JP3215282B2 - Flame retardant polyethylene terephthalate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant polyethylene terephthalate-based resin composition, and more particularly, it has excellent mechanical strength such as tensile strength, heat stability, and appearance when formed into a molded product. The present invention relates to a flame-retardant polyethylene terephthalate-based resin composition having excellent wet heat resistance.

[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 adding a reinforcing filler such as glass fiber, and thus the reinforced composition thus obtained is suitable as a material for a so-called functional component.

[0003] In recent years, in particular in the field of electric or electronic parts, the demand for fire safety has increased, and resins have been made flame-retardant. For example, organic halogen compounds or high-molecular halogen compounds have been added. 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.
The method of adding a halogenated bisphenol A type epoxy resin to 256, the method of adding a high molecular weight halogenated bisphenol A type phenoxy resin to JP-A-59-149954, and the method of adding a halogenated polystyrene resin to JP-A-50-92346 And the like have been proposed.

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 bisphenol A type epoxy resin is used as a flame retardant, since the flame retardant has a low molecular weight, bleeding occurs on the surface of the molded product, and the surface characteristics and appearance are reduced. Is worse. On the other hand, when a high molecular weight halogenated bisphenol A-type phenoxy resin or halogenated polystyrene resin is used, the problem of bleeding is improved. Dispersibility is also poor, and there are problems such as deterioration of mechanical properties and deterioration of appearance of a molded article. further,
These halogenated bisphenol A type epoxy and / or
Alternatively, when a polyester-based resin composition using a phenoxy resin is molded by injection molding, there is a problem that the flame retardant is deteriorated due to heat generated by shearing, and burns occur to cause yellowing.

The inventors of the present invention have conducted intensive studies on such a problem and found that a specific halogenated bisphenol A-type epoxy resin contains an antimony compound and a halogen atom-free compound having two or more epoxy groups in a molecule. It has been found that a composition excellent in mechanical strength and thermal stability and having good appearance of a molded article can be obtained by adding an epoxy compound in combination. However, it has been found that the flame-retardant polyethylene terephthalate-based resin composition obtained by such a method is insufficient for the requirement of wet heat resistance. Further, in the method proposed in JP-A-59-129253, since a high-molecular-weight halogenated bisphenol A-type copolymerized phenoxy resin is used, problems occur in mechanical strength and the like, and the moisture resistance of the polyethylene terephthalate-based resin is increased. The demand for improved thermal properties is insufficient.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems, and as a result, a specific polyethylene terephthalate-based thermoplastic resin produced by using a germanium-based compound as a catalyst. Using a polyester resin, a halogenated bisphenol A-type epoxy resin, an antimony compound and a polyfunctional epoxy compound can be added in combination to improve the above problems,
It has been found that the wet heat resistance is significantly improved. Furthermore, by using an inorganic compound selected from the group consisting of a silicate compound and a silicic acid, a flame-retardant polyethylene terephthalate-based resin having good mold releasability at the time of molding by injection molding or the like and capable of high cycle molding. The inventors have found that a composition can be obtained, and have reached 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 (I)

[0011]

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Wherein X represents a hydrogen atom, a chlorine atom or a bromine atom, and n represents an average degree of polymerization of less than 12. The halogenation ratio is 10% by weight or more, and 1 to 50 parts by weight of a halogenated bisphenol A type epoxy resin having a point of 85 to 195 ° C, (C) 0.1 to 20 parts by weight of an antimony compound, and (D) a halogen having two or more epoxy groups in a molecule. 0.05 to 15 parts by weight of an atom-free epoxy compound and (E) a reinforcing filler 0 to 1
50 parts by weight of a flame-retardant polyethylene terephthalate-based resin composition,

A second 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 and produced by using a germanium-based compound as a catalyst, and (B) The following general formula (I)

[0014]

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(Wherein X represents a hydrogen atom, a chlorine atom or a bromine atom, and n represents an average degree of polymerization of less than 12), a halogenation ratio of 10% by weight or more, and softening. 1 to 50 parts by weight of a halogenated bisphenol A type epoxy resin having a point of 85 to 195 ° C, (C) 0.1 to 20 parts by weight of an antimony compound, and (D) a halogen having two or more epoxy groups in a molecule. 0.05 to 15 parts by weight of atom-free epoxy compound, (E) reinforcing filler 0 to 150
Parts by weight, and (F) at least one inorganic compound selected from the group consisting of a silicate compound and silicic acid in an amount of 0.1 to 60 parts by weight. Is what you do.

