JP2773807B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a heat-resistant polyester comprising a thermoplastic polyester and at least an .alpha.,. Beta.-unsaturated cyclic imide derivative and a copolymer containing aromatic vinyl and vinyl cyanide as monomers. The present invention relates to a thermoplastic resin composition having a good balance of mechanical properties such as properties, rigidity, strength, and ligability, and excellent in moldability. The thermoplastic resin composition of the present invention is used for machine parts, automobile parts,
Can be used in a wide range of fields such as electronic components.

[0002]

2. Description of the Related Art Thermoplastic polyesters represented by polyethylene terephthalate and polybutylene terephthalate have mechanical properties, heat resistance and chemical resistance in a relatively well-balanced manner, and are used in electric / electronic parts and automobile parts. Although widely used, their heat resistance, represented by the deflection temperature under high load, is low, and their molding shrinkage during injection molding is large and their dimensional stability is insufficient. Is desired.

In addition, since thermoplastic polyester has a higher specific gravity than other resins, it has been particularly desired in recent years to reduce the weight of automobile parts using the same.

On the other hand, copolymers of α, β-unsaturated cyclic imides represented by N-phenylmaleimide and vinyl monomers such as styrene and acrylonitrile are excellent in heat deformation resistance, dimensional stability and weather resistance. And blended with ABS resin and widely used for housings of electric / electronic devices and automobile parts. However, at present, the mechanical strength, the resistance to various oil agents, gasoline, and the like are not sufficient, and the range of use is limited at present.

Conventionally, there has been known a means of blending with an ABS resin in order to improve the thermal flexibility or impact resistance of a thermoplastic polyester (JP-B-47-30421).
JP, JP-A-49-97081, JP-A-50-97081
No. 23449, JP-A-56-14546). However, these methods are insufficient to improve heat resistance. To further improve heat resistance, α-
A method is known in which an ABS resin containing methylstyrene, a maleimide derivative or the like as a comonomer component is blended with an aromatic polyester (JP-A-57-610).
No. 47).

On the other hand, as a method for improving mechanical properties such as impact resistance, there is known a method of further adding an epoxy compound, particularly an ethylene-glycidyl methacrylate copolymer (Japanese Patent Application Laid-Open No. 59-149951, See Japanese Unexamined Patent Publication (Kokai) No. 63-248836).

Further, as a method of using both means in combination,
A resin composition comprising a vinyl copolymer comprising an aromatic vinyl monomer and an unsaturated cyclic imide compound and a polyepoxy compound with respect to an aromatic polyester has been reported (see JP-A-59-98159). ). However, in these methods, although heat resistance and impact resistance are improved, it is inevitable that the flowability at the time of molding processing is reduced. In addition, due to insufficient thermodynamic stability of the resin composition, the structure of the resin composition is not stable during the production of the resin composition and the molding processing conditions, and the physical properties of a molded article obtained from the resin composition may vary. And the range of use was often limited.

In the methods generally proposed so far,
It cannot be said that compatibility, heat resistance, mechanical properties, fluidity and stability of properties are imparted in a well-balanced manner.

[0009]

The object of the present invention is to provide the aromatic polyester having good mechanical properties, fluidity, moldability and chemical resistance.
Thermoplastic with excellent balance of various properties that have both heat resistance and high rigidity of α, β-unsaturated cyclic imide-containing vinyl copolymer, less influence of molding processing conditions, and excellent molding processing stability It is an object to obtain a resin composition.

[0010]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that a thermoplastic polyester, at least an α, β-unsaturated cyclic imide derivative, an aromatic vinyl and a vinyl cyanide compound It has been found that a compound satisfying the above objects can be obtained by blending a copolymer containing as a copolymer component and a specific vinyl copolymer having an epoxy group in a specific ratio, and arrived at the present invention.

That is, the present invention comprises, as a copolymer component, 98 to 2 parts by weight of a thermoplastic polyester (A), at least an α, β-unsaturated cyclic imide or a derivative thereof and an aromatic vinyl and vinyl cyanide compound. To 100 parts by weight of the resin composition consisting of 2 to 98 parts by weight of the copolymer (B), gel permeation chromatography was used.
The determined polystyrene equivalent weight average molecular weight is 2,000
0 to 100,000, and a vinyl copolymer (C) having an epoxy group equivalent number of less than 2 per molecule is 1 to 30.
It is a thermoplastic resin composition characterized by blending parts by weight.

