JPH1135809A - Flame-retardant polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having good flame retardant, hardly causing a dripping phenomenon by including a thermoplastic polyester resin, a specific (assistant) flame-retardant, a specified resin, a specific polymer and a specified antioxidant. SOLUTION: This flame-retardant polyester resin composition comprises (A) 100 pts.wt. thermoplastic polyester resin (e.g. polyethylene terephthalate), (B) 1-30 pts.wt. halogen-containing organic flame retardant, preferably halogenated aromatic bisimide compound, halogenated aromatic epoxy compound, etc., (C) 1-20 pts.wt. inorganic assistant flame retardant (e.g. antimony trioxide), (D) 0.1-5 pts.wt. fluororesin (e.g. polytetrafluoroethylene), (E) 0.5-10 pts.wt. olefinic polymer (e.g. polyethylene) having 300-10,000 molecular weight preferably in the weight ratio to the component D regulated so as to be 1.5-5, and (F) 0.05-2 pts.wt. hindered phenolic antioxidant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant polyester resin composition. More specifically, the present invention relates to a flame-retardant polyester resin composition having good flame retardancy with less dripping phenomenon and having a good molded product surface.

[0002]

2. Description of the Related Art Polyester resins, particularly polyalkylene terephthalates such as polyethylene terephthalate and polybutylene terephthalate, are used as crystalline thermoplastic resins in terms of mechanical strength, electrical properties, and other properties. Due to its excellent chemical properties, it is used as a engineering plastic in a wide range of applications such as automobiles, electric and electronic equipment. In general, for applications requiring flame retardancy, such as electric parts, flame retardancy is achieved by adding a halogen-based flame retardant, and optionally antimony trioxide in combination. As a criterion for determining the degree of flame retardancy, the UL-94 standard established by Underwriters Laboratory is widely used. In this UL-94 flame-retardant standard, in the ranks of V-0, V-1 and 5V, which are classified as flame-retardant, it is important that molten resin does not drip or fireballs fall from burning test specimens. Is seen. As a method for reducing the dripping phenomenon of the molten resin at the time of combustion, Japanese Patent Application Laid-Open No.
It is well known to add the polytetrafluoroethylene resin described in No. 6. However, although the addition of the polytetrafluoroethylene resin can reduce the dripping phenomenon at the time of the target combustion, when the resin is molded, there is a problem that white spots due to the polytetrafluoroethylene resin are generated on the surface of the molded product. there were.

[0003]

In view of such demands, the present inventors can prevent white spots formed on the surface of molded articles without impairing excellent flame retardancy and non-dropping property of molten resin during combustion. As a result of intensive studies to obtain a flame-retardant polyester composition, the present invention has been achieved. That is, the present invention relates to (A) 100 parts by weight of a thermoplastic polyester resin, (B) 1 to 30 parts by weight of a halogen-containing organic flame retardant, and (C) 1 to 3 parts of an inorganic flame retardant.
20 parts by weight, (D) 0.1 to 5 parts by weight of a fluorine resin, (E) 0.5 to 10 parts by weight of an olefin polymer, and (F) 0.05 to 2 parts by weight of a hindered phenolic antioxidant. The present invention relates to a flame-retardant polyester resin composition.

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION The components of the present invention will be described below in detail. First, the thermoplastic polyester resin (A) as the base resin of the present invention is a polyester obtained by polycondensation of a dicarboxylic acid compound and a dihydroxy compound, polycondensation of an oxycarboxylic acid compound, or polycondensation of these three-component compounds. The present invention is effective for any of polyester, homopolyester and copolyester. Illustrative examples of the dicarboxylic acid compound constituting the thermoplastic polyester resin used here include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenylethanedicarboxylic acid, cyclohexanedicarboxylic acid, adipic acid, Known dicarboxylic acids such as sebacic acid and alkyl, alkoxy or halogen-substituted products thereof.
These dicarboxylic acid compounds can also be used for polymerization in the form of a derivative capable of forming an ester, for example, a lower alcohol ester such as dimethyl ester.
Next, examples of the dihydroxy compound constituting the polyester (A) of the present invention include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hydroquinone, resorcin, dihydroxyphenyl, naphthalene diol, dihydroxydiphenyl ether, cyclohexanediol, 2 , 2-bis (4-hydroxyphenyl) propane, dihydroxy compounds such as diethoxylated bisphenol A, polyoxyalkylene glycols and their alkyl, alkoxy or halogen-substituted products, etc., and one or more of them can be used in combination. it can. Examples of oxycarboxylic acids include oxycarboxylic acids such as oxybenzoic acid, oxynaphthoic acid, and diphenyleneoxycarboxylic acid, and alkyl, alkoxy or halogen-substituted products thereof.
Further, derivatives of these compounds capable of forming an ester can also be used. In the present invention, one or more of these compounds are used. In addition, polyesters having a branched or crosslinked structure using a small amount of a trifunctional monomer, that is, trimetic acid, trimesic acid, pyromellitic acid, pentaerythritol, trimethylolpropane, or the like may be used. In the present invention, any of the thermoplastic polyesters produced by polycondensation using the above-mentioned compound as a monomer component can be used as the component (A) of the present invention, and can be used alone or in combination of two or more. However, preferably, polyalkylene terephthalate, more preferably polybutylene terephthalate and a copolymer mainly composed of polybutylene terephthalate are used.

