KR100399833B1 - Flame Retardent Polypropylene Resin Composition - Google Patents

Abstract

The present invention is (A) 46 to 80.5% by weight of polypropylene resin, (B) 16 to 27% by weight of ammonium polyphosphate, (C) 1.5 to 12% by weight of phenolic aromatic phosphate ester compound, and (D) 1, 3 , To provide a flame retardant polypropylene resin composition containing 2 to 15% by weight of a 5-triazine derivative, excellent flame retardancy and mechanical strength and does not generate toxic gas during combustion, useful for electrical appliances, automobile parts and building materials Can be used.

Description

Flame Retardent Polypropylene Resin Composition

The present invention relates to a flame retardant polypropylene resin composition exhibiting flame retardancy and high mechanical strength, and more particularly, to a resin composition having excellent flame retardancy comprising a polypropylene resin as a main component and a phosphorus-based flame retardant and a nitrogen compound having a specific ratio and content. will be.

Polypropylene resin is widely used in household electrical appliances, building materials, interior decoration materials, automobile parts, etc. due to its excellent processing characteristics, chemical resistance, weather resistance, and mechanical strength, and is inherently flammable. A flame retardant is added and used.

Examples of the flame retardant polypropylene resin composition containing such a flame retardant include a composition obtained by adding a hydrous inorganic compound such as magnesium hydroxide, aluminum hydroxide or hydrotalcite to a polypropylene resin (Japanese Patent Laid-Open No. 53-92855, 54- 29350, 54-77658, 56-26954, 57-87462, and 60-110738), polyethylenes having a melt index of 0.01 to 2.0, halogen compounds (e.g., decabromodiphenyl ether or dodeca Chloro-dodecahydromethanodibenzocyclooctene) and a composition obtained by adding at least one inorganic filler selected from the group consisting of powder talc, kaolin, celestial stone, silica and diatomite to a polypropylene resin (Japanese Patent Publication No. 55- 30739) and ammonium phosphate (or amine phosphate), a nitrogen compound having an aldehyde with = C = O (or = C = S or = NH) in the ring structure The response oligomer (or polymer) of the product, or 1,3,5-triazine derivatives by the polypropylene resin and the like a composition (Japanese Patent Laid-open No. 52-146452 and No. 59-147050 arc) obtained.

However, a composition prepared by adding an inorganic compound such as magnesium hydroxide to a polypropylene resin in order to prepare a highly flame retardant composition has a low moldability and a composition obtained by adding a decabromo phenyl-based compound to polypropylene is molded in use. The property is not so bad and the flame retardancy of the composition is high, but has a problem that toxic gas is generated during secondary processing or combustion.

In addition, when the compositions described in Japanese Patent Laid-Open Nos. 52-146452 and 59-147050 are used, the secondary processability of the composition is hardly degraded, and neither corrosive gas nor toxic gas is generated, and UL Subject 94 ( A test based on the vertical combustion test (hereinafter abbreviated as UL94 vertical combustion test) of the "Combustibility Test on Plastic Materials for Mechanical Components" of Underwrites Laboratories Incorporation), to obtain flame retardancy of V-0 at 1/16 inch thickness. Although it has good flame retardancy, its impact strength and heat resistance are poor, making it unsuitable for use in parts requiring such physical properties.

Meanwhile, as a phosphorus-based flame retardant, a thermoplastic flame-retardant resin is prepared by adding ammonium polyphosphate and 1,3,5-triazine-based nitrogen compound, but in this case, in order to obtain flame retardancy of V-0 at a thickness of 1/16 inch, The requirement of ammonium phosphate is high and the thermoplastic resin prepared from this composition has a problem that the impact resistance is sharply inferior. In addition, according to Japanese Patent Laid-Open No. 11-140245, a thermoplastic flame retardant resin was prepared by applying an aromatic phosphate ester compound to a polyphenylene ether resin and a hydrogenated copolymer and adding a nitrogen compound of 1,3,5-triazine. As a result of evaluation by the inventors, not only the flame retardancy of UL94 V-0 is difficult to be expressed, but also the heat resistance is sharply lowered, so that it is very difficult to secure practical heat resistance.

Therefore, the present inventors have intensively studied to solve the drawbacks of the polypropylene flame-retardant resin composition so far, and as a condensation phosphate, ammonium polyphosphate and aromatic phosphate ester of phenol structure are contained at a specific ratio, -The resin composition containing the triazine-based nitrogen compound is excellent in flame retardancy and at the same time excellent impact resistance and heat resistance was completed the present invention.

