JPH064735B2 - Flame-retardant polypropylene resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a flame-retardant polypropylene resin composition. More specifically, polypropylene resin as the main component does not generate corrosive gas or toxic gas, and there is little deterioration in molding processability, and it has high flame retardancy when formed into a molded product.
The present invention relates to a flame-retardant polypropylene resin composition capable of obtaining a molded product having very little bleeding of the flame retardant used on the surface of the molded product under high humidity conditions.

Conventionally, polypropylene resin has been used for processability, chemical resistance,
Due to its good weather resistance, electrical characteristics and mechanical strength, it is widely used in various fields such as household electrical appliances, buildings, upholstery and automobile parts.

(Prior Art) Originally, polypropylene resin is a resin that easily burns, but with the expansion of the applications in which it is used, polypropylene resin is required to have performance as a flame-retardant material, and the performance required every year becomes difficult. There is. Various flame-retardant polypropylene resin compositions have been proposed to meet these demands.

For example, JP-A-53-92855 and JP-A-54-2
9350, JP-A-54-77658, JP-A-56-26954, JP-A-57-87462, JP-A-60-110738, etc. A composition obtained by adding (eg, magnesium hydroxide, aluminum hydroxide, hydrotalcite, etc.) to a polypropylene resin, such as JP-B-5
As disclosed in JP-A-5-30739, halogen-based compounds such as polyethylene having a melt index of 0.01 to 2.0 and decapromo diphenyl ether or dodecachlorododecahydromethanodibenzocyclooctene, and powdered talc, kaolinite, serine. site,
Composition in which one or more inorganic fillers selected from silica and diatomaceous earth are added to polypropylene resin, JP-A-52-14645
No. 2, JP-A-59-147050, ammonium phosphate (or amine phosphate) and> C═O group or> inserted in the cyclic structure.
A reaction product of a nitrogen-containing compound having a C = S group or> NH group and an aldehyde, or a composition obtained by adding an oligomer (or polymer) of a 1,3,5-triazine derivative to a polypropylene resin has been proposed. .

However, in order to impart a high degree of flame retardant in a composition obtained by adding a water-containing inorganic compound to a polypropylene resin, for example, a composition containing magnesium hydroxide, it is necessary to add a large amount of the water-containing inorganic compound. , The composition causes deterioration of molding processability.

Further, a composition containing a halogen-based compound has relatively little deterioration in molding processability, and a molded product having a high degree of flame retardancy can be obtained, but a corrosive gas or a toxic gas is generated during processing or combustion. There is a drawback that it occurs.

Further, JP-A-52-146452 and JP-A-59-
The flame-retardant polypropylene resin composition disclosed in Japanese Patent No. 147050 has a relatively small decrease in moldability, and a corrosive gas and a toxic gas are less likely to be generated during processing or burning.

However, the composition is UL Subject 94 (Underwriter Laboratories, Inc.)
In the test based on the vertical combustion test of "Combustion test of plastic materials for parts of equipment" (hereinafter referred to as UL94 combustion test), the flammability rank is V-0 at 1/8 inch wall thickness, but it is more advanced. In the 5V test that requires the flame retardancy of
It is highly flame-retardant because of the dropping of burning pieces due to dropping and melting of droplets (hereinafter, these droppings and falling objects are called drip, and the property that causes drip is called drip property). It is difficult to achieve flame resistance of 5V with an inch wall thickness. Further, due to the hygroscopicity of ammonium phosphate or amine phosphate in the composition, under high humidity conditions such as during the rainy season, the vigorous bleeding phenomenon of ammonium phosphate (or amine phosphate) on the surface of the obtained molded article may occur. Since it occurs and the electric resistance value of the molded product is significantly lowered, there is a drawback that it cannot be used as an electric insulating material or the like under high humidity conditions.

(Problems to be Solved by the Invention) The inventors of the present invention have conducted a high flame retardance, that is, a vertical combustion test of UL Subject 94 (Underwriter Laboratories, Inc.) "Combustion test of plastic materials for parts of equipment". In a compliant test (hereinafter referred to as UL94 combustion test), it has a flammability rank of 1/8 inch wall thickness and 5V flame retardancy, and generates corrosive gas and toxic gas during processing and combustion. In order to obtain a flame-retardant polypropylene resin composition, which does not cause deterioration of molding processability, and can obtain a molded product with very little bleeding of the flame-retardant component on the surface of the molded product even under high humidity conditions such as the rainy season. I studied hard.

