JP3146142B2 - Flame retardant polyethylene terephthalate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a flame-retardant polyethylene terephthalate resin composition,
The present invention relates to a flame-retardant polyethylene terephthalate-based resin composition which is excellent in flame retardancy, mechanical strength such as tensile strength, retention heat stability, and has good balance between wet heat resistance and fluidity.

[0002]

2. Description of the Related Art Polyethylene terephthalate has been widely used as a fiber, film, molding material and the like because of its excellent mechanical properties and electrical properties. In particular, the mechanical strength and the thermal properties are greatly improved by blending a fiber reinforcing material such as glass fiber, and thus the thus obtained reinforced composition is suitable as a material for a so-called functional component.

In recent years, in particular, in the field of electric or electronic parts, the demand for fire safety has been increased, and in response to this demand, flame retardation of resins has been carried out. For example, organic halogen compounds or polymer halogen compounds have been added. ing. Furthermore, some of the electric or electronic components that use such a flame-retardant material are in direct or indirect contact with water or water vapor, and in such fields, they are exposed to high temperature and high humidity. In addition, high wet heat resistance, which does not cause a sudden decrease in mechanical strength, is required in addition to flame retardancy.

[0004] The flame retardancy of thermoplastic polyester is described in, for example, JP-A-50-35257 and JP-A-62-15.
A method of adding a halogenated epoxy compound to 256,
JP-A-59-149954 proposes a method of adding a high molecular weight halogenated bisphenol A type phenoxy resin, and JP-A-50-92346 proposes a method of adding a halogenated polystyrene resin.

Further, a method of adding a carbodiimide compound to improve the moist heat resistance of polyethylene terephthalate has been known for a long time, and a method of improving the moist heat resistance while imparting flame retardancy is described in, for example, JP-A-59-129253. Has proposed a method of adding an epoxy compound and / or a carbodiimide compound together with a high-molecular halogenated bisphenol A-type copolymerized phenoxy resin.

On the other hand, electric or electronic parts using such a flame-retardant material usually have a mixture of a relatively thin part and a thick part. In addition, a material that has good molding fluidity even in thin parts and good release properties even in thick parts is required. Type is required.

[0007]

However, when a halogenated epoxy compound is used as a flame retardant, the flame retardant has a reactivity with a polyethylene terephthalate resin, so that the fluidity of the resin due to the reaction at the time of molding at a high temperature is increased. Is worse.

In order to solve such a problem, the present inventors have used a halogenated epoxy resin having a specific skeleton of 1500 to 2500 and having a specific skeleton as a flame retardant, using a polyethylene terephthalate resin polymerized using a germanium catalyst. It was discovered that the use of a compound can improve both fluidity and wet heat resistance (Japanese Patent Application No. 7-180666). However,
When such a resin composition is used, when molding is performed under special molding conditions such as long-term residence at a high temperature, a part of the compounding agent is decomposed, and a molding failure such as flash tends to occur. It has been found.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, a specific polyethylene terephthalate thermoplastic polyester resin produced using a germanium compound as a catalyst. Using an epoxy equivalent having a specific skeleton 2600
By adding a 6000 halogenated epoxy compound and antimony oxide in combination, it is possible to obtain a resin composition having excellent flame retardancy, mechanical strength, retention heat stability, and a good balance between wet heat resistance and fluidity. I found it. Furthermore, by using an inorganic compound selected from a silicate compound and a silicic acid, a flame-retardant polyethylene terephthalate-based resin composition having good releasability and a high cycle of molding when molding by injection molding or the like is provided. The inventors have found out that they have obtained the present invention.

That is, the first aspect of the present invention is that (A) 100 parts by weight of a polyethylene terephthalate-based thermoplastic polyester containing ethylene terephthalate units as a main component produced by using a germanium-based compound as a catalyst, and (B) The following general formula (III)

[0011]

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(Where X is a hydrogen atom or a halogen atom, Y is a C1-C10 alkylene group, a C2-C10 alkylidene group, a C3-C10 cycloalkane group, a carbonyl group, -O-, -S-, —SO ₂ — or a direct bond, n represents a number average degree of polymerization of 6 to 20), a halogenation rate of 10% by weight or more, and an epoxy equivalent of 2600 to 6000. 10 to 60 parts by weight of a halogenated epoxy compound, (C) 0.1 to 20 parts by weight of an antimony oxide compound, and (D) a reinforcing filler of 0 to 15 parts.
It contains a flame-retardant polyethylene terephthalate resin composition containing 0 parts by weight.

