JPH01144453A - Flame-retardant polyester resin composition having excellent impact resistance - Google Patents

Abstract

PURPOSE:To obtain the title resin composition having improved impact strength and excellent flame retardance, by blending a copolyester of a specific composition with a metallic salt of a copolymer of an alpha-olefin and alpha,beta-unsaturated carboxylic acid and flame retardant. CONSTITUTION:A composition consisting of (A) 100 pts.wt. copolyester, consisting of structural units expressed by formulas I-IV (R is bifunctional group after removing COOH from a >=9C, preferably 16-54C aliphatic dicarboxylic acid; n is 8-84, preferably 8-28), and characterized by the units expressed by formulas I and II respectively bonded to the units expressed by formulas III and/or IV in the total number of mol of the units expressed by formulas I and II equal to that of the units expressed by formulas III and IV, etc., (B) 3-100 pts.wt. metallic salt of a copolymer of an alpha-olefin and alpha,beta-unsaturated carboxylic acid and, as necessary, other vinyl monomers [preferably Na, K salts, etc., of ethylene (meth)acrylic acid copolymer] and (C) 3-50 pts.wt. flame retardant.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a polyester with improved physical properties, particularly improved impact strength, excellent anti-flammability properties, and excellent molding processability such as injection molding. The present invention relates to a resin composition.

[Conventional technology]

Polyethylene terephthalate (hereinafter sometimes referred to as PET) has excellent heat resistance, chemical resistance, mechanical properties, electrical properties, etc., and is used in many industrial products as fibers, films, etc. In particular, 9P reinforced with inorganic fillers such as glass fibers has been widely used in engineering plastics and the like in recent years because it has significantly improved thermal and mechanical properties.

However, the impact resistance of PET molded products is not necessarily sufficient, and problems often occur in which the molded products break during secondary processing, transportation, and use. Poly(1,4-butylene terephthalate) (hereinafter referred to as PBT), which is the same thermoplastic polyester
(sometimes abbreviated as ), its impact resistance is inferior.

As a method for improving the impact resistance of PET, it is common to blend a certain kind of elastic polymer into PET. Copolymers of α-olefin and α-olefin have been disclosed as impact modifiers for polyester resins. Japanese Patent Publication No. 45-26224 discloses a copolymer of acrylic acid ester and conjugated diene as an impact modifier for polyester resin. Special Public Service 1977
Publication No. 26225 discloses an ionomer as an impact modifier for polyester resin. However, it cannot be said that the desired impact strength of the molded product obtained by the above method is sufficiently improved.

Various other methods are known for modifying the impact strength of polyester resins. For example, JP-A-51-1444
No. 52, JP-A-52-32045, JP-A-Sho 5
3-117049 etc., α-olefin and α,
A method of blending a copolymer comprising β-unionized carboxylic acid glycidyl ester with a polyester resin is disclosed. In addition to this copolymer, a method of using an ethylene copolymer as a third component was disclosed in JP-A-58-17.
148 and JP-A-58-17151, a method of using polyphenylene sulfide in combination is disclosed in JP-A-57-1989.
It is disclosed in Japanese Patent No. 92044.

Even with these methods, it is difficult to say that sufficient impact strength can be obtained.

Aromatic polycarbonate resin is well known as the resin with the highest impact resistance among plastics.
There have been attempts to improve the plaster resistance of PET by blending it with ET for a long time.
5). Recent patents such as U.S. Patent No. 425793
No. 7 discloses a combination of polyacrylate resin and aromatic polycarbonate resin as an impact strength modifier for polyester resin. With this method, considerably high impact strength can be obtained9. Furthermore, JP-A-59-16146
In Publication No. 0, when modifying the impact strength of PET with polyacrylate resin and aromatic polycarbonate resin, an effective amount of BoIJ (1,4-butylene terephthalate) is added.
)1-It was shown that when used in combination, the impact resistance was further improved. However, even at its highest value, the impact strength (Izod impact strength) obtained with this method is only close to that of the PBT/polyacrylate resin/aromatic polycarbonate resin composition, and has not reached a higher value. The inventors previously published Japanese Patent Application Laid-Open No. 61-2074.
In No. 59, a predetermined amount of P is added to PET polyester.
It is disclosed that the impact strength of the molded product is extremely high by using a BT polyester in combination and further modifying with a predetermined amount of a metal salt of a polymer having a specific carboxyl group.

