JP3212848B2 - Flame retardant polyethylene terephthalate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant polyethylene terephthalate resin composition. More specifically, it relates to a flame-retardant polyethylene terephthalate-based resin composition that can be suitably used as a molding material for various molded articles.

[0002]

2. Description of the Related Art Polyethylene terephthalate has been widely used as a material for molding fibers and films because of its excellent mechanical properties and electrical properties. In particular, the mechanical strength and thermal properties are greatly improved by blending fiber reinforced materials such as glass fibers, so that reinforced compositions blended with fiber reinforced materials are suitable as so-called functional component materials. is there.

[0003] In recent years, in particular in the field of electric and electronic parts, the demand for fire safety has been increased, and flame retardant materials obtained by adding an organic halogen compound, a polymer halogen compound, or the like to a resin have been used for electric or electronic parts. ing. Some of these electrical and electronic components are in direct or indirect contact with water or water vapor.
In addition to flame retardancy, high moisture and heat resistance is required, in which a sharp decrease in mechanical strength and the like is suppressed even when exposed to high temperature and high humidity.

As a method for making a thermoplastic polyester flame-retardant, for example, a method of adding a halogenated epoxy compound (JP-A-50-35257 and JP-A-62-1)
No. 5256), a method of adding a high molecular weight halogenated phenoxy resin (JP-A-59-149954), and a method of using a brominated phenoxy resin and a brominated epoxy compound in combination (JP-A-62-169847). ) Has been proposed.

Further, a method of adding a carbodiimide compound has been known for improving the moist heat resistance of polyethylene terephthalate. Methods for improving the moist heat resistance together with imparting flame retardancy include, for example, a high molecular weight halogenated copolymer. A method of adding an epoxy compound and / or a carbodiimide compound together with a polymerized phenoxy resin has been proposed (JP-A-59-129253).

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

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 flowability of the resin deteriorates due to the reaction during molding at a high temperature. There's a problem.

In the above-mentioned method using a high-molecular-weight halogenated phenoxy resin, since a high-molecular-weight halogenated copolymerized phenoxy resin is used, problems arise in mechanical strength and the like, and the moisture resistance of the polyethylene terephthalate-based resin is increased. The improvement in thermal properties is still insufficient.

Further, in the method of using a brominated phenoxy resin and a brominated epoxy compound in combination, the same problem as when a halogenated epoxy compound is used as a flame retardant is intended to improve the flame resistance and the wet heat resistance. Occurs.

[0010]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and while maintaining flame retardancy,
The primary object of the present invention is to provide a polyethylene terephthalate-based resin composition capable of improving wet heat resistance and fluidity at low cost, and has a good releasability of a thick portion and a high cycle of molding when molding by injection molding or the like. It is a second object of the present invention to provide a flame-retardant polyethylene terephthalate-based resin composition which can be converted into a resin.

[0011]

The present invention relates to (A) a polyethylene terephthalate-based thermoplastic polyester containing ethylene terephthalate units as a main component prepared by using a germanium-based compound as a catalyst; and (B) a general formula (I) ):

[0012]

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(Wherein X ¹ , X ² , X ³ and X ⁴ are each independently a hydrogen atom or a halogen atom, Y ¹ is an alkylene group having 1 to 10 carbon atoms, an alkylidene group having 2 to 10 carbon atoms, A cycloalkane group having 3 to 10 carbon atoms, a carbonyl group, a —O— group, a —S— group, a —SO ₂ — group or a direct bond, and m represents an average degree of polymerization of 12 to 150). A halogenated phenoxy resin having a halogen content of 30% by weight or more and an epoxy equivalent of 4000 or more, (C) a general formula (II):

[0014]

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Wherein X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ ,
X ¹⁰ , X ¹¹ and X ¹² are each independently a hydrogen atom or a halogen atom, Y ² and Y ³ are each independently an alkylene group having 1 to 10 carbon atoms, an alkylidene group having 2 to 10 carbon atoms, and a carbon atom having 3 carbon atoms. A cycloalkane group, a carbonyl group, a —O— group, a —S— group, a —SO ₂ — group or a direct bond, and n represents an average degree of polymerization of 0 to 8). It contains a halogenated epoxy compound having a content of 10% by weight or more and an epoxy equivalent of 800 to 2500, an antimony compound (D) and a reinforcing filler (E), and 100 parts by weight of the polyethylene terephthalate-based thermoplastic polyester. On the other hand, the total blending amount of the halogenated phenoxy resin and the halogenated epoxy compound is 5 to 50 parts by weight, The amount is 3 parts by weight or more, the compounding amount of the antimony compound is 0.1 to 20 parts by weight, the compounding amount of the reinforcing filler is 150 parts by weight or less, and the halogenated phenoxy resin and the halogen are mixed. The present invention relates to a flame-retardant polyethylene terephthalate resin composition, wherein the weight ratio (halogenated phenoxy resin / halogenated epoxy compound) to the halogenated epoxy compound is from 1/99 to 90/10.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, the flame-retardant polyethylene terephthalate-based resin composition of the present invention comprises a polyethylene having ethylene terephthalate units as a main component prepared by using (A) a germanium-based compound as a catalyst. Terephthalate thermoplastic polyester, (B)
General formula (I):

[0017]