The thermoplastic resin composition of the present invention has the mechanical properties, chemical resistance, and moldability of thermoplastic polyester, and the heat resistance, rigidity and rigidity of α, β-unsaturated cyclic imide-containing vinyl copolymer. It is a thermoplastic resin composition having dimensional stability. As used herein, the term "vinyl copolymer" refers to a copolymer composed of vinyl monomers. The fact that the number of epoxy group equivalents per molecule of an epoxy group-containing vinyl copolymer is less than 2 means that the epoxy equivalent per 1 g of an epoxy group-containing vinyl copolymer is multiplied by the molecular weight. The resulting value is 2.
It means less than 0. The epoxy group equivalent number can be determined, for example, according to JIS K-7236,
The molecular weight is the weight average molecular weight in terms of polystyrene determined by gel permeation chromatography, etc.
That is, a number average molecular weight can be employed.

Hereinafter, the present invention will be described in detail.
Thermoplastic polyester (A) of the present invention (hereinafter component (A)
There is that. ) Is terephthalic acid, isophthalic acid,
Na lid dicarboxylic acid, diphenylethane -4, 4-
Aromatic dicarboxylic acids such as dicarboxylic acids, sebacic Thin acid,
Aliphatic dicarboxylic acids such as adipic acid and derivatives thereof, and ethylene glycol, propylene glycol,
It is a polymer obtained by condensation polymerization with a compound having a divalent hydroxyl group such as butylene glycol, hexanediol, cyclohexanedimethanol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A and bisphenol F. These dicarboxylic acids and diols can be used alone or in combination of two or more.

Specific examples of the thermoplastic polyester (A) include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polycyclohexane dimethylene terephthalate, and copolymers thereof. Of these, polybutylene terephthalate, polyethylene terephthalate, and polyethylene terephthalate / cyclohexane dimethylene terephthalate copolymer are preferred. Among them, polybutylene terephthalate is particularly preferred. As the molecular weight of the thermoplastic polyester (A), those having an intrinsic viscosity of 0.5 to 1.5 dl / g at 30 ° C. in a mixed solvent of phenol / tetrachloroethane in an equivalent amount are those having mechanical properties and molding properties. It is preferable from the viewpoint of fluidity at the time.

A copolymer (B) containing at least an α, β-unsaturated cyclic imide or a derivative thereof (hereinafter referred to as component (B)
There is that. Examples of the α, β-unsaturated cyclic imide of the above) include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, Nt-butylmaleimide, N-lauroylmaleimide, and N- (p-chlorophenyl) maleimide. , N- (p-bromophenyl) maleimide, N-phenylmaleimide and N-cyclohexylmaleimide can be used. Among these, maleimide, N-phenylmaleimide and N-cyclohexylmaleimide are preferably used.

The aromatic vinyl and vinyl cyanide compound monomers to be copolymerized with the α, β-unsaturated cyclic imide and derivatives thereof include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, and styrene.
Examples thereof include aromatic vinyl monomers such as α-methylstyrene, p-methylstyrene, pt-butylstyrene, and styrenesulfonic acid. In addition, acrylic acid,
Vinyl carboxylic acids such as methacrylic acid and their methyl-, ethyl-, propyl-, n-butyl-, t-
Vinyl carboxylate esters such as butyl-, phenyl- and cyclohexyl esters, α, β-unsaturated anhydrides such as maleic anhydride and itaconic anhydride and their methyl-, ethyl-, propyl-, n-butyl- , T-
Vinyl dicarboxylic acid mono- and diesters such as butyl-, phenyl- and cyclohexyl-esters can be used. Among these, acrylonitrile, styrene, α-methylstyrene, methyl methacrylate,
Methyl acrylate is preferably used.

Examples of the copolymer (B) containing an α, β-unsaturated cyclic imide and its derivative include N-phenylmaleimide-acrylonitrile-styrene copolymer and N-phenylmaleimide-acrylonitrile-α-methylstyrene copolymer. A copolymer, an N-phenylmaleimide-styrene copolymer, and an N-phenylmaleimide-α-methylstyrene copolymer are preferably used.

