JPH09157503A - Flame-retardant polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant polyester resin compsn. which does not emit a corrosive gas and has excellent properties by compounding a polyester resin with a specific phosphoric ester compd., melamine cyanurate, a reinforcing filler, and a specific compd. SOLUTION: This resin compsn. contains 100 pts.wt. polyester resin, 0.1-15 pts.wt. compd. represented by formula I (wherein R<1> to R<8> are each H or a 6C or lower alkyl; (n) is 0 or 1-10; and R9 is a group represented by formula II, III, or IV), 0.1-15 pts.wt. melamine cyanurate, 0-10 pts.wt. reinforcing filler, and 0.01-2 pts.wt. compd. such as represented by formula V [wherein R<10> is a (hydroxylated) 8-50C (un)satd. fatty acid residue; and R<11> is H or a 1-30C alkyl] or formula VI [wherein R<12> and R<14> are each a (hydroxylated) 8-50C (un)satd. fatty acid residue; and R<13> is a 1-30C alkylene]. Contg. no halogen compd., the compsn. does not emit a corrosive gas during molding, does not emit an irritative gas, a corrosive gas, and black smoke during burning, and is excellent in reliability, flame retardancy, mechanical properties, and hydrolysis resistance.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyester resin composition. For details, flame retardancy, low smoke generation,
The present invention relates to a polyester resin composition having excellent fluidity, hydrolysis resistance, mold release property and mechanical properties.

[0002]

2. Description of the Related Art Recently, polyester resins have been widely used in automobile parts, household electric appliances parts, office parts, industrial parts, textile products, construction materials, miscellaneous goods, etc. Needless to say, materials having flame retardancy have been required. Various inorganic flame retardants and organic flame retardants are known as flame retardants, and halogen organic flame retardants have hitherto 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. However, it has a drawback that it hinders evacuation. Moreover, recently, there is a report pointing out the risk of dioxin generation as a thermal decomposition product of a halogen compound,
From the viewpoint of environmental protection, the use of halogen compounds is being controlled.

A method using a water-containing inorganic compound such as magnesium hydroxide or aluminum hydroxide as a non-halogen flame retardant is known, but it is necessary to add a large amount to a resin, and therefore mechanical properties are remarkably deteriorated. To do. In addition to these water-containing inorganic compounds, Japanese Patent Publication No. 58-5939
As disclosed in JP-B No. 60-33850 and JP-B No. 60-33850, examples of using a nitrogen compound having a triazine ring are known, but these not only have low flame retardancy but also significantly reduce the toughness of a molded product. Or cause the flame retardant to adhere to the mold (plate out) or bleed out to the resin surface. On the other hand, Japanese Patent Publication No. 51-19858, Japanese Patent Publication No. 51-39271, and Japanese Patent Publication No. 6-5045.
As disclosed in Japanese Patent Laid-Open No. 63-63, various methods of using a phosphoric acid ester-based flame retardant are known, but all of them not only have insufficient flame retardancy, but also significantly increase the crystallinity of the resin. It also has a drawback that it lowers the moldability and remarkably deteriorates the moldability. In order to solve these drawbacks, a method of combining melamine cyanurate and a phosphate ester flame retardant has also been proposed. For example, JP-A-7-233311
In the publication, a heterocyclic compound containing a nitrogen atom such as melamine cyanurate and a compound having two or more functional groups such as a phosphorus-based flame retardant and an epoxy group are combined to make a polyester flame-retardant. However, the compound having a functional group such as an epoxy group contained in these compositions thickens the system and causes a decrease in fluidity, resulting in a marked deterioration in moldability.

Further, these systems have the drawbacks that the releasability during injection molding is poor and the productivity is extremely low.
Usually, in order to improve the productivity, a hydrocarbon type or silicone type releasing agent is used to improve the releasing property. However, in particular, in the flame-retardant polyester using a non-halogen flame retardant, there is a drawback that the flame retardancy is remarkably lowered by adding an extremely small amount of these release agents.

