KR100529142B1 - Halogen free flame retardant polybutyleneterephthalate resin composition containing ammonium polyphosphate - Google Patents

Abstract

The ammonium polyphosphate-containing non-halogen flame-retardant polybutylene terephthalate resin composition according to the present invention comprises (A) 73 to 97% by weight of polybutylene terephthalate resin (PBT), and (B) a structure of formula 1 as a first flame retardant

[Formula 1]

2-15% by weight of an alkylphosphonic acid compound represented by (wherein R is a linear or branched alkyl group having 1 to 4 carbon atoms and X is 0 or 1), and (C) as a second flame retardant 1 to 12% by weight of ammonium polyphosphate, the second flame retardant ammonium polyphosphate is characterized in that the polymerization degree (n) is 100 or more, the decomposition temperature is 270 ℃.

Description

Halogen free flame retardant polybutyleneterephthalate resin composition containing ammonium polyphosphate

The present invention relates to a non-halogen flame-retardant polybutyleneterephthalate resin composition, and more particularly, by using an alkylphosphonic acid compound and an ammonium polyphosphate in an appropriate ratio as a non-halogen flame retardant to a polybutylene terephthalate resin. Its excellent flame retardancy by the synergy of these flame retardants prevents the generation of toxic gas during processing and the deterioration of color and physical properties, and the stability of resin at high temperature by eliminating red and metal compounds, and the content of other flame retardant aids. The present invention relates to an environmentally friendly, ammonium polyphosphate-containing non-halogen flame-retardant polybutylene terephthalate resin composition while minimizing and maintaining the inherent physical properties of the polybutylene terephthalate resin.

Polybutylene terephthalate is a crystalline thermoplastic polyester resin that is tough and has high rigidity, excellent heat resistance, heat aging resistance (maintains good mechanical properties even at high temperatures), etc., and has good electrical properties and a low water absorption at a wide temperature range. It also has excellent weather resistance and chemical resistance. Due to such excellent chemical resistance, mechanical strength and electrical insulation, polybutylene terephthalate is used in housings, connectors and the like of electrical, electronic and automotive parts. However, in order to be applied to these various applications, polybutylene terephthalate materials require flame retardancy.

In general, as a method of imparting flame retardancy to polybutylene terephthalate resins, preparations such as halogen flame retardants, antimony oxide flame retardants, and metal oxides are used. However, halogenated compounds not only produce large amounts of HBr or HCl during high temperature processing and combustion, but also halogenated polyhalogenated aromatic dioxin, a highly toxic carcinogen that is very harmful to the human body when burned under oxygen-free conditions. There is a problem of generating furan (polyhalogenated aromatic furan).

Due to the corrosion and environmental problems of processing equipment, the development of non-halogen flame-retardant systems without halogen-based flame retardants is expanding worldwide. In Europe, the use of halogen-based flame retardants through the TCO regulations (The Swedish Confederation of professional employees) Is legally restricted.

Non-halogen flame-retardant techniques of polybutylene terephthalate resins known to date include methods using phosphorus and other flame-retardant aids (US Pat. Nos. 6,084,012 and 6,133,358), and ammonium polyphosphate and metal hydroxides or organic phosphorus-nitrogen compounds. US Patent Nos. 4,957,950 and 5,484,830, and methods using red, melamine-based flame retardants, metal hydroxides, and the like, and Korean Patent Application Nos. 1999-040577 and 1996-051070. .

However, in the case of using a red flame retardant, phosphine gas, a toxic gas, is generated due to deterioration of stability during processing at high temperatures, and the phosphine gas not only deteriorates the working environment but also inherent red color of the red color. As a result, it is difficult to develop a product.

In addition, in the case of using phosphate esters and metal hydroxides such as phosphate esters and magnesium hydroxide, there is a problem in that physical properties are lowered due to the addition of a large amount, and heat resistance and electrical properties are reduced.

