JPH11199764A - Flame retardant polyester resin composition - Google Patents

Abstract

(57) [Summary] [Problem] To have good strength, rigidity, heat resistance, fluidity and impact resistance which are inherent properties of a polyester resin, and to have appearance characteristics and flame retardancy, especially dripping prevention during burning. And to provide a flame-retardant polyester resin composition having excellent heat resistance. SOLUTION: (A) Thermoplastic polyester resin 100
Parts by weight, (B) 3 to 50 parts by weight of a bromine-based aromatic compound,
(C) 1 to 30 parts by weight of an antimony oxide compound, (D) 0.1 to 5 parts by weight of polytetrafluoroethylene having fibril-forming ability, (E) olefin-based polymer 0.5
A flame-retardant polyester resin composition, which comprises 5 to 90 parts by weight of (F) an inorganic filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant polyester resin composition, and more particularly to a flame-retardant polyester resin composition excellent in preventing dripping during burning and a molded article produced therefrom.

[0002]

2. Description of the Related Art Flame-retardant polyester resins are excellent in mechanical strength, chemical resistance, electrical insulation and the like, and are widely used in electric and electronic parts, automobile parts, other electric parts, and mechanical parts. In recent years, electric and electronic parts and electrical components have been reduced in thickness due to the trend of miniaturization and weight reduction of various devices, and various molded products used therefor have also been reduced in size and thickness, and flame retardant. Good fluidity is also required for the conductive resin material.

In many cases, such molded products are required to have flame retardancy corresponding to the thinnest part, and the flame retardancy is a flame retardancy of rank V-0 specified in UL-94. Is done. According to this standard, a strip-shaped test piece is ignited by the flame of a gas burner. Is difficult to achieve.

[0004] In order to prevent the falling of the burning material during flame contact,
The addition of a fluorine-containing polyolefin such as polytetrafluoroethylene is disclosed in JP-A-47-42942. However, when the addition amount of the fluorine-containing polyolefin is increased, the fluidity and appearance characteristics of the flame-retardant resin deteriorate. Therefore, it was difficult to obtain a flame-retardant polyester resin composition excellent in prevention of dripping during combustion and excellent appearance characteristics.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyester resin having good properties such as good strength, rigidity, heat resistance, fluidity and impact resistance. An object of the present invention is to provide a flame-retardant polyester resin composition having excellent dripping prevention properties during combustion.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and the gist of the present invention is as follows.
100 parts by weight of a thermoplastic polyester resin, (B) 3 to 50 parts by weight of a brominated aromatic compound, (C) 1 to 30 parts by weight of an antimony oxide compound, and (D) polytetrafluoroethylene 0.1 having a fibril-forming ability. ~ 5 parts by weight,
It is present in a flame-retardant polyester resin composition comprising (E) 0.5 to 5 parts by weight of an olefin polymer and (F) 5 to 90 parts by weight of an inorganic filler.

[0007] As the thermoplastic polyester resin (A) in the present invention, a known aromatic polyester resin can be used. The aromatic polyester resin is a polyester having an aromatic ring in a chain unit of a polymer, and is obtained by a polycondensation reaction containing an aromatic dicarboxylic acid and a diol (and an ester-forming derivative thereof) as main components. A coalescence or a copolymer is mentioned.

The aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid,
2,6-naphthalenedicarboxylic acid, biphenyl-2,
2'-dicarboxylic acid, biphenyl-3,3'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-
4,4'-dicarboxylic acid, diphenylisopropylidene-4,4'-dicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, anthracene-
Examples thereof include 2,5-dicarboxylic acid, anthracene-2,6-dicarboxylic acid, p-terphenylene-4,4′-dicarboxylic acid, and pyridine-2,5-dicarboxylic acid, and preferably terephthalic acid.

These aromatic dicarboxylic acids may be used as a mixture of two or more. In addition, a small amount of these aromatic dicarboxylic acids along with adipic acid, azelaic acid,
One or more alicyclic dicarboxylic acids such as dodecanedioic acid and sebacic acid can be used as a mixture.

The diol component includes aliphatic diols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methylpropane-1,3-diol, diethylene glycol and triethylene glycol, and cyclohexane-1. And alicyclic diols such as 4,4-dimethanol, and mixtures thereof. In addition, if it is a small amount, a long-chain diol having a molecular weight of 400 to 6,000,
That is, one or more kinds of polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, and the like may be copolymerized.

