardancy in a composition obtained by adding a hydrous inorganic compound to a polypropylene resin, for example, a composition in which magnesium hydroxide is added, it is necessary to add a large amount of the hydrous inorganic compound. , The composition often suffers from poor moldability.

Further, the flame-retardant polypropylene resin compositions disclosed in JP-A-52-146452 and JP-A-59-147050 show relatively little deterioration in molding processability and are corrosive during processing or burning. The generation of gas or toxic gas is also suppressed.

However, due to the hygroscopicity of ammonium phosphate (or amine phosphate) in the composition, under the high temperature and high humidity conditions such as the rainy season, ammonium phosphate (or amine phosphate) on the surface of the molded article is A severe bleeding phenomenon occurs. As a result, the electrical resistance value of the molded product is significantly reduced, and there is a drawback that it cannot be used as an electrical insulating material under high temperature and high humidity conditions. Furthermore, in order to improve the rigidity of the composition, when a filler which is usually used in polypropylene resin is added, the bleeding phenomenon of ammonium phosphate (or amine phosphate) on the surface of the molded article under high humidity condition is further increased. There are also drawbacks such as increasing the intensity.

[Problems to be Solved by the Invention] The present inventors generate almost no corrosive gas or toxic gas at the time of processing or burning of the composition, and the deterioration of moldability becomes a practical problem. A flame-retardant prescription of a polyolefin resin that does not cause bleeding of flame-retardant components on the surface of the molded article even under high temperature and high humidity conditions such as the rainy season. Earnestly conducted to obtain a functional composition.

As a result, (A) ammonium polyphosphate or melamine-modified ammonium polyphosphate, (B) one or more selected from the following group: a ring composed of a 5-membered or more heterocyclic ring containing 2 or more nitrogen atoms in the ring A reaction product group of a ketone and formaldehyde, a reaction product group of a cyclic thioketone consisting of a five or more-membered heterocycle containing two or more nitrogen atoms in the ring and formaldehyde, or represented by the following general formula [I] Group containing 1,3,5-triazine derivatives [In the formula, X is a morpholino group or piperidino group, Y is a divalent group derived from piperazine, and n is a positive number of 2 to 50] and (E) a petroleum resin-based polyolefin resin (H It has been found that the composition formulated in () does not substantially involve the above-mentioned problems.

In order to obtain even higher mechanical strength, it was found that a composition in which a specific amount of fibrous filler (C) is blended with polyolefin resin (H) solves the above problems, and the present invention is based on this finding. completed.

The flame-retardant composition of the above polyolefin resin (H) only produces non-flammable gas and carbonaceous residue due to the synergistic action of the components in the composition even when it is pyrolyzed.

As is clear from the above description, an object of the present invention is to solve the above-mentioned problems and to provide a flame-retardant composition of a polyolefin resin which can be used as a material for a molded article having a high degree of flame retardancy.

[Means for Solving the Problems] The flame-retardant composition of the polyolefin resin of the present invention has the following constitution.

(1) Flame-retardant composition of polyolefin resin characterized by comprising the following components (A), (B), (E) and (H), the total amount of which is 100% by weight: (A ) Ammonium polyphosphate or melamine-modified ammonium polyphosphate 12 to 25% by weight (B) One or more selected from the following group: 5 to 10% by weight A heterocyclic ring having five or more members containing two or more nitrogen atoms in the ring. A group of reaction products of a cyclic ketone with formaldehyde, a group of reaction products of a cyclic thioketone consisting of a five or more-membered heterocyclic ring containing two or more nitrogen atoms in the ring and formaldehyde, or the following general formula [I ] 1,3,5-triazine derivatives containing a structure represented by [Wherein, X is a morpholino group or a piperidino group, Y is a divalent group derived from piperazine, and n is a positive number of 2 to 50] (E) Petroleum resin 1 to 20% by weight (H) Polyolefin resin 82-55% by weight.

In order to further improve the mechanical strength and the like, the purpose can be achieved by blending (C) the fibrous filler in an amount of 5 to 25% by weight based on the composition.

