JPH04142348A - Flame-retardant polyolefin resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. scarcely generating corrosive or toxic gas during thermal decomposition by compounding a polyolefin resin with (a modified) ammonium polyphosphate, a reaction product of a cyclic (thio)ketone with formaldehyde or a triazine deriv., and a petroleum resin. CONSTITUTION:The title compsn. comprises 12-25wt.% (melamine-modified) ammonium polyphosphate, 5-10wt.% at least one compd. selected from the group consisting of reaction products of 5-membered or higher heterocyclic ketones having two or more nitrogen atoms in the heterocyclic ring with formaldehyde, reaction products of 5-membered or higher heterocyclic thioketones having two or more nitrogen atoms in the heterocyclic ring with formaldehyde, and 1,3,5-triazine derivs. of the formula, 1-20wt.% petroleum resin, and 82-85wt.% polyolefin resin, the sum of all the components being 100wt.%.

Description

[Detailed description of the invention] [Industrial application field 1 The present invention relates to flame retardant compositions of polyolefin resins.

Specifically, it is a composition whose main component is a polyolefin resin, particularly a polypropylene resin, which generates almost no corrosive gas or toxic gas when the composition is thermally decomposed, and the molded product obtained from it is not subject to high temperature and high humidity conditions. A flame retardant composition of a polyolefin resin that hardly causes the flame retardant to bleed onto the surface of the molded article is created.

Traditionally, polyolefin resins have been known for their hygiene, processability,
Utilizing its superior properties such as chemical resistance, weather resistance, electrical properties, and mechanical strength, it is widely used in various fields such as industrial and household electrical products, buildings, interior decoration products, and automobile parts. has been done.

[Prior Art] Polyolefin resins are originally easily combustible resins. However, as the applications for which they are used have expanded, polyolefin resins have also begun to be required to have performance as flame retardant materials, and the required performance has become stricter year by year. In particular, in the formulation of halogen compounds or the combination of halogen compounds and antimony oxide, which has recently been the mainstream of conventional flame retardant technology, the toxicity of halogen-based gases generated during combustion or molding of flame retardant compositions has been reduced. It is seen as a problem.

Therefore, flame-retardant polyolefin resins are required to not 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-54-2
Hydrous inorganic compounds as disclosed in JP-A No. 9350, JP-A-54-77658, JP-A-56-26954, JP-A-57-87462, JP-A-60-110738, etc. (e.g. magnesium hydroxide,
A composition in which aluminum hydroxide, hydrotalcite, etc.) is added to polypropylene resin or JP-A-52-146
Ammonium phosphate (or phosphoric acid amine)
and oligomers (or polymers) of 1,3,5-triazine derivatives or reaction products of aldehydes and nitrogen-containing compounds containing groups >C=O (or >C=S or >NH) inserted into the cyclic structure. Compositions have been proposed in which polypropylene resin is added to polypropylene resin.

However, in order to exhibit a high degree of flame retardancy in a composition in which a hydrous inorganic compound is added 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 a decrease in moldability.

Also, JP-A-52-146452, JP-A-59-
The flame-retardant polypropylene resin composition disclosed in Japanese Patent No. 147050 exhibits relatively little deterioration in moldability, and also suppresses the generation of corrosive gas or toxic gas during processing or combustion.

However, due to the hygroscopicity of ammonium phosphate (or amine phosphate) in the composition, ammonium phosphate (or amine phosphate) may be absorbed onto the surface of the molded product under high temperature conditions such as during the rainy season. A severe bleed phenomenon occurs. As a result, the electrical resistance value of the molded product decreases significantly, leaving the drawback that it cannot be used as an electrical insulating material under high temperature conditions. Furthermore, in order to improve the rigidity of the composition, adding a filler commonly used in polypropylene resin further reduces the bleeding phenomenon of ammonium phosphate (or amine phosphate) to the surface of the molded product under high humidity conditions. It also has the disadvantage of making it more intense.

[Problems to be Solved by the Invention] The present inventors have discovered a composition that generates almost no corrosive or toxic gas when processing or burning the composition, and that the deterioration of moldability becomes a practical problem. This is a flame retardant formulation of polyolefin resin that does not cause any flame retardant components to bleed onto the surface of the molded product even under high temperature and high humidity conditions such as during the rainy season. We conducted intensive research to obtain a sex composition.