Specific examples of the thermoplastic polyester resin include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene-1,2-bis (phenoxy) ethane-4,4'-.
Dicarboxylate, polycyclohexane dimethanol terephthalate, and the like. Further, as a polymerization component of these thermoplastic polyester resins, isophthalic acid, decanedicarboxylic acid, 4,4′-isopropylidene-bis
[(2,6-dibromophenoxy) ethoxy-2-ethanol], 4,4′-isopropylidene-bis [(2,6
-Dibromophenoxy) ethanol], and thermoplastic polyester resins obtained by copolymerizing monomers such as 4,4'-isopropylidene-bis (phenoxyethoxy-2-ethanol) and 4,4'-isopropylidene-bis (phenoxyethanol). And preferably polybutylene terephthalate.

When the thermoplastic polyester resin is polybutylene terephthalate, the intrinsic viscosity of the polybutylene terephthalate is preferably 1.1 dl / g or less;
More preferably, it is 1.0 dl / g or less. The intrinsic viscosity was measured by dissolving the sample in a mixed solvent of phenol and 1,1,2,2-tetrachloroethane at a weight ratio of 1: 1.
It is measured at 30 ° C. using a Udelove viscometer.

The bromine-based aromatic compound (B) in the present invention is a compound usually used as a bromine-based flame retardant, such as an epoxy oligomer of tetrabromobisphenol A, pentabromobenzyl polyacrylate, or polybromophenyl ether. , Brominated polystyrene, brominated epoxy, brominated imide, brominated polycarbonate and the like. The amount of the brominated aromatic compound is 3 to 50 parts by weight based on 100 parts by weight of the thermoplastic polyester resin. If the amount of the brominated aromatic compound is less than 3 parts by weight, the flame retardant effect is insufficient, and
If the amount exceeds 0 parts by weight, the mechanical strength tends to decrease, and the thermal stability at the time of melting tends to decrease. The amount of the brominated aromatic compound is
The amount is preferably 5 to 40 parts by weight, more preferably 6 to 30 parts by weight, based on 100 parts by weight of the thermoplastic polyester resin.

The antimony compound (C) in the present invention includes, for example, antimony oxide and antimonate. Specific examples thereof include antimony trioxide (Sb
₂ O _3), antimony tetroxide (Sb ₂ O _4), antimony pentoxide (Sb ₂ O ₅₎ and sodium antimonate and the like. The compounding amount of the antimony compound is 1 to 30 parts by weight based on 100 parts by weight of the thermoplastic polyester resin. If the compounding amount of the antimony compound is less than 1 part by weight, a sufficient flame retardant effect cannot be obtained, and if it exceeds 30 parts by weight, the mechanical strength decreases, and the thermal stability at the time of melting tends to decrease. The compounding amount of the antimony compound is preferably 2 to 25 parts by weight, more preferably 3 to 20 parts by weight, based on 100 parts by weight of the thermoplastic polyester resin.

The polytetrafluoroethylene (D) having the ability to form fibrils in the present invention is one that easily disperses in a resin and has a tendency to form a fibrous material by combining polymers. Used as an inhibitor. Polytetrafluoroethylene having fibril-forming ability is classified into Type 3 according to ASTM standards. Polytetrafluoroethylene suitable as polytetrafluoroethylene having a fibril-forming ability is, for example, polyflon FA-500 or F-20 manufactured by Daikin Chemical Industry Co., Ltd.
1L, commercially available as Fluon CD-123 from Asahi Glass Co., Ltd., and Teflon 6J from DuPont-Mitsui Fluorochemicals Co., Ltd.

The compounding amount of polytetrafluoroethylene having a fibril forming ability is as follows.
It is 0.1 to 5 parts by weight with respect to 00 parts by weight. If the compounding amount of polytetrafluoroethylene having fibril forming ability is less than 0.1 part by weight, the effect of the present invention is not exhibited, and if it exceeds 5 parts by weight, extrudability, processability such as moldability is impaired, Impact strength and appearance decrease. The amount of polytetrafluoroethylene having fibril-forming ability is preferably 0.2 to 3.5 parts by weight, more preferably 0.3 to 3.5 parts by weight, based on 100 parts by weight of the thermoplastic polyester resin.
3 parts by weight.

Examples of the olefin polymer (E) in the present invention include polyolefins composed of at least one kind of α-olefin having 2 to 20 carbon atoms and modified polyolefins. Examples of the α-olefin include ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, and 4-methylpentene.
1,3,3-dimethylpentene-1, 3-methylhexene-1, 4-methylhexene-1, 4,4-dimethylhexene-1, 5-methylhexene-1, allylcyclopentane, allylcyclohexane, allylbenzene , 3-
Cyclohexylbutene-1, vinylcyclopropane, vinylcyclohexane, 2-vinylbicyclo [2.2.
1] Heptane, heptene-1 or octene-1 and the like. One or more of these α-olefins can be used as a polymerization component.