Examples of the polyolefin resin (H) used as the base material of the composition of the present invention include the following: -Homopolymer resin of ethylene, copolymer resin of ethylene main component and propylene or higher subcomponent; -propylene , A crystalline homopolymer resin of propylene, a crystalline copolymer resin of propylene main component with ethylene or 1-olefin of 1-butene or more; 1-butene homopolymer resin, 1-butene main component with ethylene, propylene Or 1-pentene or higher copolymer resin with 1-olefin; 4-methyl-1-pentene homopolymer resin, 4-methyl-1-pentene and ethylene, propylene, 1-butene or 1-heptene or higher A copolymer resin with 1-olefin; a resin blend comprising two or more of the above resins; and a modified product of the above resin.

Among them, preferred resins are as follows: Copolymer resin with propylene or more subcomponents; -Crystalline homopolymer resin of propylene, crystal of propylene main component and ethylene or 1-olefin of 1-butene or more. Copolymer resin.

Examples of the polypropylene resin that is a preferable resin in the present invention include the following: -Crystalline propylene homopolymer-Propylene-based polymer containing one of the following 1-olefins
Crystalline random copolymer or crystalline block copolymer containing at least one species as subcomponents: ethylene, 1-butene, 1-pentene, 1-hexene,
4-methyl-1-pentene, 1-heptene, 1-octene and 1-decene.

Mixtures of two or more of these crystalline polymers can also be mentioned as suitable resin blends. A crystalline propylene-ethylene block copolymer is particularly desirable as a molding material for the mold.

As the crystalline polypropylene resin constituting the composition of the present invention, MFR (230 ° C., 2.16 kgf) usually 0.1 to 50 g / 10 min, preferably 1 to 30 g / 10 min is selected.

The polyethylene resin used in the present invention may be any commercially available product. Normally MI (190 ℃; 2.16kgf) 0.01〜50g / 10mi
n, preferably 0.1 to 30 g / 10 min, density 0.91 to 0.97 g /
It is enough to choose the cc one.

Preferred as the ammonium polyphosphate or melamine-modified ammonium polyphosphate (A) used in the present invention are those represented by the general formula
It is represented by (NH ₄ PO ₃ ) _n (n ≧ 50). If a normal commercial product is within this range, it can be used as it is. Examples of preferred commercially available ammonium polyphosphates include the following: Trade name: Sumisafe P (Sumitomo Chemical Co., Ltd.) and trade name: Exolit 422 (Hoechst), and melamine-modified ammonium polyphosphates Trade name: Sumisafe PM (manufactured by Sumitomo Chemical Co., Ltd.) and trade name: Exolit 462 (manufactured by Hoechst) The compounding ratio of the ammonium polyphosphate or the melamine-modified ammonium polyphosphate is generally 12 to 25% by weight, preferably, It is 14 to 21% by weight. If the blending ratio is 10% by weight or less, a composition exhibiting a high degree of flame retardancy cannot be obtained. Even if 28% by weight or more is blended, further improvement in flame retardancy cannot be expected.

The component (B) used in the present invention (hereinafter sometimes abbreviated as "nitrogen-containing heterocyclic organic compound") means the following.

From a reaction product group of a cyclic ketone containing 5 or more membered heterocycles containing 2 or more nitrogen atoms in the ring and formaldehyde, from a 5 or more membered heterocycle containing 2 or more nitrogen atoms in the ring Of reaction products of cyclic thioketone and formaldehyde or 1,3,5-triazine derivatives containing the structure represented by the following general formula [I] [In the formula, X is a morpholino group or a piperidino group, Y is a divalent group derived from piperazine, and n is a positive number of 2 to 50].

When they are present in the polyolefin resin (H) together with ammonium polyphosphate or melamine-modified ammonium polyphosphate (A), they are also non-flammable gas (water, carbon dioxide, ammonia) due to thermal decomposition due to ignition or contact with flame. ,
It is a mixture or reaction product of one or more organic compounds capable of generating only a carbonaceous residue while generating (e.g. nitrogen).

Examples of these compounds are ethylene urea, ethylene thiourea, hydantoin, hexahydropyrimidine-2.
-One, piperazine-3,6-dione, barbituric acid and reaction products of these with an aldehyde, 2-piperazinylene-4-morpholino-1,3,5-triazine oligomer or polymer or 2-piperazinylene-4-piperidino Examples thereof include oligomers or polymers of -1,3,5-triazine.