As a result, (A) ammonium polyphosphate or melamine-modified ammonium polyphosphate; Reaction product group of ketone and formaldehyde, reaction product group of cyclic thioketone consisting of a five-membered or more heterocycle containing two or more nitrogen atoms in the ring and formaldehyde, or the following general formula 1, 3 containing the structure.
5-triazine derivative group [wherein, It has been found that a composition blended with a certain polyolefin resin (H) is substantially free from the above-mentioned problems.

When it is desired to obtain even higher mechanical strength, it has been discovered that a composition in which a specific amount of fibrous filler (C) is blended with polyolefin resin (H) solves the above-mentioned problems, and based on this knowledge, the present invention has been developed. completed.

Due to the synergistic effect of the components contained in the flame-retardant composition of the polyolefin resin (H), even when thermally decomposed, only non-flammable gas and carbonaceous residue are produced.

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

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

(1) The following ingredients (A), (B), (E) and ()I)
A flame-retardant composition (A) of polyolefin resin, characterized in that the total amount thereof is 100% by weight.
Ammonium polyphosphate or melamine-modified ammonium polyphosphate 12-25% by weight (B) 5-10% by weight of one or more selected from the following group From a 5-membered or more heterocycle containing 2 or more nitrogen atoms in the ring A reaction product group of a cyclic ketone and formaldehyde, a reaction product group of a cyclic thioketone consisting of a five-membered or more heterocycle containing two or more nitrogen atoms in the ring, and formaldehyde, or a reaction product group of formaldehyde and a cyclic thioketone consisting of a 5-membered or more heterocycle containing two or more nitrogen atoms in the ring, or 1, 3 containing the structure represented
．． 5-triazine derivative group [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 (1-
1) Polyolefin resin 82-55% by weight.

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

Polyolefin resin (1) as a base material of the composition of the present invention
As examples, the following can be exemplified: ・Ethylene homopolymer resin, copolymer resin of ethylene main component and propylene or higher subcomponent; ・Propylene crystalline homopolymer resin,
Crystalline copolymer resin of propylene main component and ethylene or 1-olefin of 1-butene or more; - 1-butene homopolymer resin, 1-butene main component and ethylene, propylene, or 1-olefin of 1-pentene or more Copolymer resin with olefin, homopolymer resin of 4-methyl-1-pentene, copolymer of 4-methyl-1-pentene and 1-olefin of ethylene, propylene, 1-butene or l-heptene or higher Resin; - Resin blend consisting of two or more of the above resins - Modified products of the above resins.

Among them, preferred resins are the following: copolymer resins of propylene or higher subcomponents; crystalline homopolymer resins of propylene, propylene main components and ethylene or 1-
Crystalline copolymer resin with butene or higher 1-olefin.

Examples of polypropylene resins that are preferred in the present invention include the following: ・Crystalline propylene homopolymer, ・One of the following 1-olefins containing propylene as a main component
Crystalline random copolymer or crystalline block copolymer containing ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1 as subcomponents
-heptene, 1-octene and 1-decene.

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

The crystalline polypropylene resin constituting the composition of the present invention usually has an MFR (230°C, 2.16 kgf) of 0.
1 to 50 g/10 m1n, preferably 1 to 30 g/1
Choose the one with 0m1n.

The polyethylene resin used in the present invention may be any commercially available product. Usually MI (190℃; 2.16kgf
)0.01 to 50g/10m1n, preferably 0.01 to 50g/10m1n, preferably 0.
1-30g/10mln, density 0.91-0.97g
/cc is sufficient.

Preferred ammonium polyphosphates or melamine-modified ammonium polyphosphates (A) used in the present invention have the general formula (NH, PO,). (n≧50). If a normal commercially available product falls within this range, it can be used as is. For example, preferred commercially available ammonium polyphosphates include the following product names: Sumisaf P (manufactured by Sumitomo Chemical ■) and product names:
Exolit422 (manufactured by Hoechst), melamine-modified ammonium polyphosphate, product name: Sumisaf P
M (manufactured by Sumitomo Chemical ■) and product name: Exolit462
(Manufactured by Hoechst) The blending ratio of the ammonium polyphosphate or melamine-modified ammonium polyphosphate is usually 12 to 25% by weight, preferably 14 to 21% by weight based on the composition.
It is. If the blending ratio is less than 10% by weight, a composition exhibiting a high degree of flame retardancy cannot be obtained, and even if the blending ratio is greater than 28% by weight, hardly any improvement in flame retardancy beyond that can be expected.

