KR100810686B1 - Fire retardant polyester resin composition and plastic article - Google Patents

Abstract

A fireproof polyester-based resin composition, and a plastic molded product are provided to improve fire-proofness, tensile strength, thermal stability, electrical insulation and moldability. A fireproof polyester-based resin composition comprises 100 parts by weight of a base resin which comprises 30-70 wt% of a polyester resin and 30-70 wt% of a polycarbonate resin; 5-30 parts by weight of a halogen compound; 0.5-5 parts by weight of antimony oxide; and 0.01-5 parts by weight of a resin stabilizer. Preferably the halogen compound comprises a bromine compound represented by the formula 1, wherein n is an integer of 3 or more; and the antimony oxide has an average diameter of 0.2-0.4 micrometers.

Description

Flame-retardant polyester resin composition and plastic molded article {FIRE RETARDANT POLYESTER RESIN COMPOSITION AND PLASTIC ARTICLE}

The present invention relates to a flame retardant polyester resin composition and a plastic molded article. More specifically, the present invention relates to a polyester resin composition and a plastic molded article exhibiting various physical properties such as excellent flame retardancy (flame retardancy or fire resistance) or moldability.

In recent years, as the number of large fire disasters increase and the damage to human life and property damage increase, interest in the flameproof resin material which can be used for insulation of various electronic and electrical products has been focused.

Accordingly, the glow-wire ignition temperature (GWIT) is, for example, about 775 ° C with excellent flame retardancy of UL 94 V-0 standard, which satisfies IEC 60335-1, the European home electrical appliance standard. There is a demand for a resin material that exhibits low ignition properties.

In accordance with these demands, researches and attempts on flame retardant resin materials are continuously made. However, conventionally developed flame retardant resin materials do not satisfy the above-mentioned requirements because they are not sufficiently flame retardant or ignitable, or they do not have sufficient physical properties such as thermal stability, formability or electrical insulation properties.

For example, flame retardant polyester or polyamide resin compositions containing compounds derived from triazine and organic phosphorus compounds have been disclosed, but these resin compositions have insufficient thermal stability and formability.

Accordingly, the present invention is to provide a flame-retardant polyester resin composition showing excellent flame resistance (flame retardancy or fire), and excellent in various physical properties such as moldability or thermal stability.

Another object of the present invention to provide a plastic molded article prepared using the composition.

Technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

The present invention includes a base resin containing 30 to 70% by weight of the polyester resin, and 30 to 70% by weight of the polycarbonate resin; And 5 to 30 parts by weight of a halogen compound, 0.5 to 5 parts by weight of an antimony oxide, and 0.01 to 5 parts by weight of a resin stabilizer, based on 100 parts by weight of the base resin. .

The present invention also provides a plastic molded article prepared from the flame retardant polyester resin composition.

Other specific details of the embodiments of the present invention are included in the following detailed description.

Hereinafter, specific embodiments of the present invention will be described in detail to enable those skilled in the art to clearly appreciate. However, this is presented as an example of the present invention, whereby the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

According to one embodiment of the invention, the base resin including 30 to 70% by weight of the polyester resin, and 30 to 70% by weight of the polycarbonate resin; And a flame retardant polyester resin composition comprising 5 to 30 parts by weight of a halogen compound, 0.5 to 5 parts by weight of an antimony oxide, and 0.01 to 5 parts by weight of a resin stabilizer based on 100 parts by weight of the base resin. .

Such flame retardant polyester resin composition includes a halogen compound, an antimony oxide and a resin stabilizer in a preferable content range together with a basic resin including a polyester resin and a polycarbonate which are basic constituents, for example, UL 94 V- Excellent flame retardancy of 0 standard and Glow-Wire Ignition Temperature (GWIT) is low ignition of about 775 ℃ to enable the provision of a polyester-based thermoplastic resin having excellent flame retardancy. In addition, the polyester-based thermoplastic resin is also excellent in various physical properties such as formability, thermal stability or electrical insulation properties. Accordingly, the flame retardant polyester resin composition is excellent in general physical properties such as flame retardancy and moldability, thereby providing a flame retardant polyester thermoplastic resin which can be preferably used for insulation of various electronic and electrical products.

