JPH083431A - Polyester resin composition - Google Patents

Abstract

(57) [Summary] [Structure] (a) Polybutylene terephthalate resin (PBT) treated with water and / or steam; (b) Thermoplastic resin having ester bond other than PBT (other ester bond-containing thermoplastic Resin), a polyester resin composition containing (c) an organic halogen flame retardant and (d) a flame retardant aid, or (a) P treated with water and / or steam.
A polyester resin composition containing BT and (b) at least one other ester bond-containing thermoplastic resin. [Effect] The polyester resin composition of the present invention is PBT.
And the other ester bond-containing thermoplastic resins suppress the transesterification reaction and have excellent thermal stability during melting, good moldability and releasability, no surface roughness, dimensional stability, and mechanical It is possible to obtain a molded article having excellent properties such as properties, heat resistance and appearance, and from the polyester resin composition of the present invention containing a flame retardant and a flame retardant auxiliary, a molded article having excellent flame retardancy can be obtained. can get.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester resin composition and a molded article made of the resin composition. More specifically, the present invention relates to a polyester resin composition containing a polybutylene terephthalate resin and another thermoplastic resin having an ester bond, and a molded article made of the resin composition. , The transesterification reaction between the polybutylene terephthalate resin and other thermoplastic resin having ester bond during melting is significantly suppressed, and it has excellent thermal stability during melt processing, mechanical properties and heat resistance. , A molded article having excellent properties such as dimensional stability can be obtained, and further, the polyester resin composition of the present invention containing a flame retardant and a flame retardant auxiliary is excellent in flame retardancy in addition to the above properties. Therefore, the polyester resin composition of the present invention containing or not containing a flame retardant makes use of these characteristics to produce electric / electronic parts, automatic Parts, machine parts, office supplies, daily necessities, can be effectively used for other wide range of applications.

[0002]

2. Description of the Related Art Polybutylene terephthalate resin, which is a type of polyester resin, has excellent moldability and electrical properties, heat resistance, solvent resistance, mechanical properties, etc. The amount of use and the usage are expanding year by year. With the expansion of applications, the use environment of molded products made of polybutylene terephthalate resin is diversifying, and there is a demand for products with superior properties that can withstand more severe conditions. Formability, dimensional stability, mechanical properties such as tensile strength and impact resistance, heat resistance, appearance and flame retardancy are becoming important requirements.

From this point of view, various proposals have been made for the purpose of improving the moldability, impact resistance, dimensional stability and the like of polybutylene terephthalate resins. For example, polyethylene terephthalate and polybutylene terephthalate resins have been proposed. A method for improving melt moldability by adding an inorganic filler to the resin composition containing the resin composition (JP-A-57-574).
No. 5), a polyester resin such as polybutylene terephthalate resin and a polycarbonate resin are melt-mixed to obtain a composition having improved impact resistance or dimensional stability (JP-A-58-25352, JP-A-58-25352). Kaihei 2-5
No. 4382) is known.

However, a resin composition prepared by blending two or more different resins having an ester bond lacks thermal stability when melted because of transesterification reaction between different resins, and is crystalline when melted. And the crystallization rate is likely to decrease, and in many cases, the excellent physical properties inherent in each resin are significantly impaired. And, such a transesterification reaction between different kinds of resins causes deterioration of moldability, deterioration of releasability, surface roughening of molded products, deterioration of heat resistance, dimensional stability during melt molding such as injection molding. The above-mentioned known resin composition obtained by blending a polybutylene terephthalate resin with another thermoplastic resin having an ester bond is not an exception.

On the other hand, polybutylene terephthalate resin is inherently flammable, and once ignited, it gradually burns without being digested even if the fire source is removed. Such flammable properties are
In particular, electrical parts and electronic parts have become a big problem from the viewpoint of safety against fire, but polybutylene terephthalate resin can be easily made flame-retardant by adding a flame retardant. It has been proposed in the past to prepare a flame-retardant polybutylene terephthalate-based resin composition by adding an organic halogen-based flame retardant and a flame-retardant aid to the composition (Japanese Patent Laid-Open No. 4-312058).
9-14563, JP-A-50-86550, JP-A-51-73555). The polybutylene terephthalate resin composition containing the flame retardant obtained by these conventional techniques has come to be used for electric / electronic parts, automobile parts, machine parts and the like.