As a result, polyethylene resin, olefin-based synthetic rubber and / or silane coupling agent, ammonium polyphosphate or melamine-modified ammonium polyphosphate, crosslinking aid, the following general formulas [I], [II], [III] and [I]
V] and a thiophosphite (hereinafter simply referred to as thiophosphite) selected from among those represented by the formula V) and a poly (ammonium polyphosphate) or a melamine-modified ammonium polyphosphate when combined with a polypropylene resin, are not decomposed by thermal decomposition. A composition in which a specific amount of a nitrogen-containing organic compound (hereinafter referred to as a nitrogen-containing organic compound) capable of giving a flammable gas product and a carbonaceous residue to a polypropylene resin can solve the above-mentioned problems. The inventors have found the present invention and have completed the present invention based on this finding.

[In the formula, R ₁ represents an alkyl group having 6 or more carbon atoms, a cycloalkyl group, or an aryl group. R ₂ is -S
R ₂ ′ or —R ₂ ′, R ₃ is —SR ₃ ′ or —R
_{'A, -R 2' 3, -R 3} ' represents an alkyl group or a cycloalkyl group or an aryl group having 6 or more same or different carbon atoms. X is - (CH _{2) n} - or - (CH
_{2) n -O- (CH 2)} m -, It is represented by. Here, n, m, and l represent the same or different integers of 2 to 6. As is clear from the above description, an object of the present invention is to provide a flame-retardant polypropylene resin composition which can solve the above-mentioned problems and can obtain a molded article having a high degree of flame retardancy.

(Means for Solving the Problems) The flame-retardant polypropylene resin composition of the present invention has the following four types of configurations.

(1) Assuming the total of the following components as 100% by weight (A) polyethylene resin 5 to 30% by weight (B) silane coupling agent 0.3 to 5% by weight (C) ammonium polyphosphate or melamine-modified ammonium polyate 12 ~ 25 wt% (D) Non-flammable by pyrolysis when combined with ammonium polyphosphate or melamine-modified ammonium polyphosphate when mixed with polypropylene resin
One or a mixture of two or more nitrogen-containing organic compounds capable of giving a gas product and a carbonaceous residue (hereinafter referred to as nitrogen-containing organic compound) 5 to 10% by weight (E) Crosslinking aid 1.0 to 15% by weight % (F) The following general formulas [I], [II], [III] and [IV]
One or more thiophosphites selected from those represented by (hereinafter referred to as thiophosphite).
0.05-5% by weight [In the formula, R ₁ represents an alkyl group having 6 or more carbon atoms, a cycloalkyl group, or an aryl group. R ₂ is -S
R ₂ ′ or —R ₂ ′, R ₃ is —SR ₃ ′ or —R
_{'A, -R 2' 3, -R 3} ' represents an alkyl group or a cycloalkyl group or an aryl group having 6 or more same or different carbon atoms. X is - (CH _{2) n} - or _{- (CH 2) n -O- (} CH 2) m -, It is represented by.

Here, n, m, and l represent the same or different integers of 2 to 6. ] (G) A flame-retardant polypropylene resin composition which is the remaining polypropylene resin.

(2) Assuming the total of the following components as 100% by weight (A) polyethylene resin 5-30% by weight (H) olefinic synthetic rubber 3-25% by weight (C) ammonium polyphosphate or melamine-modified ammonium polyphosphate 12-25 % By weight (D) Nitrogen-containing organic compound 5-10% by weight (E) Crosslinking aid 1.0-15% by weight (F) Thiophosphite 0.05-5% by weight (G) Flame retardant polypropylene resin Polypropylene resin composition.

(3) Assuming the total of the following components as 100% by weight (A) polyethylene resin 5-30% by weight (B) silane coupling agent 0.3-5% by weight (H) olefin-based synthetic rubber 3-25% by weight ( C) Ammonium polyphosphate or melamine-modified ammonium polyphosphate 12 to 25% by weight (D) Nitrogen-containing organic compound 5 to 10% by weight (E) Crosslinking aid 1.0 to 15% by weight (F) Thiophosphite 0.05 ~ 5 wt% (G) Flame-retardant polypropylene resin composition which is the remaining polypropylene resin.

(4) As the nitrogen-containing organic compound, a reaction product of ethylene urea and formaldehyde or a reaction product of ethylene thiourea and formaldehyde, or the following general formula [V]
Use of one kind or a mixture of two or more kinds selected from 1,3,5-triazine derivatives having a structure represented by:
The flame-retardant polypropylene resin composition according to any one of items (1) to (3).

