# Patent

## Title
Flame retardant thermoplastic polyester resin composition

## Abstract

Disclosed herein is a flame retardant thermoplastic polyester resin composition comprising: (A) about 100 parts by weight of a polyester resin; (B) about 1 to about 60 parts by weight of a cyclic oligomeric phosphazene compound; (C) about 1 to about 50 parts by weight of a melamine compound; (D) about 1 to about 20 parts by weight of a inorganic metal compound; and (E) about 0.1 to about 5 parts by weight of a fluorinated polyolefin resin. The thermoplastic polyester resin composition may further contain a filler (F).

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This non-provisional application is a continuation-in-part application of PCT Application No. PCT/KR2007/006814, filed Dec. 26, 2007, pending, which designates the U.S. and which is hereby incorporated by reference in its entirety, and claims priority therefrom under 35 USC Section 120. This application also claims priority under 35 USC Section 119 from Korean Patent Application No. 10-2006-0137435, filed Dec. 29, 2006, the entire disclosure of which is also hereby incorporated by reference.
FIELD OF THE INVENTION
The present invention relates to a thermoplastic polyester resin composition having good flame retardancy.
BACKGROUND OF THE INVENTION
Thermoplastic polyester resins can have good chemical resistance, mechanical strength, and electrical insulatability, among other properties, and have accordingly been widely used in the production of electric/electronic parts, housings of automobile parts, connectors and the like.
In the field of electric and electronic devices, flame retardancy is especially required to ensure stability during a fire. A widely known method for imparting flame retardancy is the addition of a halogen-containing compound with an antimony oxide and metal oxide as a flame-retardant aid. However, such methods are disadvantageous because halogen gases released by thermal decomposition during molding processes can corrode the mold. Further, such toxic gases are undesirable in the workplace.
In particular, halogenated dioxin generated during a fire or combustion is harmful to humans and may cause environmental contamination. Accordingly, the use of halogen-containing flame retardant s has recently been restricted by law under TCO (The Swedish Confederation of Professional Employees). Thus, currently efforts are ongoing worldwide to develop technologies using halogen-free flame retardants as a substitute for halogen-containing flame retardants.
Japanese patent application laid-open No. 10-195283 discloses a polybutylene terephthalate resin composition using a phosphoric acid ester as a flame retardant. However, in this case, a large amount of flame retardant is needed to obtain sufficient flame retardancy. As a result, production costs may increase and the mechanical properties of the resin composition can be deteriorated.
U.S. Pat. No. 6,569,928 discloses a polyester resin composition comprising a melamine compound (melamine cyanurate) and phosphoric acid ester. However, this composition also requires a large amount of flame retardant to obtain flame retardancy, which results in deterioration of moldability and mechanical properties.
SUMMARY OF THE INVENTION
The present inventors have developed a thermoplastic polyester resin composition having good flame retardancy without deterioration of mechanical properties and which does not generate toxic halogen gas. The invention uses an oligomeric phosphazene compound, a melamine compound, an inorganic metal compound, a fluorinated polyolefin resin and a filler with a polyester base resin in a specific ratio.
Accordingly, one aspect of the invention provides a flame retardant thermoplastic polyester resin composition. The resin composition comprises (A) about 100 parts by weight of a polyester resin; (B) about 1 to about 60 parts by weight of a cyclic oligomeric phosphazene compound; (C) about 1 to about 50 parts by weight of a melamine compound; (D) about 1 to about 20 parts by weight of a inorganic metal compound; and (E) about 0.1 to about 5 parts by weight of a fluorinated polyolefin resin.
The thermoplastic polyester resin composition may further comprise a filler (F) in an amount of about 100 parts by weight or less. The filler (F) may comprise carbon fiber, glass fiber, glass beads, glass flake, carbon black, talc, clay, kaolin, mica, calcium carbonate, or a combination thereof.
The thermoplastic polyester resin composition may further comprise an additive selected from flame retardant aids, lubricants, release agents, nucleating agents, antistatic agents, stabilizers, reinforcing agents and combinations thereof.