Based on the above-mentioned conventional technique, the present inventors have blended a resin composition of a polybutylene terephthalate resin and another thermoplastic resin having an ester bond with an organic halogen flame retardant and a flame retardant auxiliary. I tried to make it flame-retardant. As a result, although the flame retardancy was improved to some extent, the transesterification reaction during heating and melting between the polybutylene terephthalate resin and another thermoplastic resin having an ester bond could not be suppressed, and the thermal stability during melting Lacking in properties, the crystallization rate and crystallinity of the resin composition are remarkably reduced, and moldability, releasability, surface roughness of the molded product, heat resistance,
It has not been possible to improve various properties such as dimensional stability and mechanical properties.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to suppress the transesterification reaction between a polybutylene terephthalate resin and another thermoplastic resin having an ester bond at the time of heating and melting, and to prevent heat during melt processing. Stability is good,
It has excellent moldability and releasability, has a good appearance without surface roughness of the molded product, has excellent physical properties such as dimensional stability, mechanical properties and heat resistance, and also has excellent flame retardancy. Electronic components,
It is an object of the present invention to provide a flame-retardant polyester-based resin composition suitable for the production of automobile parts, machine parts, office supplies and other various molded products, especially electric / electronic parts. Further, an object of the present invention is to effectively suppress the transesterification reaction at the time of melting between the polybutylene terephthalate-based resin and another thermoplastic resin having an ester bond, and the thermal stability at the time of melt processing is improved. It has excellent moldability and releasability, has a good appearance without surface roughness of molded products, has excellent characteristics such as dimensional stability, mechanical properties, heat resistance, etc. The present invention provides a polyester resin composition that can be effectively used for the molded article. And
The present invention is to provide a molded article comprising the above polyester resin composition.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object and found that a resin composition containing a polybutylene terephthalate resin and another thermoplastic resin having an ester bond is used. In preparing a flame-retardant polyester resin composition containing an organic halogen-based flame retardant and a flame retardant aid, using a polybutylene terephthalate resin previously treated with water and / or steam, The transesterification reaction at the time of melting between the polybutylene terephthalate resin and another thermoplastic resin having an ester bond is effectively suppressed, the stability at the time of melt processing is improved, and the moldability and mold releasability are improved. It has been found that the molded product obtained from the resin composition is excellent and has various properties such as dimensional stability, mechanical properties, heat resistance, appearance and flame retardancy. And completed the present invention Te.

Further, the present invention provides the above-mentioned technique developed by the present inventors for preparing a flame-retardant polyester resin composition using a polybutylene terephthalate resin previously treated with water and / or steam. Used as a molded article for applications where flame retardancy is not so demanded, containing no flame retardant, it was applied to a resin composition of a polybutylene terephthalate resin and another thermoplastic resin having an ester bond, As in the case of the flame-retardant polyester resin composition, the transesterification reaction at the time of melting between the polybutylene terephthalate resin and another thermoplastic resin having an ester bond is effectively suppressed, and the melt processing is performed. The stability at time is improved, the moldability and mold releasability are improved, and the molded products obtained from the polyester resin composition are dimensionally stable. , Mechanical properties, heat resistance, and completed the present invention found that excellent properties such as appearance.

Accordingly, the present invention provides (1) (a) a polybutylene terephthalate resin treated with water and / or steam; (b) a thermoplastic resin having an ester bond other than the polybutylene terephthalate resin (hereinafter referred to as "others"). Of "ester bond-containing thermoplastic resin"); (c) Organic halogen-based flame retardant, and (d) Flame-retardant auxiliary agent; (2) A polyester resin composition containing (a) a polybutylene terephthalate resin treated with water and / or steam, and (b) at least one kind of other ester bond-containing thermoplastic resin; is there.

The present invention also includes a molded article made of the above polyester resin composition (1) or polyester resin composition (2).

Polyester resin composition (1) of the present invention
Alternatively, in the polybutylene terephthalate resin (hereinafter sometimes referred to as “PBT resin”) used in the polyester resin composition (2), at least 70 mol% of the acid component constituting the polybutylene terephthalate resin is terephthalic acid or its A polyester resin comprising an ester-forming derivative and at least 70 mol% of the diol component being 1,4-butanediol, and other copolymerizable acid components and / or other copolymerization components in the range of 30 mol% or less. A polymerized diol component may be used. At that time, when an ester-forming derivative of terephthalic acid is used as an acid component, a dialkyl ester, a diaryl ester of terephthalic acid or the like can be used.

Examples of other copolymerizable acid components that can be used in the range of 30 mol% or less include aromatic dicarboxylic acids such as isophthalic acid, diphenyldicarboxylic acid and naphthalene-1,4-dicarboxylic acid; adipic acid, Sebacic acid,
Examples thereof include aliphatic dicarboxylic acids such as mazelaic acid, succinic acid and oxalic acid; oxycarboxylic acids such as β-oxyethoxybenzoic acid and p-oxybenzoic acid; or ester-forming derivatives thereof. The polymerized acid component may be used alone or in combination of two or more.

Further, examples of the copolymerized diol component which can be used in the range of 30 mol% or less include ethylene glycol, propylene glycol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5.
-Pentanediol, 1,6-hexanediol, 1,
Aliphatic diols having 2 to 10 carbon atoms such as 9-nonanediol, 2-methyl-1,8-octanediol and decamethylenediol; alicyclic diols such as cyclohexanediol; aromatic diols such as bisphenol A and bisphenol S Polyalkylene glycols such as polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, etc. may be mentioned, and these copolymerized diol components may be used alone or 2
More than one species may be used.

The method for producing the PBT-based resin is not particularly limited, and it is conventional to use the above-mentioned acid component mainly composed of terephthalic acid or its ester-forming derivative and the above-mentioned diol component mainly composed of 1,4-butanediol. Any of the known aromatic polyesters produced by the transesterification reaction or the direct esterification reaction can be used.

In the present invention, as the PBT resin, an intrinsic viscosity of 0.7-1.1.0 when measured at 30 ° C. using a phenol / tetrachloroethane (1: 1 weight ratio) mixed solvent.
It is preferable to use one in the range of 3 dl / g,
A PBT resin in the range of 0.7 to 1 dl / g is more preferable. When a PBT-based resin having an intrinsic viscosity of less than 0.7 dl / g is used, the toughness of a molded article obtained from the polyester-based resin composition tends to be insufficient, while the intrinsic viscosity is 1.3 dl / g.
If the PBT-based resin in excess of g is used, the melt viscosity at the time of molding becomes too high and the moldability decreases, and molding tends to be difficult, especially in the case of injection molding.