However, since the nuclear kneaded polyester is kneaded with PET-based polyester and PBT-based polyester at high temperatures, transesterification reactions are likely to occur.
When trying to recover and effectively utilize raw materials by mixing them with unformed raw materials, there are inadequacies such as the high impact strength that may not be obtained when molding with only unformed raw materials.

Furthermore, in a composition in which a conventional elastic polymer is blended with a polyester resin, a decrease in impact strength was observed when exposed to high temperatures for a long period of time. Another problem is that molding processability is poor, making it impossible to obtain molded products with good surface gloss and mold releasability.

On the other hand, as the use of polyethylene terephthalate as an engineering plastic expands, there is an increasing demand for fire safety, especially in electrical and electronic parts, automobile parts, and building materials. There is a need for things to be flame retardant, and the U.S. UL
Various regulations regarding flame retardancy, such as standards, are being strengthened or made mandatory. Polyethylene terephthalate itself is flammable, and it is necessary to use various flame retardants to achieve UL94V-Q in flammability evaluation according to UL standards. Conventionally, techniques have been proposed to add various halogenated organic compounds to polyethylene terephthalate to impart flame retardancy. Aromatic halogen compounds with a relatively high carbon content, as well as inorganic compounds such as antimony trioxide, are used in combination as flame retardant aids. Also, regarding the method of using halogenated bisphenol A type epoxy resin as a flame retardant.

The epoxy group at one end of the resin is reacted with a halogenated phenol to produce a one-terminally blocked epoxy resin having one epoxy group in the molecule (Japanese Patent Publication No. 18068/1983, 15256/1983, No. 56-32538) and a method using a high-density halogenated bisphenol A type epoxy resin with a high degree of polymerization (JP-A No. 58-118849,
No. 60-171713, No. 61-293257, U
SP4605708) etc. are known.

However, in order to improve impact resistance and impart flame retardancy, it has been difficult to achieve both performance by simply combining conventional techniques. The presence of flame retardants or flame retardant aids, which are added in order to impart flame retardancy, often lowers impact resistance.

[Problem that the invention seeks to solve]

The first object of the present invention is to create a flame-retardant polyester that maintains the excellent physical properties of conventional polyethylene terephthalate, has extremely improved impact strength, and suppresses the drop in impact resistance when exposed to high temperatures for long periods of time. An object of the present invention is to provide a resin composition. A second object of the present invention is to provide a polyethylene terephthalate resin composition that provides a molded article with excellent surface gloss and mold releasability.

[Means for solving problems]

As a result of intensive studies aimed at achieving the above objectives, the present inventors modified a copolyester of a specific composition with a metal salt of a copolymer of an α-olefin and an α,β-unsaturated carboxylic acid. By doing this, the impact resistance of the molded products becomes extremely high, and flame retardancy can be imparted by adding flame retardants. Even if it is mixed with raw materials and molded, only the unformed raw materials are molded, and tt! The composition of the present invention exhibits a high impact strength almost equivalent to that of a polyethylene terephthalate resin composition, and more surprisingly, it maintains high impact strength even when exposed to a high temperature of 150°C for a long time. The present invention was accomplished by discovering that the original properties (such as heat resistance and mechanical strength) of the material are sufficiently maintained.