That is, the present invention (A) 46 to 80.5% by weight of polypropylene resin having a melt flow index of 0.1 to 40g / 10 minutes, (B) 16 to 27% by weight of ammonium polyphosphate, (C) phenolic aromatic phosphate ester 1.5 to 12 2% to 15% by weight, and (D) 1,3,5-triazine derivative, wherein the weight ratio of (B) / (C) is 1.3 to 15.3, and the total amount of the two components is 24 to 32% by weight. It is a flame-retardant resin composition characterized in that.

In the present invention, "polypropylene" means a propylene olefin block copolymer and a propylene homopolymer containing 50 wt% or more of propylene polymerized units. More specifically, the polypropylene resin in the present invention is a crystalline polypropylene homopolymer, or ethylene, 1-butene, 1-pentene, 1-hexene, 4-methylpentene, 1-heptin, 1-octene and 1-decene A crystalline copolymer of at least one compound selected from the group consisting of or a mixture of at least two compounds selected from the group and a polypropylene as a main component is used, and the polypropylene resin may have a melt flow index of 0.1 to 40 g / 10 minutes. Preferably, it is 0.2-30 g / 10min. Regarding the stereoregularity of such a polypropylene composition, any polypropylene which achieves the object of the present invention may be used as long as it is crystalline polypropylene without particular limitation. Specifically, the isotactic pentad fraction measured by 13 C-NMR (nuclear magnetic resonance spectrum) is 0.80-0.99, preferably 0.85-0.99, and particularly preferably 0.90-0.99.

The resin composition of this invention is comprised as (A)-(D) component as a base component as mentioned above.

In the present invention, the polypropylene-based resin (A) is measured at a load of 2.16 kg at 230 ° C. and has a melt index of 0.1 g / 10 min to 40 g / 10 min. If the melt index of the polypropylene resin is less than 0.1g / 10 minutes, flow marks are likely to occur on the surface of the molded body during injection molding, and are easily prone to defects in appearance, and when more than 40g / 10 minutes, the impact resistance of the molded product is rapidly lowered. There is a flaw.

In this invention, the compounding quantity of (A) polypropylene resin is 46-80.5 weight%, More preferably, it is 46-75 weight%. When the blending amount is less than 46% by weight, the obtained resin composition is excellent in heat resistance, but the molding processability and impact resistance are sharply inferior, and when it exceeds 80.5% by weight, the moldability is good, but it is difficult to obtain V-0 grade flame retardancy. It is difficult and undesirable.

The ammonium polyphosphate (B) used in the present invention generates only decomposable non-flammable gases (steam, carbon dioxide, nitrogen, etc.) and carbonaceous residues due to high temperature or contact with flames, and generates corrosive gas, halogen gas or toxic gas. Has most of the advantages that do not accompany it, but may be used as it is commercially available. In addition, it can be used by adding and / or attaching melamine, specifically, trade name Teraju C-60 (manufactured by Chisso).

The aromatic phosphate ester of (C) phenol structure used in this invention is an aromatic phosphate ester of triphenyl phosphate, a hindered phenol structure, a phosphate (2, 6-dimethylphenyl) phosphate, and a tri (2, 6-degree) Butylphenyl) phosphate, and the like, and typical compounds include the following formula (1). Here, as the phosphate ester monomer, for example, triphenyl phosphate, tricrezyl phosphate, trixenol phosphate, etc. can be used. In general, n may have a value of 1 to 5 as a condensate, preferably 3 is an average value, and at least one of R 1, R 2, R 3 and R 4 is preferably an aryl group, and particularly preferably R 1, R 2, R 3 and All of R4 are aryl groups. Preferred aryl groups include phenyl, xylenol, cresyl or such halogenated derivatives. Moreover, as a preferable allylene group of X, it is possible that the residue which two hydroxyl groups departed from resorcinol hydroquinone, bisphenol A, biphenol, or these halogenated derivatives, respectively is contained. Although the above phosphate ester may be applied singly or mixed, it is not preferable to apply a compound having a molecular weight of 1500 or more in the structure because the effect of imparting flame retardancy is small. Preferably, the phosphate ester whose melting | fusing point is 80 degreeC or more is applied.

(Wherein X is an allylene group, R 1, R 2, R 3 and R 4 are preferably aryl groups and n is an integer of 1 to 5).