[0005]

Under the above circumstances, the present invention has been made to solve the above-mentioned drawbacks of the prior art. The object of the present invention is to dehalogenate the composition and thereby to perform the molding process. It suppresses the generation of corrosive gas, dramatically suppresses the generation of irritating gas, corrosive gas, and black smoke at the time of combustion, and also has flame retardancy, mechanical properties, hydrolysis resistance, and releasability. Another object of the present invention is to provide a flame-retardant polyester resin composition having excellent moldability.

[0006]

As a result of extensive studies on the above problems, the present inventor has found that a polyester resin composition comprising a specific component having a specific structure has a particularly excellent flame retardancy and low smoke generation property. The present invention has been accomplished by finding out that it has releasability, moldability and mechanical properties. That is, the gist of the present invention is: (A) 100 parts by weight of a polyester resin (B) 0.1 to 15 parts by weight of a compound represented by the general formula (I)

[0007]

Embedded image

(In the formula, R ^{1 to} R ⁸ are hydrogen atoms or alkyl groups having 6 or less carbon atoms, n is 0 or an integer of 1 or more and 10 or less, and R ⁹ is a structure selected from the following.)

[0009]

Embedded image

(C) Melamine cyanurate 0.1 to 15 parts by weight (D) Reinforcing filler 0 to 10 parts by weight (E) Compound represented by any of the general formulas (II) to (VI) or glyceride of fatty acid Ester, 0.01-2 parts by weight

[0011]

Embedded image

(Wherein R ¹⁰ is a saturated or unsaturated fatty acid residue having 8 to 50 carbon atoms which may be substituted with a hydroxyl group, R ¹¹
Represents hydrogen or an alkyl group having 1 to 30 carbon atoms. )

[0013]

Embedded image

(In the formula, R ¹² and R ¹⁴ represent a saturated or unsaturated fatty acid residue having 8 to 50 carbon atoms which may be substituted with a hydroxyl group, and R ¹³ represents an alkylene group having 1 to 30 carbon atoms.)

[0015]

[Image Omitted] R ¹⁵ COOR ¹⁶ (IV)

(Wherein R ¹⁵ is a saturated or unsaturated fatty acid residue having 8 to 50 carbon atoms which may be substituted with a hydroxyl group, R ¹⁶
Represents an alkyl group having 1 to 50 carbon atoms. )

[0017]

[Image Omitted] R ¹⁷ COOM (V)

(In the formula, R ¹⁷ represents a saturated or unsaturated fatty acid residue having 8 to 50 carbon atoms which may be substituted with a hydroxyl group, and M represents hydrogen or a group IA, IIA or IIB of the periodic table. Represents a metal.)

[0019]

Embedded image R ¹⁸ OH (VI)

A flame-retardant polyester resin composition, characterized in that R ¹⁸ represents an alkyl group having 8 to 50 carbon atoms which may be substituted with a hydroxyl group. This is to solve the above-mentioned drawbacks of the prior art.