DETAILED DESCRIPTION OF THE INVENTION
The present invention now will be described more fully hereinafter in the following detailed description of the invention, in which some, but not all embodiments of the invention are described. Indeed, this invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will satisfy applicable legal requirements.
(A) Polyester Resin
The polyester resin used as a base resin in the present invention may include thermoplastic polyester, copolyester, or a combination thereof. In exemplary embodiments of the invention, the polyester resin may include a polyalkylene terephthalate such as polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate, a polyalkylene naphthalate such as polyethylene naphthalate, polypropylene naphthalate, and polybutylene naphthalate, a dibenzoate such as polyethylene dibenzoate, and the like, and copolyesters and combinations thereof.
The polyethylene terephthalate can be a polycondensation polymer prepared by transesterification or esterification of terephthalic acid or dimethyl terephthalate with ethylene glycol.
The polybutylene terephthalate can be a polycondensation polymer prepared by transesterification or esterification of terephthalic acid or dimethyl terephthalate with 1,4-butandiol.
In exemplary embodiments of the invention, the polybutylene terephthalate can be modified by copolymerizing with one or more comonomers such as polytetramethylene glycol (PTMG), polyethylene glycol (PEG), polypropylene glycol (PPG), low-molecular-weight aliphatic polyester or aliphatic polyamide, and the like, and combinations thereof to improve the impact strength of the resin. In another embodiment, a modified polybutylene terephthalate prepared by blending an impact modifier can be used.
In exemplary embodiments of the invention, the polyester resin comprises polybutylene terephthalate having an intrinsic viscosity [η] of about 0.36 to about 1.6, for example about 0.52 to about 1.25, as measured in a solvent of o-chlorophenol at a temperature of 25° C. If the intrinsic viscosity [η] of the polybutylene terephthalate is in the range of about 0.36 to about 1.6, the resin composition may have an improved balance of physical properties such as mechanical properties and moldability.
(B) Cyclic Oligomeric Phosphazene Compound
The cyclic oligomeric phosphazene compound can be represented by Formula (I) in which cyclic phosphazenes are linked by a R2 group. The cyclic oligomeric phosphazene compound may be used singly or in combination.




