JPH04142352A - Flame-retardant polypropylene resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. giving a molded article excellent in flame retardance and mechanical strengths by compounding a polypropylene resin with wollastonite, a polyethylene resin, a petroleum resin, a silane coupling agent, and three specific components. 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, or 1,3,5-triazine derivs. of the formula, 5-25wt.% wollastonite. 5-25wt.% polyethylene resin, 1-10wt.% petroleum resin, 3-25wt.% polypropylene modified with an unsatd. carboxylic acid, 0.3-5wt.% silane coupling agent, and 15-68wt.% polypropylene resin, the sum of all the components being 100wt.%.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to flame retardant compositions of polypropylene resin.

Specifically, it is a composition whose main component is polypropylene resin, which generates almost no corrosive or toxic gas when thermally decomposed, and the molded products obtained from it have a high degree of flame retardant performance. The present invention relates to a flame-retardant composition of polypropylene resin that has excellent mechanical strength and hardly causes a flame retardant to bleed onto the surface of the molded article under high temperature and high humidity conditions.

[Conventional technology] Polypropylene resin has traditionally been known for its hygiene, processability,
Taking advantage of 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. ing.

Originally, polypropylene resin is an easily combustible resin. However, as the applications for which it is used have expanded, polypropylene resin has also begun to be required to have performance as a flame retardant material.1. Moreover, the required performance is becoming stricter year by year. In particular, in the formulation of halogen compounds or the combination of halogen compounds and antimony oxide, which is the mainstream of conventional flame retardant technology, the toxicity of halogen gases generated during combustion or molding of flame retardant compositions has become a problem. being watched.

Therefore, flame-retardant polypropylene resins are required to not generate these halogen-based gases either during combustion or molding. In order to meet this demand, various flame-retardant polypropylene 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. (For example, magnesium hydroxide, aluminum hydroxide, hydrotalcite, etc.) is added to polypropylene resin or JP-A-52-14
As disclosed in JP-A No. 6452 and JP-A-59-147050, ammonium phosphate (or amine phosphate) and the group >C=O (or >C=S or >NH) inserted into the cyclic structure are Compositions have been proposed in which a reaction product of a nitrogen-containing compound and an aldehyde or an oligomer (or polymer) of a 1,3,5-triazine derivative is added to a 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 and JP-A-59
-1471) The flame-retardant polypropylene resin composition disclosed in Publication No. 50 has relatively little deterioration in moldability, and the generation of corrosive gas or toxic gas during processing or combustion is suppressed to a low level. .

However, when a filler, which is normally used in polypropylene resin, is added to improve the mechanical strength of the composition, the hygroscopicity of ammonium phosphate (or amine phosphate) in the composition makes it difficult to use during the rainy season. Under such high-temperature conditions, severe bleeding of ammonium phosphate (or amine phosphate) onto the surface of the molded product occurs. This bleed significantly lowers the electrical resistance of the molded product, leaving the drawback that it cannot be used as an electrical insulating material under high temperature and high humidity conditions. In addition, a test (hereinafter referred to as
In the UL94 flammability test), it is difficult to achieve a flammability rank of ■-0 with a test piece having a wall thickness of 1/32 inches.

[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. It is a flame-retardant formulation of polypropylene resin that does not cause any flame retardant, and the molded products obtained from it have both a high degree of flame retardancy and excellent mechanical strength. We have conducted extensive research in order to obtain a flame retardant composition of polypropylene resin that can form molded articles with almost no bleeding of the flame retardant component.

As a result, it was discovered that the flame retardant composition described below is substantially free from the above-mentioned problems, and based on this knowledge, the present invention was completed.

As is clear from the above description, the object of the present invention is to solve the above-mentioned problems and to provide a flame-retardant composition of polypropylene resin that can form molded articles having a high degree of flame retardancy and excellent mechanical strength. Our goal is to provide the following.

Means for Solving Problem C] The flame-retardant composition of polypropylene resin of the present invention has the following configuration.

The following components (A), (B), (C), (D), (E),
A flame-retardant composition of polypropylene resin comprising (F), (G) and (H), the total amount of which is 100% by weight: (A) polyphosphoric acid Ammonium or melamine-modified ammonium polyphosphate 12-25% by weight (B) 5-10% by weight of one or more selected from the following group (B1) 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 (B2) 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 (B3) A group of 1,3,5-triazine derivatives containing the structure represented by the following general formula [I] [wherein, X is a morpholino group or a piperidino group, Y is a divalent group derived from piperazine, and n is is a positive number from 2 to 50], (C) Wollastonite 5 to 25% by weight (D)
Polyethylene resin 5-25% by weight (E) Petroleum resin 1-10% by weight (F) Unsaturated carboxylic acid-modified polypropylene 3-25% by weight (G) Silane coupling agent 0.3-5% by weight (H)
Polypropylene resin 15 to 68% by weight Examples of the polypropylene resin that serves as the base material of the composition of the present invention include: - Crystalline propylene homopolymer - Propylene is the main component, and one of the following 1-olefins
Crystalline random copolymer or crystalline block copolymer containing ethylene, l-butene, l-pentene, 1-hexene, 4-methyl-1-pentene, 1-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 desirable as the molding material for the molded article.

A suitable crystalline polypropylene resin constituting the composition of the present invention has an MFR (230°C; 2.16 kgf) usually 0.1 to 50 g/10 m1n, preferably 1 to 30 g
/10m1n.

Preferred ammonium polyphosphates or melamine-modified ammonium polyphosphates used in the present invention as component (A) are those represented by the general formula (NH4POs) (a positive number of n250 or more).

Preferred commercially available ammonium polyphosphates include those shown below.

Product name: Sumisafe P (manufactured by Sumitomo Chemical) and product name:
Exolit 422 (manufactured by Hoechst): Commercially available melamine-modified ammonium polyphosphates include those shown below.

Product name: Sumisafe PM (manufactured by Sumitomo Chemical) and product name:
Exolit 462 (manufactured by Hoechst).

The blending ratio of the ammonium polyphosphate is usually 12 to 25% by weight, preferably 14 to 21% by weight based on the composition. When the blending ratio is 10% by weight or less, it has a high degree of flame retardancy.It has a V-
A composition that achieves 0 is not obtained, and even if it is blended in an amount exceeding 28% by weight, there is hardly any further improvement in flame retardancy.

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 5-membered or more heterocycle containing 2 or more nitrogen atoms in the ring, ・5-membered or more heterocycle containing 2 or more nitrogen atoms in the ring A group of reaction products of a cyclic thioketone consisting of a ring and formaldehyde, or 1゜3 containing a structure represented by the following general formula [I]
, 5-) riazine 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 from 2 to 50], these are ammonium polyphosphate or melamine modified Ammonium polyphosphate (A) and polypropylene resin (H)
One or two organic compounds that can produce almost only carbonaceous residue together with non-flammable gases (water, carbon dioxide, ammonia, nitrogen, etc.) by ignition or thermal decomposition by contact with flame, etc. It is a mixture or reaction product of more than one species.

Examples of these nitrogen-containing heterocyclic organic compounds include ethylene urea, ethylene thiourea, hydantoin, hexahydropyrimidin-2-one, piperazine-3,6-thion, barbylic acid and reaction products of these with aldehydes, or 2-piverazinylene-4-morpholino-1
, 3,5-triazine oligomers or polymers,
Examples include oligomers or polymers of 2-biverazinylene-4-piperidino-1,3,5-triazine.