The (A) polyethylene terephthalate-based thermoplastic polyester used in the present invention is a terephthalic acid or an ester-forming derivative 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 dioxide is particularly preferred.

The amount of the germanium compound 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). is there. 0.
If the amount is less than 005% by weight, the polymerization of the polyethylene terephthalate-based resin hardly proceeds, and if the amount exceeds 0.1% by weight, an undesired side reaction may occur because many germanium-based catalysts remain in the obtained resin. . Also,
The timing of addition may be any time before the start of the polymerization reaction.

The polyethylene terephthalate-based thermoplastic polyester has flame retardancy, moldability, mold release properties,
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,
Examples thereof include an alicyclic compound having 6 to 20 carbon atoms, an aromatic compound having 6 to 40 carbon atoms and having two or more hydroxyl groups in a molecule, and an ester-forming derivative thereof.

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.

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, the detailed reason is unknown at this time, but when kept under high temperature and high humidity. The heat and moisture resistance is not sufficient due to a large decrease in mechanical strength and the like. This is presumed to be due to the fact that the polyethylene terephthalate-based thermoplastic polyester obtained by using a compound other than the germanium-based compound easily causes a hydrolysis reaction.

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 (B) halogenated bisphenol A type epoxy resin is used for the purpose of imparting flame retardancy. The halogenated bisphenol A type epoxy resin has the general formula (I)

[0026]

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(Wherein, X represents a hydrogen atom, a chlorine atom or a bromine atom, and n represents an average degree of polymerization of less than 12). The halogenated bisphenol A type epoxy resin has a halogenation ratio of 10% by weight or more and JIS K
The softening point measured by -7234 "Testing method for softening point of epoxy resin (ring and ball method)" is 85 to 195C. The halogenation ratio is preferably at least 20% by weight, more preferably at least 25% by weight. Halogenation rate is 10
If it is less than 10% by weight, the flame retardancy is insufficient. The softening point is preferably at least 95 ° C, more preferably at least 105 ° C. When the softening point is lower than 85 ° C., the mechanical properties of the flame-retardant resin composition and the surface properties of the molded article are deteriorated, while 195
When the temperature exceeds ℃, the molding fluidity, the dispersibility of the flame retardant, and the appearance of the molded product are deteriorated. In general formula (I), X is preferably a bromine atom from the viewpoint of flame retardancy. N is 1
When it is 2 or more, the fluidity and mechanical strength of the flame-retardant resin composition decrease.

The amount of the halogenated bisphenol A type epoxy resin used depends on the degree of halogenation and the degree of polymerization, but may be sufficient to make the above-mentioned (A) polyethylene terephthalate thermoplastic polyester flame-retardant. 1 to 50 parts by weight, preferably 5 to 45 parts by weight, more preferably 10 to 100 parts by weight of the thermoplastic polyester.
３５35 parts by weight. If the amount is less than 1 part by weight, the flame retardancy is insufficient. If the amount exceeds 50 parts by weight, the molding processability of the flame-retardant resin composition is reduced and the appearance of the obtained molded article is deteriorated.

Addition of the antimony compound (C) to the composition of the present invention significantly enhances the flame retardant effect, and addition of the antimony compound together with the epoxy compound improves the thermal stability and appearance of the molded article. Examples of the antimony compound include antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, antimony phosphate, and the like. Antimony trioxide and / or sodium antimonate are particularly preferable in view of the above effects.

