JPH05339479A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition useful in a wide field, having excellent heat resistance, rigidity, mechanical characteristics and moldability and processability by blending a composition of a thermoplastic polyester and a specific vinyl copolymer with a specific epoxy-containing vinyl copolymer. CONSTITUTION:100 pts.wt. resin composition comprising (A) 98-2 pts.wt. thermoplastic polyester (preferably polybutylene terephthalate) and (B) 2-98 pts.wt. copolymer obtained from an alpha, beta-unsaturated cyclic imide or its derivative and an aromatic vinyl and a vinyl cyanide compound (preferably N- phenylmaleimide/acrylonitrile/styrene copolymer) are blended with (C) 1-30 pts.wt. vinyl copolymer having <2 epoxy group equivalent (e.g. glycidyl methacrylate/acrylonitrile/styrene copolymer) to give the objective composition. The phase separation configuration of the component A and the component B in the composition is preferably mutually continuous structure or powder dispersed structure.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a heat-resisting polymer containing a thermoplastic polyester, a copolymer containing at least an α, β-unsaturated cyclic imide derivative, an aromatic vinyl and a vinyl cyanide compound as monomers as main components. The present invention relates to a thermoplastic resin composition having a good balance of mechanical properties such as properties, rigidity, strength, and drossiness, and excellent in moldability. The thermoplastic resin composition of the present invention is used for mechanical parts, automobile parts, electric
It can be used in a wide range of fields such as electronic parts.

[0002]

2. Description of the Related Art Thermoplastic polyesters typified by polyethylene terephthalate and polybutylene terephthalate have a relatively well-balanced mechanical property, heat resistance, and chemical resistance. It is widely used, but its heat resistance typified by the deflection temperature under load under high load is low, and the molding shrinkage rate during injection molding is large, resulting in insufficient dimensional stability. Is desired.

Further, 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, a copolymer of an α, β-unsaturated cyclic imide represented by N-phenylmaleimide and a vinyl monomer such as styrene or acrylonitrile is excellent in heat distortion resistance, dimensional stability and weather resistance. Therefore, it is blended with ABS resin and widely used for housings of electric / electronic devices and automobile parts. However, the mechanical strength and resistance to various oil agents, gasoline, etc. are not sufficient, and the usage range is limited at present.

Conventionally, a means for blending with an ABS resin has been known in order to improve the thermal flexibility or impact resistance of thermoplastic polyester (Japanese Patent Publication No. 47-30421).
JP-A-49-97081, JP-A-50-
23,449, and JP-A-56-14546). However, these methods do not sufficiently improve the heat resistance. To further improve heat resistance, α-
A method is known in which an ABS resin containing methyl styrene, a maleimide derivative or the like as a comonomer component is blended with an aromatic polyester (JP-A-57-610).
47 gazette).

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

Furthermore, as a method of using both means in combination,
A resin composition comprising a vinyl-based copolymer comprising an aromatic vinyl monomer and an unsaturated cyclic imide compound and a polyvalent epoxy compound has been reported for an aromatic polyester (see JP-A-59-98159). ). However, with these methods, although heat resistance and impact resistance are improved, it is unavoidable that fluidity at the time of molding is lowered. In addition, since the thermodynamic stability of the resin composition is insufficient, the structure of the resin composition is not stable during the production of the resin composition and the molding processing conditions thereof, and the physical properties of the molded article obtained from the resin composition vary. However, 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 with good mechanical properties, fluidity, moldability and chemical resistance.
Thermoplastics with excellent balance of various characteristics that have both heat resistance and high rigidity of α, β-unsaturated cyclic imide-containing vinyl copolymer, little influence of molding processing conditions, and excellent molding processing stability An object is to obtain a resin composition.

[0010]

Means for Solving the Problems As a result of intensive studies for achieving the above object, the present inventors have found that a thermoplastic polyester and at least an α, β-unsaturated cyclic imide derivative, an aromatic vinyl and a vinyl cyanide compound are used. The inventors have found that by blending a copolymer containing ## STR1 ## as a copolymer component and a specific vinyl copolymer having an epoxy group in a specific ratio, one satisfying the above-mentioned object can be obtained, and the present invention has been accomplished.