In the copolymer composition of the above copolymer,
The ratio of α, β-unsaturated cyclic imide and its derivative is 5
Suitably, it is ３０30 mol%. When the amount is 5 mol% or less, the heat resistance of the copolymer is insufficient, and when the amount is 30 mol% or more, the fluidity during molding and the cost are increased, which is disadvantageous.

The molecular weight of the copolymer (B) containing the α, β-unsaturated cyclic imide and its derivative is from 20,000 to 200,000 in terms of polystyrene equivalent weight average molecular weight determined by gel permeation chromatography.
Suitably, it is zero.

The method for producing the component (B) is not particularly limited, but a commonly known method such as bulk polymerization, suspension polymerization, emulsion polymerization and solution polymerization can be used in the presence of a radical initiator.

Further, the vinyl copolymer having an epoxy group (C) of the present invention (hereinafter sometimes referred to as component (C)) is a copolymer obtained by copolymerizing a monomer compound having a vinyl group. It has an epoxy group on the side chain of the coalescence,
It is obtained by copolymerization of a vinyl monomer having an epoxy group and another vinyl monomer compound. It is preferable that the proportion of the epoxy group be one or more and less than two in one molecular chain of the copolymer.

If the proportion of the epoxy group is less than one on average in one molecular chain of the copolymer, the compatibility between the thermoplastic polyester and the α, β-unsaturated cyclic imide copolymer is insufficient. It is difficult to obtain a good micro phase separation structure, and it is not possible to obtain stable mechanical properties due to the influence of the processing history. If it is two or more, the molding fluidity of the obtained resin composition decreases, which is not preferable.

The glycidyl group-containing vinyl monomer which forms the epoxy group-containing vinyl copolymer used herein includes glycidyl methacrylate and glycidyl acrylate. Further, as a vinyl monomer copolymerizable therewith, acrylonitrile, vinyl cyanide monomer such as methacrylonitrile, styrene,
aromatic vinyl derivatives such as α-methylstyrene, p-methylstyrene, pt-butylstyrene, acrylic acid,
Vinyl mosquito carboxylic acid such as methacrylic acid, and their methyl -, ethyl -, propyl -, n-butyl -, t-
Vinyl carboxylic acid esters such as butyl-, phenyl-, cyclohexyl-ester, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, Nt-butylmaleimide, N-lauroylmaleimide, N- (p- Chlorophenyl) maleimide, N
Α, β such as-(p-bromophenyl) maleimide, N-phenylmaleimide, N-cyclohexylmaleimide
-Unsaturated cyclic imides and derivatives thereof can be used. Among these, acrylonitrile, styrene, α-methylstyrene, methyl methacrylate, methyl acrylate, N-phenylmaleimide, and N-
Cyclohexylmaleimide is preferred. Among them, those containing glycidyl methacrylate, styrene and acrylonitrile in the copolymer component are preferably used.

The vinyl copolymer having an epoxy group as the component (C) includes glycidyl methacrylate / acrylonitrile / styrene copolymer, glycidyl methacrylate / acrylonitrile / α-methylstyrene copolymer, glycidyl methacrylate / styrene / acrylonitrile / Examples thereof include N-phenylmaleimide copolymer, glycidyl methacrylate / styrene / acrylonitrile / α-methylstyrene / N-phenylmaleimide copolymer and glycidyl methacrylate / styrene / methyl methacrylate copolymer. In the copolymer of the component (C), the amount of the aromatic vinyl-based monomer in the copolymer composition excluding the monomer containing an epoxy group is 40 mol% or more, but the affinity with the component (B) is high. It is appropriate from the point of.

The molecular weight of the vinyl copolymer having an epoxy group used for the component (C) is 2,000 to 100,000 in terms of polystyrene equivalent weight average molecular weight determined by gel permeation chromatography. Is required .

