JPH07138463A - Polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyester resin composition causing little generation of corrosive gas in molding and irritative gas, etc., in combustion, having excellent flame-retardance and mechanical properties and useful for automotive parts, etc., by adding a polyphosphoric acid amide to a polyester resin. CONSTITUTION:This resin composition contains (A) 100 pts.wt. of a polyester resin (preferably polybutylene terephthalate resin) and (B) 5-40 pts.wt. of a polyphosphoric acid amide obtained preferably by the condensation reaction of ammonium polyphosphate with melamine.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyester resin composition.

[0002]

2. Description of the Related Art Conventionally, polyester resins have been widely used for automobile parts, household electric appliances parts, office parts, industrial parts, textile products, construction materials, miscellaneous goods, etc. Materials having flame retardancy as well as properties have been demanded.

As inorganic flame retardants, various inorganic flame retardants and organic flame retardants are known, and halogen type organic flame retardants have been widely used for flame retarding polyester resins. However, polyester resins using halogen-based organic flame retardants corrode molds and the like during molding and processing due to hydrogen halide generated by thermal decomposition, and generate a large amount of black smoke and toxic halogen-containing gas when a fire occurs. It has the drawback of Further, there is also a report pointing out the risk of generation of dioxin as a thermal decomposition product of a halogen compound, and the use of the halogen compound is being suppressed.

As the non-halogen flame retardant, a hydrated inorganic compound such as magnesium hydroxide or aluminum hydroxide is used, but it is necessary to add a large amount to the resin, which has the drawback that the mechanical properties are remarkably deteriorated. is doing.
Further, a method of using a phosphate ester-based flame retardant, ammonium phosphate, or a triazine-containing ring compound separately from these hydrated inorganic compounds is disclosed in JP-B-51-39271, JP-B-55-50506, and JP-A-50-50. 105744, JP-A-53-18660, JP-B-60-3
It is known from Japanese Patent No. 3850, Japanese Patent Laid-Open No. 57-96039, and the like.

However, none of them are necessarily sufficient in flame retardancy, and they are not satisfactory in terms of smoke emission, mechanical properties, electrical properties and economy. In some cases, it also has a drawback that it accelerates the generation of decomposed gas, hinders molding, and contaminates the mold.

[0006]

An object of the present invention is to provide a non-halogenated composition, which suppresses the generation of corrosive gas during molding, and stimulates irritating gas, corrosive gas and black smoke during combustion. It is an object of the present invention to provide a flame-retardant polyester resin composition which suppresses the occurrence of the above and which is excellent in flame retardancy and mechanical properties with a smaller addition amount than conventional flame retardants.

[0007]

The present invention has been made to solve the above-mentioned problems, and its gist is that 100 parts by weight of a polyester resin contains 5 to 40 parts by weight of polyphosphoric acid amide. In the polyester resin composition. Hereinafter, the present invention will be described in detail.

The polyester resin used in the present invention is a thermoplastic resin having an intrinsic viscosity of 0.40 or more obtained by polycondensation of at least one bifunctional carboxylic acid component and at least one glycol component or oxycarboxylic acid. Specific examples of the bifunctional carboxylic acid component of polyester are terephthalic acid, isophthalic acid, 2,
6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, P, P'-diphenyldicarboxylic acid, P,
P'-diphenyl ether dicarboxylic acid, adipic acid,
Sebacic acid, dodecane diacid, suberic acid, azelaic acid, 5-sodium sulfoisophthalic acid or their ester-forming derivatives may be used as specific examples of the glycol component of the general formula: HO (CH ₂ ) _n OH (n is 2 ~ 20
Α, ω-alkylene glycol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, polyoxyethylene glycol, polyoxytetramethylene glycol, or these Ester-forming derivatives and the like, and specific examples of the oxycarboxylic acid include oxybenzoic acid and 4- (2-hydroxyethoxy).
Examples thereof include benzoic acid and ester-forming derivatives thereof. Further, any copolymer may be used as long as 70 mol% or more of all acid components or all diol components forming such a polyester is a single component.
Furthermore, even a mixture of 60% by weight or more of such a polyester resin and 40% by weight or less of another thermoplastic resin can be applied to the present invention.

As the polyphosphoric acid amide, ammonium polyphosphate, urea phosphate, phosphoric anhydride, condensed phosphoric acid or phosphoric acid is used as the phosphoric acid source, and melamine is used as the nitrogen source.
It is a polymer compound having nitrogen in the amide state, which is obtained by using a cyanamide derivative such as dicyandiamide, guanidine, guanylurea, etc. in the presence of urea or phosphoric acid urea as a condensing agent, and conducting a condensation reaction. Depending on the case, a part of the dehydration action occurs, and a compound having a phosphorylamide or phosphorylimide bond may be included, or a compound having a urea bond partially remaining may be included. It should be noted that urea and urea phosphate as the condensing agent also partially function as a nitrogen source. The polyphosphoric acid amide is preferably obtained by a condensation reaction of ammonium polyphosphate and melamine, and specific examples thereof include "Sumisafe PM" (manufactured by Sumitomo Chemical Co., Ltd.).