In the present invention, the amount of the compounds of (B) and (C) described above is preferably 16 to 27% by weight for (B) and 1.5 to 12% by weight for (C), but the use of (B) / (C) Most preferably, the ratio is 1.3 to 15.3 and the total amount of (B) and (C) is 24 to 32% by weight. Even if it is smaller than the above-mentioned use ratio, sufficient flame-retardant synergistic effect cannot be obtained, and since a large amount of flame retardants are required, it is not preferable. In addition, if the two types of compounding amount is less than 24% by weight, the flame retardant function is insufficient, and if more than 32% by weight, the impact resistance is extremely low.

The (D) 1,3,5-triazine derivative used in the present invention is a non-halogen flame retardant and a derivative of a cyclic ring compound containing a nitrogen atom at positions 1, 3, and 5, and is represented by the following formula (2) Compound.

(Wherein X is a morpholino group or a piperazinino group, Y is a piperazine group, m is 1 or 2, and n is an integer of 1 to 50).

As a specific example of such a 1, 3, 5-triazine derivative component, 2-piperazinylene whose substituent X is a morpholino group, 2-piperazinylene 4-piperizino 1, 3 whose substituent X is a piperizino group , Oligomers or polymers of 5-triazine are possible. Specifically, for example, the polymer of 2- 6-dibromo 4-porolino 1, 3, 5-triazine can be produced by the following method. That is, 2, 6-dihalo 4-morpholino 1, 3, 5-triazine of the same molar content (for example, 2, 6-dichloro 4-morpholino 1, 3, 5-triazine or 2, 6-dibromo 4-phospholino 1, 3, 5-triazine) and piperazine are converted into organic bases (e.g. triethylamine or tributylamine) or inorganic bases (e.g. sodium hydroxide, In the presence of potassium hydroxide or sodium carbonate), and reacted by heating to an inert solvent such as xylene at a temperature below the boiling point of the inert solvent. After completion of the reaction, the reaction mixture is filtered, the solids are separated and the separated solids are washed with boiling water and then the salts of the by-products produced in the reaction are dissolved in and removed from the boiling water, then the remaining solids are dried. When the thus obtained 1, 3, 5-triazine derivative component is blended in the resin composition of the present invention, preferably 2 to 15% by weight, non-flammable gas (carbon dioxide, Nitrogen)) and carbonaceous residues only, and there is an advantage that does not involve the generation of corrosive gas, halogen gas or toxic gas. In addition, the 1,3,5-triazine derivative also has a synergistic effect with the above-mentioned organophosphate ester compound and ammonium polyphosphate, and imparts excellent flame retardancy to the resin composition of the present invention.

In the present invention, a plasticizer, a heat stabilizer, an antioxidant, a light stabilizer, and the like may be added to the composition as necessary, and organic or inorganic pigments and inorganic fillers such as dyes, talc, silica, and glass fibers may be added.

The flame retardant polypropylene resin composition of the present invention can be prepared according to the following method. That is, 1, 3, 5-triazine having a chemical structure represented by the specified amount of (A) polypropylene resin, (B) polyammonium phosphate, (C) phenolic aromatic phosphate ester, and (D) chemical formula (1) The derivative and the various additives described above are charged to a stirring-mixer (e.g., a Hessen mixer, a super mixer or a tumbler mixer), the compound is stirred-mixed for 1 to 10 minutes and a rolling or extruder at a temperature of 200 to 250 ° C. Melt and knead using to obtain pellets.

The following examples are intended to further illustrate the present invention, but the following examples are for illustrative purposes of the present invention and are not intended to limit the scope of protection defined by the appended specific claims.

Property measurement method

1) Izod impact strength

The injection molded molded article had a thickness of 3.2 mm and was based on the ASTM D256 test specification.

2) heat deflection temperature

Test specimens having a length of 127.0 mm, a width of 12.7 mm, and a thickness of 6.4 mm were formed by using an injection molding machine, and were subjected to a load of 18.5 kgf / cm 2 of ASTM D648 test standard.

3) flammability

The vertical combustion test of UL subject 94 (Underwrites Laboratories Incorporation) "Combustibility Test of Plastic Material for Mechanical Components" was based on the vertical phase. The thickness of the specimen used was 1/16 inch.