The halogen-containing organic flame retardant (B) used in the present invention may be any organic halogen compound generally used as a flame retardant for thermoplastic polyesters. Examples include halogenated diphenyl ethers, halogenated aromatic bisimide compounds, halogenated aromatic epoxy compounds, low molecular weight organic halogen compounds of bisphenol A, halogenated polycarbonates, halogenated polystyrene, halogenated benzyl acrylate compounds, and the like. Here, the halogen is generally preferably bromo. The flame retardant is 1
Species or a mixture of two or more species may be used. The object of the present invention can be achieved by using any of the above flame retardants, but halogenated aromatic bisimide compounds, halogenated aromatic epoxy compounds, halogenated benzyl acrylate compounds, and halogenated polycarbonates are particularly preferred.
Here, the halogenated aromatic bisimide compound is represented by the following general formula (1), wherein R ₁ is a divalent organic group, and is generally an alkylene group, an arylene group or the like. Desirable are lower alkylene groups. or,
X is at least one or more halogens, advantageously the halogen atoms have at least 25% by weight of the molecule and are preferably bromo.

[0006]

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Preferred halogenated aromatic bisimide compounds include lower alkylene bistetrabromophthalimide, especially N, N'-ethylenebistetrabromophthalimide. The halogenated aromatic epoxy compound, which is a preferred flame retardant among the components (B), is a bisphenol A type epoxy compound represented by the following general formula (2), wherein X represents at least one halogen. And n is a number of 2 or more. Preferred average degree of polymerization n is 2
-30, more preferably 10-20.

[0008]

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Such a halogenated aromatic epoxy compound is, for example, a halogenated bisphenol A diglycidyl ether obtained by condensing epichlorohydrin with bisphenol A alone or, if necessary, in combination with bisphenol A, if necessary. Further, halogenated bisphenol A alone or bisphenol A
Can be obtained by heating to 80 to 250 ° C. in the presence of a catalyst.

The halogenated benzyl acrylate compound, which is a preferred flame retardant of the component (B), is a compound represented by the following general formula (3), wherein X is at least one halogen. And m is a number from 2 to 6. The average molecular weight of the halogenated benzyl acrylate compound is preferably 500,000 or less, and particularly preferably 10,000 to
200,000.

[0011]

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The content of the component (B) is 1 to 30 parts by weight, preferably 5 to 100 parts by weight of the polyester resin.
~ 25 parts by weight. If too large, mechanical and physical properties,
It is not preferable because heat stability and the like are impaired and the appearance of the resin is impaired. If the amount is too small, the flame retardancy becomes insufficient.

Next, representative examples of the inorganic flame retardant aid of the component (C) include antimony trioxide, antimony tetroxide,
And antimony-based flame retardants such as antimony pentoxide and sodium pyroantimonate. The addition amount of the inorganic flame retardant aid (C) is 1 to 20 parts by weight, preferably 3 to 15 parts by weight based on 100 parts by weight of the polyester resin.

The fluorine resin (D) used in the present invention is added for the purpose of preventing the molten resin from dropping during combustion. As the fluorine resin of the component (D), polytetrafluoroethylene produced by polymerizing tetrafluoroethylene is most preferably used, but other polymers such as hexafluoropropylene and vinylidene fluoride can also be used. . The content of the component (D) is 0.1 to 5 parts by weight, preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the polyester resin. If the amount of the component (D) is less than 0.1 part by weight, the desired non-dropping property is not sufficient. If the amount exceeds 5 parts by weight, the viscosity of the material increases and the moldability deteriorates.

The olefin polymer of the component (E) used in the present invention refers to a polymer or copolymer mainly composed of olefinic structural units, such as polyethylene, polypropylene, ethylene-propylene polymer and These modifications are mentioned. In particular, those olefin polymers having a small molecular weight are suitable for the purpose of the present invention, and those having a molecular weight in the range of 300 to 10,000 are particularly preferable. The purpose of the component (E) is to prevent the formation of white spots on the surface of the molded article caused by the fluorine resin of the component (D). The content is 0.5 to 10 with respect to 100 parts by weight of the polyester resin.
Parts by weight, preferably 1 to 4 parts by weight. If the amount is less than 0.5 part by weight, the intended effect of reducing white spots is not sufficient. If the amount is more than 10 parts by weight, the mechanical properties of the material deteriorate and the surface of the molded product oozes out. In addition, as described above (E)
For the purpose of adding the component, the component (D)
It is particularly preferred that the ratio of the olefin polymer of the component (E) is 1.5 to 5 (weight basis).