The method for producing the component (C) is not particularly limited, but it can be obtained by a generally known method such as bulk polymerization, suspension polymerization, emulsion polymerization and solution polymerization in the presence of a radical initiator. Specifically, for example, described below.
As shown in Reference Example 2, under a nitrogen stream, cooling pipe,
10-liter flask equipped with lower funnel and stirrer
5 liters of methyl ethyl ketone and acryloni
756 g (37.8% by weight) of toril, styrene 1214
g (60.7% by weight), glycidyl methacrylate 30
g (1.5% by weight) along with azobisisobutyronito
Slowly drop methyl ethyl ketone solution containing 21 g of ril
While stirring at a temperature of 80 ° C. for 5 hours, followed by
After cooling the reaction mixture to room temperature, filtering and concentrating,
Pour into methanol to precipitate the polymer,
After filtration, the precipitate was dissolved and reprecipitated with acetone and methanol.
Is repeated twice, and finally by filtration and drying,
One of the specific examples of the component (C), the number average molecular weight is 1
3,800 and an epoxy equivalent number of 1.4 per molecule.
eq / mol acrylonitrile-styrene-glycidide
To produce 1500 g of methacrylate copolymer.
it can.

The resin composition of the present invention comprises 98 to 2 parts by weight of the thermoplastic polyester of the component (A) and α, β-component of the component (B).
Epoxy is used based on 2 to 98 parts by weight of a copolymer obtained by copolymerizing an unsaturated cyclic imide or a derivative thereof and a monomer copolymerizable therewith, and 100 parts by weight of components (A) and (B) in total. Group-containing vinyl copolymer (C) 1 to 30
Parts by weight, and preferably 90 to 1 component (A).
0 parts by weight, 10 to 90 parts by weight of component (B) and components
Component (C) based on a total of 100 parts by weight of (A) and (B )
It consists of 1 to 20 parts by weight.

In a total of 100 parts by weight of the components (A) and (B), the amount of the thermoplastic polyester used as the component (A) is less than 2 parts by weight, and the amount of the component (B) used is more than 98 parts by weight. In this case, the moldability and mechanical strength are not sufficient, while the amount of component (A) used is more than 98 parts by weight and the amount of component (B) used is less than 2 parts by weight, rigidity and molding Dimensional stability and heat resistance are insufficient, which is not preferable. Further, the amount of the vinyl copolymer having an epoxy group of the component (C) used is 1 in total of the component (A) and the component (B).
If the amount is less than 1 part by weight, the compatibility between the component (A) and the component (B) is not sufficient, resulting in poor dispersion. Also not preferred because the amount of the component (C) is that and thermoplastic polyester Le If larger than the above upper limit alpha, characterized with the respective copolymer containing β- unsaturated cyclic imide or a derivative thereof are both lost.

In the resin composition of the present invention, the phase separation form of the thermoplastic polyester and the copolymer containing the α, β-unsaturated cyclic imide or its derivative is changed by forming a bicontinuous structure or a particle dispersed structure, respectively. A resin composition having characteristic performance can be obtained. One preferred structure of the present invention is that the thermoplastic polyester phase of the component (A) and the copolymer phase containing the α, β-unsaturated cyclic imide or the derivative thereof of the component (B) are co-continuous phases. . The term "co-continuous" as used herein means that both the component (A) and the component (B), which are mixed components, are phase-separated and both exist as a substantially continuous phase. Another preferred structure of the present invention is one in which the component (A) or the component (B) forms a dispersed phase in the form of fine particles in another continuous phase. The tissue structure of these resin compositions can be confirmed, for example, by observing ultra-thin sections thereof with a transmission electron microscope.

The formation of these tissue structures is based on the components (A),
It can be obtained by using components (B) and (C) having a specific range of melt viscosity. That is, in order to obtain a resin composition having a bicontinuous structure, the unsaturated cyclic imide copolymer (B) having a melt viscosity of the component (A) at a shear rate of 200 to 300 sec ^{-1 at} the kneading temperature.
It is appropriate to use one having a ratio of 0.4 to 5.0.

For example, when polybutylene terephthalate, which is one of the most preferred thermoplastic polyesters in the present invention, is used, the temperature of component (A) is 250 ° C., and the shear rate is 2.
The ratio of the melt viscosity at 00 to 300 sec ^{-1 to that} of the unsaturated cyclic imide copolymer (B) is from 0.4 to 5.
0 can be used. In this case, preferably, the total of component (A) and component (B) in the resin composition is 1
30 to 75 parts by weight of the component (A) out of 00 parts by weight
That the content is obtained with respect to 100 parts by weight of components (A) and (B), a resin composition having an organizational structure of co-continuous structure by 2 to 25 parts by weight ratio of component (C) Can be.