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

A group of reaction products of formaldehyde and cyclic ketones consisting of a five-membered or more heterocycle containing two or more nitrogen atoms in the ring, from a five-membered or more heterocycle containing two or more nitrogen atoms in the ring A group of reaction products of a cyclic thioketone and formaldehyde, or 1,3 containing a structure represented by the following general formula [I]
．． In the 5-triazine derivative group formula, X is a morpholino group or a piperidino group, Y is a divalent group derived from piperazine, and n is a positive number from 2 to 50] These are ammonium polyphosphate or melamine-modified polyphosphoric acid. Polyolefin resin (H) along with ammonium (A)
A type of organic compound that can generate non-flammable gases (water, carbon dioxide, ammonia, nitrogen, etc.) and only carbonaceous residues even when thermally decomposed by ignition or contact with flame when present in Or a mixture or reaction product of two or more.

Examples of these compounds include ethyleneurea, ethylenethiourea, hydantoin, hexahydropyrimidine-2
-one, piperazine-3,6-dione, barbylic acid and reaction products of these with aldehydes, oligomers or polymers of 2-biverazinylene-4-morpholino-1,3,5-triazine, or 2-biverazinylene-4
Examples include oligomers or polymers of -piperidino-1,3,5-triazine.

Among these, the following are preferable from the viewpoint of imparting a high degree of flame retardancy: ・Reaction product of ethylene urea and formaldehyde, ・Reaction product of ethylene thiourea and formaldehyde, or ・Reaction product of the following general formula [ 1, 3.5 having the structure represented by I]
- 2-biperazinylene-4- which is a triazine derivative
Oligomers or polymers of morpholino-1,3,5-triazine and oligomers or polymers of 2-biperazinylene-4-piperidino-1,35-triazine [wherein X is a morpholino group or piperidino group, and Y is derived from piperazine] n is a positive number from 2 to 50. The properties of the 1,3,5-triazine derivative used in the present invention are as follows. Solubility: In water and organic solvents under electric current. Insoluble;・Melting point: None; decomposition point: around 310℃);・True specific gravity: 20.3・Name:・2-Biperazinylene-4-morpholino-13
Polymer of 5-triazine; -Structural formula -Following formula.

In addition, the reaction product of the above-mentioned ethylene urea and formaldehyde, which is one type of the nitrogen-containing heterocyclic organic compound, or the reaction product of ethylene thiourea and formaldehyde, or 2-biverazinylene-4-morpholino-1,3,
Oligomers or polymers of 5-triazine and 2
-Biberazinylene-4-piperidino-L3.5- The oligomer or polymer of 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 an amount of water at 1 °C and p) Adjust to. The reaction solution was heated to 90%
``C, and an aqueous solution of formaldehyde with a concentration of 37% by weight was added to the ethylene thiourea solution with CI (20/
Add dropwise until the molar ratio of ethylenethiourea is equal to 2, and stir vigorously 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.

Furthermore, the same method as above can be applied to obtain a reaction product of ethylene urea and formaldehyde.

To obtain oligomers or polymers of 2-biperazinylene-4-morpholino-1,35-triazine, equimolar amounts of 2,6-cyhalo-4-morpholino-1,35-
Triazines (e.g. 2,6-dichloro-4-morpholino-13,5-triazine or 2,6-dipromo-4
-morpholino-1,3,5-triazine) and piperazine in the coexistence of an organic or inorganic base (e.g. triethylamine, tributylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, etc.) in an inert solvent such as xylene. The reaction is carried out under heating, preferably below the boiling point of the inert solvent. After the reaction is completed, the reaction mixture is filtered to separate the solid matter, the solid matter is washed with boiling water to remove the by-product salt by dissolving it in the boiling water, and the remaining solid matter is dried. .

Alternatively, there is the following method.