Already, the present invention provides (1)) a copolymerized polyester consisting essentially of structural units represented by the following (1) to (IV), and (II)
I)÷0-CH2-CH2-0-)(■)+0+cH2
cCH2CH2CH2-0su+ (However, R is a divalent group obtained by removing the carboxyl group from an aliphatic dicarboxylic acid with 9 μ carbon atoms, and n is the ring number of 8 to 84.) (1) is (II ) and/or (IV), (■) is bonded to (rl) and /ma9 is bonded to (IV), and substantially the total number of moles of (1) and (II) is ( I
equal to the total number of moles of f) and (IV), and (II) is 0 to ioo moles of (i) in the copolymerized polyester.
．． At a ratio of 2 to 10 moles, (■) is +CH2CH2CH
The repeating unit of 2CH20÷ is contained in a proportion of 1 to 20 moles. 100 parts by weight of copolyester α-
Metal salt of a copolymer of an olefin and an α,β-nonosmotic carboxylic acid and optionally a third vinyl monomer 3 to 100
Parts by weight (C): A polyester resin composition with excellent impact resistance, consisting of 3 to 50 parts by weight of refractory agent. The present invention will be explained in detail below.

The copolymerized polyester (A) used in the present invention has one of the major drawbacks of polyethylene terephthalate. : It is a t-copolymerized polyester with dramatically improved lle properties. The present inventors have conducted extensive studies with the aim of improving the eyelid properties of polyethylene terephthalate and imparting strong toughness, and have developed polyethylene terephthalate (■).
We succeeded in improving the sound quality by introducing the units of and (■).9. The high impact resistance of the composition of the present invention is based on the fact that the composition contains the copolyester. Copolymerized polyester (6)
The unit represented by (I) is a unit derived from ester-forming derivatives of terephthalic acid, such as dimethyl terephthalate and diethyl terephthalate. A small amount of the unit (1) may be replaced with a unit based on a dicarboxylic acid component other than terephthalic acid or its ester-forming derivative μ within a range that does not completely impair the effects of the present invention.

The unit represented by (II) is a unit derived from an aliphatic dicarboxylic acid having 9 or more carbon atoms or an ester-forming derivative thereof. Regarding the number of carbon atoms in the aliphatic dicarboxylic acid, the number of carbon atoms in the main chain between the carboxyl groups of the dicarboxylic acid (excluding carbon atoms in the carboxyl group) is preferably 7 or more, and the main chain may optionally have a branch chain. or may partially form a ring. Among aliphatic dicarboxylic acids forming a ring, the number of carbon atoms between carboxyl groups is the minimum. Such aliphatic dicarboxylic acids having 9 or more carbon atoms include, for example, azelaic acid, sepacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid, eicosandicarboxylic acid, and dimer acid. , dimer acid hydrogenated products, or ester-forming derivatives thereof. The aliphatic dicarboxylic acids or their ester-forming derivatives may be used alone or in combination of two or more. Particularly preferred dicarboxylic acids in the present invention are dimer acids and dimer acid hydrogenated products. The dimer acids in the present invention include unsaturated fatty acids containing 18 carbon atoms such as meric acid and lylunic acid, or their monovalent dicarboxylic acids. It is produced from alcohol ester, and its main component is dimer acid with 36 carbon atoms, but -
Some basic acids and trimer acids are also included. In order to achieve the object of the present invention, it is preferable to use a dimer acid with a low content of -basic acid and trimer acid.

The unit of (n) is 0.2 per 100 moles of the unit of (1)
It is preferably contained in a proportion of mol or more and 10 mol or less, preferably 5 mol or less, and more preferably 3 mol or less. Within this range, the crystallized product of the copolyester maintains high stiffness and exhibits excellent ductility, thereby imparting high impact strength to the composition of the present invention. 0.2
If the ratio is less than mol, the toughness cannot be sufficiently improved as in the case where polytetramethylene glycol is used alone as a copolymer component. Seriously, if the ratio exceeds 10 moles,
The melting point of the crystallized product decreases greatly and the rigidity is also impaired, which is not suitable for the purpose of the present invention.

Furthermore, in the present invention, poly(tetramethylene oxide) is
The brittleness of polyethylene terephthalate crystallized products, which is slightly improved by modification with glycol alone, is dramatically improved. This effect is not achieved with aliphatic dicarboxylic acids having less than 9 carbon atoms.