Among these, preferred from the viewpoint of imparting a high degree of flame retardance are: -reaction product of ethylene urea and formaldehyde-reaction product of ethylene thiourea and formaldehyde or-the following general formula 2-piperazinylene-4-morpholino-1,3, which is a 1,3,5-triazine derivative having a structure represented by [I],
5-triazine oligomers or polymers and 2-piperazinylene-4-piperidino-1,3,5-triazine oligomers or polymers.

[Wherein, X is a morpholino group or piperidino group, Y is a divalent group derived from piperazine, and n is a positive number of 2 to 50] Properties of 1,3,5-triazine derivative used in the present invention Are as follows: -Solubility: insoluble in water and ordinary organic solvents; -Melting point: none (decomposition point near 310 ° C);-True specific gravity: 1.2-Name: 2-piperazinylene-4-morpholino- Polymer of 1,3,5-triazine; Structural formula:

Further, a reaction product of the above-mentioned ethylene urea and formaldehyde which is one of the nitrogen-containing heterocyclic organic compounds, or a reaction product of ethylene thiourea and formaldehyde, or 2-piperazinylene-4-morpholino-1,3, Five
-Triazine oligomers or polymers and 2-
The oligomer or polymer of piperazinylene-4-puperidino-1,3,5-triazine can be obtained, for example, by the following method.

To obtain the reaction product of ethylene thiourea and formaldehyde, 50 g of ethylene thiourea is dissolved in 1 liter of water and the pH in the solution is adjusted to 2 by mixing with a dilute acid (eg sulfuric acid or phosphoric acid). 90 ° C of the reaction solution
Then, the aqueous solution of formaldehyde having a concentration of 37% by weight is appropriately added to the ethylenethiourea solution until the molar ratio of CH ₂ O / ethylenethiourea becomes equal to 2, and vigorously stirred while maintaining the temperature at 90 ° C. The desired product can be obtained by filtering the precipitate obtained in the form of a very fine powder, washing with water and drying.

Also, when obtaining a reaction product of ethylene urea and formaldehyde, the same method as described above can be applied.

To obtain an oligomer or polymer of 2-piperazinylene-4-morpholino-1,3,5-triazine, proceed as follows: equimolar 2,6-dihalo-4-morpholino-1,3,5- Triazines (e.g. 2,6-dichloro-4-morpholino-1,3,
5-triazine or 2,6-dibromo-4-morpholino-1,3,5-triazine) and piperazine as an organic base or an inorganic base (for example, triethylamine, tributylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, etc.) In the coexistence with, the reaction is carried out in an inert solvent such as xylene under heating, preferably at a boiling point of the inert solvent or lower.
After completion of the reaction, the reaction mixture is filtered to separate the fixed matter,
The solid matter is washed with boiling water to remove the by-product salt by dissolving it in the boiling water, and then the remaining solid matter is dried.

Alternatively, there is the following method.

The oligomer or polymer of 2-piperazinylene-4-biperidino-1,3,5-triazine is an equimolar amount of 2,6-dihalo-4-piperidino-1,3,5-triazine (e.g. 2,6-dichloro-4- Piperidino-1,3,5-triazine or
2,6-dibromo-4-piperidino-1,3,5-triazine) and piperazine as an organic base or an inorganic base (for example, triethylamine, tributylamine, sodium hydroxide,
In the presence of potassium hydroxide, sodium carbonate, etc.), an inert solvent such as triisopropylbenzene is used and reacted under heating, preferably at a temperature not higher than the boiling point of the inert solvent.

After completion of the reaction, the reaction mixture is filtered to separate solids, and then the solids are washed with boiling water to dissolve and remove by-product salts in the boiling water. dry.

The compounding ratio of the nitrogen-containing heterocyclic organic compound (B) is 5 to 10% by weight based on the composition. When the blending ratio is 3% by weight or less, a composition exhibiting a high degree of flame retardancy cannot be obtained.
Even if blended in an amount of more than wt.%, No further improvement in flame retardancy can be seen.