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(Wherein X ¹ , X ² , X ³ and X ⁴ are each independently a hydrogen atom or a halogen atom, Y ¹ is an alkylene group having 1 to 10 carbon atoms, an alkylidene group having 2 to 10 carbon atoms, A cycloalkane group having 3 to 10 carbon atoms, a carbonyl group, a —O— group, a —S— group, a —SO ₂ — group or a direct bond, and m represents an average degree of polymerization of 12 to 150). A halogenated phenoxy resin having a halogen content of 30% by weight or more and an epoxy equivalent of 4000 or more, (C) a general formula (II):

[0019]

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Wherein X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ ,
X ¹⁰ , X ¹¹ and X ¹² are each independently a hydrogen atom or a halogen atom, Y ² and Y ³ are each independently an alkylene group having 1 to 10 carbon atoms, an alkylidene group having 2 to 10 carbon atoms, and a carbon atom having 3 carbon atoms. A cycloalkane group, a carbonyl group, a —O— group, a —S— group, a —SO ₂ — group or a direct bond, and n represents an average degree of polymerization of 0 to 8). It contains a halogenated epoxy compound having a content of 10% by weight or more and an epoxy equivalent of 800 to 2500, an antimony compound (D) and a reinforcing filler (E), and 100 parts by weight of the polyethylene terephthalate-based thermoplastic polyester. On the other hand, the total blending amount of the halogenated phenoxy resin and the halogenated epoxy compound is 5 to 50 parts by weight, The amount is 3 parts by weight or more, the compounding amount of the antimony compound is 0.1 to 20 parts by weight, the compounding amount of the reinforcing filler is 150 parts by weight or less, and the halogenated phenoxy resin and the halogen are mixed. Wherein the weight ratio to the halogenated epoxy compound (halogenated phenoxy resin / halogenated epoxy compound) is 1/99 to 90/10.

The polyethylene terephthalate-based thermoplastic polyester (A) used in the present invention comprises a germanium-based compound as a catalyst, terephthalic acid or its derivative having ester-form properties as an acid component, and ethylene glycol or its ester as a glycol component. It is a polyester resin containing an ethylene terephthalate unit as a main component obtained by polycondensing a polymerization component containing a derivative having a forming ability.

In the present invention, the germanium-based compound is used as a catalyst for advancing the polycondensation of the polymerization component. And a resin composition having both fluidity and fluidity. Examples of the germanium-based compound include germanium oxides such as germanium dioxide, germanium tetraethoxide, germanium alkoxides such as germanium tetraisopropoxide, germanium hydroxide and alkali metal salts thereof, germanium glycolate,
Examples include germanium chloride and germanium acetate. These germanium compounds can be used alone or
A mixture of more than one species is used. Among these germanium compounds, germanium dioxide is particularly preferred.

From the viewpoint that the polycondensation proceeds at a sufficient polymerization rate, the amount of the germanium-based compound is 0.005% by weight or more, preferably 0.01% by weight, based on the obtained polyethylene terephthalate-based thermoplastic polyester.
It is preferably at least 0.1% by weight, and more preferably at most 0.1% by weight, particularly preferably at most 0.05% by weight, in order to prevent any adverse effect at the time of molding the obtained resin composition. The germanium compound may be added at any time before the start of the polymerization reaction.

The polymerization component used for the polyethylene terephthalate-based thermoplastic polyester includes wet heat resistance,
A copolymerizable component can be used within a range that does not impair moldability, mold release properties, mechanical properties, and the like. Examples of the copolymerizable component include a divalent or higher valent aromatic carboxylic acid having 8 to 22 carbon atoms, a divalent or higher valent aliphatic carboxylic acid having 4 to 12 carbon atoms, and a divalent or higher valent having 8 to 15 carbon atoms. Carboxylic acids such as alicyclic carboxylic acids and their ester-forming derivatives, aliphatic compounds having 3 to 15 carbon atoms, alicyclic compounds having 6 to 20 carbon atoms, and aromatic compounds having 6 to 40 carbon atoms; Examples include compounds having two or more hydroxyl groups in the molecule, and ester-forming derivatives thereof.

Specific examples of the copolymerizable component include:
For example, isophthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methaneanthracenedicarboxylic 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,
Carboxylic acids such as 1,4-cyclohexanedicarboxylic acid and decahydronaphthalenedicarboxylic acid or derivatives thereof capable of forming esters; propylene glycol, butanediol, hexanediol, decanediol, neopentyl glycol, cyclohexanedimethanol, cyclohexanediol, A hydroxyl-containing compound such as 2,2'-bis (4-hydroxyphenyl) propane, 2,2'-bis (4-hydroxycyclohexyl) propane, hydroquinone, glycerin, pentaerythritol, or a derivative thereof having an ester form; Oxyacids such as benzoic acid and p-hydroxyethoxybenzoic acid and ester-forming derivatives thereof; cyclic esters such as ε-caprolactone; polyethylene glycol;
Polyalkylene glycol units such as polypropylene glycol, poly (ethylene oxide / propylene oxide) block copolymer, poly (ethylene oxide / propylene oxide) random copolymer, bisphenol A copolymerized polyethylene glycol and polytetramethylene glycol Among them, those partially copolymerized are exemplified. The amount of the copolymerizable component used is
About 20% by weight or less, preferably
It is desirable that the content be 5% by weight or less, more preferably 10% by weight or less.