The α-olefin is preferably ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene.
Examples thereof include 1,3-methylhexene-1, and particularly preferable examples include ethylene and propylene. As other components, 4-methyl-1,4-hexadiene, 5
-Methyl-1,4-hexadiene, 5-methyl-1,4
Hexadiene, 7-methyl-1,6 octadiene, 1,
A non-conjugated diene such as 9-decadiene may be used as a part of the polymerization component.

The polyolefin comprising at least one kind of α-olefin having 2 to 20 carbon atoms is preferably a polymer containing ethylene or propylene as a main component, more preferably polypropylene, polyethylene, ethylene copolymer and Propylene-based copolymers are exemplified. Examples of the modified polyolefin include a modified polyolefin or a copolymer of a modified polyolefin containing a functional group such as a carboxylic acid group, an acid anhydride group, an epoxy group, an oxazolinyl group, an acid imide group and / or a hydroxyl group.

As the crystallinity of the olefin polymer, the crystallinity at room temperature by X-ray diffraction is preferably 10 or less.
% Or more, more preferably 20% or more. The melting point of the olefin-based polymer is preferably 40 ° C. or higher. When the olefin-based polymer is a polymer containing ethylene or propylene as a main component, JIS K67
Test temperature 230 ° C, test load 2.16k
The melt flow rate measured by gf is preferably 0.0
1 to 200 g / 10 min, more preferably 0.05
１００100 g / 10 min.

The amount of the olefin polymer is 0.5 to 5 parts by weight based on 100 parts by weight of the thermoplastic polyester resin.
Parts by weight. If the amount of the olefin-based polymer is too small or too large, the effect of the present invention is not exhibited, and the flame retardancy tends to be impaired. The compounding amount of the olefin polymer is
It is preferably 0.8 to 4 parts by weight, more preferably 1 to 3 parts by weight, based on 100 parts by weight of the thermoplastic polyester resin.
Parts by weight.

As the inorganic filler (F) in the present invention, calcium carbonate, titanium oxide, feldspar-based mineral, clay, tricalcium phosphate, zinc borate, white carbon,
Granular or amorphous fillers such as carbon black and glass beads, plate-like fillers such as kaolin, clay, talc, and graphite; flake-like fillers such as glass flakes and mica; glass fiber; carbon fiber; And fibrous fillers such as knight and potassium titanate.

The amount of the inorganic filler is 5 to 90 parts by weight based on 100 parts by weight of the thermoplastic polyester resin. If the amount of the inorganic filler is less than 5 parts by weight, the rigidity and heat resistance are not sufficient, and if it exceeds 90 parts by weight, the fluidity is reduced and the mechanical properties are liable to be reduced. The compounding amount of the inorganic filler is preferably 6 to 80 parts by weight, more preferably 7 to 70 parts by weight, based on 100 parts by weight of the thermoplastic polyester resin.

In addition to the above components, the thermoplastic polyester resin composition of the present invention may be used according to the purpose at the time of kneading and molding the resin, as long as the physical properties, fluidity and flame retardancy are not impaired. Other additives, such as various elastomer components, stabilizers, antioxidants, weathering agents, lubricants, mold release agents, crystal nucleating agents, plasticizers, antistatic agents, coloring agents, etc. can be blended. , Polymethyl methacrylate, an AS resin, an ABS resin, and the like.

The method for producing the flame-retardant polyester resin composition of the present invention is not particularly limited, and examples thereof include a thermoplastic polyester resin, a brominated aromatic compound,
A batch blending method in which an antimony oxide compound, polytetrafluoroethylene having a fibril-forming ability, an olefin-based polymer, an inorganic filler, and other additives are blended and prepared into pellets by a screw-type extruder, or a screw-type extruder. A split blending method in which a thermoplastic polyester resin is first supplied to an extruder and melted, and a filler and an additive are supplied and kneaded through another supply port to prepare pellets, and the like, may be used.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

EXAMPLES The following components were used in Examples and Comparative Examples. (1) Thermoplastic polyester resin: intrinsic viscosity is 0.85
Polybutylene terephthalate, NOVADUR500
8AS, manufactured by Mitsubishi Engineering Plastics.
(Hereinafter, also referred to as PBT.)