The second aspect of the present invention is that (A) 100 parts by weight of a polyethylene terephthalate-based thermoplastic polyester having ethylene terephthalate units as a main component and produced by using a germanium-based compound as a catalyst, and (B) The following general formula (IV)

[0014]

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(Where X is a hydrogen atom or a halogen atom, Y is a C1-C10 alkylene group, a C2-C10 alkylidene group, a C3-C10 cycloalkane group, a carbonyl group, -O-, -S-, —SO ₂ — or a direct bond, n represents a number average degree of polymerization of 6 to 20), a halogenation rate of 10% by weight or more, and an epoxy equivalent of 2600 to 6000. 10 to 60 parts by weight of a halogenated epoxy compound, (C) antimony oxide
1 to 20 parts by weight, (D) 0 to 150 parts by weight of a reinforcing filler,
And (E) a flame-retardant polyethylene terephthalate resin composition containing 0.1 to 60 parts by weight of at least one inorganic compound selected from the group consisting of a silicate compound and a silicic acid. .

The (A) polyethylene terephthalate-based thermoplastic polyester used in the present invention is a terephthalic acid or a derivative having an ester-forming ability thereof as an acid component using a germanium-based compound as a catalyst, and ethylene glycol or an ester thereof as a glycol component. It is a polyester resin containing ethylene terephthalate units as a main component, which is obtained using a derivative having a forming ability.

Examples of the germanium compound used as the catalyst include germanium oxides such as germanium dioxide, germanium alkoxides such as germanium tetraethoxide and germanium tetraisopropoxide, germanium hydroxide and alkali metal salts thereof, germanium glycolate, and chloride. Germanium, germanium acetate and the like can be mentioned, and these can be used alone or in combination of two or more. Among such germanium-based compounds, germanium oxide is preferred from the viewpoint of reactivity and ease of handling, and germanium dioxide is particularly preferred.

The amount of the germanium compound added is preferably 0.005 to 0.1% by weight, more preferably 0.01 to 0.05% by weight, based on the obtained polyethylene terephthalate-based thermoplastic polyester (A). It is. If the amount is less than 0.005% by weight, the polymerization of the polyethylene terephthalate-based resin hardly progresses, and 0.1% by weight.
If it exceeds, many germanium-based catalysts remain in the obtained resin, so that undesirable side reactions may occur. The addition may be made at any time before the start of the polymerization reaction.

The polyethylene terephthalate thermoplastic polyester has flame retardancy, fluidity, mold releasability,
Known copolymerizable components can be used as long as the mechanical properties and the like are not impaired. The component includes 2-8 carbon atoms.
Carboxylic acids such as aromatic carboxylic acids having a valency of 4 or more, aliphatic carboxylic acids having a valency of 4 to 12 carbon atoms, and carboxylic acids such as an alicyclic carboxylic acid having 8 to 15 carbon atoms and esters thereof. Derivatives, aliphatic compounds having 3 to 15 carbon atoms,
Alicyclic compounds having 6 to 20 carbon atoms, aromatic compounds having 6 to 40 carbon atoms and having two or more hydroxyl groups in a molecule, and ester-forming derivatives thereof, and the like. They are used alone or in combination of two or more.

Specifically, examples of the carboxylic acids include, in addition to terephthalic acid, for example, isophthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methaneanthracene dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 1,2 -Bis (phenoxy) ethane-4,4'-
Dicarboxylic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, maleic acid, trimesic acid, trimellitic acid, pyromellitic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, decahydronaphthalenedicarboxylic acid Carboxylic acids such as acids or derivatives thereof capable of forming esters, and the like,
As the hydroxyl group-containing compounds, in addition to ethylene glycol, propylene glycol, butanediol, hexanediol, decanediol, neopentyl glycol,
Cyclohexanedimethanol, cyclohexanediol, 2,2'-bis (4-hydroxyphenyl) propane, 2,2'-bis (4-hydroxycyclohexyl)
Examples thereof include compounds such as propane, hydroquinone, glycerin, and pentaerythritol, and derivatives thereof having an ester-forming ability. Also, oxyacids such as p-oxybenzoic acid and p-hydroxyethoxybenzoic acid, and ester-forming derivatives thereof, and cyclic esters such as ε-caprolactone can be used. Furthermore, polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) blocks and / or
Alternatively, a polyalkylene glycol unit such as a random copolymer, polytetramethylene glycol, an ethylene oxide addition polymer of bisphenol, a propylene oxide addition polymer of bisphenol A, and a tetrahydrofuran addition polymer of bisphenol A is partially copolymerized in a polymer chain. Those that have been used can also be used. These may be used alone or in combination of two or more. The copolymerization amount of the above components is generally not more than 20% by weight, preferably 15% by weight.
Or less, more preferably 10% by weight or less. If the copolymerization amount exceeds 20% by weight, excellent properties of the polyethylene terephthalate-based thermoplastic polyester tend to be lost.

The intrinsic viscosity of the polyethylene terephthalate thermoplastic polyester [phenol: 1, 1, 2, 2
-Measured at 25 ° C. using a 1: 1 (weight ratio) mixed solvent of tetrachloroethane] is 0.35 or more, preferably 0.4 to 1.20, more preferably 0.50 to 0.
95. If it is less than 0.35, the mechanical strength is insufficient, and if it exceeds 1.20, the moldability is deteriorated, which is not preferable. The polyethylene terephthalate-based thermoplastic polyester is used singly or as a mixture of two or more copolymer components and / or those having different intrinsic viscosities.