That is, the present invention contains 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 a cyanide compound as a copolymer component. 1 to 30 parts by weight of a vinyl-based copolymer (C) having an epoxy group equivalent number of less than 2 per 100 parts by weight of a resin composition consisting of 2 to 98 parts by weight of the copolymer (B). It is a thermoplastic resin composition characterized by being blended.

The thermoplastic resin composition of the present invention has mechanical properties, chemical resistance, molding processability of the thermoplastic polyester, and heat resistance, rigidity and rigidity of the α, β-unsaturated cyclic imide-containing vinyl copolymer. It is a thermoplastic resin composition that also has dimensional stability. The vinyl-based copolymer referred to here is a copolymer composed of vinyl-based monomers. The fact that the number of epoxy group equivalents per molecule of the epoxy group-containing vinyl copolymer is less than 2 means that the epoxy equivalent per 1g of the epoxy group-containing vinyl copolymer is multiplied by the molecular weight. The value obtained is 2.
It means less than 0. The epoxy group equivalent number can be determined according to JIS K-7236, for example,
As the molecular weight, a number average molecular weight determined by gel permeation chromatography or the like can be adopted.

[0013]

The present invention will be described in detail below. The thermoplastic polyester (A) of the present invention (hereinafter sometimes referred to as component (A)) is terephthalic acid, isophthalic acid, nephthalenedicarboxylic acid, aromatic dicarboxylic acid such as diphenylethane-4,4-dicarboxylic acid, sebacine. Acids, aliphatic dicarboxylic acids such as adipic acid and their derivatives, and ethylene glycol, propylene glycol, butylene glycol, hexanediol, cyclohexanedimethanol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, bisphenol F, etc. It is a polymer obtained by condensation polymerization with a compound having a divalent hydroxyl group.
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 / cyclohexanedimethylene terephthalate copolymers are preferred. Of these, polybutylene terephthalate is particularly preferable. As for 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 an equivalent solvent mixture of phenol / tetrachloroethane have mechanical properties and molding properties. It is preferable from the viewpoint of fluidity at the time.

Copolymer (B) containing at least α, β-unsaturated cyclic imide or its derivative (hereinafter referred to as component (B)
There is a thing. A), β-unsaturated cyclic imide, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, Nt-butylmaleimide, N-lauroylmaleimide, 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.

Aromatic vinyl and vinyl cyanide compound monomers to be copolymerized with α, β-unsaturated cyclic imide and its derivatives include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, and styrene,
Aromatic vinyl monomers such as α-methyl styrene, p-methyl styrene, pt-butyl styrene and styrene sulfonic acid can be mentioned. In addition, acrylic acid,
Vinylcarboxylic acids such as methacrylic acid and their methyl-, ethyl-, propyl-, n-butyl-, t-
Vinylcarboxylic acid esters such as butyl-, phenyl-, cyclohexyl-esters, α, β-unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride and their methyl-, ethyl-, propyl-, n-butyl- , T-
Vinyl dicarboxylic acid mono and diesters such as butyl-, phenyl-, cyclohexyl-esters can be used. Among these, acrylonitrile, styrene, α-methylstyrene, methylmethacrylate,
Methyl acrylate is preferably used.

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

Of the copolymerization composition of the above copolymer,
The ratio of α, β-unsaturated cyclic imide and its derivative is 5
Appropriately is about 30 mol%. If it is 5 mol% or less, the heat resistance of the copolymer is insufficient, and if it is 30 mol% or more, the fluidity at the time of molding is lowered and the cost is increased, which is disadvantageous.

The molecular weight of the copolymer (B) containing the α, β-unsaturated cyclic imide and its derivative is 20,000 to 200,000 in polystyrene equivalent weight average molecular weight determined by gel permeation chromatography.
A value of 0 is suitable.

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

Further, the vinyl-based copolymer (C) having an epoxy group (hereinafter sometimes referred to as the component (C)) of the present invention is a copolymer obtained by copolymerizing a monomer compound having a vinyl group. It has an epoxy group in its side chain,
It is obtained by copolymerizing a vinyl monomer having an epoxy group with another vinyl monomer compound. It is preferable that the existence ratio of the epoxy group is 1 or more and less than 2 in one molecular chain of the copolymer.