(2) Olefin polymer-1: polypropylene, MFR 0.9 g / 10 min, Novatec P
P / TA-8, manufactured by Nippon Polychem. (Hereinafter abbreviated as PP1) (3) Olefin-based polymer-2: polypropylene, M
FR10g / 10min, Novatec PP / TA-3,
Made by Nippon Polychem. (Hereinafter abbreviated as PP2) (4) Olefin-based polymer-3: polyethylene, MF
R1.7g / 10min, Novatec HD / HY54
0, manufactured by Nippon Polychem. (Hereinafter abbreviated as PE)

(5) Brominated aromatic compound-1: Brominated polybenzyl acrylate, trade name PBBPA, manufactured by Bromochem Far East Co. (6) Brominated aromatic compound-2: brominated epoxy, trade name SRT-48, manufactured by Sakamoto Yakuhin. (7) Brominated aromatic compound-3: brominated polycarbonate, trade name BC-58, manufactured by Great Lakes. (8) Antimony compound: antimony trioxide, manufactured by Morirokusha. (9) Polytetrafluoroethylene: Polyflon FA-
500, manufactured by Daikin Industries, Ltd. (Hereinafter also abbreviated as PTFE.) (10) Inorganic filler: glass fiber, diameter 13 μm, T-
123, manufactured by NEC Corporation.

The evaluation test of the resin composition was performed as follows. (11) Tensile strength: measured in accordance with ASTM D-638. (12) Impact strength: Measured according to ASTM D-256. (13) Appearance characteristics: Visual observation of 1 kg of pellets
When there was no foreign matter of 00 microns or more, it was evaluated as ○, and when there was foreign matter of 500 microns or more, it was evaluated as x.

(14) Flame retardancy test: Five test pieces were subjected to a burn test for classification of UL-94 "material by Underwriters Laboratories, Inc. (hereinafter UL-94).
94) According to the test method shown in "), the test material was tested at a thickness of 1/32 inch, and the test material was selected from UL-94 V-0, V-1 and V-2 based on the results of five samples. The criteria for each V rating for UL-94 are as follows: V-0: The average flame holding time after removing the ignition flame is 5 seconds or less, and for all samples. V-1: The average flame holding time after removing the ignition flame is 25 seconds or less, and all the samples do not drop the fine flame igniting the absorbent cotton. The average flame holding time after removing the igniting flame is less than 25 seconds, and these samples fall a fine flame igniting absorbent cotton.

Examples 1 to 5 and Comparative Examples 1 to 4 Twin screw extruders (screw diameter 30 m
m) using a barrel set temperature of 250 ° C. Rotation speed 200
Extruded pellets were made at rpm. Using the obtained pellets, an injection molding machine (Nestal SG7 manufactured by Sumitomo Heavy Industries, Ltd.)
Using 5-SYCAP-MIIIA), injection molding was performed at a temperature of 255 ° C. to obtain a molded body. At the time of molding, the resin composition was dried at 120 ° C. for 6 to 8 hours immediately before the molding. Table 1 shows the evaluation results.

[0032]

[Table 1]

[0033]

Industrial Applicability The flame-retardant polyester resin composition of the present invention has good strength, rigidity, heat resistance, fluidity and impact resistance inherent to the polyester resin, and also has appearance characteristics and flame retardancy, especially Excellent drip prevention during combustion. 0.8 m produced from the flame-retardant polyester resin composition of the present invention
A molded article having a thin portion of not more than m has excellent flame retardancy in the thin portion and is very useful as various industrial parts such as electric, electronic, automobile, and machine parts.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 27:18 23:00)

Claims (5)

[Claims] (A) a thermoplastic polyester resin 100
Parts by weight, (B) 3 to 50 parts by weight of a bromine-based aromatic compound,
(C) 1 to 30 parts by weight of an antimony oxide compound, (D) 0.1 to 5 parts by weight of polytetrafluoroethylene having fibril-forming ability, (E) olefin-based polymer 0.5
A flame-retardant polyester resin composition, which comprises 5 to 90 parts by weight of (F) an inorganic filler. 2. The flame-retardant polyester resin composition according to claim 1, wherein the thermoplastic polyester resin is polybutylene terephthalate. 3. The flame-retardant polyester resin composition according to claim 1, wherein the olefin-based polymer is polypropylene, polyethylene, an ethylene-based copolymer or a propylene-based copolymer. 4. The composition according to claim 1, wherein the compounding amount of the polytetrafluoroethylene having a fibril forming ability is 0.2 to 3.5 parts by weight based on 100 parts by weight of the thermoplastic polyester resin. The flame-retardant polyester resin composition according to any one of the above. 5. A molded article comprising the flame-retardant polyester resin composition according to claim 1, which has a thin portion having a thickness of 0.8 mm or less.