[In the formula, X is a morpholino group or piperidino group Y is a divalent group of piperazine, and n is an integer of 2 to 50. The polypropylene resin used in the present invention contains propylene as a main component, propylene, ethylene and butene-
1, pentene-1, hexene-1, 4-methylpentene-1, heptene-1, octene-1, decene-1, and a crystalline copolymer with one or more thereof, or a mixture of two or more thereof. Can be raised. A crystalline ethylene-propylene block copolymer is particularly desirable.

The polyethylene resin used in the present invention may be any of high-density polyethylene, medium-density polyethylene, and low-density polyethylene, but it is desirable to use high-density polyethylene in order to prevent the rigidity of the molded product from being lowered.

The mixing ratio of the polyethylene resin is 5 to 3 with respect to the composition.
It is 0% by weight, preferably 7 to 20% by weight, particularly preferably 10 to 20% by weight. If the blending ratio is less than 5% by weight, flame retardance of 5V cannot be achieved at 1/8 inch wall thickness in UL94 combustion test, and if it exceeds 30% by weight, it will be 1/8.
It is not preferable because it is impossible to achieve flame retardancy of 5 V with an inch wall thickness.

The silane coupling agent used in the present invention has the general formula R
R'SiX ₂ (wherein R is a hydrocarbon group containing a vinyl group, a chloro group, an amino group, a mercapto group, etc., X is an organic group capable of being hydrolyzed, R'is R or X, and A silane compound represented by R (when there are two Rs) and each X may be different from each other. For example, vinyltrimethoxysilane, vinyltriethoxysilane, 3
-Aminopropyltriethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3
-Glycidoxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like. Of these, vinyltrimethoxysilane, vinyltriethoxysilane, and 3-mercaptopropyltrimethoxysilane are preferably used from the viewpoint of preventing bleeding of ammonium polyphosphate or melamine-modified ammonium polyphosphate used under high humidity conditions. The blending ratio of the silane coupling agent is 0.3 to 5% by weight, preferably 0.5 to 3% by weight, particularly preferably 0.5 to 1% by weight, based on the composition. The blending ratio is 0.3% by weight
When it is less than 5, the bleed preventing effect of ammonium polyphosphate or melamine-modified ammonium polyphosphate used under high humidity conditions is poor, and when it exceeds 5% by weight, UL94
It is not preferable because it becomes impossible to achieve flame retardancy of 5V with a 1/8 inch wall thickness in a combustion test.

Examples of the olefinic synthetic rubber used in the present invention include ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-1-butene rubber, ethylene-vinyl acetate rubber and the like. Above all, it is preferable to use ethylene-propylene rubber and ethylene-propylene-diene rubber from the viewpoint of maintaining high flame retardancy. The compounding ratio of the olefinic synthetic rubber is 2 to 25% by weight, preferably 3 to 20% by weight, particularly preferably 3 to 20% by weight based on the composition.
It is 15% by weight. If the blending ratio is less than 3% by weight, the bleeding-preventing effect of ammonium polyphosphate or melamine-modified ammonium polyphosphate used under high humidity conditions is poor, and if it exceeds 5% by weight, the rigidity is lowered and polypropylene is excellent. Mechanical strength and heat resistance are lost, which is not preferable.

As the ammonium polyphosphate or the melamine-modified ammonium polyphosphate used in the present invention, a commercially available product may be used as it is. As a commercially available product, for example, ammonium polyphosphate is Sumisafe P (trade name, Sumitomo Chemical Co., Ltd.).
And Exolit 422 (trade name, manufactured by Hoechst), as melamine-modified ammonium polyphosphate Sumisafe PM (trade name, manufactured by Sumitomo Chemical Co., Ltd.) and Exolit 462 (trade name, manufactured by Hoechst) Etc. can be given. The compounding ratio of the ammonium polyphosphate or the melamine-modified ammonium polyphosphate is 12 to 25% by weight based on the composition. If the blending ratio is less than 12% by weight, a composition which achieves flame retardancy of 5V at a thickness of 1/8 inch cannot be obtained in UL94 combustion test.
Even if blended in an amount of more than wt.%, No further improvement in flame retardancy can be obtained.