Then, in the polyester resin composition (1) and the polyester resin composition (2) of the present invention,
As the PBT resin, one treated with water and / or steam is used. Here, the “PBT resin treated with water and / or steam” in the present invention means a PBT resin treated by contacting the PBT resin with water, water and steam or steam.

The temperature and treatment time of water and / or steam used for treating the PBT resin may vary depending on the shape and size of the PBT resin, the presence or absence of the copolymerization component in the PBT resin, and the like. The temperature of water and / or steam contacted with the resin is 60 to 150 ° C.
Then, the contact time is set to 15 seconds to 20 hours so that the processing time does not become extremely long and the PBT-based resin is allowed to uniformly and quickly absorb a predetermined amount of water, and other ester bond-containing thermoplastic It is preferable in that a PBT-based resin having less transesterification reaction with the resin can be obtained, and the treatment is performed with water and / or steam at a temperature of 70 to 130 ° C. for 1 minute to 15 hours. Is more preferable. If the temperature of water used for treatment is lower than 60 ° C, PBT
Unless the contact time between the water-based resin and water is extremely long, it becomes difficult to absorb water up to a predetermined moisture content, while if the temperature of water (hot water) and / or steam is higher than 150 ° C, the PBT system during treatment The degree of polymerization of the resin decreases, and the mechanical properties of the molded product obtained from the polyester resin composition are likely to deteriorate.

Generally, it is preferable to appropriately select the treatment time depending on the temperature of water and / or steam. When the temperature of water and / or steam is low, the treatment time is lengthened so that the temperature of water and / or steam is high. If it is higher, it is better to shorten the processing time. From this point of view, when using steam, a shorter treatment time is generally adopted than when using water (hot water). For example, when hot water of 60 to 100 ° C. is used, the treatment time is generally preferably 3 to 15 hours, and when steam of 100 to 150 ° C. is used, the treatment time is 30 seconds to 3 hours. Is preferred.

By treating the PBT resin with water and / or steam as described above, the PB resin is treated.
The T-based resin is in a state of absorbing water, but from the viewpoint of the water content of the PBT-based resin, water and / or water is added until the water content of the PBT-based resin becomes about 0.2 to 0.6% by weight. Alternatively, it is preferable to perform the treatment with steam, and the moisture content is 0.3 to 0.
More preferably, the treatment is carried out with water and / or steam up to 5% by weight.

The treatment of the PBT resin with water and / or steam is carried out by using the polyester resin composition (1) of the present invention.
Alternatively, the polyester-based resin composition (2) may be continuously produced at a stage before the production of the polyester-based resin composition (2) or the polyester-based resin composition. It may be carried out in advance completely separately from the production process of (1) or the polyester resin composition (2), and is not particularly limited.

When the PBT resin is treated with water and / or steam, the PBT resin is pelletized, powdered, ground, short fiber, long fiber, strand, film,
It is preferable to use a sheet having a large surface area so that the treatment can be effectively performed in a short time. In particular, when the PBT resin is in the form of pellets, powder, short fibers, etc., the maximum dimension should be about 5 mm or less, but if the PBT resin is continuous fibers or strands, the diameter Should be 3 mm or less, and if the PBT resin is a film or sheet, the thickness should be 2 mm.
It is preferable that the thickness is less than or equal to mm because water absorption can be performed quickly and uniformly in a short time. Further, as a method of bringing water and / or steam into contact with the PBT resin, a method of immersing the PBT resin in water, a method of spraying, spraying or jetting water and / or steam to the PBT resin are preferably used. .

The PBT resin treated with water and / or steam as described above is dried to a water content suitable for molding before being blended with other ester bond-containing thermoplastic resin and other components. use. PB after drying
The water content of the T-based resin is preferably set to the same level as or lower than that of the PBT-based resin normally used for molding, and specifically, the water content is preferably set to 50 ppm or less, and 30 ppm or less. Is more preferable. Any drying means may be used as long as it does not cause thermal decomposition of the PBT-based resin, deterioration of the degree of polymerization and modification of the PBT-based resin. For example, heating drying with hot air, an infrared heater, reduced pressure drying, natural drying, etc. Drying can be mentioned,
Hot air drying and reduced pressure drying are preferred from the viewpoint that water can be quickly removed. PB treated with water and / or steam
When the T-based resin is used as it is for the preparation of the polyester-based resin composition without being dried, foaming due to a large amount of water,
Care must be taken because problems such as molecular weight reduction due to hydrolysis are likely to occur.