The antimony compound is used singly or as a mixture of two or more kinds. The amount of the antimony compound is 0.1 to 20 parts by weight, preferably 1 to 100 parts by weight of the (A) polyethylene terephthalate-based thermoplastic polyester. １５15 parts by weight. 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 polyethylene terephthalate-based polyester resin composition decreases.

The present invention further comprises (D) a halogen-free epoxy compound having two or more epoxy groups in the molecule. Examples of the epoxy compound include bisphenol type epoxy resins, novolak type epoxy resins, polyvalent aliphatic, alicyclic, aromatic glycidyl ether compounds, polyvalent aliphatic, alicyclic, aromatic glycidyl ester compounds, and unsaturated compounds. Examples thereof include an epoxy compound obtained by epoxidizing an aliphatic or alicyclic compound having a plurality of groups with acetic acid and peracetic acid, and a polyvalent aliphatic, alicyclic, or aromatic glycidylamine compound.

As specific examples of these, for example, the following formula (II)

[0033]

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(Wherein, m represents an average degree of polymerization of 0 to 20)
A bisphenol A type epoxy resin represented by the following formula (III):

[0035]

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(Wherein 1 represents an average degree of polymerization, 1 to 40,
R is hydrogen or a methyl group) novolak type epoxy resin; ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl Alkylene glycol diglycidyl ethers such as ethers; polyethylene glycol diglycidyl ether, polybutanediol diglycidyl ether, polypropylene glycol diglycidyl ether,
Polyalkylene glycol diglycidyl ethers such as polyneopentyl glycol diglycidyl ether and polytetramethylene glycol diglycidyl ether; resorcin diglycidyl ether, erythrit polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, hydroquinone di Glycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether,
Sorbitol polyglycidyl ether, bisphenol S diglycidyl ether, diglycidyl terephthalate, diglycidyl isophthalate, diglycidyl adipic ester, diglycidylaniline, tetraglycidyl 4,4′-diaminodiphenylmethane, triglycidyl tris (2-hydroxy Ethyl) isocyanurate, polyepoxidized higher oils and fats, and the like. Among these epoxy compounds, particularly preferred are bisphenol A type epoxy resins and / or novolak type epoxy resins, for example, Epicoat 828,
It is commercially available as Epicoat 152 (both are registered trademarks of Yuka Shell Epoxy Co., Ltd.). The epoxy compounds are used alone or in combination of two or more. In the above formula (II), when m exceeds 20, the effects such as the thermal stability of the flame-retardant resin composition and the improvement of the surface of the molded article are small.
In the above formula (III), if 1 is less than 1, the effect of improving the thermal stability of the flame-retardant resin composition and the surface properties of the molded article is small, and if it exceeds 40, the molding fluidity is lowered, which is not preferable. .

The amount of the polyfunctional epoxy compound is as follows:
Depending on the epoxy equivalent of the epoxy compound,
(A) 0.05 to 15 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.2 to 7 parts by weight, based on 100 parts by weight of polyethylene terephthalate-based thermoplastic polyester.
Parts by weight. If the amount used is less than 0.05 parts by weight,
If the surface property of the molded body is reduced and exceeds 15 parts by weight, molding fluidity and mechanical strength are reduced.

The flame-retardant polyethylene terephthalate resin composition of the present invention includes, in addition to the above-mentioned components, a composition further comprising (E) a reinforcing filler, that is, a reinforced flame-retardant polyethylene terephthalate composition. A known reinforcing filler can be used as it is. For example, glass fiber, carbon fiber, potassium titanate fiber, glass beads, glass flake, calcium carbonate, calcium sulfate, barium sulfate and the like can be mentioned. 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, the moldability, the surface properties of the molded product, etc. deteriorate, which is not preferable.