wherein each R1 is independently C1-C20 alkyl, C6-C30 aryl, C6-C30 alkyl substituted aryl, C6-C30 arylakyl, C1-C20 alkoxy, C6-C30 aryloxy, amino, or hydroxyl, wherein the alkoxy or the aryloxy can optionally be substituted with C1-C20 alkyl, C6-C30 aryl, amino, or hydroxy group;
each k and m is independently 0 or integers from 1 to 10;
R2 is C6-30 dioxyaryl or alkyl substituted C6-30 dioxyaryl derivative; and
n is a number-average degree of polymerization and the average value of n is from about 0.3 to about 3.
In exemplary embodiments, the cyclic oligomeric phosphazene compound (B) can be used in an amount of about 1 to about 60 parts by weight, based on about 100 parts by weight of polyester resin (A). If the amount of the cyclic oligomeric phosphazene compound is less than 1 parts by weight, the resin composition may not have sufficient flame retardancy. If the amount of the cyclic oligomeric phosphazene compound is more than 60 parts by weight, the production cost may increase and the mechanical strength of the resin composition may be deteriorated. In exemplary embodiments of the invention, the cyclic oligomeric phosphazene compound may be used in an amount of about 10 to about 55 parts by weight, for example from about 20 to about 54 parts by weight, and as another example from about 25 to about 53 parts by weight.
(C) Melamine Compound
The melamine compound of the present invention may include a nitrogen-containing compound, a nitrogen-phosphorus-containing compound, or a combination thereof. Exemplary nitrogen-containing compounds may include without limitation melamine, melamine cyanurate, and the like, and combinations thereof. Exemplary nitrogen-phosphorus-containing compounds may include without limitation melamine phosphate, melamine pyrophosphate, melamine polyphosphate, and the like, and combinations thereof.
The melamine compound can be used in an amount of about 1 to about 50 parts by weight, for example about 5 to about 45 parts by weight, and as another example about 7 to about 40 parts by weight, based on about 100 parts by weight of the polyester resin (A). If the amount of the melamine compound is less than about 1 part by weight, the flame retardancy may be degraded. On the other hand, if the amount of the melamine compound is more than about 50 parts by weight, the mechanical properties may become lower.
(D) Inorganic Metal Compound
The inorganic metal compound is used to improve the flame retardancy. Exemplary inorganic metal compounds may include without limitation aluminum hydroxide, magnesium hydroxide, calcium hydroxide, zinc sulfide, zinc oxide, titanium oxide, magnesium calcium carbonate, magnesium carbonate, calcium carbonate, zinc borate, zinc borate hydrate, magnesium sulfate hydrate and the like, and combinations thereof. The inorganic metal compound(s) may be used singly or in combination.
The amount of the inorganic metal compound may be about 1 to about 20 parts by weight, for example about 5 to about 18.5 parts by weight, and as another example about 7 to about 17 parts by weight, based on about 100 parts by weight of the polyester resin (A). If the amount of the inorganic metal compound is less than about 1 part by weight, the flame retardancy may be degraded. On the other hand, if the amount of the inorganic metal compound is more than about 20 parts by weight, the mechanical properties may become lower.
(E) Fluorinated Polyolefin Resin
Exemplary fluorinated polyolefin resins may include, but are not limited to, polytetrafluoroethylene, polyvinylidenefluoride, tetrafluoroethylene/vinylidenefluoride copolymer, tetrafluoroethylene/hexafluoropropylene copolymer, and ethylene/tetrafluoroethylene copolymer and the like. These resins may be used singly or in combination.
The fluorinated polyolefin resin functions to form a fibrillar network in the resin composition when the resin composition is extruded, thereby decreasing melt viscosity of the resin composition and increasing shrinkage during combustion so as to prevent the dripping phenomena.
The fluorinated polyolefin resin can be prepared via polymerization techniques known in the art. According to exemplary embodiments, the fluorinated polyolefin resin can be prepared in an aqueous medium under a pressure of between about 7 and about 71 kg/cm2 at a temperature of between about 0 and about 200° C., for example about 20 and about 100° C., in the presence of a free radical-forming catalyst such as sodium, potassium or ammonium peroxydisulfate, and the like.
According to exemplary embodiments, the fluorinated polyolefin resin can be used in an emulsive or powder state. When used as an emulsion, dispersion of the fluorinated polyolefin resin may be good, but the process will be somewhat complicated. Accordingly, the fluorinated polyolefin resin can be used as a powder state to uniformly disperse it in the entire resin composition to form the fibrillar network structure.
According to exemplary embodiments, the fluorinated polyolefin resin may be polytetrafluoroethylene having an average particle size ranging from about 0.05 and about 1,000 μm and a density ranging from about 1.2 and about 2.3 g/cm3.
The fluorinated polyolefin resin can be used in an amount of about 0.1 to about 5 parts by weight, for example about 0.3 to about 4 parts by weight, and as another example about 0.4 to about 3 parts by weight, based on about 100 parts by weight of the polyester resin (A).
(F) Filler
In some embodiments, the composition may additionally comprise fillers of various particle sizes to increase mechanical properties, heat-resistance, dimensional stability and the like.
In exemplary embodiments, the filler can be a conventional inorganic or organic filler, or a combination thereof. Exemplary fillers may include, but are not limited to, carbon fiber, glass fiber, glass beads, glass flake, carbon black, talc, clay, kaolin, mica, calcium carbonate, and the like and combinations thereof. These fillers can be used alone or in combination with one another.
The filler can be used in an amount of about 100 parts by weight or less, for example about 5 to about 80 parts by weight, as another example about 10 to about 75 parts by weight, and as another example about 15 to about 70 parts by weight, based on about 100 parts by weight of the polyester resin (A).
The flame retardant thermoplastic polyester resin composition may additionally comprise conventional additives such as flame retardant aids, lubricants, release agents, nucleating agents, antistatic agents, stabilizers, reinforcing agents and the like. These additives can be used alone or in combination with one another.
The flame retardant thermoplastic polyester resin composition according to the present invention can be extruded in the form of pellets. In some embodiments, the resin composition can be molded into an electronic or electric sockets and connectors for use in a variety of products including TVs, computers, printers, washing machines, cassette players, audio systems and the like.
The flame retardant thermoplastic polyester resin composition according to the present invention can be widely used in many fields which require good flame retardancy and high mechanical properties.
The invention may be better understood by reference to the following examples which are intended for the purpose of illustration and are not to be construed as in any way limiting the scope of the present invention, which is defined in the claims appended hereto.
EXAMPLE
(A) Polyester Resin
Polybutylene terephthalate having an intrinsic viscosity [η] of 1.0 as measured in a solvent of o-chlorophenol at a temperature of 25° C. is used.
(B) Cyclic Oligomeric Phosphazene Compound
Phosphazene (SPS-100) manufactured by Otsuka Chemical Co. of Japan is used.
(C) Melamine Compound
Melamine cyanurate (MC-120A) manufactured by Universal Chemtech Co. of Korea is used.
(D) Inorganic Metal Compound
Magnesium hydroxide (H-5) manufactured by Albemarle Co. is used.
(E) Fluorinated Polyolefin Resin
Teflon 800-J manufactured by Dupont Company is used.
(F) Filler
VETROTEX 952 glass fibers manufactured by Vetrotex are used.
(G) Phosphoric Acid Ester
RDP (PX-200) manufactured by Daihachi Co. of Japan is used.
Examples 1-5 and Comparative Examples 1-8
The components as shown in Table 1 are melted and kneaded through a twin-screw melt extruder at 240 to 280° C. to prepare a resin composition in a chip shape. The chips are dried at 130° C. for 5 hours or more, and molded into test specimens for measuring flame retardancy and mechanical properties using a screw type injection molding machine at 240 to 280° C.