The present invention will be described in detail below. The (A) polyester resin used for producing the polyester resin composition of the present invention is obtained by polycondensation of at least one bifunctional carboxylic acid component and at least one glycol component or oxycarboxylic acid. It means a thermoplastic polyester having an intrinsic viscosity of 0.40 or more, and specific examples of the bifunctional carboxylic acid component include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, P, P'-diphenyl dicarboxylic acid, P, P'-diphenyl ether dicarboxylic acid, adipic acid, sebacic acid, dodecane diacid,
Examples thereof include suberic acid, azelaic acid, 5-sodium sulfoisophthalic acid, or alkyl ester thereof, and ester-forming derivatives such as acid halides. Among them, aromatic dicarboxylic acids or ester-forming derivatives thereof are preferable, and particularly, Is preferably terephthalic acid or terephthalic acid diester. Specific examples of the glycol component include α, ω-alkylene glycol, neopentyl glycol, 1,4-cyclohexanediol, and 1 represented by the general formula: HO (CH ₂ ) _m OH (m is an integer of 2 to 20). , 4-cyclohexanedimethanol, bisphenol A, polyoxyethylene glycol, polyoxytetramethylene glycol, or ester-forming derivatives thereof, among which α, ω-, such as ethylene glycol and 1,4-butanediol. Alkylene glycol is preferable, and 1,4-butanediol is particularly preferable. Further, specific examples of the oxycarboxylic acid include:
Examples thereof include oxybenzoic acid, 4- (2-hydroxyethoxy) benzoic acid, or ester-forming derivatives such as alkyl esters and acid halides 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. Further, with respect to 100 parts by weight of such polyester, polycarbonate, ABS resin,
70% by weight or less of another thermoplastic polymer such as polyphenylene ether may be mixed and used in the present invention.

The polyester resin composition of the present invention is produced.
The component (B) used for the purpose is represented by the general formula (I).
A phosphoric acid ester compound represented by the formula R¹~ R⁸Is hydrogen
An atom or an alkyl group having 6 or less carbon atoms, which is resistant to hydrolysis
In order to improve the degradability, an alkyl group having 6 or less carbon atoms
Of these, a methyl group is preferable. n is 0 or 1
It is a number of 10 or more and 10 or less, preferably 1 or more and 3 or less, and medium
However, 1 is preferable. R ⁹Indicates a structure selected from
And

[0023]

Embedded image

Is preferably used. The amount of component (B) added is 0.1 to 15 parts by weight based on 100 parts by weight of the polyester resin.
Parts by weight, preferably 0.5 to 10 parts by weight, particularly preferably 1 to 8 parts by weight. If the amount of (B) is less than 0.1 parts by weight, the flame retardancy becomes insufficient, and if it is more than 15 parts by weight, the elongation at break and the hydrolysis resistance decrease.

[0025]

Embedded image

The melamine cyanurate (C) used for producing the polyester resin composition of the present invention is an equimolar reaction product of cyanuric acid and melamine, for example, an aqueous solution of cyanuric acid and an aqueous solution of melamine. And mix 90
It can be obtained by reacting at a temperature of -100 ° C with stirring and filtering the formed precipitate. Some of the amino groups or hydroxyl groups of melamine cyanurate may be substituted with other substituents. The amount of melamine cyanurate added is 0.1 to 100 parts by weight of the polyester resin.
It is 15 parts by weight, preferably 1 to 10 parts by weight, particularly preferably 2 to 8 parts by weight. If the amount of melamine cyanurate added is less than 0.1 part by weight, the flame retardancy becomes insufficient and 1
If the amount is more than 5 parts by weight, toughness and ductility are reduced, and bleed out and plate out are caused.

The ratio of the component (B) to the melamine cyanurate (C) is not particularly limited, but is usually 1:10.
To 10 to 1, and especially 2 to 10 to 10: 2 are preferable. The (D) reinforcing filler used for producing the polyester resin composition of the present invention is a fibrous or granular or powdery organic substance or inorganic substance, and examples of the fibrous reinforcing filler include: Examples thereof include glass fiber, alumina fiber, silicon carbide fiber, boron fiber, carbon fiber and aramid fiber. Examples of the granular or powdery reinforcing filler include wollastonite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, silicates such as alumina silicate, alumina, silicon oxide, magnesium oxide, aluminum oxide. , Metal oxides such as zirconium oxide and titanium oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, glass flakes, boron nitride and silicon carbide. These reinforcing fillers (D) may be used alone or in combination of two or more, and if necessary, may be pretreated with a silane-based or titanium-based coupling agent or the like. The amount of the reinforcing filler (D) added is 0 to 10 parts by weight, preferably 0 to 3 parts by weight, particularly preferably 0 to 1 part by weight, based on 100 parts by weight of polyester. If it is more than 10 parts by weight, not only the ductility and fluidity are lowered, but also the flame retardancy is remarkably lowered. (E) used for producing the polyester resin composition of the present invention is represented by the following general formula (I
A compound represented by any one of I) to (VI), a glycerin ester of a fatty acid, or a mixture thereof.