The oligomer or polymer of 2-biverazinylene-4-piperidino-1,3,5-triazine is prepared in equal moles of 2
,6-cyhalo4-piperidino-1,3,5-triazine (e.g. 2,6-dichloro-4-piperidino-1,3
, 5-triazine or 2,6-dipromo-4-piperidino-1,3,5-triazine) and piperazine in an organic or inorganic base (e.g. triethylamine, tributylamine, sodium hydroxide, potassium hydroxide,
The reaction is carried out using an inert solvent such as triisopropylbenzene in the presence of sodium carbonate, etc.) under heating, preferably at the boiling point of the inert solvent.

After the reaction is completed, the reaction mixture is filtered to separate the solids, and then the solids are washed with boiling water to remove the by-product salts by dissolving them in the boiling water, and the remaining solids are removed. dry.

The blending ratio of the nitrogen-containing heterocyclic organic compound (B) is 5 to 10% based on the composition. The blending ratio is 3% by weight
If the amount is below, a composition exhibiting a high degree of flame retardancy cannot be obtained, and even if 13% by weight or more is added, no further improvement in flame retardancy is observed.

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 made of resin. Among cracked oil fractions, C6 (aliphatic) petroleum resin made from C5 fraction, C1 (aromatic) petroleum resin made from C9 fraction, and C6/C9 made from the same. Copolymerized petroleum resin, C6
A dicyclopentadiene-based petroleum resin made from dicyclopentadiene obtained by thermal dimerization of cyclopentadiene contained in the distillate, and the double bonds in the petroleum resin are hydrogenated (hydrogenated). (alicyclic type). Particularly preferred is hydrogenated (hydrogenated) petroleum resin, which has excellent heat resistance and weather resistance.

For the purpose of the present invention, the petroleum resin (E) has a softening point of 70 to 180°C, preferably 7o to 140°C by the ring and ball method.
, the hue is 15 or less according to the Gardner method, and the bromine number is 70.
(Br-g/100g) or less, preferably 30 (Br-g/100g) or less, preferably 30 (Br
-g/100g) or less.

The blending ratio of the petroleum resin (E) to the composition is 1 to 20
% by weight, preferably from 3 to 15% by weight. If the blending ratio is less than 0.5% by weight, the effect of preventing bleed under high humidity conditions is lacking. Moreover, if it is more than 25% by weight, the impact resistance will be lowered and the good mechanical strength inherent to polyolefin, especially polypropylene, will be lost.

The fibrous filler (C) used in the present invention includes wollastonite, dawsonite, glass fiber, processed mineral fiber rock wool, gypsum fiber, metal whisker, potassium titanate whisker, carbon fiber, boron fiber, and silicon carbide fiber. , alumina fiber, wholly aromatic polyamide fiber, and wholly aromatic polyester. Particular preference is given to using glass fibers and rock wool. These fibrous fillers (C) are preferably surface-treated with a tackiness or adhesion-imparting polymer as exemplified below: a modified polyolefin resin, an elastomer, a modified elastomer, a silane coupling agent, etc.

In addition, in order to improve the interfacial adhesion between the surface of these fibrous fillers (C) and the polypropylene resin (H), adhesion-imparting resins such as maleic anhydride-modified polypropylene resins are added to the base resin (H). It is extremely beneficial to use them in combination. When using maleic anhydride-modified polypropylene resin, the amount used is the amount of the added fibrous filler (
0.5 to 2 times by weight, preferably 0.5 to 2 times the amount of C).
Choose between 5 and 1 times. However, in order to avoid deteriorating the performance of the composition, the amount added should be 50% by weight based on the composition.
It is preferable to limit it to the following.

The blending ratio of the fibrous filler (C) is usually 5 to 25% by weight, preferably 10 to 20% by weight based on the composition.

If the blending ratio is less than 3% by weight, the effect of improving mechanical strength due to filler blending is insufficient, while if it is greater than 28% by weight, the flame retardance will be lowered.

The flame retardant composition of the present invention contains various additives normally added to polyolefin resins, such as antioxidants, ultraviolet inhibitors, antistatic agents, copper inhibitors, lubricants, and neutralizing agents (stearic acid Metal salts, hydrotalcite, manaceite, etc.) or pigments can be used in combination as appropriate.

In addition, the present inventors have previously filed Japanese Patent Application No. 1-191.
As described in the specification of No. 960, the addition of a silane coupling agent or olefin-based synthetic rubber that has the effect of suppressing the bleeding of ammonium polyphosphate (A) under high-temperature conditions, and the addition of olefin-based synthetic rubber to further improve flame retardancy. A polyethylene resin described in Japanese Patent Application No. 19298/1988 previously filed by the inventors may be added.