The method for producing the polyethylene terephthalate-based thermoplastic polyester is not particularly limited except for the catalyst used, and a known polymerization method can be used. For example,
First, a low-polymerized polymer is synthesized by a method of directly esterifying terephthalic acid and ethylene glycol in the presence or absence of a catalyst or a method of transesterifying dimethyl terephthalate and ethylene glycol in the presence of a catalyst. Then, the low-polymerized polymer and the germanium-based compound are heated at a temperature of, for example, about 250 to 300 ° C.,
For example, a method of producing a polyethylene terephthalate-based thermoplastic polyester by carrying out condensation polymerization by melt polycondensation or solid phase polycondensation while maintaining a vacuum of 1 Torr or less.

When condensation-polymerizing a polymer having a low degree of polymerization,
When a compound other than a germanium-based compound, for example, a polyethylene terephthalate-based thermoplastic polyester polymerized using an antimony-based catalyst or the like is used, a decrease in mechanical strength or the like when held at a high temperature and a high humidity greatly increases the humidity and heat resistance. It is not preferable because the fluidity is not sufficient and the fluidity is greatly reduced.

When producing a polyethylene terephthalate thermoplastic polyester, a phenolic antioxidant, a phosphorus compound or an antioxidant, a sulfur-based oxidant, etc. are used for the purpose of suppressing coloring, thermal deterioration, oxidative deterioration and the like. An antioxidant such as an inhibitor, a heat stabilizer, a coloring inhibitor and the like may be added before, during or after the reaction. Further, a catalyst deactivator such as a phosphorus compound may be added during or after the reaction.

In the present invention, a specific halogenated epoxy compound (B) is used for the purpose of imparting flame retardancy. The halogenated epoxy compound has the general formula (I)

[0026]

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(Where X is a hydrogen atom or a halogen atom, Y is a C1-C10 alkylene group, a C2-C10 alkylidene group, a C3-C10 cycloalkane group, a carbonyl group, -O-, -S-, —SO ₂ — or a direct bond, and n represents a number average degree of polymerization of 6 to 20).
The halogenation ratio of the halogenated epoxy compound is 10% by weight or more, and the epoxy equivalent is 2600 to 6000.
It is. The halogenation rate is preferably at least 20% by weight,
More preferably, it is at least 25% by weight. When the halogenation ratio is less than 10% by weight, the flame retardancy is insufficient. The epoxy equivalent is preferably from 2620 to 5850, more preferably from 2650 to 5600. Epoxy equivalent is 6
If it exceeds 000, the wet heat resistance of the flame-retardant resin composition decreases, while if the epoxy equivalent is less than 2600, when molding is performed under special molding conditions such that the resin stays at a high temperature for a long time, Partially decomposes and molding defects such as flash occur. In general formula (I), n is 6-20. n
Is more than 20, the wet heat resistance is reduced, and if n is less than 6, the appearance is degraded during stay molding. In the general formula (I), X is preferably a hydrogen atom or a bromine atom from the viewpoint of flame retardancy. More preferably, X is a bromine atom. In the general formula (I), Y is preferably -C (CH3) _2- in terms of mechanical strength.

The amount of the halogenated epoxy compound used is:
Depending on the halogenation rate, epoxy equivalent, etc.,
The amount is 10 to 60 parts by weight, preferably 11 to 55 parts by weight, more preferably 12 to 50 parts by weight based on 100 parts by weight of the polyethylene terephthalate-based thermoplastic polyester (A). If the amount is less than 10 parts by weight, the flame retardancy is insufficient. If the amount exceeds 60 parts by weight, the fluidity of the flame retardant resin composition is lowered and the appearance of the obtained molded article is deteriorated.

The flame retardant effect can be remarkably enhanced by adding the antimony oxide compound (C) to the composition of the present invention. Examples of antimony oxide include antimony trioxide, antimony tetroxide, antimony pentoxide, and the like. These may be used alone or in combination of two or more. Among them, from the viewpoints of wet heat resistance, fluidity, mechanical strength, and the like, trimonium oxide is preferred. Antimony oxide is preferred.

The amount of the antimony oxide compound used is:
(A) 0.1 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of polyethylene terephthalate-based thermoplastic polyester. If the amount is less than 0.1 part by weight, the flame retardancy is insufficient, and if it exceeds 20 parts by weight, the mechanical strength of the flame-retardant polyester-based resin composition decreases.