[0028]

Embedded image

(In the formula, R ¹⁰ is a saturated or unsaturated fatty acid residue having 8 to 50, preferably 10 to 40, particularly preferably 18 to 30 carbon atoms which may be substituted with a hydroxyl group, and R ¹¹ is hydrogen or carbon. An alkyl group having 1 to 30 carbon atoms, preferably hydrogen or an alkyl group having 1 to 20 carbon atoms, and hydrogen is particularly preferable.

[0030]

Embedded image

(In the formula, R ¹² and R ¹⁴ are saturated or unsaturated fatty acid residues having 8 to 50, preferably 10 to 40, particularly preferably 18 to 30 carbon atoms which may be substituted with a hydroxyl group,
R ¹³ represents an alkylene group having 1 to 30 carbon atoms, preferably 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms. )

[0032]

Embedded image R ¹⁵ COOR ¹⁶ (IV)

(In the formula, R ¹⁵ is a saturated or unsaturated fatty acid residue having 8 to 50, preferably 10 to 40, more preferably 18 to 35 carbon atoms which may be substituted with a hydroxyl group, and R ¹⁶ is 1 carbon atom. .About.50, preferably 1 to 30, more preferably 4 to 25, particularly preferably 4 to 20 alkyl groups.)

[0034]

Embedded image R ¹⁷ COOM (V)

(In the formula, R ¹⁷ represents a saturated or unsaturated fatty acid residue having 8 to 50, preferably 10 to 40, and more preferably 18 to 35 carbon atoms which may be substituted with a hydroxyl group, and M is hydrogen. Or metal of Group IA, Group IIA, or Group IIB of the Periodic Table, especially hydrogen or Li, Na, K, Mg, Ca,
Ba and Zn are preferable, and Na is particularly preferable. )

[0036]

Embedded image R ¹⁸ OH (VI)

(In the formula, R ¹⁸ represents an alkyl group having 8 to 50 carbon atoms, which may be substituted with a hydroxyl group, preferably 10 to 35, and more preferably 18 to 30 carbon atoms.)

Specific examples of the compound represented by the general formula (II) include caprylic acid, pelargonic acid, lauric acid, pentadecylic acid, heptadecyl acid, stearic acid, nonadecanoic acid, behenic acid, serotic acid, montanic acid, and laxel. Amides of saturated fatty acids such as acids, oleic acid, linoleic acid,
Examples thereof include amides of unsaturated fatty acids such as linoleic acid, and amides of hydroxyl-substituted fatty acids such as hydroxystearic acid, hydroxybehenic acid, and hydroxymontanic acid. Among them, carbon number is 8 to 50, preferably 10 to 40, and more preferably 18 to 30 saturated fatty acid amides are preferable, and stearic acid, behenic acid, and montanic acid amides are particularly preferable.

Specific examples of the compound represented by the general formula (III) include ethylenebisstearylamide, propylenebisstearylamide, butylenebisstearylamide,
Linear alkyl fatty acid bisamides such as ethylene bismontanylamide, propylene bismontanylamide, butylene bismontanylamide, aromatic alkyl fatty acid bisamides such as xylylenebisstearylamide, xylylenebismontanylamide, etc. Among them, stearyl amide is preferable, and ethylene bis stearyl amide or xylylene bis stearyl amide is particularly preferable.