Polyester resin composition (1) of the present invention
Alternatively, the polyester resin composition (2) contains water and / or
Alternatively, other ester bond-containing thermoplastic resin is contained as the component (b) together with the PBT resin treated with steam. Other ester bond-containing thermoplastic resins include PB
There may be mentioned thermoplastic polyester resins and polycarbonate resins other than T-based resins, and other ester bond-containing thermoplastic resins may be used alone or in combination of two or more. When two or more other ester bond-containing thermoplastic resins are used, even if two or more different thermoplastic polyester resins are used in combination, one kind or two or more kinds of thermoplastic polyester resins and one kind are used. Alternatively, two or more polycarbonate resins may be used in combination, or two or more different polycarbonate resins may be used in combination. Among them, polycarbonate resin and polyethylene terephthalate resin are preferable as other ester bond-containing thermoplastic resin used together with PBT resin, and when these resins are used, dimensional stability is improved and surface gloss is improved. It is possible to obtain effects such as improvement of

When a thermoplastic polyester resin other than the PBT-based resin is used as the other ester bond-containing thermoplastic resin, for example, an aliphatic dicarboxylic acid such as sebacic acid or adipic acid; isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc. Aromatic dicarboxylic acids; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid or their ester-forming derivatives, and hydroxyl groups such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, cyclohexanedimethanol, polytetramethyl glycol, bisphenol A It is possible to use a thermoplastic polyester obtained by a polycondensation reaction with a compound having two. More specific examples include polyethylene terephthalate, polypropylene terephthalate, polyethylene naphthalate, polycyclohexane dimethyl terephthalate, and copolymers thereof.

When a polycarbonate resin is used as the other ester bond-containing thermoplastic resin, a known non-halogenated polycarbonate resin obtained by reacting carbonic acid or a derivative thereof with glycol or a divalent phenol compound is used. Any of them can be used, and the production method of the polycarbonate resin is not particularly limited. Among them, a bisphenol-type polycarbonate resin obtained by reacting one or more bisphenol-based compounds such as bisphenol A or a nuclear alkylated derivative thereof with a carbonic acid ester or phosgene has good moldability and mechanical properties of molded articles. It is preferable in terms of low warpage and heat resistance. However, it is of course possible to use a branched polycarbonate resin in which a part of bisphenol A is replaced with a trifunctional or higher polyfunctional phenol such as a triphenol compound.

In the polyester resin composition (1) of the present invention, a halogenated polycarbonate is preferably used as a kind of the organohalogen flame retardant which is the component (c) as described below, but other ester bond is used. When a polycarbonate resin is used as the contained thermoplastic resin, a non-halogenated polycarbonate resin is generally used, and in this respect, the polycarbonate resin used as the other ester bond-containing thermoplastic resin is a component (c) (organic halogen-based hard resin). It is distinguished from the halogenated polycarbonate resin used as one type of (flammable agent).

Polyester resin composition (1) of the present invention
And in the polyester resin composition (2), [PBT
The ratio of [based resin]: [other thermoplastic resin containing ester bond] is preferably 95: 5 to 50:50 by weight,
It is more preferably 90:10 to 60:40. PB
Based on the total weight of the T-based resin and the other ester bond-containing thermoplastic resin, the proportion of the other ester bond-containing thermoplastic resin is less than 5% by weight (the proportion of the PBT-based resin is 95%.
If it is more than 5% by weight), the dimensional accuracy of the molded product, surface gloss, etc. will deteriorate, while the other ester bond-containing thermoplastic resin will be 5%.
If the amount is more than 0% by weight (the amount of PBT-based resin is less than 50% by weight), the solidification rate is lowered and the molding cycle is delayed.

The polyester resin composition (1) of the present invention further contains an organohalogen flame retardant as the component (c), in addition to the PBT resin and the other thermoplastic resin containing an ester bond. As the organic halogen-based flame retardant, any of known low molecular weight organic compounds and high molecular weight organic compounds having a halogen atom in the molecule known to have a flame retardant effect can be used, and among them, halogen is bromine. The organic halogen-based flame retardant is preferably used. Further, in the organic halogen-based flame retardant, the halogen content in the molecule is preferably 20% by weight or more. When the halogen content in the molecule is less than 20% by weight, the flame retarding effect becomes small, and it becomes necessary to add a large amount of flame retardant, and accordingly, the necessary amount of the flame retardant aid also increases. The mechanical properties of the molded product are likely to deteriorate.

Specific examples of the organic halogen flame retardant include:
High molecular weight organic halogen compounds such as halogenated polycarbonate, halogenated acrylic resin, halogenated epoxy resin, halogenated phenoxy resin, halogenated polystyrene and halogenated polyphenylene ether; decabromodiphenyl ether, hexabromophenol, tetrabromobisphenol A, tetrabromo Mixture of bisphenol A and phenol, epoxidized tetrabromobisphenol A, tetrabromobisphenol A
-Ethyl ether oligomer, tetrabromobisphenol A-bis (2,3-dibromopropyl ether),
Brominated bisphenol A such as tetrabromobisphenol A.bis (allyl ether), tetrabromobisphenol A.2-hydroxyethyl ether, carbonate oligomer of tetrabromobisphenol A, hexabromobenzene, tetrabromophthalic anhydride, tribromophenol, bis (Tribromophenoxy) ethane, polydibromophenylene oxide, bis (pentabromophenoxy) ethane, ethylenebistetrabromophthalimide, brominated styrene, tetrabromobisphenol S, tetrabromobisphenol S bis (2,2
Examples thereof include low molecular weight organic halogen compounds such as 3-dibromopropyl ether), and these organic halogen flame retardants may be used alone or in combination of two or more kinds. Among the above organic halogen-based flame retardants, halogenated polycarbonate, halogenated phenoxy resin, halogenated polystyrene, halogenated acrylic resin and the like are preferable from the viewpoint of flame retarding effect and safety.