The nitrogen-containing organic compound used in the present invention is as follows. That is, when mixed with polypropylene resin in combination with ammonium polyphosphate or melamine-modified ammonium polyphosphate, non-flammable gas products (water, carbon dioxide, ammonia, nitrogen, etc.) due to thermal decomposition due to ignition or contact with flames, and It is one or a mixture of two or more nitrogen-containing organic compounds or a reaction product capable of producing a carbonaceous residue. Examples of these compounds include ethylene urea, ethylene thiourea, hydantoin,
Hexahydropyrimidin-2-one, piperazine-3,
6 Diones, barbituric acid, uric acid, dicyandiamide and reaction products of these with aldehydes, or reaction products of piperazine with diphenyl carbonate, reaction products of imidazolidin-2-one with diphenyl carbonate, or 2
-Piperazinylene-4-morpholino-1,3,5-triazine oligomer or polymer, 2-piperazinylene-4-piperidino-1,3,5-triazine oligomer or polymer and the like. Among these, a reaction product of ethylene urea and formaldehyde, a reaction product of ethylene thiourea and formaldehyde, and a 1,3,5-triazine derivative having a structure represented by the following general formula [V]: Piperazinylene-4-morpholino-1,3,5-
It is preferable to use an oligomer or polymer of triazine or an oligomer or polymer of 2-piperazinylene-4-piperidino-1,3,5-triazine from the viewpoint of maintaining high flame retardancy.

[In the formula, X is a morpholino group or piperidino group Y is a divalent group of piperazine, and n is an integer of 2 to 50. ] The blending ratio of the nitrogen-containing organic compound is 5 to the composition.
It is 10% by weight. If the blending ratio is less than 5% by weight, it is highly flame-retardant.
The flame retardancy of V cannot be achieved, and even if it is compounded in an amount exceeding 10% by weight, the effect of further improving the flame retardancy cannot be obtained.

Further, the reaction product of the above-mentioned ethylene urea and formaldehyde, which is the nitrogen-containing organic compound, the reaction product of ethylene thiourea and formaldehyde, an oligomer or polymer of 2-piperazinylene-4-morpholino-1,3,5-triazine. Alternatively, the oligomer or polymer of 2-piperazinylene-4-piperidino-1,3,5-triazine can be obtained, for example, by the following method.

To obtain the reaction product of ethylene thiourea and formaldehyde, ethylene thiourea is dissolved in water in an amount of 50 g /, acidified to pH 2 by mixing with a dilute acid (eg sulfuric acid or phosphoric acid) and the mixture is adjusted to 90%. After heating to ℃, keep the mixture at 90 ℃ and under strong stirring 37% by weight
Is added dropwise until an aqueous CH ₂ O / ethylene thiourea molar ratio of 2 is reached. It can be obtained by passing the precipitate obtained in the form of a very fine powder, washing with water and drying. Also, when a reaction product of ethylene urea and formaldehyde is obtained, it can be obtained by the same method as described above.

To obtain an oligomer or polymer of 2-piperazinylene-4-morpholino-1,3,5-triazine, equimolar amounts of 2,6-dihalo-4-morpholino-1,3,5-triazine (e.g. 2,6- Dichloro-4-morpholino-1,3,5-triazine or 2,6-dibromo-4-morpholino-1,3,5
-Triazine) and piperazine in the presence of an organic or inorganic base (eg triethylamine, tributylamine, sodium hydroxide, potassium hydroxide, sodium carbonate) in an inert solvent such as xylene under heating, preferably the inert It can be obtained by reacting at the boiling point of a solvent, and after the reaction is complete, the reaction mixture is filtered, washed with boiling water to remove by-product salts, and dried.

To obtain an oligomer or polymer of 2-piperazinylene-4-piveridino-1,3,5-triazine, equimolar amounts 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 under heating in the presence of an organic or inorganic base (eg triethylamine, tributylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, etc.) with an inert solvent such as triisopropylbenzene. The reaction can be carried out under the boiling point of the inert solvent, and after completion of the reaction, the reaction mixture is passed through a furnace, washed with boiling water to remove salts of by-products, and dried.

Examples of the crosslinking aid used in the present invention include polyfunctional monomers, oxime nitroso compounds, maleimide compounds and the like. As specific examples, for example, triallyl isocyanurate, (di) ethylene glycol di (meth) acrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate,
Trimethylol ethylene triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, divinylbenzene, diallyl phthalate, divinylpyridine, quinonedioxime, benzoquinonedioxime, p-nitrosphenol, N, N'-
Examples thereof include m-phenylene bismaleimide, but polyfunctional (meth) acrylic acid esters such as trimethylolpropane tri (meth) acrylate and pentaerythritol triacrylate are preferable.

The blending ratio of the crosslinking aid is 1.0 to 15% by weight, more preferably 1 to 7% by weight. If less than 1.0% by weight,
There is almost no drip prevention effect during combustion, and it may be added in an amount of more than 15% by weight, but this is meaningless because the improvement of the drip prevention effect is lost.