Example 1

6.8 kg of crystalline ethylene-propylene block copolymer, polyammonium phosphate, with a melt index (melt flow rate of the melt for 10 minutes at 230 ° C. under a load of 2.16 kg) as a polypropylene resin. Chisso Co.] 2.0 kg, Daihachi Nippon Tri (2,6-dimethylphenyl) phosphate (trade name: PX-200, Nippon Daihachi Co., Ltd.) 500 g, 700 g of 1, 3, 5-triazine derivative, 10 g of calcium stearate as an additive The Hensel mixer was charged and stirred-mixed for 3 minutes The resulting mixture was melt-extruded at 200-250 ° C. using an extruder with a diameter of 30 mm to make pellets.

Example 2

The same components as in Example 1 were charged into a Hensel mixer, stirred-mixed, except that the compounding amount of the polypropylene resin and the compounding amount of the aromatic phosphate ester of the phenyl structure were replaced with the content ratios shown in Table 1. The prepared mixture was melt-extruded under the same conditions as in Example 1 to prepare pellets.

The pellets obtained in Examples 1 and 2 were dried at 100 ° C. for 3 hours, and molded using an injection molding machine having a maximum temperature of 230 ° C. to prepare a constant test piece for testing flame resistance and mechanical properties. After that, the results of measuring flame retardancy and mechanical properties are shown in Table 1.

As can be seen in Table 1, in Examples 1 to 2 prepared according to the present invention, the heat deformation temperature is 69 ℃ or more properties and the impact strength of 14kg.cm / cm or more and flame retardancy of each V-0 It has good flame retardant properties.

Example 3

6.5 kg of crystalline ethylene-propylene block copolymer having a melt index (melt flow rate of the melt for 10 minutes at 230 ° C. under a load of 2.16 kg) as a polypropylene resin, ammonium polyphosphate [trade name C60, Japan] Chisso Co.] 1.6 kg, Tri (2,6-dimethylphenyl) phosphate from Daihachi, Japan (trade name: PX-200, Daihachi, Japan) 1.2 kg, 700 g of 1, 3, 5-triazine derivative, 10 g of calcium stearate as an additive The Hensel mixer was charged and stirred-mixed for 3 minutes The resulting mixture was melt-extruded at 200-260 ° C. using an extruder with a diameter of 30 mm to make pellets.

Examples 4-5 and Comparative Examples 1-4

The same ingredients as in Example 3 were charged to a Hensel mixer except that the mixing ratio of the polypropylene resin with the aromatic phosphate ester of the ammonium polyphosphate and phenyl structure was replaced with the contents shown in Tables 1 and 2, followed by stirring-mixing. After the preparation, the resulting mixture was melt-extruded under the same conditions as in Example 3 to prepare pellets.

The pellets obtained in Examples 3 to 5 and Comparative Examples 1 to 4 were dried at 100 ° C. for 3 hours, and molded using an injection molding machine in which the maximum temperature of the cylinder was fixed at 230 ° C. to test the flame resistance and mechanical properties. After preparing a predetermined test piece for the, the results of measuring the flame retardancy, mechanical properties are shown in Table 1 and Table 2.

As can be seen from Table 1 and Table 2, in Examples 3 to 5 prepared according to the present invention, the blending ratio of ammonium polyphosphate and aromatic phosphate ester of phenyl structure is 1.3 to 15.3, and ammonium polyphosphate and phenyl structure When the total weight of the aromatic phosphate ester is 24 to 32% by weight, the Izod impact strength is excellent at 10 to 21 kg.cm/cm, the heat resistance is at least 68 ° C. and the flame retardancy is V-0, respectively. Holds. However, in Comparative Examples 1 to 4, a product having excellent flame retardancy, impact strength, and heat resistance at the same time could not be obtained.

Example 6

7.3 kg of crystalline ethylene-propylene block copolymer, polyammonium phosphate with a melt index (melt flow rate of melted resin for 10 minutes at 230 ° C. under a load of 2.16 kg) as a polypropylene resin [trade name C60, Japan] Chisso Co.] 2.0 kg, Daihachi Nippon Tri (2,6-dimethylphenyl) phosphate (trade name: PX-200, Nippon Daihachi Co., Ltd.) 500 g, 1, 3, 5-triazine derivative 200 g, additive 10 g calcium stearate The Hensel mixer was charged and stirred-mixed for 3 minutes The resulting mixture was melt-extruded at 200-260 ° C. using an extruder with a diameter of 30 mm to make pellets.