The content of the organic halogen-based flame retardant is PBT.
Total of 10 series resins and other ester bond-containing thermoplastic resins
It is preferably 10 to 40 parts by weight, more preferably 15 to 30 parts by weight, based on 0 parts by weight. When the content of the organic halogen-based flame retardant is less than 10 parts by weight, the flame retardancy of the polyester resin composition (1) and a molded product obtained therefrom tends to be insufficient, while when it is more than 40 parts by weight, the molded product is increased. The mechanical properties of are likely to deteriorate.

The flame-retardant polyester resin composition (1) of the present invention comprises (d) together with an organic halogen-based flame retardant.
It also contains a flame retardant aid as a component. As the flame retardant aid, an inorganic flame retardant aid is preferable, and specifically, antimony oxides (antimony trioxide, antimony tetraoxide, antimony pentoxide, etc.), antimony compounds such as sodium antimonate, barium metaborate, zinc borate. Examples thereof include boron compounds. The content of the flame retardant aid in the polyester resin composition (1) is 100 in total of the PBT resin and other ester bond-containing thermoplastic resin.
It is preferably 3 to 15 parts by weight with respect to parts by weight,
It is more preferably 6 to 12 parts by weight. Content of flame retardant aid is 3
If it is less than 15 parts by weight, it becomes difficult to obtain a sufficient flame retardant effect, while if it is more than 15 parts by weight, the mechanical properties of the molded article obtained from the polyester resin composition (1) deteriorate.
It is not preferable because heat resistance is deteriorated. Further, in the polyester resin composition (1) of the present invention, other flame retardant aids such as boron oxide, zirconium oxide, iron oxide and the like may be used together with the above flame retardant aid. .

Polyester resin composition (1) of the present invention
In addition to the above components, the polyester resin composition (2) effectively suppresses the transesterification reaction between the PBT resin and another thermoplastic resin containing an ester bond, and melts, if necessary. In order to improve the stability, one kind or two or more kinds of metal deactivators can be contained.
Specific examples of the metal deactivator include an alkyl acid phosphate compound, an oxalic acid amide compound, and a hydrazide compound. These may be used alone or in combination of two or more. When the metal deactivator is contained, the content of the metal deactivator is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight in total of the PBT-based resin and the other ester bond-containing thermoplastic resin, 0.1 to 1 part by weight is more preferable. Content of metal deactivator is 0.01
If it is less than the above range, the transesterification reaction between the PBT-based resin and the other ester bond-containing thermoplastic resin may not be effectively suppressed, while even if the content of the metal deactivator is more than 5 parts by weight. The effect of suppressing the transesterification reaction is not further improved, but conversely, problems such as deterioration in hydrolysis resistance and thermal coloring during melting tend to occur.

Furthermore, the polyester resin composition (1) and the polyester resin composition (2) of the present invention may contain various conventionally known inorganic fillers and organic fillers, if necessary. Examples of such a filler, surface-treated or not, glass fibers, carbon fibers, aluminum fibers, stainless fibers, metal fibers such as brass fibers, silicon nitride whiskers, aluminum silicate whiskers, magnesium silicate whiskers such as Inorganic fiber compounds, glass flakes, mica, talc, kaolin, wollastonite, calcium carbonate, inorganic fillers such as potassium titanate, aramid fibers, organic fillers such as powdered epoxy compounds and the like, these can be mentioned. They can be used alone or in combination of two or more. Further, the polyester-based resin composition (1) and the polyester-based resin composition (2) of the present invention further include various conventionally known additives such as an ultraviolet absorber, a lubricant, a release agent, and an antistatic agent, if necessary. Agents, antioxidants, crystal nucleating agents, colorants such as dyes and pigments, plasticizers, and thermoplastic elastomers.

The polyester resin composition (1) of the present invention containing PBT-based resin, other ester bond-containing thermoplastic resin, organic halogen-based flame retardant and flame retardant auxiliary as essential components is polybutylene. The transesterification reaction between the terephthalate-based resin and the other thermoplastic resin having an ester bond is suppressed, the stability during melt processing is improved, and the moldability and releasability are excellent, and the molded product obtained from it Has a good appearance without surface roughness, has excellent physical properties such as dimensional stability, mechanical properties, heat resistance, etc., and is extremely excellent in flame resistance due to the inclusion of organic halogen-based flame retardants and flame retardant aids. It has flammability, dimensional stability,
It can be effectively used for applications such as electric parts and electronic parts, which are strongly required to have flame retardancy as well as mechanical properties and heat resistance.

On the other hand, the polyester resin composition (2) of the present invention containing the PBT resin and the other thermoplastic resin containing an ester bond and containing neither the organic halogen flame retardant nor the flame retardant auxiliary is flame retardant. However, the transesterification reaction between the polybutylene terephthalate-based resin and the other thermoplastic resin having an ester bond is suppressed during heating and melting, which improves the stability during melt processing and improves moldability and release. It has excellent moldability, and the molded product obtained from it has a good appearance without surface roughness, and has excellent physical properties such as dimensional stability, mechanical properties, and heat resistance.
While being required to have excellent properties such as mechanical properties and heat resistance, it can be effectively used for applications such as automobile parts and office supplies where flame retardancy is not required so much. The polyester resin composition (2) containing no organic halogen-based flame retardant and flame retardant auxiliary is inferior to the polyester resin composition (1) in flame retardance, but Since it does not contain a flame retardant aid, it is generally superior to the polyester-based resin composition (1) in terms of mechanical properties, particularly toughness, and should be used effectively in the above-mentioned applications by taking advantage of these properties. You can