The reinforcing fillers can be used alone or as a mixture of two or more. The amount of the reinforcing filler used is up to 150 parts by weight, preferably 12 parts by weight, per 100 parts by weight of the (A) polyethylene terephthalate-based thermoplastic polyester.
0 parts by weight. More preferably, it is 2 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 one or more inorganic compounds selected from the group consisting of (F) a silicate compound and a silicic acid, the releasability can be improved, and the demand for a high cycle molding can be improved. Thus, a sufficiently satisfactory composition can be obtained. Among the inorganic compounds, the silicate compound is a compound having a chemical composition having a shape such as powder, granule, needle, plate, etc. containing SiO ₂ units, for example, magnesium silicate, aluminum silicate, Calcium silicate,
Talc, mica, wollastonite, kaolin, diatomaceous earth,
Bentonite, clay and the like can be mentioned. Among them, talc, mica, kaolin and wollastonite are preferred.

These inorganic compounds can be used alone or in admixture of two or more. The amount of the inorganic compound used is 0.1 to 60 parts by weight, preferably 100 parts by weight of (A) the polyethylene terephthalate-based thermoplastic polyester. It is 1 to 45 parts by weight, more preferably 3 to 30 parts by weight. When the amount is less than 0.1 part by weight, the effect on the fluidity and the releasability becomes small, and when it exceeds 60 parts by weight, the mechanical strength of the flame-retardant resin composition decreases. The inorganic compound may be added before, during or after the reaction when producing the above-mentioned polyethylene terephthalate-based thermoplastic polyester, or when producing the composition of the present invention, a flame retardant, an antimony compound, or an epoxy compound. You may add together.

By adding a crystallization accelerator to the flame-retardant polyethylene terephthalate resin composition of the present invention, the releasability can be further improved and the gloss of the surface of the molded article can be improved. 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 polymer of bisphenols or polyalkylene glycols such as terminal epoxy-modified compounds, terminal ester-modified compounds, aliphatic polyesters such as poly-ε-caprolactone, polyethylene terephthalate, polypropylene terephthalate, Polytetramethylene terephthalate, polyhexamethylene terephthalate, polyethylene naphthalate, polybutylene na Tallates, a polyester units such as poly cyclohexanedimethanol terephthalate, the following general formula (IV) and / or the general formula (V)

[0045]

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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)

[0047]

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(Wherein, R ² represents an alkyl group having 2 to 5 carbon atoms, X represents a divalent linking group or a direct bond, p and q are each an integer of 1 or more, and p + q is an integer of 3 or more. Wherein p and q 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
-Caprolactone copolymer, polytetramethylene glycol-poly-ε-caprolactone copolymer, etc., a polyester having a lower glass transition temperature than polyethylene terephthalate-based thermoplastic polyester-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. It is not preferable to use a metal carboxylate of an organic or high molecular compound as the crystallization accelerator because the wet heat resistance is 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 in terms of mechanical strength, moldability, mold release properties, and the like.

The polyether unit is a unit represented by the general formula (IV) and / or the general formula (V). Specific examples of R ^{1 in} the general formula (IV) include, for example, ethylene , Propylene, isopropylene, tetramethylene group and the like. Specific examples of R ² in the general formula (V) include, for example, ethylene, propylene, isopropylene, tetramethylene and the like, and further specific examples of X Is
For _{example, -C (CH 3) 2 -} , - CH 2 -, - S -, -
Examples thereof include a divalent bonding group such as SO ₂ — and —CO— or a direct bond. Further, in the polyether unit,
K in the general formula (IV) is an integer of 5 or more; p and q in the general formula (V) are positive integers of 1 or more, and p + q is an integer of 3 or more; These are the units. The molecular weight of the polyether unit is more preferably from 600 to 6000, even more preferably from 800 to 30.
00. When 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 product is small, and
If it exceeds 000, it is difficult to obtain a homogeneous copolymer, and when it is added to the flame-retardant resin composition, the mechanical strength is lowered, which is not preferable. 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 or bisphenol S And a residue such as an alkylene oxide addition polymer of bisphenols such as ethylene oxide, propylene oxide, and tetrahydrofuran.
These may be used alone or as a mixture of two or more kinds. In particular, when one or more kinds of the polyether units represented by the general formula (V) are used, the heat stability and the obtained flame-retardant resin composition are reduced. It is preferable from the viewpoints of mold releasability when molded with a low-temperature mold and surface properties of a molded article. Among these, an ethylene oxide addition polymer of bisphenol A, a propylene oxide addition polymer of bisphenol A, a tetrahydrofuran addition polymer of bisphenol A, an ethylene oxide / propylene oxide addition polymer of bisphenol A, an ethylene oxide addition polymer of bisphenol S,
A propylene oxide addition polymer of bisphenol S, a tetrahydrofuran addition polymer of bisphenol S, and an ethylene oxide / propylene oxide addition polymer of bisphenol S 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 it is less than 3% by weight, the releasability and surface gloss when molded with a low-temperature mold are insufficient, and if it exceeds 60% by weight, the mechanical strength and wet heat resistance of the molded article tend to be reduced. Absent.