The structure of such a flame-retardant polyester-based resin composition is specifically as follows for each component.

The polyester-based resin composition includes a base resin including a polyester resin and a polycarbonate resin.

As the polyester resin included in the base resin, a thermoplastic polyester resin or a copolyester resin may be used without limitation. For example, such a polyester resin may include polyethylene terephthalate (PET) and polybutylene terephthalate ( Polyalkylene terephthalates such as PBT) or polytrimethylene terephthalate (PTT); Polyalkylene naphthalates such as polyethylene naphthalate (PEN), polypropylene naphthalate or polybutylene naphthalate (PBN); Or resins, such as polyalkylene dibenzoate, such as polyethylene bibenzoate and its copolyester, can be used without a restriction | limiting. It is also possible to use two or more copolymer resins or two or more mixtures of these resins.

Such polyester resin is included in the content range of 30 to 70% by weight in the base resin. If the content of the polyester resin included in the base resin is less than 30% by weight, the electrical insulation properties of the flame-retardant polyester resin composition and the polyester-based thermoplastic resin formed therethrough may be lowered, and 70% by weight. When exceeding, the flammability of the said polyester type thermoplastic resin etc. becomes high, for example, GWIT may not satisfy | fill the low flammability requirement which is about 775 degreeC.

On the other hand, the polycarbonate resin contained in the base resin can be produced by reacting a dihydric phenol compound and phosgene in the presence of a molecular weight regulator and a catalyst according to a conventional production method. In another embodiment, the polycarbonate resin may be prepared using an ester interchange reaction of a dihydric phenol compound and a carbonate precursor such as diphenyl carbonate.

In the production method of such a polycarbonate resin, a bisphenol compound may be used as the dihydric phenol compound, and preferably 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) may be used. . In this case, the bisphenol A may be partially or wholly replaced by another type of dihydric phenol compound. Examples of other types of dihydric phenolic compounds that can be used include hydroquinone, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane and 1,1-bis (4-hydroxyphenyl) cyclo Hexane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) Halogenated bisphenols such as sulfoxide, bis (4-hydroxyphenyl) ketone or bis (4-hydroxyphenyl) ether, and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane Can be mentioned.

However, the type of dihydric phenolic compound that can be used for the production of the polycarbonate resin is not limited thereto, and the polycarbonate resin may be manufactured using any dihydric phenolic compound.

In addition, the polycarbonate resin may be a homopolymer using one type of dihydric phenolic compound, a copolymer using two or more types of dihydric phenolic compounds, or a mixture thereof.

In general, the polycarbonate resin may take the form of a linear polycarbonate resin, a branched polycarbonate resin, or a polyester carbonate copolymer resin, and the like, and the polycarbonate resin included in the polycarbonate resin composition may be formed in a specific form. Without limitation, all of these linear polycarbonate resins, branched polycarbonate resins, polyester carbonate copolymer resins, and the like can be used.

Among these, as said linear polycarbonate resin, a bisphenol-A polycarbonate resin can be used, for example, As said branched polycarbonate resin, For example, polyfunctionality, such as trimellitic anhydride or trimellitic acid, Those prepared by reacting an aromatic compound with a dihydric phenolic compound and a carbonate precursor can be used. As the polyester carbonate copolymer resin, for example, one produced by reacting a bifunctional carboxylic acid with a dihydric phenol and a carbonate precursor can be used. In addition, conventional linear polycarbonate resins, branched polycarbonate resins, or polyester carbonate copolymer resins can be used without limitation.

The polycarbonate resin described above is included in the content range of 30 to 70% by weight in the base resin. If the content of the polycarbonate resin contained in the base resin is less than 30% by weight, the flame retardant polyester resin composition and the polyester-based thermoplastic resin formed therethrough are high in ignition, for example, GWIT is about 775 ℃ The low flammability may not be satisfied. On the contrary, when the content exceeds 70% by weight, electrical insulation properties of the polyester-based thermoplastic resin and the like may be deteriorated.