Among these, the following are preferred from the viewpoint of imparting a high degree of flame retardancy. : (B1) A reaction product of ethylene urea and formaldehyde, (B2) A reaction product of ethylene thiourea and formaldehyde, or (B3) 1 having a structure represented by the following - large amount [I],
3゜Oligomers or polymers of 2-biverazinylene-4-morpholino-1,3,5-)riazine which are 5-triazine derivatives, and 2-biverazinylene-4-piperidino-1,3,5-
) 1,1 azide oligomer or polymer [wherein X is a morpholino group or a piperidino group, Y is a divalent group derived from piperazine, and n is an integer of 2 to 50; The compounding ratio of compound (B) is usually 5 to 10% based on the composition. If the blending ratio is less than 3% by weight, a composition that achieves ■-0 in a 1732-inch wall thickness test piece of the UL94 flame test, which is highly flame retardant, cannot be obtained; It is difficult to expect flame retardancy to improve beyond this level.

In addition, a reaction product of the above-mentioned ethylene urea and formaldehyde, which is one type of the nitrogen-containing heterocyclic organic compound, or a reaction product of ethylene thiourea and formaldehyde, or 2-biverazinylene-4-morpholino-1,3,
Oligomers or polymers of 5-triazine and 2
The oligomer or polymer of -biperazinylene-4-piperidino-1,3,5-triazine can be obtained, for example, by the following method.

Reaction of ethylene thiourea with formaldehyde To obtain the acid product, dissolve 50 g of ethylene thiourea in a volume of 1 liter of water and adjust the pH in the solution to 2 by mixing dilute acid (for example sulfuric acid or phosphoric acid). and the reaction solution was diluted with 9
Heating to 0°C, the aqueous solution of 37% by weight formaldehyde is added dropwise to the ethylenethiourea solution until the CH2O/ethylenethiourea molar ratio is 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. Furthermore, a reaction product of ethylene urea and formaldehyde can also be obtained by the same method as above.

To obtain oligomers or polymers of 2-biverazinylene-4-morpholino-1,3,5-triazine, proceed as follows: equimolar 2,6-cyhalo-4-morpholino-1,3,5
- triazine (e.g. 2,6-dichloro-4-morpholino-1,3,5-triazine or 2,6-dipromo-4-morpholino-1,3,5-triazine) and piperazine with an organic or inorganic base (e.g. triethylamine) , tributylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, etc.) in an inert solvent such as xylene under heating, preferably at a temperature below the boiling point of the inert solvent. After the reaction is completed, the reaction mixture is filtered to separate the solids, the solids are washed with boiling water to remove by-product salts by dissolving them in the boiling water, and the remaining solids are dried. . The properties of the obtained 2-piperazine-4-morpholino-1゜3,5-triazine polymer are that it is insoluble in water and ordinary organic solvents, and has no melting point (decomposition temperature of about 304℃, true density of 0.3g). /cc, n = 1
1, the molecular weight was 2770.

Also, when obtaining an oligomer or polymer of 2-piverazinylene-4-piperidino-1,3゜5-triazine, 2,6-cyhalo-4-piperidino-1,3,5
- The same method as above can be applied using triazine as a raw material.

Wollastonite (C) used in the present invention is obtained by crushing and refining natural wollastonite, and has a chemical structure of β-calcium silicate (β-CaSiOs), and its shape may be rod-like or Fibrous ones are preferred. The blending ratio of the wollastonite is 5 to 25% of the composition.
% by weight, preferably 10-20% by weight. When the blending ratio is 3% by weight or less, the mechanical strength of the composition is deteriorated, while when it is 27% by weight or more, the content ratio of the polypropylene resin in the composition becomes too small, resulting in a decrease in moldability of the composition. It doesn't fall within the permissible range.

The polyethylene resin used in the present invention may be high-density polyethylene, medium-density polyethylene, or low-density polyethylene, but in order to prevent a decrease in the rigidity of the molded product, high-density polyethylene (density 0.94 g/cc or more) is used. It is desirable to do so.

The blending ratio of the polyethylene resin is 5 to 25% based on the composition.
% by weight, preferably 7-20% by weight. If the blending ratio is less than 3% by weight, it is extremely difficult to achieve v-0 in a UL94 flame test with a wall thickness of 1/32 inch, which is a high degree of flame retardancy. It becomes extremely difficult to achieve flame retardancy.

The petroleum resin (E) used in the present invention is useful as a petrochemical raw material from diolefins and monoolefins and/or aromatic compounds contained in cracked oil fractions generated during petroleum refining, petroleum cracking, etc. Thermoplastic material obtained by thermal polymerization or cationic polymerization of diolefins, monoolefins, and/or aromatic compounds remaining after removing and comparing 1-olefins of 02 to C1 degrees, diolefins of C4, Cs, and benzene, toluene, xylene, etc. It is resin. C6 (aliphatic) petroleum resin made from C5 fraction among cracked oil fractions, C8 (aromatic) petroleum resin made from C, fraction, and Cs made from a mixture of both. Co-copolymerized petroleum resins, dicyclopentadiene-based petroleum resins made from dicyclopentadiene obtained by thermal dimerization of cyclopentadiene contained in the C3 fraction, and double bonds in the above petroleum resins. Examples include hydrogenated (hydrogenated) products (alicyclic). In particular, alicyclic petroleum resins are preferred because they have excellent heat resistance and weather resistance. For the purpose of the present invention, the petroleum resin (E) has a softening point of 70 to 70 by the ring and ball method.
180°C, preferably 70 to 140°C, the hue is 15 or less according to the Gardner method, and the bromine number is 70 Br.
-g/100g or less, preferably 30Br-g/100
Use one with a weight of less than g.

The blending ratio of the petroleum resin is 1 to 10% by weight based on the composition,
Preferably it is 3 to 7% by weight. If the blending ratio is less than 0.5% by weight, the bleed prevention effect under high humidity conditions will not reach the desired level. On the other hand, if it exceeds 12% by weight, the impact resistance decreases and the good mechanical strength inherent to polypropylene is lost.

The unsaturated carboxylic acid-modified polypropylene used in the present invention is a polar group-containing polypropylene resin obtained by grafting polypropylene resin with one or more compounds selected from unsaturated carboxylic acids or their anhydrides. .

Examples of the carboxylic acid include the following: maleic acid, acrylic acid, methacrylic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, incrotonic acid, mesaconic acid, angelic acid, and anhydrides of the carboxylic acid. Examples include the following: maleic anhydride, citraconic anhydride, itaconic anhydride, and the like.

Among them, maleic anhydride gives favorable results in terms of adhesion and the like. Examples of the polypropylene resin used as the raw material for the unsaturated carboxylic acid-modified polypropylene include the following.

・Crystalline propylene homopolymer, ・Mainly composed of propylene, containing one of the following 1-olefins:
Crystalline random copolymer or crystalline block copolymer containing at least one species as a subcomponent; ethylene, 1-butene, l-
Pentene, 1-hexene, 4-methyl-1-pentene,
1-heptene, 1-octene and 1-decene.