The flame-retardant polyethylene terephthalate resin composition of the present invention includes, in addition to the above components, a composition further comprising (D) a reinforcing filler, that is, a reinforced flame-retardant polyethylene terephthalate resin composition. A known reinforcing filler can be used as it is. Examples of the reinforcing filler include glass fiber, carbon fiber, potassium titanate fiber, glass beads, glass flake, calcium carbonate, calcium sulfate, barium sulfate, and the like, and these are used alone or in combination of two or more. As the reinforcing filler, a fibrous reinforcing agent such as glass fiber or carbon fiber is preferable, and chopped strand glass fiber treated with a sizing agent is preferably used from the viewpoint of workability. Further, in order to enhance the adhesiveness between the resin and the fibrous reinforcing agent, it is preferable that the surface of the fibrous reinforcing agent is treated with a coupling agent, and a material using a binder may be used.

As the coupling agent, for example, γ-
Aminopropyltriethoxysilane, alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, and as the binder, for example, epoxy resin,
A urethane resin or the like is preferably used, but is not limited thereto. These coupling agents and binders are used alone or in combination of two or more.

When glass fiber is used for the reinforcing filler,
The diameter is preferably about 1 to 20 μm and the length is about 0.01 to 50 mm. If the fiber length is too short, the reinforcing effect is not sufficient, and if it is too long, the extrusion processability and the moldability tend to be poor.

The amount of the reinforcing filler to be used is up to 150 parts by weight, preferably 2 to 1 part, per 100 parts by weight of the polyethylene terephthalate-based thermoplastic polyester (A).
It is up to 20 parts by weight, more preferably 5 to 100 parts by weight. If the amount of the reinforcing filler exceeds 150 parts by weight, the extrusion processability and the molding processability deteriorate, which is not preferable.

Further, in the present invention, by using (E) one or more inorganic compounds selected from the group consisting of a silicate compound and a silicic acid, the releasability can be improved. A sufficiently satisfactory composition can be obtained. Among the inorganic compounds, the silicate compound is a powdery or granular material containing a SiO ₂ unit in a chemical composition.
Needle, a compound having a plate-like shape, for example,
Magnesium silicate, aluminum silicate, calcium silicate, talc, mica, kaolin, hydrotalcite,
Examples include diatomaceous earth, bentonite, montmorillonite, and clay. Of these, talc, mica and kaolin are preferred.

The amount of the inorganic compound used is 0.1 to 60 parts by weight, preferably 1 to 45 parts by weight, more preferably 3 to 30 parts by weight, based on 100 parts by weight of the polyethylene terephthalate-based thermoplastic polyester. . When the amount is less than 0.1 part by weight, the effect on the releasability is reduced, and when it exceeds 60 parts by weight, the mechanical strength of the flame-retardant resin composition is reduced. The inorganic compound when producing the polyethylene terephthalate-based thermoplastic polyester,
It may be added before, during or after the reaction, or may be added together with the flame retardant and antimony oxide when producing the composition of the present invention.

The flame retardant polyethylene terephthalate resin composition of the present invention can further improve the releasability and the gloss of the surface of the molded article by adding a crystallization accelerator (F). In particular, the releasability and surface gloss in a low-temperature mold can be improved. Examples of the crystallization accelerator include polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, ethylene oxide addition polymer of bisphenol, and propylene oxide of bisphenol. Polymers, polyalkylene glycols such as tetrahydrofuran addition polymers of bisphenols or polyalkylene glycols such as terminal epoxy-modified compounds and terminal ester-modified compounds, poly-ε-
Polyester units such as aliphatic polyesters such as caprolactone, polyethylene terephthalate, polypropylene terephthalate, polytetramethylene terephthalate, polyhexamethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycyclohexane dimethylene terephthalate, and the following general formula (I
I)

[0038]

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(Wherein R ¹ is an alkyl group having 2 to 5 carbon atoms, k is an integer of 5 or more, and k R ^{1 s} may be different from each other) and / or general formula (III)

[0040]

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(Wherein, R ² represents an alkyl group having 2 to 5 carbon atoms, Z represents a divalent linking group or a direct bond, m and n each represent an integer of 1 or more, and m + n represents an integer of 3 or more.) Wherein m and n R ² may be different from each other.) Polyester units having a glass transition temperature lower than that of a polyethylene terephthalate-based thermoplastic polyester, comprising a polyether unit having a molecular weight of 400 or more represented by Polymer, polyethylene terephthalate-poly-ε
Polyester having lower glass transition temperature than polyethylene terephthalate-based thermoplastic polyester such as caprolactone copolymer, polytetramethylene glycol-poly-ε-caprolactone copolymer-aliphatic polyester copolymer, neopentyl glycol dibenzoate, dioctyl Phthalate, triphenyl phosphate, butane-1,3-diol adipate oligomer, butane-
1,4-diol adipate oligomer, hexane-
Plasticizers such as 1,6-diol adipate oligomer, dibutyl sebacate and dioctyl sebacate may be mentioned, and these may be used alone or in combination of two or more. The use of a metal carboxylate of an organic or high molecular compound as the crystallization accelerator is not preferred because the wet heat resistance and the fluidity are reduced.