The intrinsic viscosity of the copolymer is at least 0.35, preferably from 0.40 to 2.00, more preferably from 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 decreases, and the mechanical strength of the obtained flame-retardant resin composition decreases, which is not preferable.

The amount of the crystallization accelerator varies depending on the type and molecular weight of the crystallization accelerator, but is generally 0.05 to 50 parts by weight based on 100 parts by weight of the polyethylene terephthalate-based thermoplastic polyester. , A low molecular weight crystallization accelerator such as polyalkylene glycols, aliphatic polyesters, and plasticizers,
0 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,
Such as tris (2,4-di-t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite Phosphorus antioxidants, 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 pigment, a dye, an antistatic agent,
Additives such as 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 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, moldability and the like 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, or the like may be added alone or in combination of two or more.

The method for producing the flame-retardant polyethylene terephthalate resin composition of the present invention is not particularly limited. For example, after the above-mentioned components are uniformly mixed in advance, the mixture is supplied to a single-screw or multi-screw extruder, and 200 to 30
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.

[0059]

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, a cylinder temperature of 270 was measured 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: Flame retardancy was evaluated using a 1/16 inch bar 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. Moist heat resistance: A dumbbell was held at 121 ° C. under saturated pressurized steam for 40 hours to perform a moist heat resistance treatment. A dumbbell before and after the wet heat resistance 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. Tensile strength after moist heat resistance test Tensile strength retention = ────────────── × 100 (%) Tensile strength before moist heat resistance test Appearance of molded article: Visual observation of dumbbell surface Then, evaluation was made according to the following criteria. ：: good △: slightly glossy and sticky, or partially poor gloss and sticky ×: poor gloss or sticky

Releasability: After drying the obtained resin composition at 140 ° C. for 4 hours or more, using a 50-t injection molding machine, the cylinder temperature was 300 ° C., the mold temperature was 140 ° C., and the thickness was 1/100.
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: 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) (intrinsic viscosity: 0.65) manufactured using germanium dioxide as a catalyst
The softening point (JIS K-7234 “Testing method for softening point of epoxy resin (ring and ball method)”) is 130 ° C. for 0 parts by weight.
Of tetrabromobisphenol A type epoxy resin (1) (average degree of polymerization: about 3, bromination rate: about 50%)
Part, sodium antimonate (Sun Epoque NA-10)
70L: 4 parts of Nissan Chemical Co., Ltd.), 1.00 part of polyfunctional epoxy compound (A) (Epicoat 828: Yuka Shell Epoxy Co., Ltd .: bisphenol A type epoxy), phenolic antioxidant 0.35 parts of an agent (ADK STAB AO-60: trade name of Asahi Denka Co., Ltd.) was dry-blended in advance, and the cylinder temperature was raised to 260.
The twin-screw extruder (TEX44: trade name, manufactured by Nippon Steel Works Co., Ltd.) with vent set at ℃ is supplied to the hopper,
A resin composition was obtained by adding 52 parts of glass fiber (T-195H / PS: trade name of Nippon Electric Glass Co., Ltd.) in the middle and extruding the mixture. Table 1 shows the evaluation results of the resin composition.