The thiophosphites represented by the above general formulas [I], [II], [III] and [IV] used in the present invention include trilauryltrithiophosphite, tridecyltrithiophosphite and tribenzyltrithiophosphite. , Tricyclohexyltrithiophosphite, tri (2-ethylhexyl) trithiophosphite, trinaphthyltrithiophosphite, diphenyldecyltrithiophosphite, diphenyllauryltrithiophosphite, tetralauryl-4-oxabutylene-1,7-tetra Thiophosphite, tetrakis (mercaptolauryl) -1,6
-Dimercaptohexylene diphosphite, pentakis (mercaptolauryl) bis (1,6-hexylene-dimercapto) trithiophosphite, tetrakis (mercaptolauryl) -2,9-dimercapto-para-menthylene diphosphite, bis (mercapto) Lauryl) -1,6
-Dimercaptohexylene-bis (benzenephosphonite), tetrakis (mercaptolauryl) -2,9-dimercapto-para-menthylene diphosphite, dioctyl dithiopentaerythritol diphosphite, dilauryl dithiopentaerythritol diphosphite, Mention may be made of enyllauryl dithiopentaerythritol diphosphite and mixtures of two or more thereof.

The compounding ratio of the thiophosphite is 0.05 to 5% by weight, more preferably 0.1 to 2% by weight. If the blending ratio is less than 0.05% by weight, the drip prevention effect is poor, and it is 5% by weight.
It is meaningless to add more than 5% because the effect of preventing drip is not improved.

In the composition of the present invention, various additives usually added to polypropylene resin, such as an antioxidant, an antistatic agent, a lubricant, a neutralizing agent (metal stearate, hydrotalcite, etc.), and a pigment should be used in combination. You can

The flame-retardant polypropylene resin composition of the present invention can be produced, for example, by the following method.

That is, the above-mentioned polyethylene resin in polypropylene resin, silane coupling agent or olefinic synthetic rubber (or both), ammonium polyphosphate or melamine-modified ammonium polyphosphate, nitrogen-containing organic compound,
A predetermined amount of the cross-linking aid, thiophosphite and the above-mentioned various additives is put in a stirring and mixing device, for example, Henschel mixer (trade name), super mixer, tumbler mixer,
It can also be obtained by stirring and mixing for 1 to 10 minutes, or by melt-kneading the obtained mixture at a melt-kneading temperature of 170 to 220 ° C. using a roll, an extruder or the like, and pelletizing.

(Examples) Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation methods used in Examples and Comparative Examples were as follows.

1) Flame retardance Complies with the 5V combustion test of UL Subject 94 (Underwriter Laboratories, Inc.) “Combustion test of plastic materials for equipment parts”. Wall thickness of test piece, 1/8 inch.

2) Evaluation of bleeding property under high humidity conditions A test piece measuring 95 mm in length x 95 mm in width x 2 mm in thickness was molded by an injection molding machine, and the temperature and humidity were controlled at 80 ° C and 80% humidity. (Made by Tabai MFG) and left for each day. The removed test piece is dried for 2 hours in a constant temperature dryer (manufactured by Sanyo Denki) adjusted to a temperature of 80 ° C., and left in a desiccator at room temperature overnight, and then visually observed for the bleeding state of the flame retardant on the surface of the test piece. did. Further, the surface electric resistance value of this test piece was measured by a vibration volume type micro-current electrometer (manufactured by Takeda Scientific Research).

Example 1 and Comparative Example 1 As polypropylene resin, ethylene content 8.5% by weight, melt flow rate (temperature 230 ° C., discharge amount of molten resin for 10 minutes when load 2.16 kg) 20 g / 1
0 minutes crystalline ethylene-propylene block copolymer 5
2% by weight, melt index as polyethylene resin (temperature 190 ° C., discharge amount of molten resin for 10 minutes when a load of 2.16 kg is added) 6.5 g / 10 minutes polyethylene (Chisso Polyech (trademark) M680, Chisso Corporation) Made) 15
% By weight, vinyltrimethoxysilane (Sila Ace (trademark) S210, manufactured by Chisso Corporation) 1.0% by weight, ammonium polyphosphate (Sumisafe P (trademark) manufactured by Sumitomo Chemical Co., Ltd.) 21% by weight, as a nitrogen-containing organic compound 2-
8% by weight of piperazinylene-4-morpholino-1,3,5-triazine polymer (n = 11, molecular weight about 2770),
2.5% by weight of pentaerythritol tetraacrylate,
0.5% by weight of trilauryltrithiophosphite, 2,5-di-t-butyl-p-cresol 0.15 as various additives
% By weight, 0.2% by weight of di-myristyl-.beta.,. Beta.-thiodipropionate and 0.1% by weight of calcium stearate were placed in a Hensell mixer (trade name) and mixed with stirring for 3 minutes. The resulting mixture was melt-kneaded and extruded at a melt-kneading temperature of 200 ° C. with an extruder having a diameter of 45 mm to form pellets.