Among the above-mentioned crystallization accelerators, mechanical strength,
A polyester-polyether copolymer is preferred in terms of heat resistance, blooming properties, and the like. As the polyester unit of the copolymer, a polyalkylene terephthalate having an ethylene terephthalate unit and / or a tetramethylene terephthalate unit as a main component is preferable from the viewpoint of mechanical strength, fluidity, mold release property and the like.

The polyether unit is a unit represented by the general formula (II) and / or the general formula (III). Specific examples of R ^{1 in} the general formula (II) include, for example, ethylene , Propylene, isopropylene, tetramethylene group and the like. Specific examples of R ² in the general formula (III) include, for example, ethylene, propylene, isopropylene,
Tetramethylene, and the like, specific examples of addition X, for _{example, -C (CH 3) 2 -} , - CH 2 -, - S
_{-, - SO 3 -, -} CO- 2 divalent linking group such as or a direct bond can be mentioned. Further, in the polyether unit, k in the general formula (II) is an integer of 5 or more;
M and n in I) are 1 or more positive numbers and m + n is 3
It is an integer of at least 400, and all are units having a molecular weight of 400 or more. The molecular weight of the polyether unit is more preferably from 600 to 6000, still more preferably from 800 to 6000.
3000. If the molecular weight is less than 400, the effect of improving the releasability of the flame-retardant resin composition and the surface gloss of the molded article is small, and if it exceeds 6,000, it is difficult to obtain a homogeneous copolymer, and When added, it is not preferable because mechanical strength is lowered.

Specific examples of the polyether unit include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (ethylene oxide / propylene oxide) copolymer, poly (ethylene oxide / propylene oxide / tetrahydrofuran) copolymer, bisphenol A Alternatively, there may be mentioned residues such as ethylene oxide, propylene oxide, and alkylene oxide addition polymers of bisphenols such as bisphenol S. These may be used alone or in combination of two or more.
(III) When it consists of one or more polyether units represented by the following formulas, the thermal stability and the releasability when the obtained flame-retardant resin composition is molded in a low-temperature mold, and the surface properties of the molded body. Preferred from the point. Among these, ethylene oxide addition polymer of bisphenol A, propylene oxide addition polymer of bisphenol A, tetrahydrofuran addition polymer of bisphenol A, ethylene oxide / propylene oxide addition polymer of bisphenol A, ethylene oxide addition polymer of bisphenol S, bisphenol S
Propylene oxide addition polymer, bisphenol S tetrahydrofuran addition polymer, bisphenol S ethylene oxide / propylene oxide addition polymer and the like are preferably used.

The copolymerization amount of the polyether unit in the copolymer was 3% based on 100% by weight of the obtained copolymer.
-60% by weight, preferably 20-55% by weight, more preferably 25-50% by weight. If the amount is less than 3% by weight, the releasability and the surface gloss at the time of molding with a low-temperature mold are insufficient, and if it exceeds 60% by weight, the mechanical strength, wet heat resistance and the like of the molded body tend to decrease.

The intrinsic viscosity of the copolymer is 0.35 or more, preferably 0.40 to 2.00, more preferably 0.50 to 1.50. When the intrinsic viscosity is less than 0.35, a decrease in heat resistance of the obtained flame-retardant resin composition is observed,
If it exceeds 2.00, the dispersibility tends to decrease, and the mechanical strength of the resulting flame-retardant resin composition tends to decrease.

Although the amount of the crystallization accelerator varies depending on the type and molecular weight of the crystallization accelerator, it is generally (A) polyethylene terephthalate thermoplastic polyester 100
0.05 to 50 parts by weight with respect to parts by weight, for example,
Polyalkylene glycols, aliphatic polyesters,
In the case of a low molecular weight crystallization accelerator such as a plasticizer, 0.0
5 to 30 parts by weight, and 0.5 to 50 parts by weight in the case of the above-mentioned polyester-polyether copolymer or polyester-aliphatic polyester copolymer. Further, the amount of the polyester-polyether copolymer is preferably 1 to 40 parts by weight, more preferably 2 to 35 parts by weight. If the amount is less than the lower limit, the releasability and surface gloss in a low-temperature mold are insufficient, and if the amount exceeds the upper limit, the mechanical strength and heat resistance of the flame-retardant resin composition are exceeded. This is not preferred because the heat resistance and the wet heat resistance are reduced.

The flame-retardant polyethylene terephthalate resin composition of the present invention may further contain a heat stabilizer such as an antioxidant, if necessary. Examples of the stabilizer include pentaerythrityl-tetrakis [3- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3
5-trimethyl-2,4,6-tris (3,5-di-t
-Butyl-4-hydroxybenzyl) benzene, n-octadecyl-3- (3 ', 5'-di-t-butyl-4'
-Hydroxyphenyl) propionate, N, N'-bis-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionylhexamethylenediamine, tris- (3,5-di-t-butyl) Phenolic antioxidants such as -4-hydroxybenzyl) isocyanurate,
Tris (2,4-di-t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite and the like Phosphorus antioxidant, distearyl-3,3'-thiodipropionate, pentaerythritol-tetrakis- (β-
Thioether-based antioxidants such as lauryl-thiopropionate), and these may be used alone or in combination of two or more.