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

That is, for example, polypropylene resin (1) is combined with one selected from the above-mentioned petroleum resin (E), ammonium polyphosphate or melamine-modified ammonium polyphosphate (A), and the nitrogen-containing heterocyclic organic compound (B) specified above. Or, if you want to obtain high mechanical strength, add a mixture of two or more of them, and if necessary, add a fibrous filler (C) and, if necessary, a predetermined amount of the above-mentioned various additives. Mixing equipment, e.g. Henschel mixer (trade name)
, super mixer or tumbler mixer, etc. Next, after stirring and mixing for 1 to 10 minutes, the resulting mixture is melt-kneaded using a roll mixer or screw extruder at a melt-kneading temperature of 170 to 220°C, and is pelletized to obtain the desired flame retardant property. A composition can be obtained.

Preferred Embodiments> The present invention will be specifically described below using Examples and Comparative Examples, but the present invention is not limited thereto. Evaluations in Examples and Comparative Examples were performed in accordance with the following method.

1) Compliant with the vertical combustion test stipulated in Flame Retardant UL Subject 1-94 (Underwriter Laboratories, Inc.-Boletted) "Flame Test of Plastic Materials for Equipment Parts". Test piece wall thickness 1.6+on+ (1/32 inch).

2) Evaluation of bleedability under high temperature and high humidity conditions A test piece (length 9 Smm x width 95 mm x thickness 2 mm) was molded using an injection molding machine, and the surface electrical resistance value of the test piece was measured using a vibrating volume type microcurrent electrometer ( Furthermore, the test piece was immersed in boiling water for 4 hours, then taken out, and the water droplets adhering to the test piece were wiped off with wiper paper [trade name: Kimwive (Jujo Kimberly ■!Q)]. The surface electrical resistance value of the test piece was immediately measured.If the surface electrical resistance value of the test piece significantly decreased after being immersed in boiling water, it was determined that the bleed resistance under high temperature and high humidity conditions was poor (poor).

Example 1 Crystalline propylene as polypropylene resin (H)
Ethylene block copolymer [ethylene component content 8.5
Weight%, MFR (temperature 230℃, load 2.16kgf)
20g/10m1n] f3.6 kg, ammonium polyphosphate (A) [W8 Product name: Exolit422
(manufactured by Hoechst)] 2.11ag, a polymer of 2-biverazinylene-4-morpholino-1,35-triazine (n = 11
, molecular weight approximately 2770) 800g, petroleum resin (E) [Product name: Alcon P-140 (manufactured by Arayo Kagaku Kogyo ■)] 5
500g, 15g of 2,6-di-butyl-p-cresol (BHT) as various additives, Similistil-
β,β-thiodipropionate (DMyTDP) 20
g and 10 g of calcium stearate were placed in a Henschel mixer (trade name) and mixed by stirring for 3 ml.

Extrusion of the resulting mixture 8! (diameter 45+nm) was melt-kneaded and extruded at a melt-kneading temperature of 200°C. The flammable composition was pelletized.

Comparative Example 1 The amount of polypropylene resin ()l) was 7.1 kg, and each component was mixed in a Henschel mixer (trade name) at the mixing ratio according to Example 1, except that petroleum resin (E) was not mixed.
A pellet of the composition was obtained by stirring and mixing and melt cross-extrusion according to Example 1.

Examples 2 to 4 and Comparative Examples 2 and 3 Each composition was made according to Example 1, except that the blending ratios of polypropylene resin (H) and petroleum resin (E) were changed to the blending ratios shown in Table 1. Made things into berets.

Example 5 A pellet of a flame retardant composition was obtained in accordance with Example 1 except that a reaction product of ethylene urea and formaldehyde was used as the nitrogen-containing organic compound (B).

Example 6 As polypropylene resin (H), crystalline propylene homopolymer [MFR (230°C; load 2.16 kgf) 2
A pellet was obtained in accordance with Example 1 except that 5 g/10 m1n] was used.

Examples 7 and 8 A pellet was produced in accordance with Example 1, except that the type of petroleum resin fE) was changed to the petroleum resin listed in Table 1.