Further, as Comparative Example 1, 53% by weight of polypropylene resin
In addition, except that the silane coupling agent was not blended, the respective components were put in a Henschel mixer (trade name) at a blending ratio in accordance with Example 1, stirred and mixed, melt-kneaded and extruded in accordance with Example 1, and pelletized. did.

Examples 2 to 6 Pelletization was carried out according to Example 1 except that the type of the silane coupling agent was changed to the silane coupling agent shown in Table 1.

Examples 7 to 8 and Comparative Examples 2 to 3 Pelletization was carried out according to Example 1 except that the mixing ratio of the polypropylene resin and the silane coupling agent was changed to the mixing ratio shown in Table 1.

Example 9 Pelletization was carried out according to Example 1 except that a reaction product of ethylene urea and formaldehyde was used as the nitrogen-containing organic compound.

Comparative Examples 4 to 5 Pelletization was carried out according to Example 1 except that the blending ratio of the polypropylene resin and the polyethylene resin was changed to the blending ratio shown in Table 1.

Comparative Examples 6 to 8 Example 1 except that the compounding ratios of polypropylene resin, pentaerythritol tetraacrylate and trilauryltrithiophosphite were changed to the compounding ratios shown in Table 1.
Pelletized according to.

10 pellets obtained in Examples 1-9 and Comparative Examples 1-8
After drying at a temperature of 0 ° C. for 3 hours, the pellets were used to form predetermined test pieces for flame retardancy and bleeding property evaluation by an injection molding machine in which the maximum cylinder temperature was set to 220 ° C. Using the test piece, flame retardancy and bleeding property under high temperature and high humidity conditions were evaluated. The results are shown in Table 1.

Example 10 and Comparative Example 9 As polypropylene resin, ethylene content 8.5% by weight, melt flow rate (temperature 230 ° C., discharge amount of molten resin for 10 minutes when load 2.16 kg) 20 g / 1
0 minutes crystalline ethylene-propylene block copolymer 4
8% by weight, melt index as polyethylene resin (temperature 190 ° C., discharge amount of molten resin for 10 minutes when a load of 2.16 kg is applied) 6.5 g / 10 minutes polyethylene (Chisso Polyech (trademark) M680, Chisso Corporation) Made) 10
% By weight, ethylene-propylene rubber (EP-02P, manufactured by Japan Synthetic Rubber Co., Ltd.) as an olefinic synthetic rubber 10
% By weight, ammonium polyphosphate (Sumisafe P ™)
21% by weight of Sumitomo Chemical Co., Ltd., 2-piperazinylene-4-morpholino-1,3,5 as a nitrogen-containing organic compound
A polymer of triazine (n = 11, molecular weight about 277)
0) 8% by weight, pentaerythritol tetraacrylate 2.5% by weight, trilauryltrithiophosphite 0.5% by weight, various additives 2,6-di-t-butyl-p-cresol 0.15% by weight, di-myristyl-β, Add 0.2% by weight of β-thiodipropionate and 0.1% by weight of calcium stearate to a Hensell mixer (trade name) and
Stir and mix for minutes. The resulting mixture was melt-kneaded and extruded at a melt-kneading temperature of 200 ° C. with an extruder having a diameter of 45 mm to form pellets.

Further, as Comparative Example 9, polypropylene resin 58% by weight
In addition, except that the ethylene-propylene rubber was not compounded, each compounding component was put into a Henschel mixer (trade name) in a compounding ratio according to Example 1, and stirring mixing, melt-kneading extrusion, and pelletization were carried out according to Example 10. did.

Examples 11 to 12 and Comparative Examples 10 to 11 Pelletization was carried out according to Example 10 except that the compounding ratio of the polypropylene resin and the ethylene-propylene rubber was changed to the compounding ratio shown in Table 2.

Comparative Example 12 Pelletization was carried out according to Example 10 except that the blending ratio of the polypropylene resin and the polyethylene resin was changed to the blending ratio shown in Table 2.

The pellets obtained in Examples 10 to 12 and Comparative Examples 9 to 12 were dried at a temperature of 100 ° C. for 3 hours, and then flame retarded by an injection molding machine in which the maximum temperature of the cylinder was set to 220 ° C. using the pellets. A predetermined test piece for bleeding property evaluation was molded. Using the test piece, flame retardancy and bleeding property under high temperature and high humidity conditions were evaluated. The results are shown in Table 2.