Further, there is no particular upper limit to the number of carbon atoms in the aliphatic dicarboxylic acid, but from a practical standpoint, those with 100 or less are preferably used. The aliphatic dicarboxylic acid more preferably used has carbon atoms in the range of 16 to 54. The unit represented by 0 (fll) is a unit derived from ethylene glycol.

The unit represented by (IV) is a unit derived from poly(tetramethylene oxide) glycol. The use of poly(tetramethylene oxide) glycol as a copolymerization component is necessary to improve the brittleness of the substantially non-oriented crystallized product of polyethylene terephthalate, and 100 moles of terephthalic acid units are used in the copolymerization reaction. The repeating unit in poly(tetramethylene oxide) glycol (-CH2CH2CH
2CH2-0÷ is 1 mol to 20 mol, preferably 3 mol to 15 mol, more preferably 3 mol to 10
It is preferable that it is contained in a molar or less proportion. If the copolymerization ratio is small, it will not be possible to improve the brittleness of polyethylene terephthalate, and as the copolymerization ratio increases, the rigidity of the crystallized product will decrease and the melting point will also decrease significantly, which is contrary to the purpose of the present invention. .

In addition, the molecular weight of poly(tetramethylene oxide) glycol is approximately 600 to 6,000 (degree of polymerization (n): 8 to
84). Use of poly(tetramethylene oxide) glycol having a molecular weight outside the above range is not preferred because ductility decreases.

A more preferable molecular weight range is about 600-2,000 (degree of polymerization (n): 8-28).

When obtaining the copolymerized polyester (6) of the present invention, a small amount of glycerin, trimethylalpropane, pentaerythritol, hexanetriol 1,2,6,) limethylolethane, etc., within a range that does not impair the effects of the present invention, etc. Triols or tetraols represented by , benzene tricarboxylic acid or benzene tetracarboxylic acid represented by trimellitic acid, trimesic acid, pyromellitic acid, or 3 to 4 hydroxyl groups and carboxyl groups Binding polyfunctional monomers such as polyvalent hydroxycarboxylic acids, aliphatic monocarboxylic acids such as stearic acid and oleic acid, and monofunctional monomers of aromatic monocarboxylic acids such as benzoic acid, phenylacetic acid, diphenylacetic acid, and β-naphthoic acid. Can also be used together.

The copolyester (A) in the present invention is usually produced by a known method used for producing polyester. Generally, the copolyester is prepared by heating a mixture of reaction components in the presence or absence of a catalyst at atmospheric pressure or It is produced by raising the temperature in an inert gas atmosphere under pressure.The temperature employed for carrying out these reactions is in the range of 200°C to 270°C, preferably 230°C.
It is in the range of ℃ to 260℃. After completion of this reaction, the resulting oligomer product is subjected to polycondensation. The nuclear polycondensation reaction is performed using known antimony, titanium, iron, zinc, co/(ru)
, lead, manganese, ma7?1. from about 270'C to about 300°C in the presence of a polycondensation catalyst such as a germanium catalyst at a pressure of 15 μHg or less, preferably 1 μHg or less.
It is carried out at a temperature in the range of .

The aliphatic dicarboxylic acid having 9 or more carbon atoms, poly(tetramethylene oxide) glycol, or an ester-forming derivative thereof can be added before the transesterification or esterification reaction or during the agglomeration reaction, but preferably, It is preferable to add it after the transesterification reaction or the esterification reaction, that is, in the condensation step.

The intrinsic viscosity of the copolymerized polyester used in the present invention is preferably about 0.5 or more and about 1.5 or less, more preferably about 0.5 or more and about 1.5 or less, when measured in a 50150 weight mixed solvent system of phenol and tetracumyl ethane at 30°C. is in the range of about 0.5 or more and about 1.0 or less.

In the present invention, a metal salt of a copolymer of an α-olefin and an α,β-unsaturated carboxylic acid and optionally a third vinyl monomer (hereinafter also referred to as an ionic copolymer) is copolymerized. Added to polyester. The α-olefins constituting the ionic copolymer include ethylene, propylene, etc., and the α-, β-unsaturated carboxylic acids include acrylic acid, itacrylic acid, maleic acid, fumaric acid, itaconic acid, etc. Examples of trivalent monomers include ethyl acrylate and vinyl acetate, and examples of metals include monovalent to trivalent metals, with preference given to sodium, potassium, calcium, zinc, aluminum, and the like.