The pellets obtained in Examples 1 to 8 and Comparative Examples 1 to 3 were
After drying at a temperature of 00°C for 3 hours, the pellets were molded into predetermined test pieces for flame retardancy and bleedability evaluation using an injection molding machine (the maximum temperature of the cylinder was set at 220°C). Flame retardancy and bleedability under high temperature conditions were evaluated using each test piece. 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 electrical resistance value does not decrease significantly. From this, it can be seen that in addition to the improved bleedability under high temperature and high humidity conditions, it is also necessary to set the blending ratio of petroleum resin to 1 to 20% by weight.

Example 9 A mixture was prepared based on the following recipe using a high-density ethylene homopolymer resin (true density 0.96 g/cc; MI 12 g/cc) as the material resin (H). The mixture was then pelletized according to Example 1 using an extruder. After drying the obtained pellets at a temperature of 10 (1°C) for 3 hours, the maximum cylinder temperature of the injection molding machine was adjusted to 220°C.
C, and predetermined test pieces (for flame retardancy evaluation and bleedability evaluation) were molded. The results are shown in Table 2.

(A) Ammonium polyphosphate 25% by weight (
B) Nitrogen-containing heterocyclic organic compound 10% by weight fE
) Petroleum resin 5.0ij1% (H)
High density polyethylene 60% by weight Example 1
0 and Comparative Example 4 As the polypropylene resin (H), crystalline propylene-
Ethylene block copolymer [ethylene content 8.5% by weight, MFR (230°C; load 2.16kgf) 20g
/10m1n] 5.1kg, ammonium polyphosphate (
A) [Product name: Exolit422 (manufactured by Hoechst)
] 22.1 kg 2-biperazinylene-4-morpholino-1,3,5 as nitrogen-containing heterocyclic organic compound (B)
- Polymer of triazine (n=11, molecular weight approx. 2770
) 800g, petroleum resin (E) [Product name: Alcon P-
140 (manufactured by Arayo Kagaku Kogyo ■)] 5500g wollastonite as a fibrous filler [Product name: NYAD
-G (manufactured by NYCO) 31.5 kg and 15 g of 2.6-di-t-butyl-p-cresol as various additives
5Simiristyl-β,β-thiodipropionate 20
g and 10 g of calcium stearate were placed in a Henschel mixer (trade name) and mixed by stirring for 3 m1n.

The obtained mixture was extruded using an extruder (diameter 45 mm) at a temperature of 200° C. while melt-kneading and pelletized.

Comparative Example 5 The amount of polypropylene resin (H) in Example 1 was 5.6 kg.
Example 10 except that petroleum resin (E) was not blended.
Each compounded component was charged into a Henschel mixer (trade name) at a blending ratio based on Example 10, and extruded and pelletized with stirring and melt-kneading based on Example 10.

Examples 10 to 12 and Comparative Examples 6 and 7 Example 10 was followed except that the blending ratio of polypropylene resin (H) and petroleum resin (E) in Example 1 was changed to the blending ratio in Table 2. It was pelletized.

Examples 13 and 14 The mixture was pelletized according to Example 10, except that the blending ratio of polypropylene resin (H) and wollastonite (C) in Example 1 was changed to the blending ratio in Table 2. did.

Examples 15 and 16 The mixture was pelletized according to Example 10 using rock wool and glass fiber as the fibrous filler (C).

After drying each pellet obtained in Examples 9 to 16 or Comparative Examples 4 to 9 at a temperature of 100°C for 3 hours, the pellet was used to run an injection molding machine (the maximum temperature of the cylinder was set at 220°C). Predetermined test pieces (for flame retardancy evaluation and bleedability evaluation) were molded using the same. Each test piece was used to perform each expected evaluation. The results are shown in Table 2.

From Table 2, the following things can be seen: ・Even in the fibrous filler (C) formulation, petroleum resin (E
), the surface electrical resistance value does not significantly decrease even after immersion in boiling water, ・Bleeding property under high temperature and high humidity conditions is improved, ・Blending ratio of petroleum resin (E) is required in an amount of 1 to 20% by weight.

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

[Effects of the Invention] According to the flame-retardant formulation of the present invention, it is possible to provide a polyolefin resin composition with sustained flame resistance that is particularly useful for electrical articles.