If the proportion of epoxy groups present is less than 1 on average in one molecular chain of the copolymer, the compatibility between the thermoplastic polyester and the α, β-unsaturated cyclic imide copolymer is not sufficient, It is difficult to obtain a good microphase-separated structure, and it is difficult to obtain stable mechanical properties due to the influence of processing history. Further, if the number is two or more, the molding fluidity of the obtained resin composition is lowered, which is not preferable.

Examples of the vinyl monomer having a glycidyl group which forms the vinyl copolymer having an epoxy group used here include glycidyl methacrylate and glycidyl acrylate. Further, as the vinyl-based monomer copolymerizable with these, acrylonitrile, vinyl cyanide monomers such as methacrylonitrile, styrene,
Aromatic vinyl derivatives such as α-methylstyrene, p-methylstyrene, pt-butylstyrene, acrylic acid,
Vinyl arboric acids such as methacrylic acid and their methyl-, ethyl-, propyl-, n-butyl-, t-
Butyl-, phenyl-, vinylcarboxylic acid esters such as 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 their derivatives can be used. Among these, acrylonitrile, styrene, α-methylstyrene, methyl methacrylate, methyl acrylate, N-phenylmaleimide, and N-
Cyclohexylmaleimide is preferred. Of these, it is preferable to use glycidyl methacrylate, styrene, and acrylonitrile as copolymerization components.

The component (C) epoxy group-containing vinyl copolymers include glycidyl methacrylate / acrylonitrile / styrene copolymers, glycidyl methacrylate / acrylonitrile / α-methylstyrene copolymers, glycidyl methacrylate / styrene / acrylonitrile / Examples thereof include N-phenylmaleimide copolymer, glycidyl methacrylate / styrene / acrylonitrile / α-methylstyrene / N-phenylmaleimide copolymer, and glycidyl methacrylate / styrene / methylmethacrylate copolymer. Further, in the copolymer composition of the component (C) excluding the monomer containing an epoxy group, the proportion of the aromatic vinyl-based monomer is 40 mol% or more, the affinity with the component (B) is It is suitable from the point of.

The epoxy group-containing vinyl copolymer used as the component (C) has a molecular weight of 2,000 to 100,000 in terms of polystyrene equivalent weight average molecular weight determined by gel permeation chromatography. Is preferred.

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.

The resin composition of the present invention comprises 98 to 2 parts by weight of the component (A) thermoplastic polyester and the component (B) α, β-.
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 epoxy to 100 parts by weight of the total of the components (A) and (B). Group-containing vinyl copolymer (C) 1 to 30
90 parts by weight of component (A).
0 parts by weight, 10 to 90 parts by weight of component (B) and 1 to 20 parts by weight of component (C).

In a total of 100 parts by weight of the components (A) and (B), the amount of the thermoplastic polyester as the component (A) used 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 if the amount of component (A) used is greater than 98 parts by weight and the amount of component (B) used is less than 2 parts by weight, the rigidity and molding Dimensional stability and heat resistance are insufficient, which is not preferable. In addition, the amount of the epoxy group-containing vinyl-based copolymer of the component (C) is 1 in total of the component (A) and the component (B).
When the amount is less than 1 part by weight with respect to 00 parts by weight, the compatibility between the component (A) and the component (B) is not sufficient, resulting in poor dispersion. Further, when the amount of component (C) used is larger than that of the above-mentioned eye, all the characteristics of the thermoplastic polyester and the copolymer containing the α, β-unsaturated cyclic imide or its derivative are lost, which is not preferable.

In the resin composition of the present invention, the thermoplastic polyester and the copolymer containing the α, β-unsaturated cyclic imide or the derivative thereof are phase-separated into a co-continuous structure or a particle-dispersed structure, respectively. A resin composition having characteristic performance can be obtained. One preferable 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 cocontinuous 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 are substantially present as a continuous phase. Another preferred structural structure of the present invention is that 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 their ultrathin sections by a transmission electron microscope.