It has been found that when an alkali metal such as sodium or potassium is selected as the metal, not only extremely high impact strength can be obtained, but also that the impact strength does not decrease even after being held at high temperatures for a long time.

According to the research conducted by the present inventors, such a unique phenomenon has been observed only in nine cases when a very special polyester (3) is selected.

It was found that when zinc was selected as the metal, a resin composition with less coloring was obtained, and moreover, the coloring of the composition was less even after being kept at high temperatures for a long time7'L7t.

These ionic copolymers are composed of α-olefins and α,β-
It can be produced by copolymerizing an unsaturated carboxylic acid and optionally a vinyl monomer, and then replacing part or all of the carboxylic acid with a metal salt. Another method for producing ionic copolymers is to use an α-olefin and optionally a tertiary copolymer.
There is a method in which an α,β-unsaturated carboxylic acid is polymerized into a copolymer with a vinyl monomer, followed by substitution with a metal salt. Yet another method of production is to copolymerize an α-olefin, an α,β-unsaturated carboxylic acid ester, and optionally a third vinyl monomer, and then saponify the carboxylic ester portion and then replace it with a metal salt. There is also a method of manufacturing.

Ionic copolymers obtained by any method can be employed in the present invention, but among these ionic copolymers, those that are particularly preferably used in the present invention are ethylene and acrylic acid, or ethylene and acrylic acid. It is a metal salt of a copolymer consisting of methacrylic acid.

There are many sources of such ionic copolymers. For example, it is sold by Mitsui DuPont Polychemical Company under the trade name Hi2Ran.

In the above ionic copolymer, it is necessary that the carboxylic acid units (including salt forms) occupying the copolymer account for at least 1 mole and at most 30 moles of all copolymer units. If the amount is less than 1 mole, the effect of the present invention, that is, the improvement in the impact resistance of the polyester resin will not be sufficiently achieved. If the amount exceeds 30 moles, the ionic copolymer cannot be sufficiently mixed with the polyester in a short time in a molten state. A more preferable range of the proportion of carboxylic acid units in the ionic copolymer used in the present invention is more than 2 moles and less than 10 moles.

In the present invention, it is not necessary that all carboxyl groups present in the ionic copolymer be neutralized by metal ions, but it is necessary that at least 20 moles of all carboxyl groups be neutralized by polymetallic ions. It is.

If the neutralization rate is more than 20 moles, the effect of the present invention of improving the impact resistance of the polyester resin cannot be sufficiently achieved. A preferable neutralization rate is 40% or more, particularly 60 mol% or more.

Note that the neutralization rate is measured by infrared spectrum of the copolymer. That is, νc of the carboxyl group that has become a salt =
It can be measured by the ratio of Q absorption intensity to νc=Q absorption intensity of unneutralized carboxyl group.

The amount of fraction@ to be blended is 3 to 100 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of the copolymerized polyester. If the amount is too small, the effect of improving the impact resistance of the molded cedar product will be poor, and if it exceeds 100 parts by weight, the mechanical properties of the molded product will deteriorate.

In the present invention, what can be added as the flame retardant 0 can be any known flame retardant for polyester resins.

Examples of flame retardants include organic and phosphorus-based flame retardants. Organic and chlorogenic flame retardants such as tehahexabromobenzene, hexachlorobenzene, penta7”o
Motoluene, pentachlorotoluene, bentacumophenol, hexabromo biphenyl, thecapromo biphenyl, decabromo piphenyl oxide, tetrabromobutane, hexabromocyclododecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, ethylene bis -(tetrabromophthalimide), tetrachlorobisphenol A or tetrabromobispheno-tv A (7)
Polymer, halogenated epoxy resins such as terminal epoxy compounds of halogenated polycarbonate oligomers and tetrabromobisphenol A oligomers, halogenated polystyrenes such as polychlorostyrene and polytribromostyrene, poly(dibromophenylene oxide), etc. Can be mentioned. Particularly preferably used are terminal epoxy compounds of tetrabromobisphenol A oligomers, brominated polystyrene, especially polytribromostyrene.