A mixture of two or more of these crystalline polymers can also be exemplified as a suitable material resin blend.

Examples of methods for grafting polypropylene containing unsaturated carboxylic acid or anhydride thereof include the following two methods: - In an extruder containing polypropylene, unsaturated carboxylic acid or anhydride thereof, and organic peroxide. A method of melt-kneading; - A method of adding an unsaturated carboxylic acid or its anhydride and an organic peroxide to polypropylene suspended or dissolved in a suitable solvent and stirring with heating.

The blending ratio of the unsaturated carboxylic acid-modified polypropylene is 3 to 25% by weight, preferably 5 to 15% by weight, based on the composition. If the blending ratio is less than 3% by weight, it is hardly possible to achieve excellent mechanical strength, and only molded products with insufficient impact resistance are obtained. On the other hand, even if the content exceeds 25% by weight, it is difficult to expect an improvement in mechanical strength beyond that.
Furthermore, flame retardancy deteriorates.

The silane coupling agent used in the present invention includes a large amount of R'R''5iXa [here, R1 is a hydrocarbon group containing a chlorine atom, a vinyl group, an amino group and/or a mercapto group, etc. or a hydrolyzable organic group such as a halogen atom. R2 is R1 or X, and if two or more Xs are present, they may be different from each other. Examples of the silane compounds include the following: vinyltrimethoxysilane, vinylethoxysilane, 3-aminopropyltriethoxysilane, N-(2-
aminoethyl)-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3
-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc.

One or more of these silane compounds can be used in the form of a mixture or two or more can be used in combination. Among them, it is preferable to use 3-aminopropyltriethoxysilane alone or in combination with vinyltrimethoxysilane and 3-aminopropyltriethoxysilane. The blending ratio of the silane coupling agent to the composition is 0,
3 to 5% by weight, preferably 0.5 to 3% by weight. If the blending ratio is less than 0.41% by weight, excellent mechanical strength cannot be achieved and only a molded product with insufficient impact resistance can be obtained. On the other hand, if it exceeds 7% by weight, it is difficult to expect any further improvement in mechanical strength (not only that, but the flame retardancy will actually decrease).

In preparing the flame retardant composition of the present invention, various additives that are usually added to the base polypropylene resin, such as antioxidants, ultraviolet inhibitors, antistatic agents, copper inhibitors, lubricants,
Hydrochloric acid neutralizers (metal stearate, hydrotalcite, etc.), pigments, etc. can be used in combination as appropriate.

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

That is, polypropylene resin, the above-mentioned ammonium polyphosphate or melamine-modified ammonium polyphosphate, one or more mixtures selected from the nitrogen-containing heterocyclic organic compounds specified above, wollastonite, polyethylene resin, petroleum resin, Predetermined amounts of unsaturated carboxylic acid-modified polypropylene, a silane coupling agent, and the various additives mentioned above are charged into a stirring mixing device such as a Henschel mixer (trade name), a super mixer, a tumbler mixer, or the like. After stirring and mixing for 1 to 10 minutes, the resulting mixture is charged into a roll mixer, screw extruder, or the like, and melt mixed (at a temperature of 170 to 220°C) and pelletized.

[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) Conforms to the vertical combustion test of Flame Retardant UL Subject 94 (Underwriter Laboratories, Inc.) "Flammation Test of Plastic Materials for Parts of Vessels". The wall thickness of the test piece was 0.8 mm (1/32 inch).

2) Bleedability evaluation test piece under high temperature and high humidity conditions (length 95 mm 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 vibration volume type microcurrent electrometer (Takeda). Next, the test piece was measured in a constant temperature and humidity chamber [temperature 80°C, humidity 80% (Tabai M
(manufactured by GF)], and each mortar was taken out. Before taking out each test piece, place it in a constant temperature dryer (temperature controlled at 80°C).
After drying for 2 hours in a test piece (manufactured by Sanyo Electric Co., Ltd.) and left overnight in a desiccator at room temperature, the surface electrical resistance value of the test piece was measured.

If the surface electrical resistance value of the test piece significantly decreases after being taken out from the constant temperature and humidity chamber, it is considered to have poor bleed resistance under high temperature and high humidity conditions. The number of days until the surface electrical resistance value decreased was investigated.

3) Production example of maleic anhydride-modified polypropylene Polypropylene resin had an ethylene component content of 8% by weight, a melt flow rate (temperature of 230°C, load of 2.16 kgf).
) 10 kg of crystalline propylene-ethylene block copolymer of 2.8 g/10 m1n, 50 g of maleic anhydride as the unsaturated carboxylic acid, 8 g of 1,3-bis(t-butylperoxyisopropyl)benzene as the organic peroxide.
10 g of 2.6-sheet t-petitlou p-cresol and 10 g of calcium stearate as various additives were placed in a Henschel mixer (trade name) and mixed with stirring for 53 minutes. The obtained mixture was melt mixed (temperature: 200° C.) and then extruded using an extruder (bore diameter: 45 mm) to form pellets.

The maleic anhydride component content of the obtained modified polypropylene was 0.27% by weight.

Example 1 and Comparative Example 1 As polypropylene resin (H), crystalline propylene-
Ethylene block copolymer [ethylene component content 8.5
Weight %, MFR (A degree 230” C1 load 21 kgf)
20g/10m1n] 2.7kg, ammonium polyphosphate (A) [Product name: Exo1it422 (manufactured by Hoechst, 2.1kg per month, nitrogen-containing heterocyclic organic compound (B)
as 2-biperazinylene-4-morpholino-1,3,
5-) Polymer of riazine (degree of polymerization n = specific molecular weight approximately 27
70) 800g, Wolastonite (c) [Product name:
NYAD-G (manufactured by NYCO) 11.5 kg, crystalline ethylene homopolymer [as polyethylene resin (D)]
MI (temperature 190'C; load 2.16kgf) 6.5
g/10m1n, density 0.95g/ccl 1.5k
g, petroleum resin (E) [mProduct name: Alcon P-140
(manufactured by Arayo Kagaku Kogyo ■) 1,500 g, and 800 g of maleic anhydride-modified polypropylene as unsaturated carboxylic acid-modified polypropylene (F).

As the silane coupling agent (G), 3-aminopropyltriethoxysilane [Product name: Sila Ace 5330]
(manufactured by Chisso Corporation)] 1100g 26 as various additives
-di-t-butyl-p-cresol (BHT) 15g
, Simiristyl-β, β-thiodipropionate (D
MyTDP) 20g and calcium stearate 10g
The mixture was placed in a Henschel mixer (trade name) and stirred and mixed for 3 minutes. The obtained mixture was melt mixed (temperature: 200°C) and extruded using an extruder (diameter: 45 mm) to obtain a pellet of a flame-retardant composition.

Comparative Example 1 The amount of polypropylene resin (H) was 5.6 kg, polyethylene resin (D), petroleum resin (E), maleic anhydride-modified polypropylene (F), and silane coupling agent (
Except for not including any of G), each compounded component was charged into a Henschel mixer (trade name: N) at the compounding ratio according to Example 1, and stirred, mixed, melt-kneaded, and extruded according to Example 1. As a result, a pellet of flame retardant composition was obtained.