Example 7 and Comparative Examples 7 to 8

The same ingredients as in Example 6 were charged to a Hensel mixer, stirred-mixed, except that the polypropylene resin and 1, 3, 5-triazine derivatives were replaced with the contents and ingredients shown in Tables 1 and 2 The resulting mixture was melt-extruded under the same conditions as in Example 3 to prepare pellets. Then, the obtained pellets were dried at 100 ° C. for 3 hours and molded using an injection molding machine having a maximum temperature of 230 ° C. to prepare a test piece for testing flame resistance and mechanical properties. The results of measuring mechanical properties are shown in Table 1 and Table 2.

As can be seen from Table 1 and Table 2, when the specific 1,3,5-triazine derivatives shown in the examples of the present invention are not blended or the blending ratio is below a certain amount, excellent flame retardancy of V-0 grade is obtained. I could not. When the blending ratio of the 1,3,5-triazine derivatives defined in the present invention is exceeded, the flame retardancy of V-0 can be secured, but there is a problem in that the impact resistance drops sharply.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 (A) 68 68 65 68.5 61 73 60 (B) 20 20 16 23 27 20 20 (C) -1 5 12 1.5 5 5 5 (C) -2 5 (D) -1 7 7 7 7 7 2 15 Izod impact strength (kg.cm/cm) 15 14 21 12 10 17 9 Heat deflection temperature (℃) 72 69 68 74 75 69 76 Flame retardant V-0 V-0 V-0 V-0 V-0 V-0 V-0

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 (A) 67.5 68 58 68 63 68 74 55 (B) 25 20 20 20 30 20 20 (C) -1 0.5 5 15 5 0 25 5 5 (C) -2 (D) -1 7 7 7 7 One 20 (D) -2 7 (D) -3 7 Izod impact strength (kg.cm/cm) 4 5 25 7 4 41 17 5 Heat deflection temperature (℃) 76 73 51 71 75 58 70 77 Flame retardant V-0 x V-0 x V-0 x x V-0

※ "x": indicates that V-0 grade flame retardancy cannot be obtained by burning.

※ In table 1

Component (A): polypropylene resin [BB110P (brand name); Samsung General Chemical Co., Ltd. product]

Component (B): Ammonium polyphosphate [trade name: Teraju C-60, Japan Chisso Corporation]

Component (C) -1: aromatic phosphate ester of hindered phenol structure

[Brand name: PX-200, tree (2,6-dimethylphenyl) phosphate of Daihachi, Japan]

Component (C) -2: aromatic phosphate ester of phenol structure

[Trade name: TPP, Triphenylphosphate from Daihachi, Japan]

Component (D) -1: 1, 3, 5-triazine derivative (Formula 1)

Component (D) -2: Nitrogen-containing compound [brand name: melamine, Samsung Fine Chemicals company]

Component (D) -3: Nitrogen-containing compound, melamine cyanurate

[Product name: MC610, Nissan chemical company in Japan]

As can be seen in the above examples and comparative examples, the polypropylene resin composition prepared according to the present invention is excellent in flame retardancy and exhibits flame retardancy of UL94 V0. In addition, its mechanical properties such as impact strength and heat resistance are excellent, and therefore, it is suitable for use in manufacturing electric appliances, automobile parts, building materials, interior decoration materials, etc., which require such performance.

Claims (7)

(A) 46-80.5 weight% of polypropylene resins, (B) 16- ammonium polyphosphate 27 wt%, (C) 1.5 to 12 wt% of the phenolic aromatic phosphate ester compound represented by the following formula (1), and (D) 2 to 15 wt% of the 1, 3 and 5-triazine derivative represented by the following formula (2): Flame retardant polypropylene resin composition comprising. [Formula 1] (Wherein X is an allylene group, R 1, R 2, R 3 and R 4 are preferably aryl groups and n is an integer of 1 to 5). [Formula 2] (Wherein X is a morpholino group or a piperazinino group, Y is a piperazine group, m is 1 or 2, and n is an integer of 1 to 50). The flame retardant polypropylene resin composition according to claim 1, wherein the polypropylene resin (A) is a homopolymer, an impact copolymer, or a mixture thereof. The flame retardant polypropylene resin composition according to claim 1 or 2, wherein the polypropylene-based resin (A) has a melt flow index of 0.1 to 40 g / 10 minutes. The flame-retardant polypropylene resin composition according to claim 1, wherein the compounding weight ratio of (B) ammonium polyphosphate and (C) phenolic aromatic phosphate ester compound is 1.3 to 15.3: 1. The flame retardant polypropylene resin composition according to claim 1, wherein the total amount of the (B) ammonium polyphosphate and (C) phenolic aromatic phosphate ester compound in the total composition is 24 to 32% by weight. delete delete