On the other hand, the flame-retardant polyester resin composition also contains a halogen compound. Such a halogen compound may include, for example, a brominated compound of Formula 1 below.

[Formula 1]

In the general formula (1), the degree of polymerization n represents an integer of 3 or more, preferably an integer between 4 and 100.

As the halogen compound is included, the flame retardant polyester resin composition and the polyester thermoplastic resin formed therefrom may exhibit excellent flame resistance.

The halogen compound is included in the flame retardant polyester resin composition in a content range of 5 to 30 parts by weight based on 100 parts by weight of the above-described base resin. When the content of the halogen compound is less than 5 parts by weight, the flame retardancy of the flame-retardant polyester resin composition and the polyester-based thermoplastic resin formed therefrom may be lowered. On the contrary, when the content of the halogen compound exceeds 30 parts by weight, the polyester-based thermoplastic resin or the like. Thermal stability, electrical insulation characteristics and the like can be lowered.

In addition, the flame retardant polyester resin composition comprises an antimony oxide. Such antimony oxide may include antimony trioxide or antimony pentoxide.

Such antimony oxide may synergize with the above-described halogen compound, such that the flame-retardant polyester resin composition and the polyester-based thermoplastic resin formed therefrom may exhibit, for example, excellent flame retardancy of UL 94 V-0 standard. have.

The antimony oxide, for example, may have an average particle diameter of 0.2 ~ 0.4 ㎛.

In addition, the antimony oxide is included in the flame retardant polyester resin composition in a content range of 0.5 to 5 parts by weight based on 100 parts by weight of the above-described base resin. If the content of the halogen compound is less than 0.5 parts by weight, the flame retardancy of the flame-retardant polyester resin composition and the polyester-based thermoplastic resin formed therethrough may be lowered. The mechanical properties (for example, mechanical strength such as tensile strength), thermal stability and the like may be lowered.

On the other hand, the flame-retardant polyester-based resin composition includes a resin stabilizer together with each of the above-described components. Such a resin stabilizer may be, for example, a polyester resin included in the flame retardant polyester resin composition in the process of manufacturing a polyester thermoplastic resin or a plastic molded article from the flame retardant polyester resin composition through extrusion or injection. Stabilizes polycarbonate resins and serves to inhibit these resins from being degraded (eg, pyrolyzed) or reacting with each other.

As the resin stabilizer is included, the polyester resin or the polycarbonate resin included in the polyester resin composition may better express its characteristics, and thus, the heat of the flame retardant polyester thermoplastic resin Stability or moldability may be further improved.

As the resin stabilizer, any conventionally known resin stabilizer can be used without limitation. For example, as the resin stabilizer, phosphoric acid, triphenyl phosphite, trimethyl phosphite, triisodecyl phosphite and tri- (2,4-di-t-butylphenyl) phosphite and 3,5-di- One substance or a mixture of two or more selected from the group consisting of t-butyl-4-hydroxybenzylphosphonic acid can be used.

The resin stabilizer is included in the content range of 0.01 to 5 parts by weight based on 100 parts by weight of the above-described base resin. When the resin stabilizer is included in an amount of more than 5 parts by weight, mechanical properties of the polyester-based thermoplastic resin may be lowered.

On the other hand, by mixing each of the above-described components to prepare a flame-retardant polyester resin composition, and melt-extruding such flame-retardant polyester resin composition in an extruder, from a polyester-based thermoplastic resin or The plastic molded article to be manufactured can be manufactured.

According to another embodiment of the invention, there is provided a plastic molded article prepared from the flame-retardant polyester resin composition described above. Such plastic molded articles include, for example, a resin substrate made of a base resin including a polyester resin and a polycarbonate resin; And a halogen compound dispersed in the resin substrate, an antimony oxide, and a resin stabilizer.