The flame-retardant polyethylene terephthalate resin composition of the present invention further comprises an ultraviolet absorber, a light stabilizer, a lubricant, a release agent, a plasticizer, a nucleating agent, a crystallization accelerator, a pigment, a dye, an antistatic agent. Additives such as agents, dispersants, compatibilizers, and antibacterial agents can be used alone or in combination of two or more. Further, other flame retardants, flame retardant assistants, and inorganic compounds may be used in combination.

The flame-retardant polyethylene terephthalate-based resin composition of the present invention may further contain any other thermoplastic or thermosetting resin as long as the properties such as flame retardancy, mechanical properties and moldability are not impaired. For example, saturated or unsaturated polyester resin other than polyethylene terephthalate resin, liquid crystal polyester resin, polyester ester elastomer resin, polyester ether elastomer resin, polyolefin resin, polyamide resin,
Polycarbonate resin, rubbery polymer reinforced styrene resin, polyphenylene sulfide resin, polyphenylene ether resin, polyacetal resin, polysulfone resin, polyarylate resin, polyfluorinated ethylene resin, etc. alone or in combination of two or more May be added.

The method for producing the flame-retardant polyethylene terephthalate resin composition of the present invention is not particularly limited. For example, after the components listed above are uniformly mixed in advance, the mixture is supplied to a single-screw or multi-screw extruder, and is subjected to 240-34.
It is melt mixed at 0 ° C. and subsequently cooled to produce pellets.

The method of molding the flame-retardant polyethylene terephthalate resin composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, namely, injection molding, hollow molding, extrusion molding, and the like. Various molding methods such as sheet molding, roll molding, press molding, lamination molding, film molding by melt casting, and spinning can be applied.

[0053]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
In the following description, unless otherwise specified, “parts”
Means parts by weight, and "%" means% by weight. In addition, the evaluation of the resin composition was performed by the following method.

Evaluation Method After the obtained resin composition was dried at 140 ° C. for 4 hours or more, the cylinder temperature was reduced to 270 using a 50-t injection molding machine.
Injection molding at 120 ° C, mold temperature 120 ° C, thickness 1/1
6 inch (12mm wide, 127mm long) bar, ASTM1
No. dumbbell test piece was obtained and the following evaluation was performed. Flame retardancy: Using a 1/16 inch bar, the flame retardancy was evaluated according to the vertical burning test method described in UL94. Tensile strength: A dumbbell was subjected to a tensile test according to ASTM D-638 to determine the maximum strength. Moisture / heat resistance: 3 dumbbells at 121 ° C under saturated pressurized steam
The wet heat treatment was performed by holding for 0 hour. A dumbbell before and after the wet heat treatment was subjected to a tensile test in accordance with ASTM D-638 to determine the maximum strength. The tensile strength retention was determined according to the following equation. Fluidity: Set temperature 280 according to JIS K-7210
The method B flow was measured and evaluated at 10 ° C. and a preheating time of 10 minutes.

Retention heat stability:
After drying at 0 ° C. for 4 hours or more, a bar having a thickness of 、 inch (width 12 mm, length 127 mm) at a cylinder temperature of 300 ° C. and a mold temperature of 140 ° C. was used for one shot using a 50-t injection molding machine. The molding cycle was set to be 10 minutes, and injection molding was performed. The appearance of the obtained molded body, such as a flash generation state, was visually observed and evaluated according to the following criteria. 〇: good appearance, △: slightly bad appearance, ×: bad appearance.

Releasability: After drying the obtained resin composition at 140 ° C. for 4 hours or more, using a 50-t injection molding machine, a cylinder temperature of 300 ° C., a mold temperature of 140 ° C., and a thickness 1 /
Shortest cooling time "limit cooling time" to obtain a good molded body without dents and deformations due to protrusion pins when a 4 inch (12 mm wide, 127 mm long) bar is injection molded
Was examined, and the releasability was evaluated.

Surface gloss: The obtained resin composition was heated at 140 ° C.
After drying for 4 hours or more, a flat plate (thickness 2 mm, length and width 120 mm) is molded using a 50-t injection molding machine at a cylinder temperature of 270 ° C. and a mold temperature of 90 ° C., and the surface gloss is visually observed. The evaluation was made according to the following criteria. ：: good, Δ: slightly poor gloss, ×: poor gloss.