The intrinsic viscosity of the polyethylene terephthalate-based thermoplastic polyester (phenol: 1, 1, 2, 2)
(Measured at 25 ° C. using a mixed solvent of 2-tetrachloroethane = 1: 1 (weight ratio)) is 0.35 or more, preferably 0.4 or more, and more preferably, in order to sufficiently improve the mechanical strength. Is desirably 0.5 or more, and in order to sufficiently improve moldability, it is desirably 1.2 or less, preferably 0.95 or less.

The polyethylene terephthalate-based thermoplastic polyester can be used alone or as a mixture of two or more kinds having different polymerization components and / or 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. Examples of such polymerization methods include, for example, a method in which terephthalic acid and ethylene glycol are directly esterified without a catalyst or in the presence of a catalyst, a method in which dimethyl terephthalate and ethylene glycol are transesterified in the presence of a catalyst, and the like. A polymer having a low degree of polymerization is synthesized, and then the polymer having a low degree of polymerization and a germanium compound are subjected to a temperature of, for example, about 250 to 300 ° C., for example, 1 Torr.
A method of producing a polyethylene terephthalate-based thermoplastic polyester by performing polycondensation by melt polycondensation or solid phase polycondensation under the following vacuum can be given.

When a polymer having a low degree of polymerization is subjected to polycondensation, when a compound other than a germanium compound, for example, a polyethylene terephthalate thermoplastic polyester polymerized using an antimony catalyst or the like is used, a high temperature This is not preferable because the mechanical strength and the like when held under humidity are greatly reduced, the wet heat resistance is not sufficient, and the fluidity is significantly reduced.

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

In the present invention, for the purpose of imparting flame retardancy,
(B) A halogenated phenoxy resin is used.

The halogenated phenoxy resin is a compound having a skeleton represented by the general formula (I).

The halogen content of the halogenated phenoxy resin is 30% by weight or more, preferably 40% by weight or more, and more preferably 45% by weight or more, in order to sufficiently improve the flame retardancy of the thin molded article. You.

The epoxy equivalent of the halogenated phenoxy resin is set to 4000 or more, preferably 4500 or more, more preferably 5000 or more in order to improve the fluidity when the halogenated epoxy compound (C) is used.

Further, m indicating the average degree of polymerization is 12 or more, preferably 13 or more, in order to prevent the fluidity from being lowered when used in combination with the halogenated epoxy compound (C).
It is more preferably 15 or more, and 150 or less, preferably 1 to prevent the mechanical strength from decreasing.
It is 45 or less, more preferably 140 or less.

In the general formula (I), X ¹ , X ² ,
X ³ and X ⁴ are each preferably a bromine atom from the viewpoint of flame retardancy. Further, in the general formula (I), Y
^1, -C (CH ₃₎ - is preferred in view of mechanical strength is.

The terminal group of the halogenated phenoxy resin is generally a glycidyl group and / or a hydroxyl group.
Further, these terminal groups may be blocked with carboxylic acids, phenols, amines or alcohols. When the terminal is a glycidyl group, it is preferable to use a resin having a high molecular weight or an epoxy equivalent adjusted to 4000 or more by blocking the terminal group.

In the present invention, (C) a halogenated epoxy compound is used for the purpose of imparting wet heat resistance and flame retardancy.

The halogenated epoxy compound is a compound having a skeleton represented by the general formula (II).

The halogen content of the halogenated epoxy compound is 10% by weight in order to impart sufficient flame retardancy.
Or more, preferably 20% by weight or more, more preferably 2% by weight.
5% by weight or more.

The average degree of polymerization n is set to 8 or less, preferably 7.5 or less, in order to prevent the moist heat resistance from lowering when used in combination with the halogenated phenoxy resin (B). The average degree of polymerization n is set to 0 or more, preferably 0.5 or more, in order to increase the fluidity of the obtained resin composition.

The epoxy equivalent is 2500 or less, preferably 2450 or less, and more preferably 240 or less so that the wet heat resistance of the resin composition of the present invention does not decrease.
0 or less, and in order to prevent the fluidity of the resin composition of the present invention from lowering, 800 or more, preferably 90
0 or more, more preferably 1000 or more.

In the general formula (II), X ⁵ , X ⁶ ,
X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ and X ¹² are each preferably a hydrogen atom or a bromine atom from the viewpoint of flame retardancy. More preferably, X ⁵ , X ⁶ , X ⁷ , X ⁸ ,
X ⁹ , X ¹⁰ , X ¹¹ and X ¹² are each a bromine atom.

In the general formula (II), Y ²
And Y ³ are preferably —C (CH ₃ ) ₂ — from the viewpoint of mechanical strength.

The total blending amount of the (B) halogenated phenoxy resin and the (C) halogenated epoxy compound is as follows:
It depends on the halogen content, epoxy equivalent and the like. The total compounding amount is at least 5 parts by weight, preferably at least 7.5 parts by weight, more preferably at least 7.5 parts by weight, based on 100 parts by weight of the (A) polyethylene terephthalate-based thermoplastic polyester in order to impart sufficient flame retardancy. Is 10 parts by weight or more. In order to prevent the mechanical strength of the obtained resin composition from decreasing, the total amount is
The amount is 50 parts by weight or less, preferably 45 parts by weight or less, more preferably 40 parts by weight or less, based on 100 parts by weight of the polyethylene terephthalate-based thermoplastic polyester (A).