That is, such a plastic molded article is a polyester resin and a polycarbonate resin are bonded to each other to form a resin substrate, the halogen compound, antimony oxide, resin stabilizer and the like are uniformly dispersed in the resin substrate, for example, UL Excellent flame retardancy of 94 V-0 standard and low ignition of GWIT is about 775 ℃ can have excellent flame retardancy. In addition, these plastic molded articles also have excellent physical properties such as formability, thermal stability, or electrical insulation properties.

Therefore, such a plastic molded article can be preferably used as a flame retardant material for insulation of various electronic and electrical products.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.

(A) polyester resin, (B) polycarbonate resin, (C) halogen compound, (D) antimony oxide, (E) resin stabilizer, (F) phosphazene (comparative example) used by the Example and comparative example mentioned later The specific specification of each component of the following) is as follows.

(A) polyester resin

(a ₁ ) polybutylene terephthalate

As one of the polyester resins, polybutylene terephthalate having an intrinsic viscosity [?] Of 0.83 measured at 25 ° C. under o-chlorophenol solvent was used.

(a ₂ ) Polyethylene terephthalate

As one of the polyester resins, polyethylene terephthalate having an intrinsic viscosity [η] of 0.8 measured at 25 ° C. under o-chlorophenol solvent was used.

(B) polycarbonate resin

As the polycarbonate resin, a bicarbonate-A polycarbonate resin having a weight average molecular weight (Mw) of 25,000 g / mol was used.

(C) halogen compounds

As a halogen compound, BC-58 (2,4,6-Tribromophenyl-terminated tetrabromobisphenol-A carbonate oligomer) of Great Lakes was used.

(D) antimony oxide

As antimony oxide, antimony trioxide whose average particle diameter was 0.3 micrometer was used.

(E) resin stabilizer

IRGANOX B 215 from Ciba Geigy (a 1: 2 mixture of IRGANOX 1010 (hindered phenolic antioxidant) and IRGAFOS 168 (organophosphite)) was used.

(F) phosphazene (comparative example)

As phosphazene, an organophosphorus compound derived from triazine, SPS-100 of OTSUKA Chemical Co., Ltd. was used.

Examples 1-4 and Comparative Examples 1-7

Flame-retardant polyester-based resin composition was prepared by mixing each of the above components in the content range shown in Table 1 below, melt-kneading each flame-retardant polyester-based resin composition in a twin screw melt extruder heated to 240 ~ 280 ℃ It was prepared in a chip state. Subsequently, after the obtained chip was dried at 130 ° C. for at least 5 hours, a 0.8 mm thick specimen for flame retardancy evaluation using a screw injection machine heated to 240˜280 ° C., and a flat specimen for evaluation of various physical properties such as GWIT ( 10 cm x 10 cm x 0.3 cm thick) was prepared.

TABLE 1

Various physical properties of the specimen were measured by the following method.

First, the tensile strength of the specimens was measured (mechanical strength evaluation) according to ASTM D638, a US standard measurement method for measuring the tensile strength of plastics.

In addition, the color change of the specimen was measured after storage for 10 minutes in the injection molding machine (thermal stability evaluation).

In addition, the dielectric breakdown strength of the specimen was measured according to ASTM D149, which is a standard measurement method of the United States (electrical insulation property evaluation).

In addition, the GWIT of the specimen was measured according to IEC 60692-2-13, which is a standard measurement method in Europe (ignition evaluation).

In addition, the flame resistance of the specimen was measured by the UL-94 vertical test method, which is a standard measurement method in the United States, which evaluates the flame resistance of various plastic products (flame retardancy evaluation).

In addition, the cycle time at the time of injection molding and whether the ejected resultant had an eject pin mark were measured (formation evaluation).

Various physical properties measured through this method are shown in Table 2 below.

TABLE 2

Referring to Table 2, the specimens of Examples 1 to 4 containing a basic resin containing a polyester resin and a polycarbonate resin, a halogen compound, an antimony oxide, and a resin stabilizer, a halogen compound, an antimony oxide, Compared with the specimen of Comparative Example 7, which does not contain a resin stabilizer, it is confirmed that various properties such as excellent moldability, flame retardancy, thermal stability, and tensile strength are exhibited.