Examples of phosphorus-based flame retardants include inorganic/acid salts such as ammonium polyphosphate, phosphoric acid esters such as tricresyl phosphate and triethyl phosphate, and diluted phosphoric esters.

Flame retardant 0 in the present invention is copolymerized polyester (8)i
3 to 50 parts by weight, preferably 5 to 50 parts by weight based on the ootit part
Use within a range of 30 parts by weight. If the amount used is less than 3 parts by weight, sufficient flame retardancy will not be obtained, and if it is more than 50 parts by weight, the mechanical properties of the composition will deteriorate, and some flame retardants may bleed, reducing surface gloss. let

In the present invention, the flame retardant auxiliary agent (1) is used in combination with the flame retardant 0.
l? Specifically, antimony compounds, balates, aluminum hydroxide, zirconium oxide, molybdenum oxide, etc. are used. Examples of the antimony compound include antimony trioxide, sodium antimonate, antimony tetroxide or pentoxide, and sodium pyroantimonate. Examples of the halalates include tetratt zinc oxalate, lead meta oxalate, and the like. The amount of flame retardant aid 0 used is 0.5 to 10 parts by weight, preferably 1 to 9 parts by weight, based on 100 parts by weight of #polymerized polyester (5). If the amount is less than 0.5 parts by weight, the flame retardant effect will decrease, and if it exceeds 10 parts by weight, the impact resistance will tend to decrease, which is not preferable.

In the present invention, glass fiber may be blended as necessary.

The glass vR fibers used in the present invention may be ordinary glass fibers used for reinforcing plastics, and preferably have a diameter of 3 to 30 microns.

Depending on the manufacturing method, various forms such as a-ping or chopped strands can be used. In addition, the glass fibers are preferably treated with silane treatment, chromium treatment, etc. for the purpose of improving adhesion to plastics.The blending amount is 60% by weight or less, preferably 50% by weight based on the total composition.
It is less than the weight range. When the blending amount exceeds 60 weights, the fluidity of the system becomes poor and molding becomes difficult. When the amount of glass fiber blended is 20 to 45% by weight based on the total composition, the composition of the present invention has a high impact strength and heat distortion temperature, excellent rigidity, and an extremely well-balanced composition with excellent flow characteristics. The above-mentioned copolyester, ionic copolymer, and flame retardant are usually obtained in the form of powder or particles (pellets, chips). If necessary, these can be melt-molded while simply mixing glass fibers to produce the desired polyester cedar product; however, the mixture can also be melt-kneaded and pelletized or chipped. Shiko's pellet mayu can also melt and mold desired molded products from chips. Therefore, in the present invention, the mixture of copolymerized polyester, ionic copolymer, flame retardant, and optionally glass fR fiber is not only a mixture of the respective powders or particles, but also a mixture in which both are molten. There is a crosstalk
Things are also included.

Copolymerized polyester with ionic copolymer and flame retardant,
When melt-molding a mixture of copolyester, ionic copolymer, flame retardant, and glass fiber as necessary, it is usually added to polyester. A wide variety of additives such as colorants, mold release agents, antioxidants, ultraviolet stabilizers, etc. can also be blended. Further, other resins such as polyester resins, polyolefin resins, acrylic resins, polycarbonate resins, polyamide resins, rubber-like elastic bodies, etc. may be mixed within the range that does not impair the effectiveness of the present invention.

As a method for melt mixing the composition of the present invention, commonly used methods are preferably used, but use of a twin-screw extruder is particularly preferred.

The composition of the present invention can be used to produce various molded products by melt molding methods such as extrusion molding and injection molding. The molded product obtained by extrusion molding can be in any shape such as fiber, rod, film, sheet, plate, tube, or pipe depending on the shape of the molding die.