The petroleum resin (E) used in the present invention is a thermoplastic resin obtained by thermal polymerization or cationic polymerization of diolefins and monoolefins and / or aromatic compounds contained in cracked fractions during petroleum refining and petroleum cracking. It is a resin. Of the cracked oil fractions, both C5-based (aliphatic) petroleum resin using C5 fraction as the raw material, C9-based (aromatic type) petroleum resin using C9 fraction as the raw material, and C5-C9 derived from both Polymerized petroleum resin, C5
Dicyclopentadiene-based petroleum resin prepared from dicyclopentadiene obtained by thermal dimerization of cyclopentadiene contained in a distillate, and hydrogenated (hydrogenated) double bond in the above petroleum resin (Alicyclic group) can be mentioned. In particular, hydrogenated (hydrogenated) petroleum resin having excellent heat resistance and weather resistance is preferable.

For the purpose of the present invention, the softening point of the petroleum resin (E) is 70 to 180 ° C by the ring and ball method, preferably 70 to 140 ° C, the hue is 15 or less by the Gardner method, and the bromine number is 70 (Br-g). / 100g) or less,
It is preferably 30 (Br-g / 100 g) or less.

The blending ratio of the petroleum resin (E) is selected to be 1 to 20% by weight, preferably 3 to 15% by weight based on the composition. The blending ratio is
If it is 0.5% by weight or less, the effect of preventing bleeding under high humidity conditions is lacking. On the other hand, when the content is 25% by weight or more, impact resistance is deteriorated, so that the good mechanical strength inherent to polyolefin, particularly polypropylene, is lost.

The fibrous filler (C) used in the present invention includes wollastonite, dawsonite, glass fiber, processed mineral fiber rock wool, gypsum fiber, metal whiskers, potassium titanate whiskers, carbon fibers, boron fibers, silicon carbide fibers. , Alumina fiber, wholly aromatic polyamide fiber, wholly aromatic polyester and the like. It is particularly preferable to use wollastonite, glass fiber and rock wool. These fibrous fillers (C) are preferably those surface-treated with the tackifying or adhesion-imparting polymers exemplified below: Modified polyolefin resin, elastomer or modified elastomer, silane coupling agent and the like.

In addition, in order to improve the interfacial adhesion between these fibrous filler (C) surface and polypropylene resin (H), the base resin
It is extremely useful to use (H) together with an adhesiveness-imparting resin such as a maleic anhydride-modified polypropylene resin. When the maleic anhydride-modified polypropylene resin is used in combination, the amount used is 0.5 to 2 times, preferably 0.5 to 1 times the weight of the fibrous filler (C) added. However, in order to avoid deteriorating the performance of the composition, it is preferable to limit the compounding amount to 50% by weight or less based on the composition.

The mixing ratio of the fibrous filler (C) is usually 5 based on the composition.
-25% by weight, preferably 10-20% by weight. When the blending ratio is 3% by weight or less, the effect of improving the mechanical strength by blending the filler is insufficient, while when it is 28% by weight or more, the flame retardancy decreases.

In the flame-retardant composition of the present invention, various additives that are usually added to polyolefin resins, such as antioxidants, UV inhibitors, antistatic agents, copper damage inhibitors, lubricants, neutralizing agents (stearic acid A metal salt, hydrotalcite, manaceite, or the like), a pigment, or the like can be used in combination as appropriate.

Further, as described in JP-A-3-56547 previously filed by the present inventors, a silane coupling agent showing an effect of suppressing bleeding of ammonium polyphosphate (A) under high temperature and high humidity conditions, or It is also possible to add an olefin-based synthetic rubber, and further to add a polyethylene resin described in JP-A No. 1-193347 previously filed by the present inventors in order to further improve flame retardancy.

The polyolefin flame-retardant resin composition of the present invention can be prepared, for example, by the following procedure.

That is, for example, one selected from the above-mentioned petroleum resin (E), ammonium polyphosphate or melamine-modified ammonium polyphosphate (A), and nitrogen-containing heterocyclic organic compound (B) specified above in polypropylene resin (H), or If you want to obtain high mechanical strength from a mixture of two or more types, add a fibrous filler (C) and, if necessary, the prescribed amount of the above-mentioned various additives to a suitable mixture mixer. , For example, a Henschel mixer (trade name), a super mixer or a tumbler mixer. Then
After stirring and mixing for 1 to 10 minutes, the obtained mixture is melted and kneaded at a temperature of 170 using a roll kneader or a screw extruder.
The target flame-retardant composition can be obtained by melt-kneading at ~ 220 ° C and pelletizing.