Polyester resin composition (1) of the present invention
The method for preparing the polyester resin composition (2) is not particularly limited, and any known method conventionally used for preparing a polyester resin composition can be adopted. For example, chip-shaped PB treated with water and / or steam
T-based resin, other ester-bond-containing thermoplastic resin, organic halogen-based flame retardant and flame-retardant auxiliaries; or chip-shaped PBT-based resin treated with water and / or steam and other ester-bond-containing thermoplastic resin, If necessary, other additives are mixed in advance using a mixer such as a tumbler or a Henschel mixer, then supplied to a single-screw or twin-screw extruder, melt-kneaded and extruded to an appropriate size. The polyester resin composition (1) and the polyester resin composition (2) of the present invention in the form of pellets or other forms can be obtained by cutting into pieces.
At that time, the temperature at the time of melt-kneading, the residence time in the molten state, etc. are not particularly limited, but generally, at a temperature of 230 to 270 ° C., under the condition that the time in the molten state is 20 to 90 seconds. It is preferable to carry out melt-kneading in order from the viewpoints of suppressing the transesterification reaction between the PBT-based resin and the other ester bond-containing thermoplastic resin, suppressing thermal coloring during heating and melting, and the like.

Polyester resin composition (1) of the present invention
The polyester resin composition (2) can be molded by using a molding method and a molding device that are generally used for polyester resins. For example, it can be molded by any molding method such as injection molding, extrusion molding, press molding, blow molding, calender molding, etc., whereby electric parts, electronic parts, mechanical parts, automobile parts, pipes, sheets, films, It is possible to manufacture molded products of any shape and application such as household goods, and especially electric parts, electronic parts, mechanical parts, by injection molding, etc.
Suitable for manufacturing automobile parts, office supplies, daily necessities and other molded products. The melt-kneading temperature during molding and the residence time in the molding machine are not particularly limited, but the polyester-based resin composition (1) and the polyester-based resin composition (2)
In the same manner as in the case of preparing, the melt-kneading is generally performed at a temperature of 230 to 270 ° C., and the time of being in a molten state is 20 to 90.
It is preferable to carry out the molding under the condition of a second from the viewpoints of suppressing the transesterification reaction between the PBT resin and the other ester bond-containing thermoplastic resin, and maintaining the whiteness and hue of the molded product.

[0039]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the following examples and comparative examples, the thermal stability (transesterification resistance) of the polyester resin composition during melting was evaluated as follows.

Thermal stability during melting of the polyester resin composition
Qualitative property (transesterification resistance) : melting point and crystallization peak temperature derived from the crystallinity of polyester by employing differential scanning calorimetry (DSC) for the polyester resin compositions of the following examples and comparative examples. Was measured to evaluate the thermal stability (transesterification resistance) of the polyester resin composition when melted. That is, DS
The pellets made of the polyester resin composition of each Example or Comparative Example were heated from room temperature to 290 ° C. at a heating rate of 20 ° C./min by C, and the pellets were held at 290 ° C. for 10 minutes, and then at 20 ° C. / The temperature is decreased to room temperature at a temperature decrease rate of minutes, and the temperature is again increased from room temperature to 290 ° C. at a temperature increase rate of 20 ° C./minute,
The melting point peak temperature (Tm ₁ ) and the heat of fusion (ΔHm ₁ ) during the _first temperature increase, and the crystallization temperature peak temperature (Tc) during the temperature decrease.
c) the crystallization heat (△ Hcc), and a second melting peak temperature during heating (Tm ₂₎ and heat of fusion (△ Hm ₂₎
Measured, thermal stability during melting (transesterification resistance)
Was examined to evaluate the thermal stability of the polyester resin composition during melting.

Example 1 (1) 100 parts by weight of dimethyl terephthalate, 1,4-
60 parts by weight of butanediol and 0.04 parts by weight of tetraisopropyl titanate were charged into a transesterification reaction tank and heated under a normal pressure while gradually raising the temperature from 145 ° C to 230 ° C to carry out the transesterification reaction. The transesterification reaction was stopped when part by weight was distilled (required time: about 2 hours). Now switch the system to reduced pressure,
Under reduced pressure (0.3 mmHg), the resin temperature was set to 240 ° C. and the polycondensation reaction was performed for 90 minutes. After the reaction, the reaction tank was pressurized with nitrogen gas, the PBT resin generated from the bottom of the reaction tank was extruded out of the tank, taken out, and cut into chips.
The intrinsic viscosity [η] of the obtained PBT resin chip was 0.9, and the b value (coloring value) was 3.

(2) After 100 parts by weight of the PBT resin chip obtained in the above (1) was immersed in 300 parts by weight of hot water having a temperature of 60 ° C. for 20 hours (the water content of the PBT resin chip at this time: 0 0.5% by weight) and hot air having a temperature of 60 ° C. was used to dry the PBT resin chip until the water content became 50 ppm or less. (3) Dry PBT resin chip 8 obtained in (2) above
0 parts by weight, 20 parts by weight of polycarbonate resin (“Panlite L1250” manufactured by Teijin Chemicals), 20 parts by weight of brominated polycarbonate (“BC-58” manufactured by Great Lakes) and antimony trioxide (“PATOX
L ”) 10 parts by weight are supplied to a twin-screw extruder (manufactured by Japan Steel Works), melt-kneaded at a cylinder temperature of 240 ° C., extruded from a die into a strand having a diameter of 2.5 mm, water-cooled and cut to obtain a long length. A pellet-shaped PBT resin composition having a size of about 3 mm was produced.