Next, the hindered phenol-based antioxidant of the component (F) is added to prevent a decrease in thermal stability caused by the component (E). Examples of the hindered phenol-based antioxidant (F) include 2,2′-methylenebis (4-methyl-6-t-butylphenol) and hexamethyleneglycolbis (3,5-di-t-butyl-4). -Hydroxyhydrocinnamate), tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane, triethylene glycol bis-3-
(3-t-butyl-4-hydroxy-5-methylphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene N-octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butylphenol) propionate, 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'- Butylidenebis (6-t-butyl-3
-Methylphenol), 2,2'-thiodiethylbis [3-
(3,5-di-t-butyl-4-hydroxyphenyl) propionate, distearyl-3,5-di-t-butyl-
4-hydroxybenzylphosphonate, 2-t-butyl-6- (3-t-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenyl acrylate, and the like. The content of the component (F) is 0.05 to 2 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the polyester resin (A). If the amount is less than 0.05 part by weight, the effect of thermal stability becomes insufficient, and if more than 2 parts by weight is added, there is no problem in characteristics, but there is no further improvement in effect, so that it is wasteful in terms of cost. It is.

In the resin composition of the present invention, other thermoplastic resins may be used in a small amount in an auxiliary manner as long as the object is not impaired. Any other thermoplastic resin may be used as long as it is stable at high temperatures. For example, polyamide, ABS, polyphenylene oxide, polyalkyl acrylate, polyacetal, polysulfone, polyethersulfone, polyetherimide, polyetherketone, and the like can be given. These thermoplastic resins can be used as a mixture of two or more kinds.

In order to further impart desired properties to the composition of the present invention, known substances generally added to thermoplastic resins, such as stabilizers such as ultraviolet absorbers, antistatic agents, dyes and pigments Of course, it is also possible to incorporate a coloring agent such as a lubricant, a plasticizer, a crystallization accelerator, a crystal nucleating agent, an inorganic filler and the like. As inorganic fillers, glass fibers, carbon fibers, ceramic fibers, boron fibers, potassium titanate fibers, general inorganic fibers such as asbestos, calcium carbonate, highly dispersible silicate, alumina, aluminum hydroxide,
Talc, clay, mica, glass flake, glass powder,
Glass beads, quartz powder, silica sand, wollastonite, carbon black, barium sulfate, calcined gypsum, silicon carbide, alumina, powdered and granular substances such as boron nitride and silicon nitride;
It includes plate-like inorganic compounds, whiskers, and the like. These inorganic fillers can be used alone or in combination of two or more as necessary.

The composition of the present invention can be easily prepared by known equipment and methods generally used as a conventional method for preparing a resin composition. For example, i) after mixing each component, kneading and extruding with an extruder to prepare pellets and then molding, ii) once preparing pellets having a different composition, mixing a predetermined amount of the pellets and molding. Any method can be used, such as a method of obtaining a molded article having the desired composition after the molding, and iii) a method of directly charging one or more of each component to a molding machine. Mixing and adding a part of the resin component as a fine powder with other components is a preferable method for uniformly blending these components.

[0020]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. Examples 1 to 4 and Comparative Examples 1 to 7 Using the raw materials shown in Table 1, glass fibers were optionally blended, and the blends shown in Table 2 were dry blended for 5 minutes with a ribbon blender using a twin-screw extruder. Extruded into pellets. Next, a test piece was prepared by injection molding using the pellet, and evaluated. Flammability test (UL-94)
Is a subject of Underwriters Laboratories
Five test pieces (thickness: 1/32) according to the method of 94 (UL94)
Inches). The white dot on the surface is 100mm
Create a test piece of × 2mm thickness, 0.1m diameter on the surface
It was evaluated by the number of objects having a size of m or more. Table 2 shows the results
Shown in As a thermal stability test, a 2 mmt dumbbell test piece was prepared, and this was aged at 150 ° C. for 500 hours, and evaluated by the retention of tensile strength.

[0021]

[Table 1]

[0022]

[Table 2]

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification symbol FI // (C08L 67/02 27:12 23:00 101: 04)

Claims (5)

[Claims] (A) 1 to 30 parts by weight of a halogen-containing organic flame retardant, (C) 1 to 20 parts by weight of an inorganic flame retardant, and (D) based on 100 parts by weight of a thermoplastic polyester resin. A flame-retardant polyester resin composition comprising 0.1 to 5 parts by weight of a fluorinated resin, 0.5 to 10 parts by weight of (E) an olefin polymer and 0.05 to 2 parts by weight of a hindered phenolic antioxidant. 2. The halogen-containing organic flame retardant of component (B) is selected from halogenated aromatic bisimide compounds, halogenated aromatic poex compounds, halogenated benzyl acrylate compounds, and halogenated polycarbonates. The flame-retardant polyester resin composition according to claim 1. 3. The flame-retardant polyester resin composition according to claim 1, wherein the fluorine resin as the component (D) is polytetrafluoroethylene. 4. The olefin polymer of component (E) has a molecular weight of 3
The flame-retardant polyester resin composition according to any one of claims 1 to 3, wherein the composition is from 100 to 10,000. 5. The flame retardant according to claim 1, wherein the ratio of the olefin polymer of the component (E) to the fluorine resin of the component (D) is 1.5 to 5 (weight basis). Polyester resin composition.