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

For example, when polybutylene terephthalate, which is one of the most preferable thermoplastic polyesters in the present invention, is used, the temperature of the component (A) is 250 ° C. and the shear rate is 2
The ratio of the melt viscosity of the unsaturated cyclic imide copolymer (B) at 00 to 300 sec ⁻¹ is 0.4 to
Those of 5.0 can be used. In this case, preferably, the ratio of the component (A) to the total 100 parts by weight of the component (A) and the component (B) in the resin composition is 30 to 75 parts by weight. By setting the proportion of the component (C) to 2 to 25 parts by weight with respect to 100 parts by weight in total, it is possible to obtain a resin composition having a co-continuous structure.

Further, in order to obtain a resin composition having a fine particle dispersion structure, a shear rate at a kneading temperature of 200 to 300 sec.
^The ratio of the melt viscosity of the component (A) in ^{-1 to that} of the unsaturated cyclic imide copolymer (B) is 0.05 to 0.4.
It is suitable to use one of the above. For example, when polybutylene terephthalate is used as the component (A), the ratio of the melt viscosity of the unsaturated cyclic imide copolymer (B) at 250 ° C. of the component (A) is 0.05 to 0.
4 is suitable. The ratio of the component (A) is 95 to 60 parts by weight or 30 to 5 parts by weight, and the ratio of the component (C) is 100 parts by weight, in total, of the component (A) and the component (B) in the resin composition. By setting the amount to 1 to 30 parts by weight, a resin composition having a microstructure-structured 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) of 10 and a shear rate of 20.
Values at constant shear rates in the range 0-300 sec ^-1 can be used.

The resin composition having a bicontinuous structure has the characteristics of high rigidity and high heat resistance, while the resin composition having a fine particle dispersion structure exhibits excellent 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 the components (A), (B) and (C) are pre-mixed at room temperature in the mixing ratio of the present invention,
A method of melt-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 corn blender which are used for ordinary mixing. Also,
The melt-kneading can be performed using a normal melt-kneading processing device such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader.

The thermoplastic resin composition of the present invention may be added with various kinds of reinforcing agents and fillers in various shapes such as fibrous, powdery, flake-like or matte-like form, 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, boron fiber. Inorganic and metal fibers such as stainless steel, aluminum, titanium, copper, brass and magnesium, and organic fibers such as polyamide, polyester, polyacrylonitrile and cellulose,
Metal powder such as copper, iron, nickel, zinc, tin, lead, stainless steel, aluminum, gold, silver, fumed silica,
Examples thereof 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 fibrous substances, those having an average fiber diameter of 0.1 to 30 μm and a fiber length / fiber diameter ratio of 10 or more are preferably used. These reinforcing materials and fillers may be surface-treated with known silane coupling agents or titanate coupling agents.

The amount of the reinforcing material and the 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, in the thermoplastic resin composition of the present invention,
As necessary, antioxidants and heat stabilizers such as hindered phenol, hydroquinone, thioether, phosphite, amines and their substitution products and copper compounds, resorcinol, salicylate, benzotriazole, UV 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, halogen-based, phosphoric acid ester-based, melamine or cyanuric acid-based organic flame retardants, flame retardant aids such as antimony trioxide, sodium dodecylbenzene sulfonate, antistatic properties such as polyalkylene glycol It is possible to add one or more additives such as agents, crystallization accelerators, dyes and pigments.

Further, the thermoplastic resin composition of the present invention comprises a suitable amount of polyethylene within a range not impairing the object of the present invention.
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 phenol resin, melamine resin, urea resin, silicone resin, and epoxy resin 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, extrusion molding and the like.