(4) Using the pellets of the PBT resin composition obtained in the above (3), the melting point peak temperature (Tm ₁ ) and the heat of fusion (ΔH
m _1), heat peak temperature (Tcc) and crystallization of the crystallization temperature during cooling (△ Hcc), and a second melting peak temperature during heating (Tm ₂₎ and heat of fusion (△ Hm ₂₎ The measurement was performed to examine the thermal stability during melting (transesterification resistance). The results are shown in Table 1 below.

Example 2 In the step (2) of Example 1, the PBT resin chip was immersed in hot water at 80 ° C.
Was carried out in hot water for 5 hours (water content of PBT resin chip at this time: 0.6% by weight), the same procedure as in Example 1 was carried out to treat PBT resin with water (hot water) and PBT resin. Composition pellets were produced, and the obtained PBT resin composition pellets were used to perform melting point peak temperature (Tm ₁ ) and heat of fusion (ΔHm
_1), heat peak temperature (Tcc) and crystallization of the crystallization temperature during cooling (△ Hcc), and a second melting peak temperature during heating (Tm ₂₎ and heat of fusion (△ Hm ₂₎ Measurement Then, the thermal stability at the time of melting (transesterification resistance) was examined. The results are shown in Table 1 below.

Example 3 In the step (2) of Example 1, instead of immersing the PBT resin chip in hot water of 60 ° C. for 20 hours, the PBT resin chip was sprayed and contacted with steam of 120 ° C. for 2 minutes. (Water content of PBT resin chip at this point: 0.6% by weight) and subsequent drying is performed for 12
The same procedure as in Example 1 was repeated except that the moisture content of the PBT resin chip was reduced to 50 ppm or less with hot air at 0 ° C.,
Steam treatment of PBT resin and production of PBT resin composition pellets were performed, and using the obtained PBT resin composition pellets, melting point peak temperature (Tm ₁ ) at the time of the _first temperature rise and melting Amount of heat (ΔHm ₁ ), peak temperature of crystallization temperature (Tcc) at the time of temperature decrease and heat amount of crystallization (ΔHcc), and melting point peak temperature (Tm ₂ ) at the time of the second temperature rise and heat of fusion (Δ) Hm ₂ ) was measured to examine the thermal stability (transesterification resistance) during melting. The results are shown in Table 1 below.

Example 4 150 PBT resin chips
℃ steam was sprayed and contacted for 30 seconds (P at this point)
(Moisture content of BT resin chip: 0.6% by weight), the same procedure as in Example 3 was performed to perform steam treatment of PBT resin and P treatment.
PBT obtained by producing BT resin composition pellets
Using the pellets of the resin composition, the melting point peak temperature (Tm ₁ ) and the heat of fusion (ΔHm ₁ ) at the time of the _first temperature rise, and the peak temperature (Tm) of the crystallization temperature at the time of temperature decrease (T
cc) and the heat of crystallization (ΔHcc), and the melting point peak temperature (Tm ₂ ) and the heat of fusion (ΔHm) during the _second temperature increase.
₂ ) Measured to examine the thermal stability (transesterification resistance) during melting. The results are shown in Table 1 below.

Comparative Example 1 Using the PBT resin chip obtained in the step (1) of Example 1 as it is, a pellet of the PBT resin composition was produced in the same manner as in the step (3) of Example 1, Using the pellets of the PBT resin composition thus obtained, the melting point peak temperature (Tm ₁ ) and the heat of fusion (ΔHm ₁ ) at the time of the _first temperature increase and the crystallization temperature at the time of temperature decrease were measured by the above-mentioned DSC. peak temperature (Tcc) and crystallization heat (△ Hcc), and a second melting peak temperature during heating (Tm ₂₎ and heat of fusion (△ Hm ₂₎ were measured, the thermal stability during melting ( Transesterification resistance) was investigated. The results are shown in Table 1 below.

Example 5 In the step (3) of the example 1, 80 parts by weight of the dry PBT resin obtained in the step (2) of the example 1 was added without adding the flame retardant and the flame retardant auxiliary. 20 parts by weight of a polycarbonate resin is fed to a twin-screw extruder, melt-kneaded at a cylinder temperature of 240 ° C., and a diameter of 2.5 from a die.
mm extruded into a strand, water-cooled and cut to produce a pellet-shaped PBT resin composition having a length of about 3 mm. Using the pellets of the obtained PBT resin composition, the above DS
The melting point peak temperature (Tm ₁ ) during the _first temperature rise due to C
And heat of fusion (△ Hm ₁ ), peak temperature of crystallization temperature (Tcc) during cooling and heat of crystallization (△ Hcc), and melting point peak temperature (Tm ₂ ) and heat of fusion during second heating (△
Hm ₂ ) was measured to examine the thermal stability (transesterification resistance) during melting. The results are shown in Table 1 below.

