JP2000080257A - Polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyester resin composition having excellent flame retardancy and suitable for electric parts, electronic parts, automotive parts, etc., by mixing a specific thermoplastic polyester copolymer with a red phosphorus-based flame retardant. SOLUTION: This polyester composition comprises (A) a thermoplastic polyester copolymer composed of (i) an acid component preferably consisting mainly of terephthalic acid and (ii) a diol component comprising 5-40 mol.% of a bisphenol compound (derivative) and, if necessary, ethylene glycol, 1,4-butanediol, etc., and (B) a red phosphorus-based flame retardant. The component (i) includes compounds of formulas I and II [R is CH2CH2, CH2CH2OCH2CH2, CH(CH3)CH2 or CH2CH(CH3); X is O, S, SO2, SO, CO or the like; Y1-Y8 are each H, an alkyl or an alkoxy, preferably H].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester resin composition having excellent flame retardancy, and is suitably used in fields where flame retardancy is required for electric / electronic parts and automobile parts. The present invention relates to a polyester resin composition.

[0002]

2. Description of the Related Art Thermoplastic polyester resins represented by polybutylene terephthalate resin and polyethylene terephthalate resin are excellent in mechanical properties and electrical properties, and are relatively easily flame-retarded. Therefore, it is widely used for electric / electronic parts and automobile parts. Many proposals have been made on flame retardancy of these polyester resins. For example, decabromodiphenyl ether, a polyester material having flame retardancy secured by using a bromine-containing compound such as ethylenebistetrabromophthalimide or pentabromobenzyl acrylate and antimony trioxide in combination with a polyester resin is actually used, From the viewpoint of environmental issues, there is an increasing demand from the industrial world for the development of polyester materials which have disadvantages such as a large amount of smoke generated during combustion and do not contain halogen compounds and antimony compounds and have flame retardancy. To solve this problem, many methods of blending a phosphorus-based flame retardant have been proposed.
It has been proposed for a long time to blend with various thermoplastic resins to impart flame retardancy. However, when red phosphorus is blended with polybutylene terephthalate resin and polyethylene terephthalate resin, although flame retardancy is improved, it is difficult to secure high flame retardancy, and mechanical properties are also reduced. Therefore, a composition that can be used practically cannot be provided.

[0003]

Means for Solving the Problems The present inventors have studied the provision of flame retardancy of a thermoplastic polyester resin such as a polybutylene terephthalate resin or a polyethylene terephthalate resin, and as a result, it has been found that any thermoplastic polyester copolymer having a specific skeleton can be obtained. For example, they have found that a compound having excellent flame retardancy can be obtained by blending red phosphorus, and have completed the present invention. That is, the present invention relates to a thermoplastic polyester copolymer using bisphenols or a derivative thereof as a part of the diol component constituting the thermoplastic polyester in an amount of 5 to 40 mol% based on 100 mol% of the total diol component, and adding a red phosphorus-based flame retardant to the thermoplastic polyester copolymer. And a polyester resin composition containing the same.

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The polyester used in the present invention is generally a polyester synthesized from an acid component and a diol component represented by a polybutylene terephthalate resin and a polyethylene terephthalate resin, and a bisphenol or a derivative thereof is partially contained in the diol component. Are copolymerized. Examples of the bisphenols or derivatives thereof which are essential components constituting the polyester of the present invention include those represented by the following general formulas (I) to (II).

[0005]