TABLE 1









Examples
Comparative Examples





















1
2
3
4
5
1
2
3
4
5
6
7
8























(A) PBT
100
100
100
100
100
100
100
100
100
100
100
100
100


(B) Cyclic
30
50
30
30
30
—
80
30
30
30
30
—
30


Oligomeric


Phosphazene


(C) Melamine
10
10
25
10
10
10
10
—
60
10
10
10
—


cyanurate


(D) Inorganic
10
10
10
15
10
10
10
10
10
—
30
10
10


Metal


Compound


(E) Fluorinated
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5


Polyolefin


resin


(F) Filler
60
60
60
60
—
60
60
60
60
60
60
60
—


(G) Phosphoric
—
—
—
—
—
—
—
—
—
—
—
30
—


Acid Ester









The flame retardancy, impact strength, tensile strength, flexural strength and flexural modulus of the test specimens are measured as follows, and the results are shown in Table 2.
Property Test
(1) Flame Retardancy: The flame retardancy is measured in accordance with UL94 vertical test at a thickness of 1⁄8 inch and 1/16 inch respectively.
(2) Impact Strength: The impact strength is measured in accordance with ASTM D256 at 1⁄8′′ thickness.
(3) Tensile Strength: The tensile strength is measured in accordance with ASTM D638 at 1⁄8′′ thickness.
(4) Flexural Strength: The flexural strength is measured in accordance with ASTM D790 at 1⁄4′′ thickness.
(5) Flexural Modulus: The flexural modulus is measured in accordance with ASTM D790 at 1⁄4′′ thickness.










TABLE 2 










Comparative



Examples
examples

















1
2
3
4
5
1
2





Flame
1⁄8′′
V-0
V-0
V-0
V-0
V-0
fail
V-0


retardancy
 1/16′′
V-0
V-0
V-0
V-0
V-0
fail
V-0














Impact strength
5.6
5.0
6.3
5.1
3.3
6.0
5.0


(kgfcm/cm)


tensile strength
883
840
864
850
490
881
620


(kgfcm2)


flexural strength
1,210
1,130
1,200
1,160
630
1,200
650


(kgfcm2)


flexural modulus
73,230
72,150
80,100
73,200
20,600
82,200
65,100


(kgfcm2)












Comparative examples


















3
4
5
6
7
8







Flame
1⁄8′′
V-1
V-0
fail
V-0
fail
Fail



retardancy
 1/16′′
fail
V-0
fail
fail
fail
fail















Impact strength
5.5
4.2
6.4
3.5
4.2
3.2



(kgfcm/cm)



tensile strength
840
680
880
650
650
480



(kgfcm2)



flexural strength
1,100
710
1,170
650
720
620



(kgfcm2)



flexural modulus
75,340
67,250
80,680
62,200
68,600
19,900



(kgfcm2)