In order to obtain a resin composition having a fine particle dispersed structure, a shear rate at a kneading temperature of 200 to 300 sec.
^{-1 when} the ratio of the melt viscosity of the component (A) to that of the unsaturated cyclic imide copolymer (B) is 0.05 to 0.4.
It is appropriate to use those. For example, when polybutylene terephthalate is used as the component (A), the ratio of the melt viscosity of the component (A) to that of the unsaturated cyclic imide copolymer (B) at 250 ° C. is 0.05 to 0.1.
It is appropriate to use four. The proportion of the component (A) is 95 to 60 parts by weight or 30 to 5 parts by weight, and the proportion of the component (C) is 100 parts by weight of the total of the components (A) and (B) in the resin composition. When the content is 1 to 30 parts by weight, a resin composition having a fine particle dispersed structure can be obtained. The melt viscosity can be measured with a capillary rheometer equipped with a nozzle having a nozzle length / nozzle diameter ratio (L / D) = 10, and a shear rate of 20.
Values at a constant shear rate in the range 0-300 sec ^-1 can be used.

The resin composition having a bicontinuous structure has characteristics of high rigidity and high heat resistance, while the resin composition having a fine particle dispersed structure exhibits excellent properties in chemical resistance and elongation at break.

The method for producing the thermoplastic resin composition of the present invention is not particularly limited. For example, after preliminarily mixing the components (A), (B) and (C) at the mixing ratio of the present invention at room temperature,
A method of melting and kneading at a temperature of 230 ° C. or higher, preferably 240 to 300 ° C. can be applied. The pre-mixing can be performed by a high-speed rotary mixer such as a Henschel mixer or a juicer mixer and a low-speed rotary mixer such as a cone blender used for ordinary mixing. Also,
Melt kneading can be carried out using a conventional melt kneading apparatus such as a single-screw or twin-screw extruder, a Banbury mixer, and a kneader.

The thermoplastic resin composition of the present invention can be added and compounded with various reinforcing materials and fillers such as fibrous, powdery, flake and matte shapes as long as the moldability and physical properties are not impaired. . Specific examples of the reinforcing material and the filler include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica-alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, basic magnesium sulfate fiber, and boron fiber. Mineral and metal fibers such as stainless steel, aluminum, titanium, copper, brass, magnesium, and organic fibers such as polyamide, polyester, polyacrylonitrile, and cellulose;
Metal powders such as copper, iron, nickel, zinc, tin, lead, stainless steel, aluminum, gold, silver, fumed silica,
Examples include aluminum silicate, glass beads, carbon black, quartz powder, talc, titanium oxide, iron oxide, calcium carbonate, magnesium oxide, calcium oxide, magnesium sulfate, and diatomaceous earth. In the case of a fibrous substance, those having an average fiber diameter of 0.1 to 30 μm and a ratio of fiber length / fiber diameter of 10 or more are preferably used. These reinforcing materials and fillers may be surface-treated with a known silane coupling agent or titanate-based coupling agent.

The amount of the reinforcing material and filler used is 1 to 300 parts by weight, preferably 10 to 250 parts by weight, based on 100 parts by weight of the resin composition of the present invention. These reinforcing materials and fillers may be used alone or in combination of two or more.

Further, the thermoplastic resin composition of the present invention comprises
If necessary, hindered phenols, hydroquinones, thioethers, phosphites, antioxidants and heat stabilizers such as amines and their substituted and copper compounds, resorcinol, salicylate, benzotriazole, ultraviolet absorbers such as benzophenone, Stearic acid and its salts, release agents such as stearyl alcohol, magnesium hydroxide, aluminum hydroxide, calcium hydroxide,
Inorganic flame retardants such as hydrotalcite, organic flame retardants based on halogen, phosphoric acid ester, melamine or cyanuric acid, flame retardant aids such as antimony trioxide, antistatic such as sodium dodecylbenzenesulfonate, polyalkylene glycol It is possible to add one or more additives such as an agent, other crystallization accelerators, dyes and pigments.