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In the formula, Y _{1 to} Y ₈ are groups mainly selected from hydrogen, an alkyl group and an alkoxy group, which may be the same or different, but hydrogen is particularly preferred. Specific examples of the compound include those obtained by adding an alkylene oxide to the following bisphenols, that is, bis (4-hydroxyphenyl) sulfone, 2,2-bis (4-hydroxyphenyl) propane, and bis (4- Hydroxyphenyl) ketone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4
-Hydroxyphenyl) ether, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl)
Cyclohexane, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) alkane, 2,2-bis (3,4'-hydroxyphenyl) propane, 4,4'-diphenol, 4,4'- [1,4-phenylenebis (1-methylethylidene)] bisphenol, 1,1-
Alkylene oxides such as bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone Adducts. Among them, particularly preferred from the viewpoint of polymer preparation are bis (4-hydroxyphenyl) sulfone ethylene oxide 2 mol adduct, bis (4-hydroxyphenyl) sulfone propylene oxide 2 mol adduct, and 2,2-bis ( 2-hydroxyphenyl) propane ethylene oxide 2 mol adduct, 2,2-bis (4
2-hydroxyphenyl) propane propylene oxide 2 mol adduct, bis (4-hydroxyphenyl) sulfoxide ethylene oxide 2 mol adduct, bis (4-hydroxyphenyl) sulfoxide propylene oxide 2 mol adduct, bis (4-hydroxyphenyl) 2) adducts of ethylene oxide with 2 mol of sulfide, adducts of 2 mol of propylene oxide with bis (4-hydroxyphenyl) sulfide, adducts of 2 mol of ethylene oxide with bis (4-hydroxyphenyl) ether, and propylene of bis (4-hydroxyphenyl) ether Oxide 2 mol adduct, bis (4-hydroxyphenyl) methane ethylene oxide 2 mol adduct, bis (4-hydroxyphenyl) methane propylene oxide 2 mol adduct, 4,4′-
Diphenol ethylene oxide 2 mol adduct, 4,4'-
2 mol adduct of diphenol with propylene oxide, 2 mol adduct of bis (4-hydroxyphenyl) alkane with ethylene oxide, 2 mol adduct of bis (4-hydroxyphenyl) alkane with propylene oxide, bis (4-hydroxyphenyl) ketone Examples include a 2-mol ethylene oxide adduct and a 2-mol adduct of bis (4-hydroxyphenyl) ketone with propylene oxide. The polyester used in the present invention needs to use, as a comonomer, at least one or more selected from the above-mentioned groups as a raw material. The molar fraction of these comonomers with respect to the diol component constituting the polyester is 5 to 40 mol%. If the value of the molar fraction of the bisphenol or its derivative is less than 5 mol%, it is difficult to secure sufficient flame retardancy when red phosphorus is added. On the other hand, if it exceeds 40 mol%, the crystallinity of the copolymer is remarkably reduced, and the mechanical properties are remarkably reduced, which is not practical.

The acid component of the polyester used in the present invention includes terephthalic acid, isophthalic acid, phthalic acid,
Aromatic dicarboxylic acids such as naphthalenedicarboxylic acid and their ester-forming derivatives are used, and terephthalic acid is particularly preferably used. In addition, an aliphatic dicarboxylic acid such as adipic acid, sebacic acid and dodecane diacid can be used as a copolymer component without departing from the intended performance of the present invention.

[0008] Diol components other than bisphenols or derivatives thereof include aliphatic diols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol and dimer diol, and their ester-forming diols. Derivatives can be used according to the purpose. Particularly, ethylene glycol and 1,4-butanediol are preferably used. Further, a long-chain aliphatic ether such as polyethylene glycol and polytetramethylene glycol may be used as a part of the diol component.

Next, the red phosphorus used in the present invention can be blended with the thermoplastic polyester without any treatment, but the red phosphorus ignites during storage or gradually enters water. Since it has the property of dissolving, a material subjected to a treatment for preventing this is preferably used.
As a method of treating such red phosphorus, a method of catalytically suppressing oxidation of red phosphorus by adding a small amount of aluminum hydroxide or magnesium hydroxide to red phosphorus, coating red phosphorus with paraffin or wax, and removing water and How to control contact,
a method of stabilizing by mixing with ε-caprolactam or trioxane, a method of stabilizing by coating red phosphorus with a thermosetting resin such as a phenolic, melamine, epoxy, or unsaturated polyester type; A method of treating with an aqueous solution of a metal salt such as copper, nickel, silver, iron, aluminum and titanium to precipitate and stabilize a metal phosphorus compound on the surface of red phosphorus. Coating with titanium oxide, zinc hydroxide, etc., iron, cobalt,
Examples of the method include a method of stabilizing by coating with electroless plating with nickel, manganese, tin, or the like, and a method of combining them. Preferably, a method of stabilizing by coating red phosphorus with a thermosetting resin or a method of coating red phosphorus with aluminum hydroxide, magnesium hydroxide, titanium hydroxide, zinc hydroxide, etc., is particularly preferable. This is a method in which red phosphorus is coated with aluminum hydroxide, magnesium hydroxide, titanium hydroxide, zinc hydroxide, or the like, and is further stabilized by coating twice with a thermosetting resin. In the present invention, the compounding amount of red phosphorus is 0.1 to 100 parts by weight, preferably 3 to 50 parts by weight, more preferably 5 to 30 parts by weight based on 100 parts by weight of the thermoplastic polyester copolymer.
Parts by weight.