Specific examples of the compound represented by the general formula (IV) include caprylic acid, pelargonic acid, lauric acid, pentadecylic acid, heptadecylic acid, stearic acid, nonadecanoic acid, behenic acid, cerotic acid, montanic acid and laxel. Saturated fatty acids such as acids, oleic acid, linoleic acid, unsaturated fatty acids such as linolenic acid, hydroxystearic acid, hydroxybehenic acid, hydroxy-substituted fatty acids such as hydroxymontanic acid, and methanol, ethanol, propanol,
Butanol, pentanol, hexanol, capryl alcohol, lauryl alcohol, pentadecyl alcohol, heptadecyl alcohol, palmityl alcohol,
Esters with saturated aliphatic alcohols such as stearyl alcohol, nonadecanyl alcohol, behenyl alcohol, montanyl alcohol, and laxel alcohol can be mentioned. Among them, fatty acid having 10 to 40 carbon atoms, preferably 18 to 35 esters are preferable, Particularly preferred are stearic acid, behenic acid, and montanic acid esters, and more preferred are stearic acid esters. Among stearic acid esters, the carbon number of the alcohol residue is 4 to 25,
Particularly, those having 4 to 20 are preferable, and stearyl stearate is particularly preferable.

Specific examples of the compound represented by the general formula (V) include caprylic acid, pelargonic acid, lauric acid, pentadecylic acid, palmitic acid, stearic acid, nonadecanoic acid, behenic acid, serotic acid, montanic acid and laxel. Saturated fatty acids such as acids or their periodic table IA, IIA
Group, Group IIB metal salts, unsaturated fatty acids such as oleic acid, linoleic acid and linoleic acid, or their periodic table IA
Group, Group IIA, Group IIB metal salts, hydroxystearic acid, hydroxybehenic acid, hydroxymontanic acid, and other hydroxyl group-substituted fatty acids, or their periodic table groups IA and IIA
Examples thereof include metal salts of Group I and Group IIB, and among them, saturated fatty acids or metal salts of Group IA, Group IIA, and Group IIB of the periodic table thereof are preferable, and particularly those having 10 to 40 carbon atoms, especially 18 to 10 carbon atoms.
35 fatty acids, or Group IA, IIA of these Periodic Tables
Group I and Group IIB metal salts are preferred. Among these, Li, Na, K, Mg, Ca, Ba, and Zn salts such as stearic acid, behenic acid, and montanic acid are particularly preferably used,
Most preferably Na salt is used.

Preferred examples of the compound represented by the general formula (VI) include capryl alcohol, lauryl alcohol, pentadecyl alcohol, heptadecyl alcohol, palmityl alcohol, stearyl alcohol, nonadecanyl alcohol, behenyl alcohol and montanyl alcohol. And saturated aliphatic alcohols such as laxel alcohol, and among them, saturated aliphatic alcohols having 10 to 35 carbon atoms, particularly 18 to 30 carbon atoms are preferable, and stearyl alcohol is particularly preferable.

The glycerin ester of a saturated or unsaturated fatty acid having 8 to 50 carbon atoms which may be substituted with a hydroxyl group, which is applicable to the present invention, includes caprylic acid, pelargonic acid, lauric acid, pentadecylic acid, palmitic acid, stearin. Acids, saturated fatty acids such as nonadecanoic acid, behenic acid, cerotic acid, montanic acid and laxeric acid, or unsaturated fatty acids such as oleic acid, linoleic acid and linoleic acid, hydroxystearic acid, hydroxybehenic acid and hydroxymontanic acid Is a glycerin ester of a hydroxyl-substituted fatty acid, and among them, a glycerin ester of a fatty acid having 10 to 35 carbon atoms, particularly 10 to 25 carbon atoms is preferable. Further, the number of esterified groups of the three hydroxyl groups of glycerin is not particularly limited, but monoglycerin ester or triglycerin ester is preferably used.