In addition, the specimens of Examples 1 to 4 containing the base resin, a halogen compound, an antimony oxide, and a resin stabilizer in a preferred content range, have a content of polyester resin or polycarbonate resin contained in the base resin. Compared with the specimens of Comparative Examples 1 or 2 outside the preferred content range, it was confirmed that they exhibit excellent flame resistance (flame retardancy or fire resistance), formability or electrical insulation properties.

In addition, the specimens of Examples 1 to 4, compared to the specimens of Comparative Examples 3 to 6 in which the content of the halogen compound or antimony oxide is outside the preferred content range, have excellent flame retardancy (Comparative Examples 4 and 5) or excellent heat. It is confirmed that the stability and electrical insulation properties are shown (Comparative Examples 3 and 6).

Therefore, the specimens of Examples 1 to 4 are not only excellent in overall physical properties such as tensile strength, thermal stability, electrical insulation properties or moldability, but also have excellent flame retardancy and GWIT of UL 94 V-0 standard. It is confirmed that it has excellent flame retardance by exhibiting low ignition to about 775 ° C.

As described above, the flame retardant polyester resin composition of the present invention not only has excellent flame retardancy, but also makes it possible to provide a polyester thermoplastic resin having excellent overall physical properties such as tensile strength, thermal stability, electrical insulation properties, or moldability. do.

Therefore, the polyester-based thermoplastic resin can be preferably used for the insulation of various electronic and electrical products.

Claims (11)

Basic resins containing 30 to 70 weight% of polyester resin and 30 to 70 weight% of polycarbonate resin; And A flame retardant polyester resin composition comprising 5 to 30 parts by weight of a halogen compound, 0.5 to 5 parts by weight of an antimony oxide, and 0.01 to 5 parts by weight of a resin stabilizer based on 100 parts by weight of the base resin. The method of claim 1, wherein the polyester resin is selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate and polyethylene bibenzoate. Flame retardant polyester-based resin composition comprising one selected resin, two or more copolymer resins or two or more mixtures. The flame retardant polyester resin composition of claim 1, wherein the polycarbonate resin comprises one polymer or a mixture of two or more selected from the group consisting of linear polycarbonate resins, branched polycarbonate resins, and polyester carbonate copolymer resins. The flame retardant polyester resin composition of claim 3, wherein the linear polycarbonate resin comprises a bisphenol A-based polycarbonate resin. The flame-retardant polyester resin composition of claim 3, wherein the branched polycarbonate resin is prepared by reacting a trimellitic anhydride or a polyfunctional aromatic compound of trimellitic acid with a dihydric phenol compound and a carbonate precursor. . The flame retardant polyester resin composition according to claim 1, wherein the halogen compound comprises a brominated compound of the following general formula (1). [Formula 1]

In the general formula 1, the degree of polymerization n represents an integer of 3 or more. The flame retardant polyester resin composition of claim 1, wherein the antimony oxide comprises antimony trioxide or antimony pentoxide. The flame retardant polyester resin composition of claim 1, wherein the antimony oxide has an average particle diameter of 0.2 μm to 0.4 μm.  The resin stabilizer according to claim 1, wherein the resin stabilizer is phosphoric acid, triphenylphosphite, trimethylphosphite, triisodecylphosphite, tri (2,4-di-t-butylphenyl) phosphite and 3,5-di-t- Flame retardant polyester resin composition comprising one or a mixture of two or more selected from the group consisting of butyl-4-hydroxybenzylphosphonic acid. A plastic molded article made of the flame retardant polyester resin composition according to any one of claims 1 to 9. A resin substrate composed of a base resin comprising 30 to 70 wt% of a polyester resin and 30 to 70 wt% of a polycarbonate resin, and A plastic molded article comprising 5 to 30 parts by weight of a halogen compound dispersed in a base resin substrate, 0.5 to 5 parts by weight of antimony oxide, and 0.01 to 5 parts by weight of a resin stabilizer based on 100 parts by weight of the base resin.