<Preferred Embodiment> The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The evaluations carried out in Examples and Comparative Examples were based on the following methods.

1) Flame retardance Complies with the vertical combustion test stipulated in UL Subject 94 (Underwriter Laboratories, Inc.) "Combustion test of plastic materials for equipment parts". The thickness of the test piece is 1.6 mm (1/16 inch).

2) Evaluation of bleeding property under high temperature and high humidity conditions A test piece (length 95 mm × width 95 mm × thickness 2 mm) is molded by an injection molding machine, and the surface electric resistance value of the test piece is measured by a vibration volume type minute current potential. It was measured using a meter (manufactured by Takeda Riken). Further, the test piece was taken out after being immersed in boiling water for 4 hours, and the water droplets adhering to the test piece were wiped off with a wiper paper [trade name: Kimwipe (manufactured by Tojo Kimberley Co.)], and the surface electric resistance value of the test piece was immediately measured. did. When the surface electric resistance value of the test piece was significantly reduced after immersion in boiling water, it was regarded as poor bleeding resistance (bad) under high temperature and high humidity conditions.

Example 1 As a polyolefin resin (H), a crystalline propylene-ethylene block copolymer [ethylene content 8.5% by weight, MFR (temperature 230 ° C., load 2.16 kgf) 20 g / 10 min] 6.6 k
g, ammonium polyphosphate (A) [trade name: Exolit422 (Hoechst)] 2.1 kg, nitrogen-containing heterocyclic organic compound (B)
2-piperazinylene-4-morpholino-1,3,5-triazine polymer (n = 11, molecular weight about 2770) 800 g, petroleum resin
(E) [Product name: Archon P-140 (Arakawa Chemical Industry Co., Ltd.)] 500
g, 2,6-di-t-butyl-p-cresol (BHT) 15 g, dimyristyl-β, β-thiodipropionate (DMyTDP) 20 g and calcium stearate 10 g as various additives to a Henschel mixer (trade name) It was charged and mixed with stirring for 3 minutes.

The obtained mixture was melt-kneaded and extruded at a melt-kneading temperature of 200 ° C. using an extruder (bore diameter: 45 mm) to pelletize the flame-retardant composition.

Comparative Example 1 The amount of polyolefin resin (H) was 7.1 kg and petroleum resin (E) was used.
Charge each compounding component into a Henschel mixer (trade name) at a compounding ratio in accordance with Example 1 except not compounding
Stir-mixing and melt-kneading / extrusion were carried out according to Example 1 to obtain pellets of the composition.

Examples 2 to 4 and Comparative Examples 2 and 3 In accordance with Example 1, except that the compounding ratio of the polypropylene resin (H) and the petroleum resin (E) was changed to the compounding ratio shown in Table 1. Things were pelletized.

Example 5 Example 1 was repeated except that a reaction product of ethylene urea and formaldehyde was used as the nitrogen-containing organic compound (B).
Based on the above, pellets of the flame retardant composition were obtained.

Example 6 Pellets were obtained according to Example 1 except that a crystalline propylene homopolymer [MFR (230 ° C .; load 2.16 kgf) 25 g / 10 min] was used as the polyolefin resin (H).

Examples 7 and 8 A pellet was prepared according to Example 1 except that the type of petroleum resin (E) was changed to the petroleum resin shown in Table 1.

10 pellets obtained in Examples 1-8 and Comparative Examples 1-3
After drying at a temperature of 0 ° C. for 3 hours, the pellets were molded into predetermined test pieces for evaluation of flame retardancy and bleeding property with an injection molding machine (the maximum temperature of the cylinder was set to 220 ° C.).
Using each of the test pieces, flame retardancy and bleeding under high temperature and high humidity conditions were evaluated. The results are shown in Table 1.

From Table 1, the petroleum resin formulation shows that even after immersion in boiling water,
It can be seen that the surface electric resistance does not show a significant decrease. From this, it can be seen that in addition to the improved bleeding property under high temperature and high humidity conditions, it is necessary to set the blending ratio of the petroleum resin to 1 to 20% by weight.