Example 13 and Comparative Example 13 As polypropylene resin, ethylene content 8.5% by weight, melt flow rate (temperature 230 ° C., discharge amount of molten resin for 10 minutes when load 2.16 kg) 20 g / 1
0 minutes crystalline ethylene-propylene block copolymer 4
7% by weight, melt index as polyethylene resin (temperature 190 ° C., discharge amount of molten resin for 10 minutes when a load of 2.16 kg is applied) 6.5 g / 10 minutes polyethylene (Chisso Polyech (trademark) M680, Chisso Corporation) Made) 10
% By weight, ethylene-propylene rubber (EP-02P, manufactured by Japan Synthetic Rubber Co., Ltd.) as an olefinic synthetic rubber 10
% By weight, as a silane coupling agent, vinyltrimethoxysilane (Sila Ace (trademark) S210, manufactured by Chisso Corporation) 1.0% by weight, ammonium polyphosphate (Sumisafe P (trademark) manufactured by Sumitomo Chemical Co., Ltd.) 21% by weight, As a nitrogen-containing organic compound, 2-piperazinylene-4-morpholino-1,3,5-triazine polymer (n = 11, molecular weight about 2770) 8% by weight, pentaerythritol tetraacrylate 2.5% by weight, trilauryltrithiophosphite 0.5% by weight %, As various additives 2,6-di-t-butyl-p-cresol 0.15% by weight, di-myristyl-
0.2% by weight of β, β-thiodipropionate and 0.1% by weight of calcium stearate were placed in a Hensell mixer (trade name) and mixed with stirring for 3 minutes. The resulting mixture was melt-kneaded and extruded at a melt-kneading temperature of 200 ° C. with an extruder having a diameter of 45 mm to form pellets.

Further, as Comparative Example 13, the polypropylene resin was 58% by weight, and each compounding component was put in a Henschel mixer (trade name) at a compounding ratio according to Example 13 except that the ethylene-propylene rubber and the silane coupling agent were not compounded. In accordance with Example 13, the mixture was stirred, melt-kneaded, extruded and pelletized.

Examples 14 to 21 and Comparative Examples 14 to 16 Pelletization was carried out according to Example 13 except that the compounding ratios of the polypropylene resin, ethylene-propylene rubber and silane coupling agent were changed to the compounding ratios shown in Table 3.

Comparative Example 17 Pelletization was carried out according to Example 13 except that the blending ratio of the polypropylene resin and the polyethylene resin was changed to the blending ratio shown in Table 3.

The pellets obtained in Examples 13 to 21 and Comparative Examples 13 to 17 were dried at a temperature of 100 ° C. for 3 hours and then flame-retardant using an injection molding machine in which the maximum temperature of the cylinder was set to 220 ° C. A predetermined test piece for bleeding property evaluation was molded. The test piece was used to evaluate flame retardancy and bleedability under high temperature and high humidity conditions. The result is the third
Shown in the table.

The symbols in Tables 1 to 3 are as follows.

Component (A): Polyethylene resin M680 manufactured by Chisso Corp. Component (B): B ₁ vinyltrimethoxysilane, B ₂ 3-aminopropyltriethoxysilane, B ₃ 3-methacryloxypropyltriethoxysilane, B ₄ 3-glycidoxypropyl trimethoxysilane, B ₅ 3-chloropropyltrimethoxysilane, B ₆ 3-mercaptopropyltrimethoxysilane, component (C): ammonium polyphosphate, component (D): D ₁ 2-piperazinylene-4 -Polymer of morpholino-1,3,5-triazine (n = 11), reaction product of D ₂ ethylene urea and formaldehyde, component (E): pentaerythritol tetraacrylate, component (F): trilauryltrithiophos Fight, Component (G): As a polypropylene resin, ethylene-propylene block copolymer (containing ethylene Amount 8.5% by weight, melt index 20
g / 10 minutes), Component (H): Ethylene-propylene rubber (EP-02P manufactured by Nippon Synthetic Rubber Co., Ltd.), * 1 Surface resistance before humidification: Surface electricity before exposure in a heated humidified atmosphere. Resistance value, * 2 Surface resistance value 7 days after humidification treatment: Surface electric resistance value after exposure for 7 days at a temperature of 80 ° C and a humidity of 80%.

As is clear from Table 1, by adding the silane coupling agent, the bleeding property under high temperature and high humidity conditions was improved, and the mixing ratio of the silane coupling agent was 0.3-5.
It can be seen that weight percent is preferred.

As is clear from Table 2, the blending of ethylene-propylene rubber improves the bleeding property under high temperature and high humidity conditions, and the blending ratio of ethylene-propylene rubber is preferably 3 to 25% by weight. .