As shown in Table 2, Examples 1 to 5 according to the present invention show good mechanical properties as well as high flame retardancy. However, Comparative Example 1, which did not include the cyclic oligomeric phosphazene compound (B), Comparative Example 3, which did not include the melamine compound (C), and Comparative Example 5, which did not include the inorganic metal compound (D), exhibit poor flame retardancy. Comparative Examples 2 and 4, which include the cyclic oligomeric phosphazene compound (B) or the melamine compound (C) in an amount outside of the amount of the present invention, respectively, exhibit inferior mechanical properties. Comparative Example 6, which includes the inorganic metal compound (D) in an amount in excess of the range of the present invention, exhibits bad flame retardancy as well as inferior mechanical properties. Further, Comparative Example 7, which uses the phosphoric acid ester (G) instead of the oligomeric phosphazene compound (B), exhibits deterioration in flame retardancy and mechanical properties. Comparative Example 8, which does not include either melamine compound (C) or filler (F), also exhibits poor flame retardancy and low mechanical properties.
Many modifications and other embodiments of the invention will come to mind to one skilled in the art to which this invention pertains having the benefit of the teachings presented in the foregoing descriptions. Therefore, it is to be understood that the invention is not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation, the scope of the invention being defined in the claims.

## Claims

1. A flame retardant thermoplastic polyester resin composition comprising:
(A) about 100 parts by weight of a polyester resin, wherein said polyester resin (A) comprises polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate, polyethylene dibenzoate, a copolyester thereof, or a combination thereof;
(B) about 1 to about 60 parts by weight of a cyclic oligomeric phosphazene compound, wherein said cyclic oligomeric phosphazene compound (B) is represented by the following Formula 1:




wherein R1 is C1-C20 alkyl, C6-C30 aryl, C6-C30 alkyl substituted aryl, C6-C30 arylakyl, C1-C20 alkoxy, C6-C30 aryloxy, amino, or hydroxyl group, wherein the alkoxy or aryloxy can optionally be substituted with alkyl, aryl, amino, or hydroxyl,
each k and m is independently 0 or integers from 1 to 10;
R2 is C6-30 dioxyaryl or alkyl substituted C6-30 dioxyaryl derivative; and
n is a number-average degree of polymerization and the average value of n is from about 0.3 to about 3;
(C) about 1 to about 50 parts by weight of a melamine compound;
(D) about 1 to about 20 parts by weight of a inorganic metal compound; and
(E) about 0.1 to about 5 parts by weight of a fluorinated polyolefin resin.

2. The flame retardant thermoplastic polyester resin composition of claim 1, further comprising (F) about 100 parts by weight or less of a filler.

3. The flame retardant thermoplastic polyester resin composition of claim 1, wherein said polyester resin (A) comprises polybutylene terephthalate having an intrinsic viscosity [η] of about 0.36 to about 1.6 as measured in a solvent of o-chlorophenol at a temperature of 25° C.

4. The flame retardant thermoplastic polyester resin composition of claim 1, wherein said melamine compound (C) comprises melamine, melamine cyanurate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate or a combination thereof.

5. The flame retardant thermoplastic polyester resin composition of claim 1, wherein said inorganic metal compound (D) comprises aluminum hydroxide, magnesium hydroxide, calcium hydroxide, zinc sulfide, zinc oxide, titanium oxide, magnesium calcium carbonate, magnesium carbonate, calcium carbonate, zinc borate, zinc borate hydrate, magnesium sulfate hydrate or a combination thereof.

6. The flame retardant thermoplastic polyester resin composition of claim 1, wherein said fluorinated polyolefin resin (E) comprises polytetrafluoroethylene, polyvinylidenefluoride, tetrafluoroethylene/vinylidenefluoride copolymer, tetrafluoroethylene/hexafluoropropylene copolymer, ethylene/tetrafluoroethylene copolymer or a combination thereof.

7. The flame retardant thermoplastic polyester resin composition of claim 1, further comprising an additive selected from flame retardant aids, lubricants, release agents, nucleating agents, antistatic agents, stabilizers, reinforcing agents or a combination thereof.

8. The flame retardant thermoplastic polyester resin composition of claim 2, wherein said filler (F) comprises carbon fiber, glass fiber, glass beads, glass flake, carbon black, talc, clay, kaolin, mica, calcium carbonate, or a combination thereof.

9. A molded article prepared with the flame retardant thermoplastic polyester resin composition as defined in claim 1.