Example 2 Tetrabromobisphenol A having a softening point of 130 ° C.
20 parts of the epoxy resin (1) and 28 parts of a tetrabromobisphenol A-type epoxy resin (2) having a softening point of 160 ° C. (average degree of polymerization: about 6, bromination rate: about 50%) were mixed with sodium antimonate. 4 parts of antimony trioxide (antimony oxide C: trade name of Sumitomo Metal Mining Co., Ltd.)
3 parts, 1.00 part of polyfunctional epoxy compound (A), and polyfunctional epoxy compound (B) (Epicoat 157S70:
Oiled shell epoxy: novolak type epoxy) 0.75
Change to parts by weight, and further, a thioether-based antioxidant (ADK STAB AO-412S: trade name, manufactured by Asahi Denka Co., Ltd.)
Was obtained in the same manner as in Example 1 except that 0.15 part of was added. Table 1 shows the evaluation results of the resin composition.

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 0.85.
FE is a polytetrafluoroethylene resin (Polyflon F
104: Daikin Industries, Ltd.). Table 1 shows the evaluation results of the resin composition.

Examples 6 to 12 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 that 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: trade name, manufactured by ENGELHARD) and calcium silicate (reagent). Table 2 shows the evaluation results of the resin composition. For reference, Example 3
Were evaluated in the same manner, and the results are shown in Table 2.
Shown in

Comparative Examples 1 to 13 Resin compositions were obtained in the same manner as in Example 1 using the polyethylene terephthalate and the compounding agents shown in Tables 3 and 4. However, polyethylene terephthalate (3) has an intrinsic viscosity of 0.1 produced by using antimony trioxide as a catalyst.
65, polyethylene terephthalate (4) having an intrinsic viscosity of 0.65 produced using a titanium tetrabutoxide monomer as a catalyst, and tetrabromobisphenol A type epoxy resin (3) having a softening point of 69 ° C. ( (Average degree of polymerization: about 0, bromination rate: about 48%), brominated bisphenol A type phenoxy resin (4) has an average degree of polymerization of 12 or more, bromination rate: about 50%, and softening point exceeds 200 ° C. Things. Calcium carbonate (reagent) was also used as a comparative inorganic compound. Tables 3 and 4 show the evaluation results of the resin composition.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

[Table 3]

[0071]

[Table 4]

As is clear from comparison between Tables 1 and 2 as Examples and Tables 3 and 4 as Comparative Examples, all of the compositions of the present invention have flame retardancy, mechanical strength, and appearance of molded articles. It is understood that the heat resistance is excellent, the heat and humidity resistance is excellent, and the use of a specific inorganic compound is also excellent in the releasability.

REFERENCE EXAMPLE 1 3500 g of polyethylene terephthalate oligomer (average number of ethylene terephthalate units: 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 of No. 00 and 25 g of ADK STAB AO-60
Was poured into an autoclave (manufactured by Japan Pressure Glass Co., Ltd.) having a capacity of 10 liters, the temperature was raised to 290 ° C. while stirring under a nitrogen stream, and 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 copolymer (1). The intrinsic viscosity of the obtained copolymer was 0.7.

Reference Example 2 Polytetramethylene terephthalate (intrinsic viscosity: 0.9:
3500 g, average molecular weight of about 1000
Of bisphenol A ethylene oxide addition polymer
500 g and 25 g of ADK STAB AO-60
0 liter autoclave (made of Japan pressure glass)
The temperature was raised to 260 ° C. while stirring under a nitrogen stream, and 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, thereby obtaining a copolymer (2). The intrinsic viscosity of the obtained copolymer was 0.8.

Example 13: 100 parts by weight of polyethylene terephthalate (1) produced using germanium dioxide as a catalyst,
20 parts of tetrabromobisphenol A type epoxy resin (2), 4 parts of antimony trioxide (antimony oxide C: trade name of Sumitomo Metal Mining Co., Ltd.), 1.5 parts of polyfunctional epoxy compound (A), A resin composition composed of 9 parts of the combined product (1), 0.35 part of the phenolic antioxidant, and 52 parts of the glass fiber was obtained in the same manner as in Example 1. Table 5 shows the evaluation results of the surface gloss.