Example 1 Polyethylene terephthalate (1) produced using germanium dioxide as a catalyst (intrinsic viscosity 0.75) 1
The halogenated epoxy compound (1), which is a tetrabromobisphenol A type epoxy compound having a bromination ratio of about 50% and an epoxy equivalent of about 3500, is
Part, 1 part of antimony pentoxide (Sanaflame AM: trade name, manufactured by Sanuki Chemical Co., Ltd.), 4 parts of antimony trioxide (antimony oxide C, trade name, manufactured by Sumitomo Metal Mining Co., Ltd.), phenolic antioxidant (ADK STAB) AO-60: A twin-screw extruder equipped with a vent (TEX44: trade name, manufactured by Nippon Steel Works Co., Ltd.), in which 0.35 parts of Asahi Denka Co., Ltd. are dry-blended in advance, and the cylinder temperature is set to 260 ° C. And glass fiber (T-19)
A resin composition was obtained by adding 50 parts of 5H / PS (trade name, manufactured by Nippon Electric Glass Co., Ltd.) in the middle and performing melt extrusion. Table 1 shows the evaluation results of the resin composition.

Example 2 15 parts of the halogenated epoxy compound (1) was added to 22 parts of a halogenated epoxy compound (2) which is a tetrabromobisphenol A type epoxy resin having a bromination ratio of about 50% and an epoxy equivalent of about 5,200. , Antimony oxide was changed to 5 parts of antimony trioxide (antimony oxide C: trade name of Sumitomo Metal Mining Co., Ltd.), and 50 parts of glass fiber was changed to 60 parts. Further, a thioether-based antioxidant (ADK STAB AO-412S: Asahi) 0.15 for Denka Corporation
A resin composition was obtained in the same manner as in Example 1 except that an additional part was added. Table 1 shows the evaluation results.

Examples 3 to 5 Example 1 was repeated except that the amount of each compounding agent was changed to the amount shown in Table 1.
In the same manner as in the above, a resin composition was obtained. However, polyethylene terephthalate (2) was manufactured using germanium dioxide as a catalyst and had an intrinsic viscosity of 0.60. As PTFE, polytetrafluoroethylene resin (Polyflon F104: trade name, manufactured by Daikin Industries, Ltd.) was used. Table 1 shows the evaluation results of the resin composition.

Examples 6 to 10 Resin compositions were obtained in the same manner as in Example 1 except that the amount of each compounding agent was changed to the amount shown in Table 2 and an inorganic compound was further added. However, talc (Microace K-1: trade name of Nippon Talc Co., Ltd.) and mica (A-
21S: Mika Yamaguchi Corporation, kaolin (SA)
TINTION No. 5: ENGELHARD (trade name). For reference, the evaluation results of the resin composition of Example 5 containing no inorganic compound are also shown.

Comparative Examples 1 to 11 Resin compositions were obtained in the same manner as in Example 1 using polyethylene terephthalate and the compounding agents shown in Tables 3 and 4. However, polyethylene terephthalate (3) uses an antimony compound as a catalyst and has an intrinsic viscosity of 0.75. The halogenated epoxy compound (3) has a bromination ratio of about 48% and an epoxy equivalent of 1820. Type epoxy compound and brominated bisphenol A type phenoxy resin (4) have a bromination ratio of about 5
0%, with no epoxy group blocked by terminal epoxy group. As the polyfunctional epoxy compound, Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd. was used.

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

[Table 4]

Tables 1 and 2 of Examples and Table 3 of Comparative Examples
As is clear from the comparison of Nos. 1 to 4, the compositions of the present invention are all excellent in flame retardancy, mechanical strength, wet heat resistance, and fluidity. It turns out that it is also excellent. Comparative Examples 7 and 11
Uses a multifunctional epoxy, so that the fluidity is greatly reduced.

Reference Example 1 3500 g of polyethylene terephthalate oligomer (average number of ethylene terephthalate units of about 5 to 8) produced using germanium dioxide as a catalyst, and an average molecular weight of about 10
1,500 g of an ethylene oxide addition polymer of bisphenol A, and 25 g of Adekastab AO-60.
g into a 10-liter autoclave (made of Japan pressure-resistant glass) and stirred at 290 ° C. under a nitrogen stream.
Then, the pressure was reduced to 1 Torr or less. After stirring for 3 hours after the pressure reached 1 Torr or less, the pressure was returned to normal pressure with nitrogen to terminate the polymerization to obtain a polyester-polyether copolymer (1). The intrinsic viscosity of the obtained copolymer was 0.7.

Reference Example 2 Polytetramethylene terephthalate (intrinsic viscosity 0.9)
3500 g, 1500 g of an ethylene oxide addition polymer of bisphenol A having an average molecular weight of about 1000, and
25 g of ADK STAB AO-60 was put into a 10-liter autoclave (manufactured by Japan Pressure-resistant Glass), and heated to 260 ° C. while stirring under a nitrogen stream, and then 1 Torr
The pressure was reduced to the following. After stirring for 3 hours after the pressure reached 1 Torr or less, the pressure was returned to normal pressure with nitrogen to terminate the polymerization to obtain a polyester-polyether copolymer (2). The intrinsic viscosity of the obtained copolymer was 0.8.