Further, as is clear from Table 3, it can be seen that the bleeding property under high temperature and high humidity conditions is improved by using both the silane coupling agent and the ethylene-propylene rubber together.

(Effect of the Invention) The composition of the present invention has very little bleeding property on the surface of a molded article under high humidity conditions, and has a high flame retardance, that is, UL94.
A flame-retardant polypropylene resin composition that can be molded into a molded product that has a flame resistance of 1/8 inch and a flame resistance of 5V in a combustion test and that does not generate corrosive gas or toxic gas during processing or combustion. Therefore, it can be suitably used for manufacturing buildings, upholstery, household electric appliances, automobile parts and the like.

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Claims (5)

[Claims] 1. A polyethylene resin 5 to 30% by weight (B) a silane coupling agent 0.3 to 5% by weight (C) ammonium polyphosphate or melamine-modified ammonium polyphosphate. -25 wt% (D) Nitrogen-containing organics which, when mixed with polypropylene resin, can give nonflammable gas products and carbonaceous residues by pyrolysis in combination with ammonium polyphosphate or melamine modified ammonium polyphosphate. One of the compounds
Or a mixture of two or more kinds (hereinafter referred to as nitrogen-containing organic compound) 5 to 10% by weight (E) Crosslinking aid 1.0 to 15% by weight (F) The following general formulas [I], [II], [III] and In [IV]
One or more thiophosphites selected from those represented (hereinafter referred to as thiophosphite).
0.05-5% by weight [In the formula, R ₁ represents an alkyl group having 6 or more carbon atoms, a cycloalkyl group, or an aryl group. R ₂ is -S
R ₂ ′ or —R ₂ ′, R ₃ is —SR ₃ ′ or —R
_{'A, -R 2' 3, -R 3} ' represents an alkyl group or a cycloalkyl group or an aryl group having 6 or more same or different carbon atoms. X is - (CH _{2) n} - or _{- (CH 2) n -O- (} CH 2) m -, It is represented by. Here, n and m represent the same or different integers of 2 to 6. ] (G) Flame-retardant polypropylene resin composition which is the remaining polypropylene resin. 2. A total of the following components is 100% by weight: (A) polyethylene resin 5 to 30% by weight (H) olefinic synthetic rubber 3 to 25% by weight (C) ammonium polyphosphate or melamine-modified ammonium polyphosphate 12 ~ 25 wt% (D) Nitrogen-containing organics which, when combined with polypropylene resin, can give nonflammable gas products and carbonaceous residues by pyrolysis in combination with ammonium polyphosphate or melamine modified ammonium polyphosphate. One of the compounds
Species or a mixture of two or more species (hereinafter referred to as nitrogen-containing organic compound) 5 to 10% by weight (E) crosslinking aid 1.0 to 15% by weight (F) thiophosphite 0.05 to 5% by weight (G) A flame-retardant polypropylene resin composition containing the remaining polypropylene resin. 3. A total of the following respective components is 100% by weight: (A) polyethylene resin 5 to 30% by weight (B) silane coupling agent 0.3 to 5% by weight (H) olefinic synthetic rubber 3 to 25% by weight % (C) Ammonium polyphosphate or melamine-modified ammonium polyphosphate 12-25% by weight (D) When mixed with polypropylene resin, non-flammability due to thermal decomposition when combined with ammonium polyphosphate or melamine-modified ammonium polyphosphate One of the nitrogen-containing organic compounds that can give gas products and carbonaceous residues
Species or a mixture of two or more species (hereinafter referred to as nitrogen-containing organic compound) 5 to 10% by weight (E) crosslinking aid 1.0 to 15% by weight (F) thiophosphite 0.05 to 5% by weight (G) A flame-retardant polypropylene resin composition containing the remaining polypropylene resin. 4. As the nitrogen-containing organic compound, a reaction product of ethylene urea and formaldehyde, a reaction product of ethylene thiourea and formaldehyde, or a structure represented by the following general formula [V]: 1,3,5- The flame-retardant polypropylene resin composition according to any one of claims (1), (2) and (3), wherein one or a mixture of two or more selected from triazine derivatives is used. [In the formula, X is a morpholino group or piperidino group Y is a divalent group of piperazine, and n is an integer of 2 to 50. ] 5. Among polypropylene resins, among propylene and ethylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, heptene-1, octene-1, and decene-1, as a polypropylene resin. The flame-retardant polypropylene according to any one of claims (1), (2), (3) and (4), wherein a crystalline copolymer with one or more selected from the above and a mixture of two or more thereof are used. Resin composition.