[0010] Further, in order to further improve the flame retardancy of the resin composition of the present invention and to suppress the drop of droplets during burning, it is possible to blend a polymer containing fluorine. Examples of such fluorine-based polymers include polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer,
(Tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer, (tetrafluoroethylene / ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride / ethylene) copolymer Examples include polytetrafluoroethylene, (tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, and (tetrafluoroethylene / ethylene) copolymer. Coalescence and polyvinylidene fluoride are preferred, and polytetrafluoroethylene is particularly preferred. Such polytetrafluoroethylene is emulsion polymerization,
It can be produced by a known method such as suspension polymerization and is widely marketed. The polytetrafluoroethylene resin can be selected from those having an arbitrary degree of polymerization (viscosity) according to the purpose, such as dispersibility, processability of the composition, and other physical properties. In addition, any shape from granular to fibrous can be used, and the particle size can be adjusted over a wide range from 0.05 μm to several mm. The appropriate properties and particle size may be selected experimentally from the properties, intended properties and effects, but from the viewpoint of ease of handling in the preparation process of the composition, workability, productivity, etc. 20-800 μm in diameter, more preferably 100-700
Granules of μm are preferred. The amount of such a fluorine-containing polymer to be added is usually 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.2 to 2 parts by weight, based on 100 parts by weight of the thermoplastic polyester copolymer. is there.

[0011] Further, without departing from the object of the present invention,
The use can be further expanded by blending the fibrous filler. As the fibrous filler that can be used, glass fiber, carbon fiber, potassium titanate fiber,
Examples include stainless steel fiber, steel fiber, and ceramic fiber. By adding these fillers, heat resistance and rigidity can be improved, and dimensional stability of a molded article can be achieved. Among the fillers, glass fibers are preferably used.
The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and for example, it can be selected from long fiber type or short fiber type chopped strand, milled fiber and the like. Further, the glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer, a thermosetting resin such as an epoxy resin, or a coupling agent such as a silane-based resin or a titanate-based resin, and other materials. It may be treated with a surface treatment agent. The addition amount of the fibrous filler is preferably 5 to 100 parts by weight based on 100 parts by weight of the thermoplastic polyester copolymer.

In order to further impart desired properties to the composition of the present invention, known substances generally added to the thermoplastic resin, that is, stabilizers such as antioxidants, heat stabilizers, and ultraviolet absorbers. Of course, it is also possible to incorporate an antistatic agent, a coloring agent such as a dye or a pigment, a lubricant, a plasticizer, a crystallization accelerator, a nucleating agent, an inorganic filler other than the fibrous filler, and the like. Inorganic fillers include calcium carbonate, highly dispersible silicate, alumina, aluminum hydroxide, talc, clay, mica, glass flake, glass powder, glass beads, quartz powder, quartz sand, wollastonite, carbon black, barium sulfate , Gypsum, silicon carbide, alumina, powdered and granular substances such as boron nitride and silicon nitride, 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 is prepared by known equipment and methods generally used as a conventional method for preparing a resin composition.