The production reaction of polyphosphoric acid amide is known from Japanese Patent Publication No. 51-39271 and the like. For example, one or a mixture of the above phosphoric acid sources, one or a plurality of cyanamide derivatives as nitrogen sources. A mixture of seeds, a condensing agent and urea or urea phosphate as a nitrogen source or mixtures thereof are used as urea / phosphoric acid / cyanamide derivative = 0.
It can be produced by heating and condensing in the presence of ammonia gas at 150 to 350 ° C. for 10 minutes to 5 hours, preferably 2 to 4 hours at 8-1.5 / 1 / 0.05 to 1 (molar ratio). .

The ratio of the polyphosphoric acid amide to 100 parts by weight of the polyester resin is preferably 5 to 40 parts by weight, more preferably 10 to 30 parts by weight. If it is less than 5 parts by weight, the flame retardancy becomes insufficient, and if it exceeds 40 parts by weight, the physical properties of the polymer are remarkably deteriorated. The composition of the present invention is
Other conventional ingredients such as heat stabilizers, light stabilizers, UV absorbers, antioxidants, antistatic agents, preservatives, adhesion promoters,
Colorant, crystallization accelerator, filler, glass fiber, carbon fiber, foaming agent, lubricant, bactericide, plasticizer, release agent, thickener,
Dripproofing agents, impact modifiers, smoke suppressants and the like may be included.

The composition according to the present invention can be obtained by a known method. Examples thereof include a dry blending method using a blender and a mixer, and a melt mixing method using an extruder. It is preferable to melt-mix and extrude into a strand and pelletize. INDUSTRIAL APPLICABILITY The polyester resin composition of the present invention can be easily molded by various molding methods such as injection molding, extrusion molding and compression molding, and has high flame retardancy and excellent mechanical properties, and thus has great utility value.

[0013]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples unless it exceeds the gist thereof. In addition, "part" in an Example shows a "weight part." Also, regarding the flammability, Underwriters Laboratory (Underwriter's)
Laboratories Inc. ) UL-94 standard vertical combustion test or limiting oxygen index (LOI: AST
It was evaluated by measuring MD-2863, JIS K7201). [Example 1] Polybutylene terephthalate having an intrinsic viscosity of 0.85 (trade name, Novadur 500, manufactured by Mitsubishi Kasei Co., Ltd.)
8AS) 90 parts by weight and polyphosphoric acid amide (Sumitomo Chemical Co., Ltd., trade name Sumisafe PM) 10 parts by weight were blended, and this was kneaded at 250 ° C. using a 30 mm vent type twin-screw extruder. It was extruded into a strand to obtain pellets of the polybutylene terephthalate resin composition.

The pellets were molded at a molding temperature of 250 ° C. and a mold temperature using a 0.8 ounce injection molding machine (J28SA manufactured by Japan Steel Works, Ltd.) and a mold for UL94 combustion test pieces and a limit oxygen index. Molding was performed at 85 ° C. The flame retardancy of the obtained polybutylene terephthalate resin composition is shown in Table-1.
Shown in. [Examples 2 to 3] Pellets of a polybutylene terephthalate resin composition were obtained in exactly the same manner as in Example 1 except that the ratio of polybutylene terephthalate to polyphosphoric acid amide was changed to the ratio shown in Table 1. It was [Comparative Example 1] Polybutylene terephthalate resin pellets were obtained in the same manner as in Example 1, except that polybutylene terephthalate containing no polyphosphoric acid amide was used. [Comparative Example 2] In Example 1, instead of polyphosphoric acid amide, ammonium polyphosphate (manufactured by Sumitomo Chemical Co., Ltd.,
Pellets of the polybutylene terephthalate resin composition were obtained in exactly the same manner as in Example 1 except that the product name Sumisafe P) was used. Comparative Example 3 Example 1 except that tricresyl phosphate was used instead of polyphosphoric acid amide in Example 1.
Pellets of the polybutylene terephthalate resin composition were obtained in exactly the same manner as.

The pellets of Examples 2-3 and Comparative Examples 1 to 3 were molded in exactly the same manner as in Example 1 and the flame retardancy was measured. The results are shown in Table-1.

[0016]

[Table 1]

[0017]

EFFECTS OF THE INVENTION The polybutylene terephthalate resin composition of the present invention is unlikely to generate corrosive gas during molding, and can dramatically suppress generation of irritating gas, corrosive gas, and black smoke during combustion, Moreover, it has an advantage that it is excellent in flame retardancy and mechanical properties with a smaller amount added than conventional flame retardants.

Claims (2)

[Claims] 1. A polyester resin composition comprising 100 parts by weight of a polyester resin and 5 to 40 parts by weight of polyphosphoric acid amide. 2. The polyester resin composition according to claim 1, wherein the polyester resin is polybutylene terephthalate.