The weight ratio of the halogenated phenoxy resin (B) to the halogenated epoxy compound (C) (halogenated phenoxy resin / halogenated epoxy compound) is determined so that the wet heat resistance is sufficient. 90/1
0 or less, preferably 85/15 or less, more preferably 80/20 or less, so that the fluidity of the resin composition of the present invention does not decrease and the appearance of the obtained molded article does not deteriorate. Therefore, it is set to 1/99 or more, preferably 5/95 or more, and more preferably 10/90 or more.

The amount of the halogenated epoxy compound (C) is preferably at least 3 parts by weight based on 100 parts by weight of the (A) polyethylene terephthalate-based thermoplastic polyester in order to impart sufficient wet heat resistance. Is at least 3.5 parts by weight, more preferably at least 4 parts by weight.

In the resin composition of the present invention, (D) an antimony compound is used for the purpose of enhancing flame retardancy.

Specific examples of the antimony compound include:
For example, antimony oxide such as antimony trioxide, antimony tetroxide and antimony pentoxide, sodium antimonate, antimony phosphate and the like can be mentioned, and these can be used alone or in combination of two or more. Among these, antimony oxide is preferred because of its excellent fluidity, mechanical strength and wet heat resistance, and antimony trioxide is particularly preferred.

The amount of the antimony compound is 0.1 parts by weight or more, preferably 1 part by weight, based on 100 parts by weight of the (A) polyethylene terephthalate-based thermoplastic polyester in order to ensure sufficient flame retardancy. It is not less than 20 parts by weight, preferably not more than 15 parts by weight from the viewpoint of improving the mechanical strength of the resin composition of the present invention.

The resin composition of the present invention preferably further contains (E) a reinforcing filler.

Examples of the reinforcing filler (E) include glass fiber, carbon fiber, potassium titanate fiber, glass beads, glass flake, calcium carbonate, calcium sulfate, barium sulfate and the like. A mixture of more than one species is used. Among the reinforcing fillers, fibrous reinforcing fillers such as glass fiber and carbon fiber are preferable, and chopped strand crow fibers treated with a sizing agent are preferably used from the viewpoint of workability. In order to enhance the adhesion between the resin and the fibrous reinforcing filler, it is preferable that the surface of the fibrous reinforcing filler is treated with a coupling agent or a binder.

As the coupling agent, for example, γ
-Aminopropyltriethoxysilane, alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane and the like, and as the binder, for example, epoxy resin, urethane resin and the like,
The present invention is not limited only to these.

The amount of the reinforcing filler is preferably not more than 150 parts by weight, more preferably not more than 150 parts by weight, based on 100 parts by weight of the polyethylene terephthalate-based thermoplastic polyester in order not to reduce the extrusion processability and the molding processability. Is 120 parts by weight or less, more preferably 100 parts by weight or less. Further, in order to sufficiently exhibit the reinforcing effect by blending the reinforcing filler, 2 parts by weight or more,
In particular, it is preferably at least 5 parts by weight.

When glass fibers are used as the reinforcing filler, the glass fibers preferably have a diameter of 1 to 20 μm and a length of about 0.01 to 50 mm. If the fiber length is too short, the effect of reinforcement will not be sufficient,
On the other hand, if the length is too long, the surface properties, extrusion processability, and processability of the molded product become poor.

In the present invention, by using (F) at least one kind of silicic acid (salt) of silicic acid and silicate, fluidity and mold release that can sufficiently meet the demand for a high cycle of molding. Properties can be imparted.

The silicic acid (salt) is a compound having a shape such as powder, granules, needles, and plates containing SiO ₂ units. Representative examples of such silicic acid (salt) include, for example, magnesium silicate, aluminum silicate, calcium silicate, talc, mica, wollastonite, kaolin,
Diatomaceous earth, bentonite, clay and the like are used, and these are used alone or in combination of two or more. Of these, talc, mica and kaolin are preferred.

The amount of the above-mentioned silicic acid (salt) is adjusted according to the above (A) in order to sufficiently exhibit the effects of fluidity and mold release.
Polyethylene terephthalate thermoplastic polyester 1
0.1 parts by weight or more, preferably 1 part by weight, per 100 parts by weight
It is desirable that the amount is not less than 60 parts by weight, more preferably not more than 50 parts by weight, and more preferably not more than 40 parts by weight, in order to prevent a decrease in mechanical strength of the obtained resin composition. Parts or less.

By adding a crystallization accelerator to the resin composition of the present invention, the releasability is further improved,
The gloss of the surface of the molded article can be improved, and in particular, the releasability and the surface gloss in a low-temperature mold can be improved.

Specific examples of the crystallization accelerator include, for example, polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, and ethylene oxide addition polymer of bisphenols. Polyalkylene glycols such as propylene oxide addition polymers of bisphenols and tetrahydrofuran addition polymers of bisphenols, and polyalkylene glycols such as terminal epoxy-modified compounds and terminal ester-modified compounds, and aliphatic polyesters such as poly-ε-caprolactone , Polyethylene terephthalate, polypropylene terephthalate, polytetramethylene terephthalate, polyhexamethylene terephthalate, poly Chi naphthalate, polybutylene naphthalate, and polyester units such as poly cyclohexane dimethylene terephthalate, formula (II
I):

[0061]

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Wherein R ¹ is an alkylene group having 2 to 5 carbon atoms, which may be the same or different, and k represents an integer of 5 or more, and / or a general formula (IV):

[0063]

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(Wherein R ² and R ³ are each independently an alkylene group having 2 to 5 carbon atoms, R ⁴ is an alkylene group having 1 to 10 carbon atoms, —S— group, —SO— group, —CO A group or a direct bond, p and q each independently represent an integer of 1 or more, and p + q satisfies 3 or more.) A polyethylene terephthalate-based heat having a group represented by the following formula: Polyester-polyether copolymer having lower glass transition temperature than plastic polyester, 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, dioctyl sebacate and the like can be mentioned, and these can be used alone or in combination of two or more.