The present invention is to solve the above problems, an object of the present invention, by using an alkylphosphonic acid compound and ammonium polyphosphate in an appropriate ratio as a non-halogen flame retardant to a polybutylene terephthalate resin, their flame retardant increase It is excellent in flame retardancy by the action, and prevents the generation of toxic gas during processing and deterioration of color and physical properties. It is to provide an environmentally friendly, ammonium polyphosphate-containing non-halogen flame-retardant polybutylene terephthalate resin composition while maintaining the inherent physical properties of the polybutylene terephthalate resin.

Ammonium polyphosphate-containing non-halogen flame-retardant polybutylene terephthalate resin composition according to the present invention for achieving the above object is (A) 73 to 97% by weight of polybutylene terephthalate resin (PBT), (B) Structure of Chemical Formula 1 as First Flame Retardant

2-15% by weight of an alkylphosphonic acid compound represented by (wherein R is a linear or branched alkyl group having 1 to 4 carbon atoms and X is 0 or 1), and (C) as a second flame retardant 1 to 12% by weight of ammonium polyphosphate, the second flame retardant ammonium polyphosphate is characterized in that the polymerization degree (n) is 100 or more, the decomposition temperature is 270 ℃.

In the ammonium polyphosphate-containing non-halogen flame-retardant polybutylene terephthalate resin composition according to the present invention, the polybutylene terephthalate resin of the component (A) is polytetramethylene glycol (PTMG), polyethylene glycol (PEG), polypropylene It is characterized by being a modified polybutylene terephthalate copolymerized with glycol (PPG), low molecular weight aliphatic polyester or low molecular weight aliphatic polyamide or blended with an impact modifier.

The ammonium polyphosphate-containing non-halogen flame-retardant polybutylene terephthalate resin composition according to the present invention is characterized by containing 3% by weight to 10% by weight of an alkyl phosphonic acid compound as the first flame retardant.

The ammonium polyphosphate-containing non-halogen flame-retardant polybutylene terephthalate resin composition according to the present invention is characterized by containing 2 to 8% by weight of ammonium polyphosphate as the second flame retardant.

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In the ammonium polyphosphate-containing non-halogen flame-retardant polybutylene terephthalate resin composition according to the present invention, the resin composition is carbon fiber, glass fiber, glass beads, glass flakes, carbon black, clay, kaolin, talc, mica, calcium carbonate At least one filler selected from the group consisting of 1 to 50 parts by weight based on 100 parts by weight of the total resin composition is characterized in that it further comprises.

Hereinafter, the present invention will be described in more detail.

As the polybutylene terephthalate resin of component (A), a polymer obtained by condensation polymerization of butane-1,4-diol with terephthalate or dimethyl terephthalate through monomers via direct esterification or ester exchange reaction is used.

In addition, in the present invention, modified polybutylene terephthalate modified to increase the impact strength of the polybutylene terephthalate resin can be used. Chemical modification methods of polybutylene terephthalate include copolymerizing polytetramethylene glycol (PTMG), polyethylene glycol (PEG), polypropylene glycol (PPG), low molecular weight aliphatic polyester, or low molecular weight aliphatic polyamide during polymerization. There is a method, and the physical modification method is a method of blending the impact modifier.

The use amount of polybutylene terephthalate resin is 73 to 97 weight% in the total resin composition, Preferably it is 82 to 95 weight%.

The alkylphosphonic acid compound of the component (B) is a first flame retardant, when used with the ammonium polyphosphate of component (C) which is a second flame retardant exhibits a more effective flame retardant effect to minimize the total flame retardant content, gas during processing It can reduce the occurrence and prevent environmental pollution.

The alkyl phosphonic acid compound is used in the range of 2 to 15% by weight in the total resin composition, preferably 3 to 10% by weight. When the amount of the alkyl phosphonic acid compound is less than 2% by weight, the flame retardant effect is insignificant, and when the amount is more than 15% by weight, the plasticization effect and the blooming phenomenon of the flame retardant may cause a decrease in the physical properties of the product. Due to the manufacturing price rises.

A typical commercial product of the alkyl phosphonic acid compound is Rhodia's antiblaze 1045 (trade name), and is mainly used as a flame retardant for fibers.

Ammoniumpolyphosphate of component (C) is a nitrogen-phosphorus flame retardant as the second flame retardant. Ammonium polyphosphate generally has a structure of formula (2).