Further, by cutting such an extruded product, small pieces such as chips and pellets or particulate melt molding material can be obtained. Furthermore, by using the injection molding method, it is possible to manufacture products of any desired shape depending on the shape of the mold. The molded product obtained by any of the molding methods can be further easily made into a desired final molded product by secondary molding processing such as blow molding, drawing molding, or vacuum forming. All of these various molded products have extremely high impact strength.

As described above, the composition of the present invention not only has flame retardancy that was not expected with conventional PET polyester resins and provides molded products with extremely high impact strength, but also can withstand high temperatures for long periods of time. Even if it is exposed, there is only a small decrease in the impact strength, and the contribution it makes to this world is extremely large.

Furthermore, in the case where an alkali is selected as the metal salt of the ionic copolymer in the composition of the present invention, the polyester is sufficiently crystallized and separated by injection molding in a mold at a relatively low temperature for a pHr-based resin. It can be said to be an excellent resin in terms of bottom shape workability, as it gives molded products with good moldability and excellent surface properties.

The present invention will be explained below with reference to Examples. All parts in the examples are based on heavy electric standards unless otherwise specified.

〔Example〕

Synthesis example A (synthesis example of copolymerized polyester) As a catalyst,
After esterification from terephthalic acid and ethylene glycol at 260°C using antimony trioxide and phosphorous acid, a specified amount of aliphatic dicarboxylic acid and poly(tetramethylene oxide) glycol were added, and the pressure was reduced according to a conventional method. A polycondensation reaction is carried out below.The obtained copolymerized polyester is taken out in the form of a strand through a nozzle using a gear pump, cooled with water, and cut into a pellet using a cutter.9.

The obtained rtt copolymerized polyester was dissolved in hexafluoropropanol and analyzed for aliphatic dicarboxylic acid units and repeating units of poly(tetramethylene oxide) glycol per 100 moles of terephthalic acid units by 500 MHz 1H-NMR ( Table 1).

The obtained copolymerized polyester was dissolved in phenol/tetrachloroethane (1:1 weight ratio), and the intrinsic viscosity was completely measured (Table 1).

Synthesis Comparative Example B When producing a copolymerized polyester in the same manner as in Synthesis Example A, when no aliphatic dicarboxylic acid is added (Synthesis Comparative Example B-1), when poly(tetramethylene oxide) glycol is not added ( Various copolymerized polyesters shown in Table 1 were prepared for Synthesis Comparative Example B-2) and the case of using an aliphatic dicarboxylic acid with a small number of disasters (Synthesis Comparative Example B-3). The following margin Examples 1 to 7 To 100 weight t4 of the copolyester prepared in Synthesis Example A, the amount of ionic copolymer shown in Table 2, the stabilizer (Chipa Geigy) in the amount of 1/100 of the ionic copolymer Made by ■, p.
hosphite 168), flame retardant 25 shown in Table 2
Parts by weight and 5 parts by weight of antimony trioxide are dried and mixed in advance, and then put into the hopper of a 30 mm φ twin-screw extruder (Plastic Engineering Research Institute gBT-30-8 model) and fed while being metered with a screw feeder. Glass fiber (convergent chopped strand with cut length 3m+, Nitto Boseki ■
While supplying a predetermined amount (composition) from a vent installed in the middle of a 35-pound cylinder,
Cylinder temperature 190-270-280-285-28
The mixture was melt-kneaded and extruded at 5°C (from the hopper side), an adapter temperature of 2285°C, and a die temperature of 275°C to obtain a strand, which was cut into pellets. The pellet was then heated to a cylinder temperature of 265-285-285-285°C.
A test piece with a thickness of 3++w+ was molded using an injection molding machine with a die temperature of 280'C and a mold temperature of 110°C.

The obtained f17 is the Izo impact strength of the molded product (with notch,
(based on ASTM D256) are shown in Table 2.

All of the compositions of the present invention exhibited high impact strength, and after leaving the obtained molded products in an air bath at 150°C for 7 days, the Izot impact strength was measured and the results are shown in Table 2. . Despite being exposed to high temperatures for long periods of time, it maintains high impact strength. Furthermore, the bending strength (AS
TM D790). The results are shown in Table 2. All of the compositions of the present invention had excellent bending strength.