[0014]

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.
The physical property evaluation methods shown in the following examples are as follows.・ Flame retardancy Using a test piece for flame retardancy evaluation obtained by injection molding, UL94
The flame retardancy was evaluated in accordance with the evaluation criteria set forth in.
The evaluation results were V-0, V-1, V-2, HB
In order. -Tensile strength and elongation Tensile strength and elongation were measured according to ASTM D-638 using a dumbbell test piece having a specific shape obtained by injection molding. <Preparation Example 1 of Polyester Copolymer> 2560 parts by weight of dimethyl terephthalate, 1901 parts by weight of 1,4-butanediol, 2,2 parts by weight
834 parts by weight of a 2-mol adduct of 2-bis (4-hydroxyphenyl) propane with ethylene oxide were charged together with a predetermined amount of a transesterification catalyst (tetrabutyl titanate) into a reactor equipped with a stirrer and a distilling tube, and sufficiently purged with nitrogen. Thereafter, the temperature was raised to 160 ° C. under normal pressure, and stirring was started.
Further, the temperature was gradually increased to remove by-produced methanol. When the temperature reached 240 ° C., the pressure inside the reactor was gradually reduced, and stirring was continued at a pressure of 0.2 torr for 2.5 hours to obtain a copolymerized polyester having an intrinsic viscosity of 0.82. The value of the introduction ratio of the comonomer was H ¹ -N using trifluoroacetic acid-d1 as a solvent.
It was determined from MR measurement.

<Preparation Examples 2 to 5 of Polyester Copolymer>
Various polyester copolymers were obtained in the same manner as in Preparation Example 1 except that the types and amounts of the comonomer used were changed as shown in Table 1.

COMPARATIVE PREPARATION EXAMPLES 1-5 Polybutylene terephthalate (PBT) and various polyester copolymers were prepared by using dimethyl terephthalate and 1,4-butanediol, and optionally other comonomers at the compounding ratios shown in Table 1. I got Examples 1 to 6, Comparative Examples 1 to 5 For the polyester copolymer or PBT shown in Table 1,
Red phosphorus (Nova Excel 140, manufactured by Rin Kagaku Kogyo Kogyo Co., Ltd.) with a surface treatment was blended in the ratio shown in Table 2. After dry blending, the mixture was put into a hopper of a 30 mm twin-screw extruder and extruded into strands, followed by a pelletizer. Pelletized. After the obtained pellets were dried at 140 ° C. for 3 hours, test pieces were prepared with an injection molding machine, and the above evaluation was performed. Table 2 shows the results.

[0017]

[Table 1]

* 1 Dimethyl terephthalate * 2 1,4-butanediol * 3 Ethylene oxide 2 mol adduct of 2,2-bis (4-hydroxyphenyl) propane * 4 2 mol of ethylene oxide of bis (4-hydroxyphenyl) methane Adduct * 5 2-mol ethylene oxide adduct of bis (4-hydroxyphenyl) ether * 6 2-mol ethylene oxide adduct of bis (4-hydroxyphenyl) sulfone * 7 Ethylene glycol * 8 1,6-hexanediol

[0019]

[Table 2]

[0020]

As is apparent from the above description and Examples, as in the present invention, a composition in which a red phosphorus-based flame retardant is blended with a specific copolymerized polyester is a conventionally known red phosphorus-containing flame retardant polyester. Compared to the composition, it has a higher flame retardant effect and does not adversely affect the inherent properties of polyester, and is useful as an electric / electronic part, a mechanical part, an automobile part, and the like.

Continued on the front page F-term (reference) 4J002 CF041 CF051 CF061 CF071 DA056 FB076 FB266 FD010 FD136 4J029 AA03 AB01 AC02 AD01 AE01 BA02 BA03 BA05 BA08 BB11A BB11B BB11C BB16A BB16B BB16B DB01 BF16 BB16 DB13 HB01 JA013 JE182 KB02

Claims (2)

[Claims] 1. A red phosphorus-based flame retardant is added to a thermoplastic polyester copolymer containing bisphenols or a derivative thereof as a part of the diol component constituting the thermoplastic polyester in an amount of 5 to 40 mol% based on 100 mol% of all diol components. The polyester resin composition which was mix | blended. 2. The polyester resin according to claim 1, wherein the main acid component constituting the thermoplastic polyester copolymer is terephthalic acid, and a part of the diol component is ethylene glycol and / or 1,4-butanediol. Composition.