Comparative Examples 2 to 5 A composition containing no polyethylene resin (D), a composition containing no petroleum resin (E), a composition containing no maleic acid-modified polypropylene (F), or a silane coupling agent (G), respectively. Create a composition without blending, and
Each composition was made into pellets according to Example 1 except that the blending ratios were changed as shown in the table.

Example 2 A composition was pelletized according to Example 1, except that a reaction product of ethylene urea and formaldehyde was used as the nitrogen-containing heterocyclic organic compound fB).

Comparative Examples 6 to 8 Based on Example 1 except that the blending ratios of ammonium polyphosphate (A), nitrogen-containing heterocyclic organic compound (B), and wollastonite (C) were changed to the blending ratios shown in Table 1. Each composition was made into a pellet.

The pellets obtained in Examples 1 to 2 and Comparative Examples 1 to 8 were
After drying at a temperature of 00°C for 3 hours, the pellets were formed into predetermined test pieces for evaluating flame retardancy and bleedability using an injection molding machine (the maximum temperature of the cylinder was set at 220°C).

Using each test piece, flame retardancy and bleedability under high temperature and high humidity conditions were evaluated. The results are shown in Table 1.

From Example 1 and Comparative Examples 1 to 5 in Table 1, one of the following components is missing: polyethylene resin (D), petroleum resin (E), maleic anhydride-modified polypropylene (F), and silane coupling agent (G). However, it can be seen that the bleedability, surface electrical resistance, mechanical strength and high flame retardance under high temperature and high humidity conditions cannot be achieved.

Furthermore, preferred blending ratios of ammonium polyphosphate (A), nitrogen-containing heterocyclic organic compound CB), and wollastonite (C) can be seen from Example 2 and Comparative Examples 6 to 8.

Example 3, Example 4 and Comparative Example 9 Polypropylene resin (H) and polyethylene resin (D)
In addition to changing the blending ratio of to the blending ratio in Table 2,
Each composition was pelletized according to Example 1.

After drying the pellets obtained in Example 3, Example 4, and Comparative Example 9 at a temperature of 100°C for 3 hours, the pellets were molded into an injection molding machine (the maximum temperature of the cylinder was set at 220°C) to improve flame retardancy and Predetermined test pieces for evaluation of bleedability were molded. Using this test piece, flame retardancy and bleedability under high temperature and high humidity conditions were evaluated. The results are shown in Table 2.

From Table 2, the blending ratio of polyethylene resin FD) is 5~
It turns out that 25% by weight is preferred.

Example 5, Example 6 and Comparative Example 10 Each composition was prepared 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 3. Pelleted.

After drying the pellets obtained in Example 5, Example 6, and Comparative Example 10 at a temperature of 100°C for 3 hours, the pellets were molded into an injection molding machine (the maximum temperature of the cylinder was set at 220°C) to improve flame retardancy and Predetermined test pieces for evaluation of bleedability were molded. Using this test piece, flame retardancy and bleedability under high temperature and high humidity conditions were evaluated. The results are shown in Table 3.

From Table 3, it can be seen that the blending ratio of petroleum resin is preferably 1 to 10% by weight.

Example 7, Example 8, and Comparative Example 11 Each product was prepared in accordance with Example 1, except that the blending ratios of polypropylene resin (H) and maleic anhydride-modified polypropylene (F) were changed to the blending ratios shown in Table 4. The composition was pelletized.

Example 9, Example 1o and Comparative Example 12 Polypropylene resin (H) and silane coupling (G
) Each composition was pelletized in accordance with Example 1, except that the blending ratio of the agent was changed to the blending ratio shown in Table 4.

Example 11 and Comparative Example 12 As the silane coupling agent (G), 3-aminopropyltriethoxysilane [trade name: Sila Ace 5330
(manufactured by Chisso ■) 1 and vinyltrimethoxysilane [product name: Sila Ace 5210 (manufactured by Chisso ■) 1 = 1
Each composition was prepared according to Example 1, except that the blending ratio of polypropylene resin (H) and Silane Cup 2 nonglue (G) was changed to the blending ratio shown in Table 4. Pelleted.

From Example 7, Example 8, and Comparative Example 11 in Table 4, the blending ratio of unsaturated carboxylic acid-modified polypropylene (F) is 3 to 3.
It turns out that 25% by weight is preferred.

Furthermore, from Examples 9 to 12 and Comparative Example 12, the blending ratio of the silane coupling agent (G) is preferably 0.3 to 5% by weight, and two or more types of silane coupling agents may be used in combination. I understand.

[Effect of the invention] The molded product obtained from the flame-retardant and electrically insulating composition of the present invention hardly causes the flame retardant component to bleed onto the surface of the molded product even under high temperature and high humidity conditions, and has a high degree of flame retardancy. It has excellent mechanical strength while retaining its properties and surface electrical resistance.

Furthermore, the flame-retardant and electrically insulating composition of the present invention is a flame-retardant polypropylene resin composition that does not generate halogen gas during molding or thermal decomposition, and its properties can be utilized to create buildings, electrical products, etc. It can be suitably used for manufacturing automobile parts, etc.

Applicant: Chisso Co., Ltd. Company agent: Patent attorney: Tsuki Yamashita, 1 non-Heitai patent attorney, September 12, 1991, Patent Application No. 1990 1
Patent Application No. 3' filed on October 30th (2) Name of the invention Flame-retardant composition of polypropylene resin 3 Relationship to the case of person making an amendment Patent No. 3 'I' l+I applicant's address Kita-ku, Osaka City, Osaka Prefecture 3-6-32 Nakanoshima Name Chisso Corporation Representative Sadao Nogi 4゜Address Name (zip code 141) 15-13 Shigotan-ni-chome, Tokyo Parts Ward New Heights Nishigotan 1η804 [71 Call Tokyo (3492) 5690] (8057) Patent Attorney Excerpt 1) "Claims" and "Detailed Description of the Invention j" columns of Haruo's amended competing specification.

As per the supplementary IL content attachment (no changes to the content except for the section ``technique'' written in the column subject to amendment) Description 1, name of the invention Flame-retardant composition of polypropylene resin 2, claims (1) ) The following components (A), (B), (C), (D), (E
), (F), (G) and (H), and the total amount thereof is 100% by weight. (A) Polypropylene resin flame retardant composition (A) Ammonium phosphate or melamine-modified ammonium polyphosphate 12 to 25% by weight (B) 5 to 10% by weight of one or more selected from the following group (B1) Five-membered or more heterocyclic compound containing two or more nitrogen atoms in the ring A group of reaction products of a cyclic ketone consisting of a ring and formaldehyde, (B2) a group of reaction products of a cyclic thioketone consisting of a five-membered or more heterocycle containing two or more nitrogen atoms in the ring and formaldehyde, or (B3 ) 1,3.5-) Reazine derivative group containing the structure represented by the following general formula [I] [wherein, X is a morpholino group or a piperidino group, Y is a divalent group derived from piperazine, n is a positive number from 2 to 50, (C) Wollastonite 5 to 25% by weight (D)
Polyethylene resin 5-25% by weight (E) Petroleum resin 1-10% by weight (F) Unsaturated carboxylic acid-modified polypropylene 3-25% by weight (G) Silane coupling agent 0.3-5% by weight (H)
Polypropylene resin 15-68% by weight (2) 21
A cyclic ketone consisting of a 5 or more membered heterocycle containing one or more nitrogen atoms in the ring is ethylene urea, or a cyclic thioketone consisting of a 5 or more membered heterocycle containing 2 or more nitrogen atoms in the ring is ethylenethiourea, or 1, 3 containing the structure represented by the above general formula [I]
．． 5-) A riazine derivative is bonded to one or more piperidino groups or morpholino groups, and two or more 1.3.5-
2. The flame retardant composition according to claim 1, wherein the triazine rings are interconnected by divalent piperazine groups.