It is not preferable to use a low molecular weight or high molecular weight organic carboxylic acid metal salt as a crystallization accelerator, since the wet heat resistance and the fluidity decrease.

Among the crystallization accelerators, mechanical strength,
In terms of heat resistance and blooming properties, polyester-
Polyether copolymers are preferred.

As the polyester unit of the polyester-polyether copolymer, a polyalkylene terephthalate unit having an ethylene terephthalate unit and / or a tetramethylene terephthalate unit as a main component is used for its mechanical strength, fluidity, mold releasability and the like. Preferred from the point.

The polyether unit is a unit represented by the general formula (III) and / or the general formula (IV).

Specific examples of R ^{1 in} the general formula (III) include, for example, an ethylene group, a propylene group, an isopropylene group and a tetramethylene group.

Specific examples of R ² and R ^{3 in} the general formula (IV) include, for example, an ethylene group, a propylene group, an isopropylene group and a tetramethylene group.
Specific examples of R ⁴ include, for example, —C (CH ₃ ) ₂ —
And a divalent group such as a group, a —CH ₂ — group, a —S— group, a —SO ₂ — group, and a —CO— group, and a direct bond.

Further, in the polyether unit, k in the general formula (III) is an integer of 5 or more, and p and q in the general formula (IV) are each independently an integer of 1 or more; p + q satisfies 3 or more, and all are polyether units having a molecular weight of 400 or more. The molecular weight of the polyether unit is more preferably from 600 to 600.
0, more preferably 800 to 3000. 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 article is reduced. When the molecular weight exceeds 6000, it is difficult to obtain a homogeneous polymer, and the addition to the resin composition is difficult. In such a case, the mechanical strength is reduced. The upper limit of k in the general formula (III) and the upper limits of p, q and p + q in the general formula (IV) are as follows:
The molecular weight of the polyether unit varies depending on the number of carbon atoms of R ^{1 in} the general formula (III) and R ² , R ³ and R ^{4 in} the general formula (IV). It is appropriately adjusted so as to be not more than the degree.

Specific examples of the polyether unit include:
For example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide / propylene oxide copolymer, ethylene oxide / propylene oxide / tetrahydrofuran copolymer,
Residues such as ethylene oxide, propylene oxide, and alkylene oxide addition polymers such as tetrahydrofuran of bisphenols such as bisphenol A and bisphenol S are used alone or in combination of two or more. Among them, particularly when the resin composition is composed of a polyether unit represented by the general formula (III), heat stability, mold releasability when the obtained resin composition is molded with a low-temperature mold, surface properties of a molded body, and the like are given. It is preferable from the point of view. 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 A propylene oxide addition polymer of S, a tetrahydrofuran addition polymer of bisphenol S, an ethylene oxide / propylene oxide addition polymer of bisphenol S, and the like are preferably used.

The copolymerization amount of the polyether unit in the copolymer is 3 to 60% by weight, preferably 20 to 55% by weight, more preferably 2 to 60% by weight based on the obtained copolymer.
5 to 50% by weight. If the amount is less than 3% by weight, the releasability and surface gloss at the time of molding with a low-temperature mold will be insufficient, and if it exceeds 60% by weight, the mechanical strength, wet heat resistance and the like of the molded body will tend to decrease.

The intrinsic viscosity of the copolymer (phenol:
(Measured at 25 ° C. using a mixed solvent of 1,1,2,2-tetrachloroethane = 1: 1 (weight ratio)) is 0.35 or more, preferably 0.40 to 2.00, more preferably It is 0.50 to 1.50. When the intrinsic viscosity is less than 0.35, the heat resistance of the obtained resin composition decreases, and when it exceeds 2.00, the dispersibility decreases, and the mechanical strength of the obtained resin composition decreases. Tend.

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 (A) polyethylene terephthalate-based thermoplastic polyester. Department. For example, in the case of a low-molecular-weight crystallization accelerator such as polyalkylene glycols, aliphatic polyesters, and plasticizers, 0.05 to 30 parts by weight, or the polyester-polyether copolymer or polyester-
In the case of aliphatic polyester copolymer, etc., 0.5 to
50 parts by weight. Further, the addition amount of the polyester-polyether copolymer is preferably 1 to 40 parts by weight, more preferably 2 to 35 parts by weight. When the amount is less than the lower limit, the releasability and surface gloss in a low-temperature mold become insufficient, and when the amount exceeds the upper limit, the mechanical strength, heat resistance, wet heat resistance and the like of the resin composition decrease. Become like

In the resin composition of the present invention, if necessary, a heat stabilizer such as an antioxidant can be used.