Among these, molded products made of flame-retardant compositions of polypropylene resins show almost no bleeding of the flame-retardant imparting agent even under high temperature and high humidity conditions. The surface resistance value of the molded product is 1/1000
There are cases where it not only decreases within the range of , but actually increases.

Furthermore, by incorporating a fibrous filler (reinforcing material), mechanical strength can also be improved.

Applicant: Chisso Corporation Agent Patent Attorney Johei Yamashita 1 other person hand Continued Supplementary Positive book September 12, 1991

Claims (9)

[Claims] (1) A flame-retardant composition of polyolefin resin consisting of the following components (A), (B), (E) and (H), the total amount of which is 100% by weight: (A ) 12-25% by weight of ammonium polyphosphate or melamine-modified ammonium polyphosphate (B) 5-10% by weight of one or more selected from the following group 5-membered or more heterocycle containing 2 or more nitrogen atoms in the ring A group of reaction products between a cyclic ketone and formaldehyde consisting of a group consisting of a cyclic ketone and formaldehyde, a group of reaction products between a cyclic thioketone consisting of a five-membered or more heterocycle containing two or more nitrogen atoms in the ring and formaldehyde, or the following general formula [I 1 containing the structure represented by ],
3,5-triazine derivative group ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [I] [In the formula, X is a morpholino group or piperidino group, Y is a divalent group derived from piperazine, and n is a 2-50 is a positive number] (E) 1 to 20% by weight of petroleum resin (H) 82 to 55% by weight of polyolefin resin. (2) A cyclic ketone consisting of a five-membered or more heterocycle containing two or more nitrogen atoms in the ring is ethylene urea, or a five-membered or more heterocycle containing two or more nitrogen atoms in the ring. The cyclic thioketone consisting of is ethylenethiourea, or 1 containing the structure represented by the following general formula [I],
The 3,5-triazine derivative has a structure in which it is bonded to either a piperidino group or a morpholino group, and two or more 1,3,5-triazine rings are bonded to each other by a divalent piperazine group. The flame retardant composition according to claim 1, characterized in that: (3) Petroleum resin (E) has a softening point of 70 to 18 according to the ring and ball method.
The flame retardant composition according to claim 1, characterized in that it has a temperature of 0°C and a bromine number of 70 (Br-g/100g) or less. (4) A flame-retardant composition of polyolefin resin consisting of the following components (A), (B), (E) and (H), the total amount of which is 100% by weight: (A ) 12-25% by weight of ammonium polyphosphate or melamine-modified ammonium polyphosphate (B) 5-10% by weight of one or more selected from the following group 5-membered or more heterocycle containing 2 or more nitrogen atoms in the ring A group of reaction products between a cyclic ketone and formaldehyde consisting of a group consisting of a cyclic ketone and formaldehyde, a group of reaction products between a cyclic thioketone consisting of a five-membered or more heterocycle containing two or more nitrogen atoms in the ring and formaldehyde, or the following general formula [I 1 containing the structure represented by ],
3,5-triazine derivative group ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [I] [In the formula, X is a morpholino group or piperidino group, Y is a divalent group derived from piperazine, and n is a 2-50 is a positive number] (C) 5 to 25% by weight of fibrous filler (E) 1 to 20% by weight of petroleum resin (H) 82 to 55% by weight of polyolefin resin. (5) The flame-retardant composition according to claim 4, wherein the surface of the fibrous filler is coated with a modified polyolefin resin or modified elastomer, or treated with a silane coupling agent. (6) The polyolefin resin is polyethylene resin, polypropylene resin, poly-1-butene resin, poly-4-methyl-1-pentene resin, poly-1-hexene resin, poly-1-octene resin, and poly-1-decene resin. The flame retardant composition according to claim 1 or 4, characterized in that it is one or more resins selected from the following, or a resin blend consisting of two or more of these resins. (7) The polypropylene resin is a crystalline propylene homopolymer, propylene and ethylene whose main components are propylene,
butene-1, pentene-1, hexene-1, 4-methylpentene-1, heptene-1, octene-1, decene-1
5. The flame retardant composition according to claim 1, which is a crystalline copolymer with one or more selected from 1 or a mixture of two or more thereof. (8) An electrical device, electrical appliance, or electrical article comprising the flame retardant composition according to claim 1 or 4. (9) A board, housing, casing, or electrically insulating member for an electrical device, comprising the flame retardant composition according to claim 1 or 4.