(3) The softening point of the petroleum resin is 70 to 180°C by the ring and ball method.
The flame retardant composition according to claim 1 or 2, characterized in that it has a bromine number of 70 (Brg/100g) or less.

(4) The polypropylene resin is a crystalline propylene homopolymer, a copolymer mainly composed of propylene, which includes propylene and ethylene, l-phthene, 1-pentene, l-hexene, 4-methyl-1-pentene, 1-heptene, 1
The flame retardant composition according to any one of claims 1 to 3, which is a crystalline copolymer with one or more selected from the group of -octene and 1-decene, or a mixture of two or more thereof.

(5) An electrical device, electrical appliance, or electrical article comprising the flame retardant composition according to any one of claims 1 to 4.

(6) A substrate, housing, casing or electrical insulating member for an electrical device, characterized by being made of the flame retardant composition according to any one of claims 1 to 4.

3. Detailed description of the invention [Industrial application fields] The present invention relates to flame retardant compositions of polypropylene resin.

Specifically, it is a composition whose main component is polypropylene resin, which generates almost no corrosive or toxic gas when thermally decomposed, and the molded products obtained from it have a high degree of flame retardant performance. The present invention relates to a flame-retardant composition of polypropylene resin that has excellent mechanical strength and hardly causes a flame retardant to bleed onto the surface of the molded article under high temperature and high humidity conditions.

[Conventional technology] Polypropylene resin has traditionally been known for its hygiene, processability,
Taking advantage of 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. ing.

Originally, polypropylene resin is an easily combustible resin. However, with the expansion of the applications in which polypropylene resin is used, performance as a flame retardant material has begun to be required of polypropylene resin, and the required performance is becoming stricter year by year. In particular, in the formulation of halogen compounds or the combination of halogen compounds and antimony oxide, which is the mainstream of conventional flame retardant technology, the toxicity of halogen gases generated during combustion or molding of flame retardant compositions has become a problem. being watched.

Therefore, flame-retardant polypropylene resins are required to not generate these halogen-based gases either during combustion or molding. In order to meet this demand, various flame-retardant polypropylene resin compositions have been proposed.

For example, JP-A-53-92855, JP-A-54-12
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. (For example, magnesium hydroxide, aluminum hydroxide, hydrotalcite, etc.) is added to polypropylene resin or JP-A-52-14
As disclosed in JP-A No. 6452 and JP-A-59-147050, containing ammonium phosphate (or amine phosphate and a group >C=a (or >C=S or >NH) inserted into a cyclic structure) Compositions have been proposed in which a reaction product of a nitrogen-containing compound and an aldehyde or an oligomer (or polymer) of a 1,3,5-triazine derivative is added to a 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, such as a composition in which magnesium hydroxide is added, a large amount of the hydrous inorganic compound must be added. , the composition often suffers from a decrease in moldability.

Also, JP-A-52-146452 and JP-A-59
The flame-retardant polypropylene resin composition disclosed in JP-147050 has relatively little deterioration in molding processability.
The generation of corrosive or toxic gases during processing or combustion is also suppressed.

However, when a filler that is commonly used in polypropylene resin is added to improve the mechanical strength of the composition, ammonium phosphate (or amine phosphate) in the composition
Due to its hygroscopicity, under high temperature and high humidity conditions such as during the rainy season,
Ammonium phosphate (or amine phosphate) on the surface of the molded product
A severe bleed phenomenon occurs. This bleed significantly reduces the electrical resistance value of the molded product, leaving the drawback that it cannot be used as an electrical insulating material under high temperature and high humidity conditions. In addition, a test (hereinafter referred to as
In the "UL94 flammability test"), it is difficult to achieve a flammability rank of V-0 for a test piece with a wall thickness of 1732 inches.

[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. It is a flame-retardant formulation of polypropylene resin that does not cause flame-retardants, and the molded products obtained from it have both a high degree of flame retardancy and excellent mechanical strength. In order to obtain a flame retardant composition of polypropylene resin that can form a molded article with almost no bleeding of the flame retardant component, we conducted extensive research.

As a result, it was discovered that the flame retardant composition described below is substantially free from the above-mentioned problems, and based on this knowledge, the present invention was completed.

As is clear from the above description, the object of the present invention is to solve the above-mentioned problems and to provide a flame-retardant composition of polypropylene resin that can form molded articles having a high degree of flame retardancy and excellent mechanical strength. To provide (this).

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

The following components (A), (B), (C), (D), (E), (
A flame-retardant composition of polypropylene resin (A) PolyJ [2 Ammonium or melamine-modified ammonium polyphosphate 12-25% by weight (B) 5-10% by weight of one or more selected from the following group (B1) 5-membered or more heterocycle containing 2 or more nitrogen atoms in the ring A reaction product group of a cyclic ketone and formaldehyde consisting of (B2), 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 (B2) B3) 1 containing a structure represented by the following general formula m,
3.5-) riazine 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 from 2 to 50], (C) Wollastonite 5-25% by weight (D)
Polyethylene resin 5-25% by weight (E) Petroleum resin 1-10% by weight (F) Unsaturated carboxylic acid-modified polypropylene 3-25% by weight (G) Silane coupling agent 0.3-5% by weight (H)
Polypropylene resin 15 to 68% by weight Examples of the polypropylene resin serving as the base material of the composition of the present invention include: - Crystalline propylene homopolymer - Propylene is the main component, and one of the following 1-olefins:
Crystalline random copolymer or crystalline block copolymer containing ethylene, 1-phthene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-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 desirable as the molding material for the molded article.

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

Preferred ammonium polyphosphate or melamine-modified ammonium polyphosphate as component (A) used in the present invention is the general formula (NH4PO,). (a positive number of 8250 or more).

Preferred commercially available ammonium polyphosphates include those shown below.

Product name: Sumisafe P (manufactured by Sumitomo Chemical Co., Ltd.) and product name: E
xolit 422 (manufactured by Hoechst) Commercially available melamine-modified ammonium polyphosphates include those shown below.

Product name, Sumisafe PM (manufactured by Sumitomo Chemical Co., Ltd.) and product name:
Exolit 462 (manufactured by Hoechst).

The blending ratio of the ammonium polyphosphate is usually 12 to 25% by weight, preferably 14 to 21% by weight based on the composition. If the blending ratio is 10% by weight or less, it is highly flame retardant.V-
A composition that achieves 0 is not obtained, and even if it is blended in an amount exceeding 28% by weight, there is hardly any further improvement in flame retardancy.