Examples of the heat stabilizer include pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-t -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)
Propionyl hexamethylene diamine, tris- (3,
Phenolic antioxidants such as 5-di-t-butyl-4-hydroxybenzyl) isocyanurate;
4-di-t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, bis (2
Phosphorus antioxidants such as 6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite; distearyl-3,3'-thiodipropionate;
And thioether-based antioxidants such as pentaerythritol-tetrakis- (β-laurylthiopropionate). These can be used alone or in combination of two or more.

The 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,
Additives such as dyes, antistatic agents, dispersants, compatibilizers, and antibacterial agents can be used alone or as a mixture of two or more. Further, other flame retardants, flame retardant assistants, inorganic compounds and the like may be used in combination.

The resin composition of the present invention may further contain any other thermoplastic or thermosetting resin, such as a polyethylene terephthalate resin, as long as the flame retardancy, mechanical properties, moldability and the like are not impaired. Saturated or unsaturated polyester resin, liquid crystal polyester resin, polyester ester elastomer resin, polyester ether elastomer resin, polytetrafluoroethylene resin, polyolefin resin, polyamide resin, polycarbonate resin, rubbery polymer A reinforced styrene resin, a polyphenylene sulfide resin, a polyphenylene ether resin, a polyacetal resin, a polysulfone resin, a polyarylate resin, or the like may be added alone or in combination of two or more.

The method for producing the resin composition of the present invention is not particularly limited. For example, a method in which the above-described components are uniformly mixed in advance, and then supplied to a single-screw or multi-screw extruder, melt-mixed at 230 to 330 ° C., and subsequently cooled to produce pellets is employed. be able to.

The method of molding the 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, sheet molding, and roll molding are used. Examples include a molding method, a press molding method, a lamination molding method, a film molding method by a melt casting method, and a molding method such as a spinning method.

[0082]

EXAMPLES Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to only these examples.

Example 1 Polyethylene terephthalate (intrinsic viscosity (phenol: 1, 1) prepared using germanium dioxide as a catalyst
Using a mixed solvent of 1,2,2-tetrachloroethane = 1: 1 (weight ratio) at 25 ° C.): 0.75, P
For 100 parts by weight of ET-A, a halogenated phenoxy resin (average degree of polymerization: about 16.4, halogen (bromine) content: about 52% by weight, epoxy equivalent: about 5250)
(In the general formula (I), X ¹ , X ² , X ³ and X ⁴ each represent a bromine atom, and Y ¹ represents a —C (CH ₃ ) ₂ — group); , HPR-A), a halogenated epoxy compound (average degree of polymerization: 2.7, halogen (bromine) content: about 52% by weight, epoxy equivalent: about 2250, tetrabromobisphenol A type epoxy resin (general) Formula (I
In I), X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹
And X ¹² each represent a bromine atom; Y ² and Y ³ each represent a —C (CH ₃ ) ₂ — group; hereinafter, referred to as HER-A) 9 parts by weight and antimony trioxide 5 parts by weight; Antioxidant (ADK STAB AO- manufactured by Asahi Denka Co., Ltd.)
60) After dry blending 0.35 parts by weight in advance, supply to a hopper of a vented twin-screw extruder (TEX44, manufactured by Nippon Steel Works Ltd.) whose cylinder temperature is controlled to 260 ° C. As glass fiber (manufactured by NEC Corporation, T-195H / PS) 53
A resin composition was obtained by adding a part by weight and performing melt extrusion.

After the obtained resin composition was dried at 140 ° C. for 4 hours, injection molding was performed using a 50-t injection molding machine at a cylinder temperature of 270 ° C. and a mold temperature of 120 ° C.
STM No. 1 dumbbell; 1/4 inch thick, 12 mm wide
127mm long bar or 1/16 inch thick, 1 width
A bar having a length of 2 mm and a length of 127 mm was prepared, and the following physical properties were evaluated. Table 1 shows the results.

<Flame Retardancy> Using a 1/16 inch bar, U
Flame retardancy was evaluated according to the vertical combustion test method described in L94.

<Fluidity> According to JIS K-7210,
Measure the B method flow at 280 ° C and 15 minutes preheating time,
Fluidity was determined.

<Tensile Strength> The ASTM No. 1 dumbbell was
A tensile test was performed according to STM D-790 to determine the maximum strength.

<Moisture and heat resistance>
For 30 hours under a saturated pressurized steam. ASTM D-
A bending test was performed according to 790 to determine the maximum strength. The bending strength retention is calculated by the following formula:

[0089]

(Equation 1)

Was determined according to the following formula:

Example 2 In Example 1, instead of HPR-A, a halogenated phenoxy resin (average degree of polymerization: about 15.6, halogen (bromine) content: about 53% by weight, epoxy partially end-capped) Equivalent: 55000 tetrabromobisphenol A-type phenoxy resin (in the general formula (I), X ¹ , X ² , X
³ and X ⁴ are both bromine atoms, and Y ¹ is —C (CH ₃ ) ₂
-Indicating a group), hereinafter referred to as HPR-B)
Instead of RA, a halogenated epoxy compound (average degree of polymerization: about 1.9, halogen (bromine) content: about 53% by weight, epoxy equivalent: about 1820, tetrabromobisphenol A type epoxy resin (general formula (II) ), X
^{5, X 6, X 7,} X 8, X 9, X 10, X 11 and X ¹² are both bromine atom, Y ² and Y ³ be -C Any (CH _{3) 2}
Example 1 except that 0.15 parts by weight of a thioether-based antioxidant (Adeka Stab AO-412S, manufactured by Asahi Denka Co., Ltd.) was additionally added using HER-B). A resin composition was obtained in the same manner as described above.