Further, the thermoplastic resin composition of the present invention may contain an appropriate amount of polyethylene, as long as the object of the present invention is not impaired.
Polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, polybutadiene, acrylonitrile-butadiene copolymer, acrylonitrile-styrene-butadiene copolymer, polyamide, polyamide elastomer, polyester elastomer, Thermoplastic resins such as polycarbonate, polysulfone, polyphenylene ether, and polyphenylene sulfide, and thermosetting resins such as phenolic resins, melamine resins, urea resins, silicone resins, and epoxy resins can be added.

The thermoplastic resin composition of the present invention can be processed into molded articles for various uses by injection molding, compression molding and extrusion molding.

[0040]

The present invention will be described in more detail with reference to the following examples . However, the present invention is not limited to the examples. The measurement of mechanical properties described in Examples and Comparative Examples was performed according to the following. (1) Tensile strength: ASTM D638 (2) Tensile elongation: ASTM D638 (3) Flexural modulus: ASTM D790 (4) Deflection temperature under load: ASTM D648

Reference Example 1 Under the following conditions, unsaturated cyclic imide copolymers (I-1 to 3) were prepared. I-1: Styrene 55 wt% of acrylonitrile 25 wt%, a monomer mixture consisting of N- phenylmaleimide 20 wt% was dispersed in water at a concentration of 20%, as an initiator of azobisisobutyronitrile, 70 ° C. Under stirring for 5 hours. After filtration, washing and drying, a powdery unsaturated cyclic imide copolymer (I-1) was obtained. The weight average molecular weight of the obtained copolymer was 120,000. I-2: A monomer mixture composed of 20 % by weight of styrene, 25% by weight of acrylonitrile, 35% by weight of α-methylstyrene, and 20 % by weight of N-phenylmaleimide is dispersed in water containing an emulsifier to a concentration of 20%. Using ammonium persulfate as an initiator and stirring at a temperature of 70 ° C. for 10 hours,
Emulsion polymerization was performed, followed by filtration and washing, followed by drying to obtain a powdery unsaturated cyclic imide copolymer (I-2). The weight average molecular weight of the obtained copolymer was 133,000. I-3: A monomer mixture composed of 18% by weight of styrene, 18% by weight of acrylonitrile, 31% by weight of α-methylstyrene, and 33% by weight of N-phenylmaleimide has a concentration of 20%.
In water, and suspension polymerization was carried out for 5 hours with stirring at a temperature of 70 ° C. using azobisisobutyronitrile as an initiator. After filtration, washing and drying, a powdery unsaturated cyclic imide copolymer (I-3) was obtained. The weight average molecular weight of the obtained copolymer was 65,000.

Reference Example 2 Under the following production conditions, a vinyl copolymer containing an epoxy group (E
-1 to 5) were obtained. E-1: Under a nitrogen stream, 5 liters of methyl ethyl ketone and acrylonitrile 756 g (37.8% by weight), styrene 1214 g (60.7% by weight ), glycidyl methacrylate in a 10-liter flask equipped with a condenser, a dropping funnel, and a stirrer. While gradually dropping a methyl ethyl ketone solution containing 21 g of azobisisobutyronitrile together with 30 g (1.5% by weight), the solution was heated at 80 ° C. for 5 hours.
Stirred for hours. The reaction mixture was cooled to room temperature, filtered, concentrated, and then poured into a large amount of methanol to precipitate a polymer. After filtration, dissolution and reprecipitation were further repeated twice with acetone and methanol, followed by filtration and drying to obtain an acrylonitrile-styrene-glycidyl methacrylate copolymer (E-
1) 1500 g was obtained. The number average molecular weight of the obtained copolymer was 13,800, and the number of epoxy equivalents per molecule was 1.4 eq / mol. E-2 to 5: The charging ratio of the monomers was as shown in Table 1, and the amount of azobisisobutyronitrile was 50 g. E-
In the same manner as in Example 1, a vinyl copolymer containing an epoxy group having the properties shown in Table 2 was obtained.