(Wherein n is an integer of 1 or more)

Ammonium polyphosphate has been widely used as an additive for fiber, paper, and foaming paint due to its high char forming effect due to dehydration during combustion. The char produced during combustion reduces the combustible fuel and forms a thick barrier on the surface of the burning molecule, blocking heat and turning off the fire. In particular, the phosphorus component of ammoniumpolyphosphate is pyrolyzed to produce phosphoric acid, which acts as a dehydration catalyst in the burning material, increasing the amount of tea.

Ammonium polyphosphate is used in the range of 1 to 12% by weight of the total resin composition, preferably 2 to 8% by weight. If the amount of ammonium polyphosphate is less than 1% by weight, the flame retardant effect and the synergistic effect are insignificant. If the amount is more than 12% by weight, polybutylene terephthalate due to pyrolysis of ammonium polyphosphate and ammonium ion (NH ₄ ⁺ ) It causes the decomposition of the product and causes a problem of deterioration of the physical properties and colors of the product. Ammonium polyphosphate has a flame retardant synergistic effect when used with the first flame retardant.

On the other hand, since the processing temperature of the polybutylene terephthalate is 240 ~ 250 ℃, in order to minimize the decomposition during processing, it is preferable to use a product having a decomposition temperature of 270 ℃ or more ammonium polyphosphate. Moreover, it is preferable to use the product whose polymerization degree (n) is 100 or more as ammonium polyphosphate.

The higher the pyrolysis temperature and the degree of polymerization (n) of the ammonium polyphosphate, the better the flame retardancy and the physical properties of the resin composition to be produced.

Ammonium polyphosphate, together with the first flame retardant, exhibits an excellent flame retardant synergistic effect, reducing the overall flame retardant content, minimizing toxic gases, which are by-products of pyrolysis during processing, and facilitating processing, resulting in a resin composition that is optimal. It gives the physical properties of

An antioxidant, a lubricant, a UV stabilizer, etc. may be further added to the flame retardant resin composition as a processing aid, and may further contain various inorganic and organic fillers in various particle forms in order to increase mechanical heat resistance and dimensional stability of the composition. have. Examples of the filler that can be used include carbon fiber, glass fiber, glass beads, glass flakes, carbon black, clay, kaolin, talc, mica, calcium carbonate and the like, and are used in an amount of 1 to 50 parts by weight based on 100 parts by weight of the total resin composition.

The non-halogen flame-retardant polybutylene terephthalate resin composition according to the present invention can be usefully used for electrical and electronic parts because it is excellent in flame retardancy and color and environmentally friendly while using a small amount of flame retardant compared to the existing composition.

The objects, features and advantages of the present invention will become more apparent upon a review of the description of the preferred embodiments of the present invention. The following examples show the results of measuring the physical properties of the non-halogen flame retardant polybutylene terephthalate resin composition according to the present invention and the resin composition thus prepared. However, the present invention is not limited in scope by this embodiment.

<Example 1-3 and Comparative Example 1-4>

The raw materials were mixed with the composition components and contents shown in Table 1 below, and kneaded and extruded with a twin screw melt kneading extruder at a temperature of 240 to 250 ° C. to prepare molding pellets, and hot-air dried at 110 ° C. for 6 hours, followed by 240 to 250 ° C. The specimen was molded by injection molding at a temperature of to prepare the polybutylene terephthalate resin compositions of Examples 1 to 3 and Comparative Examples 1 to 4.

The first flame retardant alkylphosphonic acid compound used in the experiment was a transparent, high viscosity liquid, which was fed through the extruder's middle point using a liquid feeder at 100 ° C. As ammonium polyphosphate which is a 2nd flame retardant, the white powder whose polymerization degree is 1000 or more and the decomposition temperature is 270 degreeC or more was used.