Example 9 As the polyolefin resin (H), a high-density ethylene homopolymer resin (true density 0.96 g / cc; MI 12 g / 10 min) was used to prepare a mixture based on the following formulation. The mixture was then pelletized according to Example 1 with an extruder. After drying the obtained pellets at a temperature of 100 ° C for 3 hours, the cylinder maximum temperature of the injection molding machine was set to 220 ° C, and the specified test pieces (for flame retardancy evaluation and bleeding evaluation) were molded. . The results are shown in Table 1.

(A) Ammonium polyphosphate 25% by weight (B) Nitrogen-containing heterocyclic organic compound 10% by weight (E) Petroleum resin 5.0% by weight (H) High-density polyethylene 60% by weight While preserving
It can be seen that the surface electric resistance value after immersion in hot water could be slightly reduced. That is, the bleeding property under high temperature and high humidity is clearly improved.

Example 10 As a polyolefin resin (H), a crystalline propylene-ethylene block copolymer [ethylene content 8.5% by weight,
MFR (230 ℃; load 2.16kgf) 20g / 10min] 5.1kg, ammonium polyphosphate (A) [Product name: Exolit422 (Hoechst)]
2.1 kg, a polymer of 2-piperazinylene-4-morpholino-1,3,5-triazine as a nitrogen-containing heterocyclic organic compound (B) (n = 11, molecular weight about 2770) 800 g, petroleum resin (E) [trade name:
Alcon P-140 (manufactured by Arakawa Chemical Industries)] 500 g and wollastonite as fibrous filler (C) [Product name: NYAD-G (NYC
(Manufactured by O Company)]] and 1.5 g of 2,6-di-t-butyl-p-cresol as various additives, 20 g of dimyristyl-β, β-thiodipropionate and 10 g of calcium stearate.
Was charged into a Henschel mixer (trade name) and mixed by stirring for 3 minutes. The obtained mixture was extruded using an extruder (bore diameter: 45 mm) at a temperature of 200 ° C. while melt-kneading, and pelletized.

Comparative Example 4 The amount of the polypropylene resin (H) in Example 10 was 5.6 kg, and each compounding component was mixed in a Henschel mixer (trade name) at a compounding ratio in accordance with Example 10 except that the petroleum resin (E) was not compounded. Charged, extruded into pellets with stirring mixing and melt kneading according to Example 10.

Examples 11 to 13 and Comparative Examples 5 and 6 The polypropylene resin (H) and petroleum resin (E) of Example 10
Other than changing the blending ratio of to the blending ratio of Table 2,
Pelletization was carried out according to Example 10.

Examples 14 and 15 The mixture was pelletized according to Example 10 except that the mixing ratio of the polypropylene resin (H) and wollastonite (C) in Example 10 was changed to the mixing ratio shown in Table 2. did.

Examples 16 and 17 Pelletization was carried out according to Example 10 except that rock wool and glass fiber were used as the fibrous filler (C).

After drying the pellets obtained in Examples 10 to 17 or Comparative Examples 4 to 6 at a temperature of 100 ° C. for 3 hours, an injection molding machine (the maximum temperature of the cylinder was set to 220 ° C.) was used with the pellets. A predetermined test piece (for flame retardancy evaluation and bleeding property evaluation) was molded by using the test piece. Each desired evaluation was performed using each of the test pieces. The results are shown in Table 2.

From Table 2, the following facts can be seen: -By adding the petroleum resin (E) to the fibrous filler (C) compound, a large decrease in the surface electric resistance value was observed even after immersion in boiling water.・ The bleeding property under high temperature and high humidity conditions is improved ・ The blending ratio of petroleum resin (E) must be 1 to 20% by weight.

The blending ratio of the fibrous filler (C) is preferably 5 to 25% by weight.

[Effect of the Invention] According to the flame retardant formulation of the present invention, it is possible to provide a polyolefin resin composition having sustained flame retardancy, which is particularly useful for electric articles.

Above all, a molded article made of a flame-retardant composition of polypropylene resin shows almost no bleeding of the flame-retardant imparting agent even under high temperature and high humidity. The surface resistance value of the molded product is not only decreased in the range of 1/1000, but may be increased in some cases.

Further, the mechanical strength can also be improved by blending together the fibrous filler (reinforcing material).