[0043]

[Table 1]

[0044]

[Table 2]

Examples 1 to 6 Polybutylene terephthalate (PBT1, [η] -0.85), unsaturated cyclic imide copolymer (I-1 to 2) shown in Reference Example, and vinyl having an epoxy group The system copolymers (E-1 to E-4) were blended at the ratio shown in Table 3, and were melt-kneaded at a set temperature of 250 ° C. by a twin-screw extruder having a screw diameter of 30 mm to obtain a pellet-shaped resin composition. This resin composition was molded at a molding temperature of 250.
Injection molding was performed at 80 ° C. and a mold temperature of 80 ° C. to obtain a test piece for measuring physical properties. Table 3 shows the measurement results of the tensile properties, bending properties, and deflection temperatures under load. In addition, the melt viscosity of the resin composition using a capillary rheometer (measurement conditions; capillary L / D = 10/1, temperature 250 ° C., shear rate 243 s)
ec ^-1 ) is shown in Table 3.

[0046]

[Table 3]

[Comparative Example 1] Only PBT1 used in Example 1 was injection-molded under the same conditions, and physical properties were measured. Table 4 shows the characteristics.

[0048]

[Table 4]

Comparative Example 2 Only I-1 used in Example 1 was injection-molded under the same conditions, and physical properties were measured. Table 4 shows the characteristics.

[Comparative Examples 3 and 4] Example 1 or Example 3
In the above, a resin composition was prepared in the same manner as in the example, except that the epoxy group-containing copolymer was not added and at the compounding ratio shown in Table 4. Table 4 shows the characteristics.

[Comparative Examples 5 to 6] As an epoxy group-containing copolymer, the epoxy group equivalent number per molecule was 2.4 eq.
/ Mol vinyl copolymer (E-5) or epoxy group-containing ethylene copolymer (E-6, Sumitomo Chemical Co., Ltd.)
A resin composition was prepared in the same manner as in Example 2 using Bondfast E ^R manufactured by Co., Ltd., a copolymer composition; ethylene / glycidyl methacrylate = 90/10 (weight ratio). Table 4 shows the characteristics.

Examples 7 to 10 Polybutylene terephthalate ( PBT2 , [η] = 1.
15) and unsaturated cyclic imide copolymer I-2 or I
-3, the epoxy group-containing copolymer (E-
1, E-3) in the composition shown in Table 5, and
The mixture was melt-kneaded in the same manner as in the above to obtain a pellet-shaped resin composition.
Table 5 shows the characteristics.

[0053]

[Table 5]

[Examples 11 and 12] Polyethylene terephthalate (PET1, manufactured by Unitika Ltd., PET SA-1203) was used as polyester, I-1 was used as an unsaturated cyclic imide copolymer, and E was used as an epoxy group-containing copolymer. -1 at the blending ratio shown in Table 5 and the set temperature of 280 ° C.
Other than the above, melt kneading was performed in the same manner as in Example 1 to obtain a resin composition. Table 5 shows the characteristics.

[Comparative Examples 7 to 8] The resin composition was melt-kneaded at the compounding ratio shown in Table 6 in the same manner as in Example 7 or Example 8, except that the epoxy group-containing copolymer was not added. Obtained. Table 6 shows the characteristics.

[0056]

[Table 6]

Comparative Examples 9 to 10 Example 11 or Example 1 except that no epoxy group-containing copolymer was added.
In the same manner as in Example 2, the mixture was melt-kneaded at the compounding ratio shown in Table 6 to obtain a resin composition. Table 6 shows the characteristics.

[0058]

The resin of the present invention comprising a specific proportion of a thermoplastic polyester, a copolymer containing an α, β-unsaturated cyclic imide or a derivative thereof, and a vinyl copolymer containing a specific amount of an epoxy group. The composition is a resin composition having excellent heat resistance, rigidity and mechanical properties and excellent moldability, and can be used in a wide range of fields such as mechanical parts, automobile parts, and electric / electronic parts.

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Claims (1)

(57) [Claims] 1. A copolymer containing 98 to 2 parts by weight of a thermoplastic polyester (A), at least an α, β-unsaturated cyclic imide or a derivative thereof, and aromatic vinyl and a vinyl cyanide compound as monomers. (B) relative to 100 parts by weight of the resin composition consisting of 2 to 98 parts by weight, Gerupami
Polystyrene determined by Ation Chromatography
Weight-average molecular weight of 2,000 to 100,000
A thermoplastic resin composition comprising 1 to 30 parts by weight of a vinyl copolymer (C) having an epoxy group equivalent number of less than 2 per molecule.