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 a cyclic ketone consisting of a 5-membered or more heterocycle containing 2 or more nitrogen atoms in the ring, ・A group of reaction products of 5-membered or more heterocycle containing 2 or more nitrogen atoms in the ring 13. A group of reaction products of a cyclic thioketone consisting of a heterocycle and formaldehyde, or a structure represented by the following general formula [I].
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], these are ammonium polyphosphate or melamine-modified polyphosphoric acid Polypropylene resin (H) with ammonium (A)
One or two organic compounds that, when present in the liquid, can produce almost only a carbonaceous residue together with non-flammable gases (water, carbon dioxide, ammonia, nitrogen, etc.) by thermal decomposition due to ignition or contact with flame, etc. It is a mixture or reaction product of more than one species.

Examples of these nitrogen-containing heterocyclic organic compounds include ethylene urea, ethylene thiourea, hydantoin, hexahydropyrimidin-2-one, piperazine-3,6-dione, barbylic acid and reaction products of these with aldehydes, or 2-piperadiene-4-morpholino-1
,3,5-triazine oligomer or polymer
Examples include oligomers or polymers of 2-piperadiene-4-piperidino-1,3,5-triazine.

Among these, the following are preferred from the viewpoint of imparting a high degree of flame retardancy.

(B1) A reaction product between ethylene urea and formaldehyde (B2) A reaction product between ethylene thiourea and formaldehyde, or (B3) 1 having a structure represented by the following - large amount [I],
2-piperazinylene-4, a 35-triazine derivative
Oligomers or polymers of morpholino-1,3,5-) riazine and 2-piverazinylene-4-piperidino-1,3,5-
) Liazi oligomer or polymer [wherein, X is a morpholino group or a piperidino group, Y is a divalent group derived from piperazine, and n is an integer of 2 to 50], ) is usually added in an amount of 5 to 10% by weight based on the composition. If the blending ratio is less than 3% by weight, a composition that achieves V-0 in a 1732-inch thick test piece of the UL94 flame test, which is highly flame retardant, cannot be obtained; on the other hand, even if the blending ratio is 13% by weight, It is difficult to expect flame retardancy to improve beyond this level.

In addition, a reaction product of the above-mentioned ethylene urea and formaldehyde, which is one type of the nitrogen-containing heterocyclic organic compound, or a reaction product of ethylene thiourea and formaldehyde, or 2-biverazinylene-4-morpholino-1,3,
5-) Lyazine oligomer or polymer subunit 2
The oligomer or polymer of -piperadiene-4-piparidino-1,3,5-1 riazine can be obtained, for example, by the following method.

To obtain a reaction product of ethylene thiourea and formaldehyde, dissolve 50 g of ethylene thiourea in 1 liter of water and adjust the pH of the solution to 2 by mixing with a dilute acid (e.g. phosphoric acid for sulfuric acid). The reaction solution was adjusted to 9.
Heating to 0°C, the aqueous solution of 37% by weight formaldehyde is added dropwise to the ethylenethiourea solution until the molar ratio of CH2O/ethylenethiourea is equal to 2 and stirred 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, a reaction product of ethylene urea and formaldehyde can also be obtained by the same method as above.

2-piverazinylene-4-morpholino-1,3,5-)
To obtain oligomers or polymers of lyazine, equimolar amounts of 2,6-cyhalo4-morpholino-1,3,5 are prepared as follows.
-triazine (e.g. 2,6-dichloro-4-morpholino-1,3,5-triazine or 2,6-dipromo-4
-morpholino-1,3,5-)riazine) and piperazine with an organic or inorganic base (e.g. triethylamine,
tributylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, etc.) in an inert solvent such as xylene under heating, preferably at a temperature below the boiling point of the inert solvent. After the reaction is completed, the reaction mixture is filtered to separate the solids, the solids are washed with boiling water to remove by-product salts by dissolving them in the boiling water, and the remaining solids are dried. .

Obtained 2-piperazine-4-morpholino-1,3,5
- The properties of the triazine polymer are insoluble in water and ordinary organic solvents, no melting point, decomposition temperature of about 310°C, true density of 1.2 g/cc, degree of polymerization n; 11, and molecular weight of 27.
It was 70.

Also, when obtaining an oligomer or polymer of 2-piperadiene-4-piperidino-1,3゜5-triazine, 2.6-dihalo-4-piperidino-1,3,5
- The same method as above can be applied using triazine as a raw material.

Wollastonite (C) used in the present invention is obtained by crushing and refining natural wollastonite, and has a chemical structure of β-calcium silicate (β-CaSiO3), and its shape may be rod-like or Fibrous ones are preferred. The blending ratio of the wollastonite is 5 to 25% of the composition.
% by weight, preferably 10-20% by weight. If the blending ratio is less than 3% by weight, the mechanical strength of the composition will decrease, while if it is more than 27% by weight, the content of the polypropylene resin in the composition will be too small, resulting in a decrease in moldability of the composition. is no longer within the permissible range.

The polyethylene resin (D) used in the present invention may be high-density polyethylene, medium-density polyethylene, or low-density polyethylene, but in order to prevent a decrease in the rigidity of the molded product, it is necessary to ) is recommended.

The blending ratio of the polyethylene resin is 5 to 25% based on the composition.
% by weight, preferably 7-20% by weight. If the blending ratio is less than 3% by weight, it is extremely difficult to achieve V-0 in a 1732-inch thick test piece in the UL94 combustion test, which is a high degree of flame retardancy, and even if it is more than 27% by weight, it is not a high degree of flame retardancy. It becomes extremely difficult to achieve sexuality.

The petroleum resin (E) used in the present invention is useful as a petrochemical raw material from diolefins and monoolefins and/or aromatic compounds contained in cracked oil fractions generated during petroleum refining, petroleum cracking, etc. A thermoplastic resin obtained by thermally polymerizing or cationically polymerizing diolefins, monoolefins, and/or aromatic compounds remaining after removing 02~CIO 1-olefins, C4, C5 diolefins, benzene, toluene, xylene, etc. It is. Among cracked oil fractions, C5 (aliphatic) petroleum resin made from C5 fraction, C9 (aromatic) petroleum resin made from C9 fraction, and C5. C9 copolymerized petroleum resin, dicyclopentadiene petroleum resin made from dicyclopentadiene obtained by thermal dimerization of cyclopentadine contained in the C5 fraction, and further Examples include those in which the bond is hydrogenated (alicyclic type).

In particular, alicyclic petroleum resins are preferred because they have 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 70 to 140°C by the ring and ball method, a hue of 15 or less by the Gardner method, and a bromine number of 708r. -g/ 100g or less, preferably 30B
Use one with r-g/100g or less.

The blending ratio of the petroleum resin is 1 to IO% by weight based on the composition,
Preferably it is 3 to 7% by weight. If the blending ratio is less than 0.5% by weight, the bleed prevention effect under high humidity conditions will not reach the desired level. On the other hand, if it exceeds 12% by weight, the impact resistance decreases and the good mechanical strength inherent to polypropylene is lost.

Unsaturated carboxylic acid-modified polypropylene used in the present invention (
F) is a polar group-containing polypropylene resin obtained by grafting polypropylene resin with one or more compounds selected from unsaturated carboxylic acids or their anhydrides.

Examples of the carboxylic acid include maleic acid, acrylic acid, methacrylic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, mesaconic acid, angelic acid, and anhydrides of the carboxylic acid. , maleic anhydride, citraconic anhydride, itaconic anhydride, etc., which can be exemplified by the following.