These compounds (E) are used alone or as a mixture, and among them, the compounds represented by the general formulas (III), (IV),
Among (V), those represented by (III) and (V) are particularly excellent in the property of not reducing the flame retardancy while maintaining the mold releasability of the molded product, and are particularly represented by the general formula (V). Most preferred are compounds. The amount of the compound (E) added is 0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight, particularly preferably 0.1 to 0.5 part by weight, based on 100 parts by weight of the polyester resin. If the addition amount is less than 0.01 parts by weight, the releasability is insufficient, and if it is more than 2 parts by weight, the flame retardancy is significantly reduced.

The polyester resin composition of the present invention can achieve the desired flame retardancy without the addition of auxiliary flame retardants such as antimony compounds and oxygen-containing compounds which are harmful to the human body. Also other conventional ingredients such as heat stabilizers, light stabilizers,
UV absorbers, antioxidants, antistatic agents, preservatives, adhesion promoters, coloring agents, crystallization promoters, foaming agents, bactericides, plasticizers, thickeners, drip-proof agents, impact modifiers, fumes Inhibitors 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, a melt mixing method using an extruder, and the like. Usually, a screw extruder is used. It is preferable to melt-mix and extrude into a strand and pelletize. The polyester resin composition of the present invention has not only high releasability but also high flame retardancy, so that it can be easily molded by various molding methods such as injection molding, extrusion molding, compression molding, and has excellent mechanical properties. It has a great utility value because it exists. In particular, it can be suitably used for electric or electronic parts, specifically, connectors, relays, switches, coil bobbins and the like.

[0047]

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 the examples, “parts” indicates “parts by weight”. For flammability, Underwriter's Laboratories Inc.
UL-94 standard vertical combustion test or limit oxygen index (LOI: ASTM D-2863, JIS K720
It was evaluated by measuring 1).

The freezing point (Tc) of the polymer was measured by using DSC (TA-2000) manufactured by DuPont under a nitrogen atmosphere.
About 10 mg of sample was heated up to 260 ° C. at 16 ° C./min, kept in that state for 5 minutes, and then cooled down at 16 ° C./m.
The temperature was lowered to 30 ° C. in and measured. Elongation at break is A
A tensile test was conducted and measured according to STM D-638. The hydrolysis resistance was evaluated by exposing it to steam at 120 ° C. for 24 hours, then performing the above-mentioned tensile test, and measuring the retention rate of the tensile strength based on the following formula.

[0049]

(Equation 1)

The mold releasability is 100 mm × injection molding at a cylinder temperature of 255 ° C. and a mold temperature of 80 ° C. and a cooling time of 10 seconds.
When releasing the 100 mm grid-shaped molded piece from the mold,
A pressure sensor attached to the central ejector pin was used to measure and evaluate the pressure (mold release resistance value: kgf / cm ² ) applied when the molded product was released from the mold. The plate-out condition was visually inspected.

Examples 1 to 4 Polybutylene terephthalate (PB) having an intrinsic viscosity of 0.95
T: Mitsubishi Engineering Plastics Co., Ltd., trade name Novadur), a phosphoric acid ester compound represented by the following structural formula, melamine cyanurate, and sodium montanate were blended at a ratio shown in Table 1 and 30 m
m vent type twin-screw extruder was used to knead at 250 ° C., extruded strands, and pelletized.

The pellets were injection-molded at a cylinder temperature of 255 ° C. and a mold temperature of 80 ° C. by using an injection molding machine and a mold for UL94 combustion test piece and limit oxygen index, and various kinds as shown in Table-1. The physical properties were measured. As shown in Table 1, a polybutylene terephthalate resin composition excellent in flame retardancy, mold release property, mechanical properties, crystallinity, and hydrolysis resistance was obtained.

[0053]

Embedded image

Example 5 A molded product was obtained in the same manner as in Example 2 except that the phosphoric acid ester compound represented by the following structural formula was used.

[0055]

Embedded image

Example 6 A molded product was obtained in the same manner as in Example 2 except that the phosphoric acid ester compound represented by the following structural formula was used.