Further, the flame-retardant and electrically insulating composition of the present invention utilizes the characteristics thereof to produce various electric devices, electric appliances, electric articles, electric device substrates, electric device housings or casings, electric insulating members and the like. Can be suitably used.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 23/02 LCR 7107-4J 53/00 LLV 7142-4J LLW 7142-4J LLX 7142-4J // (C08L 23/02 61:02 57:02 79:04) (C08K 13/02 3:32 5: 3492 5:45 5: 3442) (C08L 53/00 61:02 57:02 79:04)

Claims (7)

[Claims] 1. A composition comprising the following components (A), (B), (E) and (H):
Flame-retardant composition of polyolefin resin, characterized in that their total amount is 100% by weight: (A) ammonium polyphosphate or melamine-modified ammonium polyphosphate 12-25% by weight (B) selected from the following group 1 to 5% by weight 5 to 10% by weight Reaction product group of cyclic ketone and formaldehyde consisting of 5 or more-membered heterocyclic ring containing 2 or more nitrogen atoms in the ring, 2 or more nitrogen atoms in the ring Group of reaction products of cyclic thioketones containing 5 or more-membered heterocycles with formaldehyde, or group of 1,3,5-triazine derivatives containing the structure represented by the following general formula [I] [Wherein, X is a morpholino group or piperidino group, Y is a divalent group derived from piperazine, and n is a positive number of 2 to 50] (E) Petroleum resin 1 to 20% by weight (H) Polyolefin resin 82-55% by weight, 2. A flame-retardant polyolefin resin characterized by comprising the following components (A), (B), (C), (E) and (H), the total amount of which is 100% by weight. Composition: (A) Ammonium polyphosphate or melamine-modified ammonium polyphosphate 12 to 25% by weight (B) One or more selected from the group below 5 to 10% by weight Two or more nitrogen atoms are contained in the ring A reaction product group of a cyclic ketone composed of a 5-membered or more heterocyclic ring and formaldehyde, a reaction product group of a cyclic thioketone composed of a 5-membered or more heterocyclic ring containing two or more nitrogen atoms in the ring, and formaldehyde, or 1,3,5-triazine derivative group containing a structure represented by the following general formula [I] [In the formula, X is a morpholino group or piperidino group, Y is a divalent group derived from piperazine, and n is a positive number of 2 to 50]. (C) Fibrous filler 5 to 25% by weight (E) Petroleum resin 1 to 20% by weight (H) Polyolefin resin 82 to 55% by weight. 3. A cyclic ketone consisting of a 5- or more-membered heterocycle containing 2 or more nitrogen atoms in the ring is ethylene urea, or a cyclic ketone containing 5 or more members containing 2 or more nitrogen atoms in the ring. The cyclic thioketone composed of a heterocycle is ethylenethiourea, or a 1,3,5-triazine derivative having a structure represented by the following general formula [I] is bonded to at least one piperidino group or morpholino group and The flame-retardant composition according to claim 1 or 2, which has a structure in which one or more 1,3,5-triazine rings are mutually bonded by a divalent piperazine group. [In the formula, X is a morpholino group or piperidino group, Y is a divalent group derived from piperazine, and n is a positive number of 2 to 50]. 4. The softening point of the petroleum resin (E) according to the ring and ball method 70 to 18
The flame-retardant composition according to any one of claims 1 to 3, which has a bromine number of 70 (Br-g / 100g) or less at 0 ° C. 5. The flame retardant according to any one of claims 2 to 4, wherein the surface of the fibrous filler is coated with a modified polyolefin resin or a modified elastomer or treated with a silane coupling agent. Sex composition. 6. The polyolefin resin is polyethylene resin,
Polypropylene resin, poly-1-butene resin, poly-4
-One or more resins selected from a methyl-1-pentene resin, a poly-1-hexene resin, a poly-1-octene resin and a poly-1-decene resin, or a resin blend consisting of two or more thereof. The flame-retardant composition according to any one of claims 1 to 5. 7. A polypropylene resin comprising a crystalline propylene homopolymer, propylene containing propylene as a main component and ethylene, 1-butene, 1-pentene, 1-hexene, 4-
Methyl-1-pentene, 1-heptene, 1-octene,
The flame-retardant composition according to claim 1, which is a crystalline copolymer with one or more selected from 1-decene or a mixture of two or more thereof.