Comparative Example 1 The same procedure as Example 2 was carried out except that the ionic copolymer was not used, but the impact strength was poor.

Comparative Examples 2 to 4 Molded products were obtained in the same manner as in Example 2 except that the copolymerized polyester prepared in Synthesis Comparative Example B was used instead of the copolymerized polyester prepared in Synthesis Example A, and the Izot impact strength and bending The strength was measured and the results are shown in Table 2. Both the impact strength after molding and the impact strength after 17 days at 150'C are inferior.90 Furthermore, the bending strength is also quite low.9.

Comparative Example 5 Abrasive limiting viscosity 0.74 dt/instead of copolymerized polyester
Example 2 except using polyethylene terephthalate f
A molded product was obtained using the same method as above, and the impact strength of the molded product was measured. The results are shown in Table 2.

In the case of polyethylene terephthalate without any modification, it was not possible to increase the impact strength even if an ionic copolymer was added.

Comparative Example 6 The same method as in Example 2 was used except for using ethylene/ethyl acrylate copolymer (trade name, Yucalon x-19Q-1, manufactured by Mitsubishi Yuka ■) instead of the ionic copolymer. Obtain a molded product and measure the impact strength of the resulting molded product. The results are shown in Table 2.

However, it is not possible to obtain high impact strength by using a polymer that does not form metal salts.

〔Effect of the invention〕

In the present invention, it has become possible to obtain a polyester resin composition that has both excellent impact resistance and flame retardancy, which could not be achieved with conventional flame-retardant polyesters.

Patent applicant RiRashi Co., Ltd.

Claims (8)

[Claims] (1) (A) A copolymerized polyester consisting essentially of structural units represented by (I) to (IV) below, and (
I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R is a divalent group obtained by removing the carboxyl group from an aliphatic dicarboxylic acid having 9 or more carbon atoms, and n is an integer of 8 to 84.) (I) is (III) and/or ( (II) is combined with (III) and/or (IV), and the total number of moles of (I) and (II) is substantially the same as that of (III) and (IV). Equal to the total number of moles, (II) is 0.2 to 1 per 100 moles of (I) in the copolymerized polyester.
100 parts by weight of a copolymerized polyester containing 1 to 20 moles of repeating units of ▲ (Formula, chemical formula, table, etc.) at a ratio of 0 mole (B) α-olefin and α , a metal salt of a copolymer with a β-unsaturated carboxylic acid and a third vinyl monomer if necessary (3 to 100 parts by weight) (C) a flame retardant with 3 to 50 parts by weight of a flame retardant having excellent impact resistance Resin composition. (2) The polyester resin composition according to claim 1, wherein in the structural unit (II), R is a divalent group obtained by removing a carboxyl group from at least one aliphatic dicarboxylic acid having 16 to 54 carbon atoms. thing. (3) In the structural unit of (II), R is a compound obtained by removing a carboxyl group from one or more dicarboxylic acids selected from the group consisting of tetradecanedicarboxylic acid, octadecanedicarboxylic acid, dimer acid, and a hydrogenated product of dimer acid. The copolymerized polyester resin composition according to claim 1, which is a polyvalent group. (4) In the structural unit (II), R is a divalent group obtained by removing a carboxyl group from one or more dicarboxylic acids selected from the group consisting of dimer acids and hydrogenated products thereof. The polyester resin composition according to item 1. (5) The polyester resin composition according to any one of claims 1 to 4, wherein in the structural unit (IV), n is 8 or more and 28 or less. (6) The polyester resin composition according to any one of claims 1 to 5, wherein component (B) is an alkali metal salt of a copolymer of ethylene, acrylic acid or methacrylic acid, and optionally a third vinyl monomer. (7) The polyester resin composition according to claim 1 or 6, wherein the metal salt of component (B) is a sodium salt or a potassium salt. (8) The polyester resin composition according to claim 1, wherein the metal salt of component (B) is a zinc salt.