Among these, maleic anhydride is responsible for favorable results in terms of adhesion. Examples of the polypropylene resin used as the raw material for the unsaturated carboxylic acid-modified polypropylene include the following.

・Crystalline propylene homopolymer, ・Mainly composed of propylene, containing one of the following 1-olefins:
Crystalline random copolymer or crystalline block copolymer containing ethylene, 1-butene, 1-pentene, 1-hexene,
4-Methyl-1-pentene, 1-hebutene, 1-octene and 1-decene.

A mixture of two or more of these crystalline polymers can also be exemplified as a suitable material resin blend.

Examples of methods for grafting unsaturated carboxylic acid or its anhydride onto polypropylene include the following two methods: Melting polypropylene, unsaturated carboxylic acid or its anhydride, and organic peroxide in an extruder. A method of kneading: - A method of adding an unsaturated carboxylic acid or its anhydride and an organic peroxide to polypropylene suspended or dissolved in a suitable solvent and stirring the mixture under heating.

The blending ratio of the unsaturated carboxylic acid-modified polypropylene is 3 to 25% by weight, preferably 5 to 15% by weight, based on the composition. If the blending ratio is less than 3% by weight, it is hardly possible to achieve excellent mechanical strength, and only molded products with insufficient impact resistance can be obtained. On the other hand, even if the content exceeds 25% by weight, it is difficult to expect an improvement in mechanical strength beyond that.
Furthermore, flame retardancy deteriorates.

As the silane coupling agent (G) used in the present invention,
- Large quantity RIR"5iX2 [Here, R1 is a hydrocarbon group containing a chlorine atom, a vinyl group, an amino group and/or a mercapto group, etc. X is a hydrolyzable organic group such as a lower alkoxy group or a halogen atom group.R2 is R1 or Mention may be made of: vinyltrimethoxysilane, vinyltriethoxysilane, 3-7minoprobyltriethoxysilane, N-
(2-Aminoethyl)-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane etc.

One or more of these silane compounds can be used in the form of a mixture or two or more can be used in combination. Among them, it is preferable to use 3-aminopropyltriethoxysilane alone or in combination with vinyltrimethoxysilane and 3-aminopropyltriethoxysilane. The blending ratio of the silane coupling agent to the composition is 0.
It is 3 to 5% by weight, preferably 0.5 to 3% by weight. If the blending ratio is less than 0.1% by weight, excellent mechanical strength cannot be achieved and only a molded product with insufficient impact resistance can be obtained. On the other hand, if it exceeds 7% by weight, it becomes difficult to expect further improvement in mechanical strength, and on the contrary, flame retardancy deteriorates.

In preparing the flame retardant composition of the present invention, various additives that are usually added to the base polypropylene resin, such as antioxidants, ultraviolet inhibitors, antistatic agents, copper inhibitors, lubricants,
Hydrochloric acid neutralizers (metal stearate, hydrotalcite, etc.), pigments, etc. can be used in combination as appropriate.

The polypropylene resin m flammable composition of the present invention can be prepared, for example, by the following method.

That is, polypropylene resin, the above-mentioned ammonium polyphosphate or melamine-modified ammonium polyphosphate, one or more mixtures selected from the above-specified nitrogen-containing heterocyclic organic compounds, aurastonite, polyethylene resin, and petroleum resin. , unsaturated carboxylic acid-modified polypropylene, a silane coupling agent, and the above-mentioned various additives in predetermined amounts are charged into a stirring and mixing device such as a Henschel mixer (trade name), a Supermixer tumbler mixer, or the like. After stirring and mixing for 1 to 10 minutes, the resulting mixture is charged into a roll kneader, screw extruder, etc., and melted and mixed (temperature: 170 to 220°C) to pelletize.

[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) For the vertical combustion test of Flame Retardant tTL Subject 94 (Underwriter Laboratories, Inc.) "Flame Test of Plastic Materials for Equipment Parts", the wall thickness of the test piece was 0.8 mm (1/32 inch). ).

2) Evaluation of bleedability under high temperature and high humidity conditions A test piece (length 95 mm 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. (manufactured by Takeda Riken). Next, the test piece was placed in a constant temperature and humidity bath (temperature: 80° C., humidity: 80% (manufactured by Tabai MGF)), and taken out after each oral administration. Each test piece was dried for 2 hours in a constant temperature dryer (manufactured by Sanyo Electric Co., Ltd.) adjusted to a temperature of 80°C, and after being left in a desiccator at room temperature overnight, the surface electrical resistance value of the test piece was determined. was measured.

If the surface electrical resistance value of the test piece significantly decreases after being removed from the constant temperature and humidity chamber, it is considered to have poor bleed resistance under high temperature and high humidity conditions. The number of days until the electrical resistance value decreased was investigated.

3) Production example of maleic anhydride-modified polypropylene Polypropylene resin, ethylene component content 8% by weight, melt flow sheet) (Fffi degree 230°C, load 2.
10 kg of crystalline propylene-ethylene block copolymer of 2.8 g/10 m1n, 50 g of maleic anhydride as the unsaturated carboxylic acid, 8 g of 1.3-bis(t-butylperoxyisopropyl)benzene as the organic peroxide, 10 g of 2,6-sheet t-petyl p-cresol and 1 calcium stearate as various additives.
0 g was placed in a Henschel mixer (trade name) and stirred and mixed for 3 minutes. The obtained mixture was passed through an extruder (diameter 45 mm)
) and then extruded and pelletized after melt-kneading (temperature 200°C).

The maleic anhydride component content of the obtained modified polypropylene was 0.27% by weight.

Example 1 and Comparative Example 1 As polypropylene resin (H), crystalline propylene-
Ethylene block copolymer [ethylene component content 8.5
Weight%, MFR (temperature 230℃, load 2.16kgf)
20g/10m1n] 2.7kg, ammonium polyphosphate (A) [trade name: Exo1it422 (manufactured by Hoechst) 12.1kg, nitrogen-containing heterocyclic organic compound (B
) as 2-piperazinisine-4-morpholino-1,3
,5-) Polymer of riazine (degree of polymerization n=11, molecular weight 2770) 800i.

Wolastonite (C) [Product name: NYAD-G (
(manufactured by NYCO) 1.5 kg, polyethylene resin (D)
Crystalline ethylene homopolymer [MI (temperature 190°C
; Load 2.16kgf) 6.5g/10m1n, density 0
．． 95g/cc] 1.5kg, petroleum resin (E) [trade name Alcon P-140 (manufactured by Arayo Kagaku Kogyo Co., Ltd.)] 55
00g Unsaturated carboxylic acid-modified polypropylene (F): 800g of maleic anhydride-modified polypropylene.

As the silane coupling agent (G), 3-aminopropyltriethoxysilane [trade name: Sila Ace 5330 (
(manufactured by Chisso Corporation) ] 100ii, as various additives 2.
6-di-t-butyl-p-cresol (BIT) 15
g, Simiristyl-β,β-thiodipropionate (DMyTDP) 20g and calcium stearate 1
0 g was placed in a Henschel mixer (trade name) and stirred and mixed for 3 minutes. The obtained mixture was passed through an extruder (diameter 45 mm)
) to obtain pellets of the viscous composition.