Examples 14 to 17 Resin compositions were obtained in the same manner as in Example 1 except that the amounts of the respective ingredients were changed to those shown in Table 5. Table 5 shows the evaluation results of the surface gloss. For reference, the resin compositions of Examples 3 and 8 were similarly evaluated, and the results are shown in Table 5.

[0077]

[Table 5]

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

Examples 18 to 20 and Comparative Examples 14 to 16 The resin compositions obtained in Examples 3, 8 and 15 (Example 1
8 to 20), a resin composition obtained by removing the antimony compound and the polyfunctional epoxy compound (A) from these resin compositions (Comparative Examples 14 to 16) was subjected to 290 ° C. and mold temperature 120 using a 150 t injection molding machine. ℃, maximum injection speed 20-8
A flat plate having a thickness of 3 mm (width 150 mm, length 120 mm) was formed at an injection speed of 0%, and the presence or absence of discoloration (yellowing) was examined. As a result, in the former resin composition, almost no discoloration was observed up to 80% of the injection speed, and only a slight discoloration (yellowing) was observed near the gate at 80%, whereas the latter resin composition In the composition, discoloration was already observed at 40%, and at 60% or more, discoloration was observed almost entirely around the gate.

[0080]

According to the present invention, flame retardancy, mechanical strength,
Provided is a flame-retardant polyethylene terephthalate-based resin composition having excellent heat stability and appearance of a molded article, excellent heat and moisture resistance, and also excellent in releasability by using a specific inorganic compound in combination. be able to.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI C08L 63:00) C08L 63:00) (56) References JP-A-5-17669 (JP, A) JP-A-2-202541 (JP, A) JP-A-1-201357 (JP, A) JP-A-59-6251 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 67/00-67 / 02

Claims (7)

(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 Wherein X represents a hydrogen atom, a chlorine atom or a bromine atom, and n represents an average degree of polymerization of less than 12.
Halogenation rate of 10% by weight or more and softening point of 85 to 85%
1 to 50 parts by weight of a halogenated bisphenol A type epoxy resin at 195 ° C .;
20 parts by weight, (D) a halogen atom-free epoxy compound having two or more epoxy groups in the molecule, from 0.05 to
A flame-retardant polyethylene terephthalate-based resin composition comprising 15 parts by weight and (E) 0 to 150 parts by weight of a reinforcing filler. 2. (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 (I): Embedded image Wherein X represents a hydrogen atom, a chlorine atom or a bromine atom, and n represents an average degree of polymerization of less than 12.
Halogenation rate of 10% by weight or more and softening point of 85 to 85%
1 to 50 parts by weight of a halogenated bisphenol A type epoxy resin at 195 ° C .;
20 parts by weight, (D) a halogen atom-free epoxy compound having two or more epoxy groups in the molecule, from 0.05 to
15 parts by weight, (E) 0 to 150 parts by weight of a reinforcing filler, and (F) 0.1 to 60 parts by weight of at least one inorganic compound selected from the group consisting of silicate compounds and silicic acid. Flammable polyethylene terephthalate resin composition. 3. The flame-retardant polyethylene terephthalate resin composition according to claim 1, wherein X in the general formula (I) is a bromine atom. 4. The flame-retardant polyethylene terephthalate resin composition according to claim 1, wherein the antimony compound is antimony trioxide and / or sodium antimonate. 5. The halogen-free epoxy compound having two or more epoxy groups in a molecule is at least one epoxy compound selected from the group consisting of a bisphenol A type epoxy compound and a novolak type epoxy compound. The flame-retardant polyethylene terephthalate-based resin composition according to claim 1. 6. The method according to claim 2, wherein the inorganic compound is at least one silicate compound selected from the group consisting of talc, mica, kaolin and wollastonite.
Item 10. The flame-retardant polyethylene terephthalate resin composition according to item 8. 7. The flame-retardant polyethylene terephthalate resin composition according to claim 1, further comprising 0.5 to 50 parts by weight of a polyester-polyether copolymer.