The physical properties of the obtained resin composition were examined in the same manner as in Example 1. Table 1 shows the results.

Examples 3 to 6 Resin compositions were obtained in the same manner as in Example 1 except that the components were changed as shown in Table 1.

The physical properties of the obtained resin composition were examined in the same manner as in Example 1. Table 1 shows the results.

The abbreviations of the components used in the examples mean the following.

PET-B: polyethylene terephthalate prepared using germanium dioxide as a catalyst (intrinsic viscosity: 0.60) HER-C: halogenated epoxy compound (average degree of polymerization:
About 1.0, halogen (bromine) content: about 50% by weight, epoxy equivalent: about 1250 tetrabromobisphenol A type epoxy resin (in the general formula (II), X ⁵ ,
X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ and X ¹² each represent a bromine atom, and Y ² and Y ³ each represent a —C (CH ₃ ) ₂ — group. Fluoroethylene (manufactured by Daikin Industries, Ltd., polyflon F104) Comparative Examples 1 to 7 A resin composition was obtained in the same manner as in Example 1 except that the components were changed as shown in Table 2.

The physical properties of the obtained resin composition were examined in the same manner as in Example 1. Table 2 shows the results.

The abbreviations of each component used in each comparative example mean the following.

PET-C: polyethylene terephthalate prepared using antimony trioxide as a catalyst (intrinsic viscosity 0.75) HER-D: halogenated epoxy compound (average degree of polymerization:
About 0, halogen (bromine) content: about 20% by weight, epoxy equivalent: about 500 brominated bisphenol A type epoxy resin) In Comparative Examples 5 to 6, a molded article could not be produced.

[0100]

[Table 1]

[0101]

[Table 2]

From the results shown in Tables 1 and 2, Examples 1 to
It can be seen that all of the resin compositions of the present invention obtained in 6 have excellent flame retardancy, high fluidity, high tensile strength, and excellent wet heat resistance.

Examples 7 to 11 In Example 1, each component was changed as shown in Table 3,
Furthermore, as a reinforcing filler, talc (Nippon Talc Co., Ltd.)
, Micro Ace K-1), Mica (Yamaguchi Mica Co., Ltd.)
A-21S) or kaolin (Engelhardt (E
NGELHARD), SATINTON No.
A resin composition was obtained in the same manner as in Example 1 except that 5) was used.

The physical properties of the obtained resin composition were examined in the same manner as in Example 1.

The releasability was examined by the following method. Table 3 shows the results.

<Release Property> The obtained resin composition was heated at 140 ° C.
After drying for 4 hours or more at a cylinder temperature of 300 ° C. and a mold temperature of 120 ° C., a bar having a thickness of 1/4 inch (width 12 mm, length 127 mm) is injection-molded using a 50-t injection molding machine. The shortest cooling time (hereinafter referred to as "limit cooling time") in which a good molded body was obtained without depression or deformation due to the protruding pin was examined, and the releasability was evaluated.

Comparative Examples 8 to 13 Resin compositions were obtained in the same manner as in Example 7, except that the components were changed as shown in Table 4.

The physical properties of the obtained resin composition were examined in the same manner as in Example 7. Table 4 shows the results.

In Comparative Example 11, a molded article could not be produced.

[0110]

[Table 3]

[0111]

[Table 4]

From the results shown in Tables 3 and 4, from Examples 7 to
The resin compositions of the present invention obtained in Example 11 are all excellent in flame retardancy, large in fluidity, high in tensile strength, and excellent in moisture and heat resistance. ) It can be seen that the compound is excellent in releasability by compounding.

Production Example 1 3500 g of a polyethylene terephthalate oligomer (average number of ethylene terephthalate units: about 5 to 8) prepared using germanium dioxide as a catalyst, 1500 g of an ethylene oxide addition polymer of bisphenol A having an average molecular weight of about 1000, and a phenolic polymer 25 g of an oxidizing agent (Adeka Stab AO-60, manufactured by Asahi Denka Co., Ltd.) was charged into a 10-liter autoclave (manufactured by Nippon Pressure Glass Co., Ltd.), and the temperature was raised to 290 ° C. while stirring under a nitrogen stream. The pressure was reduced to 1 Torr or less. 1 Torr
After stirring for 3 hours after reaching the following, the pressure was returned to normal pressure with nitrogen, and the polymerization was terminated to obtain a copolymer A. The intrinsic viscosity of the obtained copolymer A was 0.7.

Production Example 2 Polytetramethylene terephthalate (intrinsic viscosity 0.9)
3500 g, bisphenol A having an average molecular weight of about 1000
G of ethylene oxide addition polymer and phenolic antioxidant (ADK STAB AO- manufactured by Asahi Denka Co., Ltd.)
60) 25 g was put into a 10-liter autoclave (manufactured by Japan Pressure Glass Co., Ltd.), and the temperature was raised to 260 ° 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, and the polymerization was terminated to obtain a copolymer B. The intrinsic viscosity of the obtained copolymer B is 0.8
Met.

Example 12 9 parts by weight of HPR-A, 9 parts by weight of HER-A, 5 parts by weight of antimony trioxide, 9 parts by weight of copolymer A as a crystallization accelerator, and 100 parts by weight of PET-A 0.33 parts by weight of phenolic antioxidant and glass fiber
A resin composition consisting of 53 parts by weight was obtained in the same manner as in Example 1.