Example (% by weight) Comparative Example (wt%) Furtherance One 2 3 One 2 3 4 Polybutylene terephthalate ⁽¹⁾ 87 90 90 92 85 80 80 First flame retardant ⁽²⁾ 3 7 5 8 Second flame retardant ⁽³⁾ 10 3 5 15 ⁽⁴⁾ 5 5 Phosphate Ester (RDP) ⁽⁵⁾ 15 5 Magnesium Hydroxide ⁽⁶⁾ 10

(1) TRIBIT 1700S of Samyang Corporation

(2) Antiblaze 1045 (alkylphosphonic acid compound) from Rhodia

(3) APP-1 (ammonium polyphosphate) from Xingxing Flame Retardants

(4) HISHIGUARD TP-10 from Nippon Chemical

(5) resorcinol diphenyl phosphate

(6) Kyowa Chemicals Mg (OH) ₂

The physical properties of the polybutylene terephthalate resin compositions prepared according to Examples 1 to 3 and Comparative Examples 1 to 4 were measured, and the results are shown in Table 2 below. The impact strength was measured in accordance with ASTM D-256, thermal deformation temperature ASTM D-648, flame retardancy UL-94, and oxygen index ASTM D-2863.

Example Comparative example Properties One 2 3 One 2 3 4 Flame Retardant (UL 94, 1/16 ") V-0 V-0 V-0 V-2 V-2 V-0 V-2 Oxygen Index (LOI,%) 28.7 31.1 29.4 27.2 28.9 29.3 28.0 Heat Deflection Temperature (18.6Kgf / ㎠) 62.3 64.2 64.7 63.6 67.8 57.1 66.2 Impact Strength (1/8 ", kg _f cm / cm) 4 5 5 5 4 4 3 Appearance (color) Natural ivory Natural ivory Natural ivory Natural ivory Natural ivory Red scarlet Red scarlet

As shown in Table 2, Examples 1 to 3 according to the present invention can be confirmed that the flame retardancy and color is superior to Comparative Examples 1 to 4.

As described above, the non-halogen flame-retardant polybutylene terephthalate resin composition according to the present invention may be used in an amount less than that of a conventional flame retardant by using an appropriate amount of an alkylphosphonic acid compound and ammonium polyphosphate as a non-halogen flame retardant. It has excellent flame retardancy, prevents environmental pollution because no toxic gas is generated, and can be usefully used as an electric and electronic material that requires various developments by solving high temperature stability and color problems, which are disadvantages of using flame-retardants.

Claims (6)

(A) 73-97 weight% of polybutylene terephthalate resins (PBT), (B) the structure of formula 1 [Formula 1] 2-15% by weight of an alkylphosphonic acid compound represented by (wherein R is a linear or branched alkyl group having 1 to 4 carbon atoms and X is 0 or 1), and (C) 1 to 12% by weight of ammonium polyphosphate as the second flame retardant, Ammonium polyphosphate as the second flame retardant has a degree of polymerization (n) of 100 or more and a decomposition temperature of 270 ° C., wherein the ammonium polyphosphate-containing non-halogen flame-retardant polybutylene terephthalate resin composition. The method of claim 1, The polybutylene terephthalate resin of component (A) is copolymerized with polytetramethylene glycol (PTMG), polyethylene glycol (PEG), polypropylene glycol (PPG), low molecular weight aliphatic polyester or low molecular weight aliphatic polyamide, or impact Ammonium polyphosphate-containing non-halogen flame-retardant polybutylene terephthalate resin composition, characterized in that the modified polybutylene terephthalate blended with a reinforcing agent. The method of claim 1, An ammonium polyphosphate-containing non-halogen flame-retardant polybutylene terephthalate resin composition, wherein the alkylphosphonic acid compound as the first flame retardant is contained at 3 to 10% by weight. The method of claim 1, An ammonium polyphosphate-containing non-halogen flame-retardant polybutylene terephthalate resin composition comprising 2 to 8% by weight of ammonium polyphosphate as a second flame retardant. delete The method of claim 1, The resin composition is 1 to 50% by weight of one or more fillers selected from the group consisting of carbon fibers, glass fibers, glass beads, glass flakes, carbon black, clay, kaolin, talc, mica, calcium carbonate based on 100 parts by weight of the total resin composition An ammonium polyphosphate-containing non-halogen flame-retardant polybutylene terephthalate resin composition, which is further contained in a portion.