[0057]

Embedded image

Example 7 A molded product was obtained in the same manner as in Example 2 except that the phosphoric acid ester compound represented by the following structural formula was used.

[0059]

Embedded image

Example 8 A molded product was obtained in the same manner as in Example 2 except that the amount of sodium montanate was changed. Example 9 A molded product was obtained in the same manner as in Example 2 except that the amount of sodium montanate was changed. Example 10 A molded product was obtained by the same method as in Example 2 except that ethylenebisstearylamide was used instead of sodium montanate.

Example 11 A molded product was obtained in the same manner as in Example 2 except that xylylenebisstearylamide was used instead of sodium montanate. Example 12 A molded product was obtained in the same manner as in Example 2 except that stearyl stearate was used instead of sodium montanate. Example 13 A molded product was obtained in the same manner as in Example 2 except that behenic acid amide was used instead of sodium montanate.

Example 14 A molded product was obtained in the same manner as in Example 2 except that montanic acid was used instead of sodium montanate. Example 15 A molded product was obtained in the same manner as in Example 2 except that hydroxystearic acid monoglyceride was used instead of sodium montanate. Example 16 A molded product was obtained in the same manner as in Example 2 except that barium stearate was used instead of sodium montanate.

Example 17 A molded product was obtained in the same manner as in Example 2 except that stearyl alcohol was used instead of sodium montanate. Example 18 Polyethylene terephthalate (PE having an intrinsic viscosity of 0.65)
T: Mitsubishi Chemical Co., Ltd. and talc (Hayashi Kasei Co., Ltd. trade name Micron White) as a reinforcing filler, 27
A molded product was obtained by the same method as in Example 2 except that kneading was carried out at 0 ° C. and molding was carried out at 280 ° C. (mold temperature: 115 ° C.). Example 19 A molded product was obtained in the same manner as in Example 2 except that 1 part of glass fiber (manufactured by Nippon Electric Glass Co., Ltd., epoxysilane treated product, average length 3 mm) was added.

Comparative Example 1 Example 2 except that sodium montanate was not used.
A molded product was obtained by exactly the same method as described above. Table-Evaluation results
It is shown in FIG. The releasability was significantly reduced, and the flame retardancy was also reduced. Comparative Example 2 Instead of sodium montanate, a number average molecular weight of 220
A molded product was obtained in exactly the same manner as in Example 2 except that polyethylene wax having a weight average molecular weight of 7,100 (Hiwax 400P, manufactured by Mitsui Petrochemical Co., Ltd.) was used. Flame retardancy is significantly reduced. Comparative Example 3 A molded product was obtained by the same method as in Example 2 except that the amount of sodium montanate added was tripled. Flame retardancy is significantly reduced.

Comparative Example 4 A molded product was obtained in the same manner as in Example 2 except that the amount of sodium montanate added was changed to 0.005 part.
The releasability was significantly reduced. Comparative Example 5 A molded product was obtained in the same manner as in Example 2 except that silicone oil (SH200, manufactured by Toray Silicone Co., Ltd.) was used instead of sodium montanate. Flame retardancy is significantly reduced. Comparative Example 6 A molded product was obtained by the same method as in Example 2 except that melamine cyanurate was not used. Tc was significantly reduced and releasability was also deteriorated.

Comparative Example 7 Example 2 except that 40 parts of glass fiber (manufactured by Nippon Electric Glass Co., Ltd., epoxysilane treated product, average length 3 mm) was added.
A molded product was obtained by exactly the same method as described above. The elongation at break and flame retardancy were significantly reduced. Comparative Example 8 A molded product was obtained by the same method as in Example 2 except that melamine was used instead of melamine cyanurate. The flame retardance decreased and plate out was observed during molding. Comparative Example 9 A molded product was obtained in the same manner as in Example 2 except that the amount of the phosphoric acid ester compound was changed to 20 parts. The strength retention after steam exposure decreased, and plate-out during molding was observed.