Comparative Example 1 The amount of polypropylene resin (H) was 5.6 kg, polyethylene resin (D), petroleum resin (E), maleic anhydride-modified polypropylene (F), and silane coupling agent (
G) Each compounded component was mixed in a Henschel mixer (trade name) at the blending ratio according to Example 1, except that none of the above was blended.
and stirred and mixed, melted and mixed and pressed according to Example 1 to obtain pellets of a flame retardant composition.

Comparative Examples 2 to 5 A composition containing no polyethylene resin (D), a composition containing no petroleum resin (E), a composition containing no maleic acid-modified polypropylene (F), or a silane coupling agent (G), respectively. Create a composition without blending, and
Each composition was pelletized according to Example 1 except that the blending ratios were changed as shown in the table.

Example 2 A composition was pelletized according to Example 1, except that a reaction product of ethylene urea and formaldehyde was used as the nitrogen-containing heterocyclic organic compound (B).

Comparative Examples 6 to 8 Example 1 was followed except that the blending ratios of ammonium polyphosphate (A), nitrogen-containing heterocyclic organic compound (B), and wolastonite (C) were changed to the blending ratios shown in Table 1. Each composition was pelletized.

The pellets obtained in Examples 1 to 2 and Comparative Examples 1 to 8 were
After drying at a temperature of 00°C for 3 hours, the pellets were formed 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).

Using each test piece, flame retardancy and bleedability under high temperature and high humidity conditions were evaluated. The results are shown in Table 1.

From Example 1 and Comparative Examples 1 to 5 in Table 1, which one of the polyethylene resin (D), petroleum resin (E), maleic anhydride-modified polypropylene (F), and silane coupling agent (G) is missing. Furthermore, it is clear from Example 2 and Comparative Examples 6 to 8 that the bleedability, surface electrical resistance, mechanical strength, and high flame retardance under high temperature and high humidity conditions cannot be achieved even with ammonium polyphosphate (A), The preferred blending ratio of the nitrogen-containing heterocyclic organic compound (B) and wollastonite (C) can be found.

Example 3, Example 4 and Comparative Example 9 Polypropylene resin (H) and polyethylene resin (D)
In addition to changing the blending ratio of to the blending ratio in Table 2,
Each composition was pelletized according to Example 1.

After drying the pellets obtained in Example 3, Example 4, and Comparative Example 9 at a temperature of 100°C for 3 hours, the pellets were tested for flame retardancy and Predetermined test pieces for evaluation of bleedability were molded. Using this test piece, flame retardancy and bleedability under high temperature and high humidity conditions were evaluated. The results are shown in Table 2.

From Table 2, the blending ratio of polyethylene resin (D) is 5~
It turns out that 25% by weight is preferred.

Example 5, Example 6 and Comparative Example 10 Each composition was prepared 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 3. Pelleted.

After drying the pellets obtained in Example 5, Example 6, and Comparative Example 10 at a temperature of 100°C for 3 hours, the pellets were molded into an injection molding machine (the maximum temperature of the cylinder was set at 220°C) to improve flame retardancy and Predetermined test pieces for evaluation of bleedability were molded. Using this test piece, flame retardancy and bleedability under high temperature and high humidity conditions were evaluated. The results are shown in Table 3.

From Table 3, it can be seen that the blending ratio of petroleum resin is preferably 1 to 10% by weight.

Example 7, Example 8, and Comparative Example 11 Each product was prepared in accordance with Example 1, except that the blending ratios of polypropylene resin (H) and maleic anhydride-modified polypropylene (F) were changed to the blending ratios shown in Table 4. The composition was pelletized.

Example 9, Example 10 and Comparative Example 12 The procedure was as per Example 1 except that the blending ratio of polypropylene m III (H') and silane coupling (G) agent was changed to the blending ratio shown in Table 4. Each composition was pelletized.

Example 11 and Comparative Example 12 As the silane coupling agent (G), 3-aminopropyltriethoxysilane [trade name Sila Ace 5330
(manufactured by Chisso Corporation)] and vinyltrimethoxysilane [trade name: Sila Ace 5210 (manufactured by Chinoso Corporation)], and a mixture of polypropylene resin (H) and silane coupling agent (G) Each composition was pelletized in accordance with Example 1, except that the blending ratios were changed to those shown in Table 4.

From Example 7, Example 8, and Comparative Example 11 in Table 4, the blending ratio of unsaturated carboxylic acid-modified polypropylene (F) is 3 to 3.
It turns out that 25% by weight is preferred.

Furthermore, from Examples 9 to 12 and Comparative Example 12, the blending ratio of the silane coupling agent (G) is preferably 0.3 to 5% by weight, and two or more types of silane coupling agents may be used in combination. I understand.

[Effect of the invention] The molded product obtained from the flame-retardant and electrically insulating composition of the present invention hardly causes the flame retardant component to bleed onto the surface of the molded product even under high temperature and high humidity conditions, and has a high degree of flame retardancy. It has excellent mechanical strength while retaining its properties and surface electrical resistance.

Furthermore, the flame retardant and electrical properties of the present invention are #! ! ! The composition is a flame-retardant polypropylene resin composition that does not generate halogen gas during molding or thermal decomposition, and its properties make it suitable for use in the manufacture of buildings, electrical goods, automobile parts, etc. be able to.

Claims (1)

[Claims] (1) The following components (A), (B), (C), (D), (E
), (F), (G) and (H), and the total amount thereof is 100% by weight: (A) 12 to 25% by weight of ammonium polyphosphate or melamine-modified ammonium polyphosphate (B) 5 to 10% by weight of one or more selected from the following group A reaction product group of a cyclic ketone consisting of a heterocycle and formaldehyde, (B2) 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 ( B3) A group of 1,3,5-triazine derivatives containing the structure represented by the following general formula [I]▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] [In the formula, X is a morpholino group or a piperidino group , Y is a divalent group derived from piperazine, n is a positive number of 2 to 50], (C) Wollastonite 5 to 25% by weight (D) Polyethylene resin 5 to 25% by weight (E) Petroleum 1 to 10% by weight of resin (F) 3 to 25% by weight of unsaturated carboxylic acid-modified polypropylene (G) 0.3 to 5% by weight of silane coupling agent (H) 15 to 68% by weight of polypropylene resin (2) 2 or more pieces Ethylene urea is a cyclic ketone consisting of a 5 or more membered heterocycle containing 2 or more nitrogen atoms in the ring, or ethylene thioketone is a cyclic thioketone consisting of a 5 or more membered heterocycle containing 2 or more nitrogen atoms in the ring. urea or 1,3 containing the structure represented by the following general formula [I]
, a 5-triazine derivative is bonded to 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. Item 1. The flame retardant composition according to item 1. (3) The softening point of the petroleum resin is 70 to 180°C by the ring and ball method.
The flame retardant composition according to claim 1, having a bromine number of 70 (Brg/100g) or less. (4) The polypropylene resin is a crystalline propylene homopolymer, a copolymer mainly composed of propylene, and includes propylene and ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1
The flame retardant composition according to claim 1, which is a crystalline copolymer with one or more selected from the group of -octene and 1-decene, or a mixture of two or more thereof. (5) An electrical device, an electrical appliance, or an electrical article comprising the flame-retardant composition according to claim 1. (6) A board, housing, casing or electrical insulating member for an electrical device, characterized by being made of the flame retardant composition according to claim 1.