As the physical properties of the obtained resin composition, the surface gloss was examined according to the following method. Table 5 shows the results.

<Surface Gloss> The obtained resin composition was mixed with 140
After drying at 4 ° C. for 4 hours or more, a flat plate (thickness 2 mm, length and width 120 mm) was molded at a cylinder temperature of 270 ° C. and a mold temperature of 90 ° C. using a 50-t injection molding machine, and the surface gloss was visually observed. The evaluation was performed based on the following evaluation criteria.

[Evaluation Criteria] A: Good gloss is present on the entire surface of the molded product (flat plate). B: A part of the molded article lacks gloss or the gloss of the molded article is partially uneven. C: The molded article has more glossless portions, or the molded article has uneven gloss.

Examples 13 to 15 Resin compositions were obtained in the same manner as in Example 12, except that the components were changed as shown in Table 5.

The physical properties of the obtained resin composition were examined in the same manner as in Example 12. Table 5 shows the results.

For reference, the surface gloss of the resin compositions obtained in Examples 1 and 7 was examined in the same manner as in Example 12. Table 5 also shows the results.

[0122]

[Table 5]

From the results shown in Table 5, copolymer A or copolymer B was added to the resin composition of the present invention as a crystallization accelerator.
(Examples 12 to 13 and Example 14)
15) It can be seen that a molded article having a good surface gloss can be obtained even when molded with a low-temperature mold.

[0124]

The resin composition of the present invention has excellent flame retardancy, mechanical strength, fluidity, and wet heat resistance, and is released when a specific inorganic compound is added. It also has excellent moldability.

Therefore, the resin composition of the present invention can be suitably used as a molding material for various molded articles.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-17669 (JP, A) JP-A-2-202541 (JP, A) JP-A-1-201357 (JP, A) JP-A-59-1979 6251 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 67/00-67/02

Claims (7)

(57) [Claims] (A) a polyethylene terephthalate-based thermoplastic polyester having ethylene terephthalate units as a main component and prepared using a germanium-based compound as a catalyst; (B) a general formula (I): (Wherein X ¹ , X ² , X ³ and X ⁴ are each independently a hydrogen atom or a halogen atom, Y ¹ is an alkylene group having 1 to 10 carbon atoms, an alkylidene group having 2 to 10 carbon atoms, and 3 carbon atoms. To 10 cycloalkane groups, carbonyl groups, -O-
Group, -S- group, -SO ₂ - group or a direct bond, m is 12
(C) a halogenated phenoxy resin having a skeleton represented by the formula (C), having a halogen content of 30% by weight or more and an epoxy equivalent of 4000 or more:
General formula (II): (Wherein X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ and X ¹² each independently represent a hydrogen atom or a halogen atom,
Y ² and Y ³ each independently represent an alkylene group having 1 to 10 carbon atoms, an alkylidene group having 2 to 10 carbon atoms,
10 to 10 cycloalkane groups, carbonyl groups, -O- groups,
-S- group, -SO ₂ - group or a direct bond, n represents has a skeleton represented by showing the average polymerization degree of 0-8), a halogen content of 10 wt% or more, an epoxy equivalent of 800 to 25
The polyethylene terephthalate-based thermoplastic polyester 1 containing a halogenated epoxy compound, (D) an antimony compound and (E) a reinforcing filler
The total blending amount of the halogenated phenoxy resin and the halogenated epoxy compound is 5 to 5 parts by weight with respect to 00 parts by weight.
0 parts by weight, the compounding amount of the halogenated epoxy compound is 3 parts by weight or more, the compounding amount of the antimony compound is 0.1 to 20 parts by weight, and the compounding amount of the reinforcing filler is 150 parts by weight. And a weight ratio of the halogenated phenoxy resin to the halogenated epoxy compound (halogenated phenoxy resin / halogenated epoxy compound) is from 1/99 to 90/10. Terephthalate resin composition. (F) At least one silicic acid (salt) compound of silicic acid and a silicate is contained, and the compounding amount of the silicic acid (salt) compound is based on 100 parts by weight of the polyethylene terephthalate-based thermoplastic polyester. 0.1 to 6
The flame-retardant polyethylene terephthalate-based resin composition according to claim 1, which is 0 parts by weight. 3. In the general formula (I), X ¹ , X ² , X ³
2. The flame-retardant polyethylene terephthalate resin composition according to claim 1, wherein each of X and X ⁴ is a bromine atom. 4. In the general formula (II), X ⁵ , X ⁶ , X
7. The flame-retardant polyethylene terephthalate resin composition according to claim 1, wherein ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ and X ¹² are each independently a hydrogen atom or a bromine atom. 5. The flame-retardant polyethylene terephthalate resin composition according to claim 1, wherein the antimony compound is antimony oxide. 6. The flame-retardant polyethylene terephthalate resin composition according to claim 2, wherein the silicic acid (salt) compound is at least one silicate compound of talc, mica and kaolin. 7. The composition according to claim 1, wherein 0.5 to 50 parts by weight of (G) the polyester-polyether copolymer is blended with respect to 100 parts by weight of the polyethylene terephthalate-based thermoplastic polyester. Or the flame-retardant polyethylene terephthalate-based resin composition according to 6.