Comparative Example 10 A molded product was obtained in the same manner as in Example 18 except that 40 parts of talc was added. Flame retardancy is significantly reduced. Comparative Example 11 A molded product was obtained in exactly the same manner as in Example 2 except that ammonium polyphosphate (Sumitomo Chemical Co., Ltd., Sumisafe P) was used instead of the phosphate ester compound. Plate-out was observed, and elongation at break and hydrolysis resistance were significantly reduced.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

EFFECTS OF THE INVENTION Since the polyester resin composition of the present invention does not contain a halogen compound, the generation of corrosive gas during molding and the generation of irritating gas, corrosive gas, and black smoke during combustion are dramatically improved. Suppressed to. Further, since it is excellent in releasability, flame retardancy, mechanical properties, and hydrolysis resistance, it is suitable as a resin for electric / electronic parts.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 5/3477 KJZ C08K 5/3477 KJZ 5/521 5/521 (72) Inventor Shintaro Kishimoto Kanagawa 1000 Kamoshida-cho, Aoba-ku, Yokohama-shi Mitsubishi Chemical Co., Ltd.Yokohama Research Institute (72) Inventor Shigeru Muramatsu 370 Enzo, Chigasaki-shi, Kanagawa Mitsubishi Engineering Plastics Co., Ltd.Technical Center (72) Inventor Kunihiro Takenaka Kanagawa 370 Enzo, Chigasaki-shi Mitsubishi Engineering Plastics Co., Ltd. Technical Center

Claims (3)

[Claims] (A) 100 parts by weight of polyester resin (B) 0.1 to 15 parts by weight of a compound represented by general formula (I) (In the formula, R ^{1 to} R ⁸ represent a hydrogen atom or an alkyl group having 6 or less carbon atoms, n represents 0 or an integer of 1 or more and 10 or less,
R ⁹ represents a structure selected from the following. ) (C) Melamine cyanurate 0.1 to 15 parts by weight (D) Reinforcing filler 0 to 10 parts by weight (E) Compound represented by any of the following (1) to (6) 0.01 to 2 parts by weight A flame-retardant polyester resin composition containing. Embedded image (In the formula, R ¹⁰ has 8 to 8 carbon atoms which may be substituted with a hydroxyl group.
50 saturated or unsaturated fatty acid residues, R ¹¹ represents hydrogen or an alkyl group having 1 to 30 carbon atoms. ) [Chemical 4] (In the formula, R ¹² and R ¹⁴ represent a saturated or unsaturated fatty acid residue having 8 to 50 carbon atoms which may be substituted with a hydroxyl group, and R ¹³ represents an alkylene group having 1 to 30 carbon atoms.) (3) R ¹⁵ COOR ¹⁶ (IV) (In the formula, R ¹⁵ has 8 to 8 carbon atoms which may be substituted with a hydroxyl group.
50 saturated or unsaturated fatty acid residues, R ¹⁶ has 1 to 1 carbon atoms
It represents 50 alkyl groups. (4) R ¹⁷ COOM (V) (wherein R ¹⁷ has 8 carbon atoms which may be substituted with a hydroxyl group).
To 50 saturated or unsaturated fatty acid residues, M represents hydrogen or a metal of Group IA, Group IIA, or Group IIB of the periodic table. ## STR00007 ## (5) R ¹⁸ OH ... (VI) (wherein R ¹⁸ has 8 carbon atoms which may be substituted with a hydroxyl group).
Represents an alkyl group of 50. (6) Glycerin ester of saturated or unsaturated fatty acid having 8 to 50 carbon atoms which may be substituted with a hydroxyl group. 2. The flame-retardant polyester resin composition according to claim 1, wherein the polyester resin is polybutylene terephthalate. 3. An electric or electronic component obtained by molding the composition according to claim 1.