Example 11 100 parts by weight of polyethylene terephthalate (1) produced using germanium dioxide as a catalyst was
22 parts of halogenated epoxy compound (2), 5 parts of antimony trioxide (antimony oxide C: trade name, manufactured by Sumitomo Metal Mining Co., Ltd.), and 9 parts of polyester-polyether copolymer (1) obtained in Reference Example 1. Parts, 0.35 parts of a phenolic antioxidant, 0.15 parts of a thioether antioxidant,
A resin composition comprising 60 parts of glass fiber was obtained in the same manner as in Example 1. Table 5 shows the evaluation results of the surface gloss.

Examples 12 to 13 Example 11 except that the amount of each compounding agent was changed to the amount shown in Table 5.
In the same manner as in the above, a resin composition was obtained. Table 5 shows the evaluation results of the surface gloss. For reference, the resin compositions of Examples 2 and 7, which do not contain a polyester-polyether copolymer, were similarly evaluated. The evaluation results are shown in Table 5.

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[Table 5]

Table 5 shows that the addition of the polyester-polyether copolymer (1) or (2) provides good surface gloss even when molded in a low-temperature mold.

[0074]

According to the present invention, flame retardancy, mechanical strength,
Excellent balance between wet heat resistance and fluidity, hardly changes in viscosity even when staying at high temperature for a long time, and excellent release properties by using a specific inorganic compound together, furthermore, a specific crystallization accelerator By blending, a flame-retardant polyethylene terephthalate-based resin composition having good surface gloss even when molded with a low-temperature mold can be provided.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 67/00-67/04

Claims (9)

(57) [Claims] (A) 100 parts by weight of a polyethylene terephthalate-based thermoplastic polyester having an ethylene terephthalate unit as a main component produced by using a germanium-based compound as a catalyst, and (B) the following general formula (I) Embedded image (Where X is a hydrogen atom or a halogen atom, Y is C1-
A C10 alkylene group, a C2 to C10 alkylidene group,
3 to C10 cycloalkane, carbonyl, -O-,
—S—, —SO ₂ —, or a direct bond, where n represents a number average degree of polymerization of 6 to 20), a halogenation ratio of 10% by weight or more, and an epoxy equivalent of 260
Halogenated epoxy compounds having a molecular weight of 0 to 6000
A flame-retardant polyethylene terephthalate resin composition comprising 0 parts by weight, (C) 0.1 to 20 parts by weight of an antimony oxide compound, and (D) 0 to 150 parts by weight of a reinforcing filler. 2. The flame-retardant polyethylene terephthalate resin composition according to claim 1, wherein (D) the reinforcing filler is 2 to 150 parts by weight. (A) 100 parts by weight of a polyethylene terephthalate-based thermoplastic polyester having an ethylene terephthalate unit as a main component produced by using a germanium-based compound as a catalyst, and (B) the following general formula (I): Embedded image (Where X is a hydrogen atom or a halogen atom, Y is C1-
A C10 alkylene group, a C2 to C10 alkylidene group,
3 to C10 cycloalkane, carbonyl, -O-,
—S—, —SO ₂ —, or a direct bond, where n represents a number average degree of polymerization of 6 to 20), a halogenation ratio of 10% by weight or more, and an epoxy equivalent of 260
Halogenated epoxy compounds having a molecular weight of 0 to 6000
0 parts by weight, (C) 0.1 to 20 parts by weight of antimony oxide,
Flame-retardant polyethylene terephthalate obtained by mixing (D) 0 to 150 parts by weight of a reinforcing filler and (E) 0.1 to 60 parts by weight of at least one inorganic compound selected from the group consisting of a silicate compound and a silicic acid. -Based resin composition. 4. The flame-retardant polyethylene terephthalate resin composition according to claim 3, wherein the reinforcing filler (D) is 2 to 150 parts by weight. 5. The flame-retardant polyethylene terephthalate resin composition according to claim 1, wherein X in the general formula (I) is a bromine atom. 6. The flame-retardant polyethylene terephthalate resin composition according to claim 1, wherein (C) antimony oxide is antimony trioxide. 7. The flame-retardant polyethylene terephthalate resin composition according to claim 3, wherein (E) the inorganic compound is at least one silicate compound selected from the group consisting of talc, mica, and kaolin. object. 8. The method according to claim 8, wherein (F) a crystallization accelerator is used in an amount of 0.5 to 5
The flame-retardant polyethylene terephthalate-based resin composition according to any one of claims 1 to 7, which is mixed with 0 part by weight. 9. The method according to claim 9, wherein (F) the crystallization accelerator is a polyester-
9. The flame-retardant polyethylene terephthalate resin composition according to claim 8, which is a polyether copolymer.