The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the examples. The mechanical properties described in Examples and Comparative Examples were measured 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 An unsaturated cyclic imide copolymer (I-1 to 3) was prepared under the following conditions. I-1: A monomer mixture consisting of 55% by weight of styrene, 25% by weight of acrylonitrile and 20% by weight of N-phenylmaleimide was dispersed in water at a concentration of 20%, and azoisobutyronitrile was used as an initiator at 70 ° C. Suspension polymerization was carried out for 5 hours with stirring. 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: Disperse a monomer mixture consisting of 20% by weight of styrene, 25% by weight of acrylonitrile, 35% by weight of α-methylstyrene and 15% by weight of N-phenylmaleimide 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,
After emulsion polymerization, filtration and washing, and drying, a powdery unsaturated cyclic imide copolymer (I-2) was obtained. The weight average molecular weight of the obtained copolymer was 133,000. I-3: 20% by weight of a monomer mixture consisting of 18% by weight of styrene, 18% by weight of acrylonitrile, 31% by weight of α-methylstyrene and 33% by weight of N-phenylmaleimide.
Was dispersed in water with 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 A vinyl-based copolymer containing 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%), glycidyl methacrylate were placed in a 10 liter flask equipped with a cooling tube, a dropping funnel and a stirrer. While slowly adding dropwise a methyl ethyl ketone solution containing 21 g of azobisisobutyronitrile together with 30 g (1.5% by weight), the mixture was stirred at a temperature of 80 ° C. for 5 hours. The reaction mixture was cooled to room temperature, filtered, and concentrated,
The polymer was poured into a large amount of methanol to precipitate the polymer.
After separation by filtration, melt reprecipitation was further repeated twice with acetone and methanol, followed by filtration and drying to obtain acrylonitrile-styrene-glycidyl methacrylate copolymer (E-1) 1.
500 g was obtained. The number average molecular weight of the obtained copolymer is 1
It was 3,800, 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 addition amount of azobisisobutyronitrile was 50 g. E-
In the same manner as in the case of 1, a vinyl-based copolymer having an epoxy group having the characteristics shown in Table 2 was obtained.

[0043]

[Table 1]

[0044]

[Table 2]

[Examples 1 to 6] Polybutylene terephthalate (PBT1, [η] -0.85), the unsaturated cyclic imide copolymer (I-1 to 2) shown in Reference Example and vinyl having an epoxy group. The system copolymers (E-1 to 4) were blended in the proportions shown in Table 3 and melt-kneaded at a preset 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 is molded at a molding temperature of 250.
Injection molding was performed at 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, the bending properties, and the deflection temperature under load. Further, the melt viscosity of the resin composition by 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 the physical properties were measured. The characteristics are shown in Table 4.

[0048]

[Table 4]

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

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

Comparative Examples 5 to 6 As an epoxy group-containing copolymer, the number of epoxy group equivalents per molecule is 2.4 eq.
/ Mol vinyl-based 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., copolymer composition: ethylene / glycidyl methacrylate = 90/10 (weight ratio). The characteristics are shown in Table 4.

Examples 7 to 10 For polybutylene terephthalate PBT2 ([η] -1.15) and unsaturated cyclic imide copolymer I-2 or I-3, epoxy group-containing copolymer ( E-1 and E-3) were blended in the blending composition shown in Table 5 and melt-kneaded in the same manner as in Example 1 to obtain a pellet-shaped resin composition. The characteristics are shown in Table 5.

[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 the unsaturated cyclic imide copolymer, and E was used as the epoxy group-containing copolymer. -1 at a blending ratio shown in Table 5 at a set temperature of 280 ° C
Melt kneading was carried out in the same manner as in Example 1 except that the above was used to obtain a resin composition. The characteristics are shown in Table 5.

[Comparative Examples 7 to 8] The resin compositions were 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. The characteristics are shown in Table 6.

[0056]

[Table 6]

[Comparative Examples 9 to 10] Example 11 or Example 1 except that the epoxy group-containing copolymer was not added.
Melt-kneading was carried out in the same proportion as in Table 2 in the same manner as in 2, to obtain a resin composition. The characteristics are shown in Table 6.

[0058]

The resin of the present invention comprising 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 epoxy groups in a specific ratio. 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 machine parts, automobile parts, and electric / electronic parts.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location C08L 35/00 LJW 7921-4J (72) Inventor Takaichi 3-10 Nakamiyakitamachi, Hirakata City, Osaka Prefecture Ube Industries Ltd. Hirakata Laboratory

Claims (1)

[Claims] 1. A thermoplastic annotation polyester (A) 98-2.
A resin composition comprising 1 part by weight, at least an α, β-unsaturated cyclic imide or derivative thereof, and 2 to 98 parts by weight of a copolymer (B) containing aromatic vinyl and vinyl cyanide compounds as monomers. A thermoplastic resin composition comprising 100 parts by weight of 1 to 30 parts by weight of a vinyl copolymer (C) having an epoxy group equivalent number of less than 2 per molecule.