Comparative Example 2 Using the PBT resin pellet obtained in the step (1) of Example 1, as it is, 80 parts by weight of the PBT resin pellet and 20 parts by weight of the polycarbonate resin were supplied to a twin-screw extruder, The mixture was melt-kneaded at a cylinder temperature of 240 ° C., extruded from a die into a strand having a diameter of 2.5 mm, cooled with water, and then cut to obtain a pellet-shaped PBT resin composition having a length of about 3 mm. Using the pellets of the obtained PBT resin composition, the melting point peak temperature (Tm ₁ ) and the heat of fusion (ΔH
m _1), heat peak temperature (Tcc) and crystallization of the crystallization temperature during cooling (△ Hcc), and a second melting peak temperature during heating (Tm ₂₎ and heat of fusion (△ _Hm 2) The measurement was performed to examine the thermal stability during melting (transesterification resistance). The results are shown in Table 1 below.

[0050]

[Table 1]

From the results shown in Table 1 above, the polyester resin composition of the present invention containing the flame retardant and the flame retardant aid of Examples 1 to 4 using the PBT resin treated with water or steam, and In the case of the polyester resin composition of the present invention which does not contain the flame retardant and the flame retardant aid of Example 5 in which the PBT resin treated with water or steam is used, the melting point peak at the time of the first heating The difference between the temperature (Tm ₁ ) and the melting point peak temperature (Tm ₂ ) during the _second temperature increase is small, and the heat of fusion (ΔHm ₁ ) during the first temperature increase and the _second temperature increase Difference from the heat of fusion (ΔHm ₂ ) of the crystallization, and the peak temperature (Tcc) of the crystallization temperature during cooling
Is high and the amount of heat of crystallization (ΔHcc) is large, the physical properties of the polyester resin composition are not significantly deteriorated even when it is heated and melted, and the thermal stability upon melting is excellent, that is, PB.
It can be seen that the transesterification reaction between the T-based resin and the polycarbonate resin is unlikely to occur.

On the other hand, Comparative Example 1 in which the PBT resin obtained by polymerization is used as it is without being treated with water or steam.
The polyester resin composition containing the flame retardant and the flame retardant auxiliary agent, and the flame retardant and the flame retardant auxiliary agent of Comparative Example 2 which are used as they are without treating the PBT resin obtained by the polymerization with water or steam. In the case of the polyester resin composition not containing, the melting point peak temperature (T
m ₁ ) and the melting point peak temperature (Tm ₂ ) during the _second temperature increase
And the heat of fusion during the first temperature rise (△ Hm ₁ )
And the heat of fusion (ΔHm ₂ ) at the time of the second temperature rise are all significantly larger than those in Examples 1 to 5, and the peak temperature of the crystallization temperature during the temperature decrease ( Tc
c) is low and the amount of heat of crystallization (ΔHcc) is small, the physical properties of the polyester resin composition are significantly lowered by heating and melting, and the thermal stability at the time of melting is inferior.
It can be seen that the transesterification reaction between the resin and the polycarbonate resin is likely to occur.

[0053]

EFFECT OF THE INVENTION PB treated with water and / or steam
In the polyester resin composition of the present invention containing the T-based resin and the other ester bond-containing thermoplastic resin, the transesterification reaction between the PBT resin and the other ester bond-containing thermoplastic resin is effectively suppressed. Since the thermal stability at the time of melting is good, there is little deterioration in the physical properties of the polyester-based resin composition even when heated and melted, excellent moldability and mold releasability, and a good appearance without surface roughness, It is possible to smoothly obtain a molded product having extremely excellent various properties such as dimensional stability, mechanical properties and heat resistance. And, in the case of the polyester resin composition of the present invention which further contains an organic halogen flame retardant and a flame retardant auxiliary together with the PBT resin and other ester bond-containing thermoplastic resin treated with water and / or steam, It is possible to obtain a molded product which is excellent in flame retardancy in addition to the various excellent properties described above, and the molded product obtained as a result is required to be flame retardant including electric / electronic parts. It can be effectively used for the purpose.

Claims (5)

[Claims] 1. (a) Polybutylene terephthalate-based resin treated with water and / or steam; (b) At least one thermoplastic resin having an ester bond other than polybutylene terephthalate-based resin; (c) Organic halogen-based resin A flame-retardant polyester resin composition comprising a flame retardant; and (d) a flame retardant aid. 2. The ratio of the polybutylene terephthalate resin (a): the thermoplastic resin (b) having an ester bond other than the polybutylene terephthalate resin is 9 by weight.
It is 5: 5 to 50:50, and 10 to 4 of the organohalogen flame retardant (c) is added to 100 parts by weight of the polybutylene terephthalate resin (a) and the thermoplastic resin (b).
The flame-retardant polyester resin composition according to claim 1, which contains 0 part by weight and the flame retardant aid (d) in a proportion of 3 to 15 parts by weight. 3. At least one of (a) a polybutylene terephthalate resin treated with water and / or steam and (b) a thermoplastic resin having an ester bond other than the polybutylene terephthalate resin is contained. Polyester resin composition. 4. The ratio of polybutylene terephthalate resin (a): thermoplastic resin (b) having an ester bond other than polybutylene terephthalate resin is 9 by weight.
The polyester resin composition according to claim 3, which is 5: 5 to 50:50. 5. A molded article made of the polyester resin composition according to claim 1.