JP2001040190A - Polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition having an improved impact resistance and excellent properties such as processability at extrusion, heat stability, appearance of molded items and the like by blending a thermoplastic polyester resin, a copolymer comprising ethylene and a (meth)acrylic ester, and an epoxy resin in a specific composition ratio. SOLUTION: This composition comprises 30-95 wt.% of a thermoplastic polyester resin, 0.5-20 wt.% of a copolymer having an MI value (190 deg.C, 2 kg load, JIS K6730) of 1-500 g/10 min comprising 30-90 wt.% of ethylene, 5-50 wt.% of an (meth)acrylic acid 1-10C alkyl ester, carbon monoxide 0-40 wt.% and 0-10 wt.% of another co-polymerizable vinyl monomer, 1-20 wt.% of an epoxy resin of an epoxy equivalent of at least 2,000 having a structure of the formula, and 0-60 wt.% of a glass fiber. In the formula, X is H or a halogen; Y is a 1-10C alkylene, an alkylidene, a cycloalkane, carbonyl, -O-, -S-, or -SO2-; and (m) is 1 or more.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester resin composition excellent in processability, fluidity, heat stability, appearance of a molded product, impact resistance, wet heat resistance and heat cycle property during extrusion.

[0002]

2. Description of the Related Art Aromatic polyester resins represented by polyalkylene terephthalate and the like are widely used in electric and electronic equipment parts, automobile parts, and the like because of their excellent properties. However, aromatic polyesters
Due to poor impact resistance, it may not be applicable to fields requiring high impact properties such as electric and electronic devices, automobile exterior parts, drive parts, and the like, and improvement thereof has been demanded.

Accordingly, many methods have been studied to improve the impact resistance of aromatic polyesters. For example, Japanese Patent Application Laid-Open No. 58-45255 and Japanese Patent Application Laid-Open No.
In JP-A-271348, it is known to add an ethylene ethyl acrylate copolymer to polybutylene terephthalate.

[0004]

However, in these methods, although the impact resistance is improved, there is a problem that the workability during extrusion, the heat stability, and the appearance of the molded product are deteriorated. There was a request for improvement.

[0005]

The inventors of the present invention have made intensive studies to solve the above problems, and as a result, surprisingly, the thermoplastic polyester resin and the melt index (MI) have a value of 190 ° C. , 2kg load condition (JIS
1 to 500 g / 10 min.
30 to 90% by weight of an ethylene unit, 5 to 50% by weight of a (meth) acrylic acid alkyl ester unit having 1 to 10 carbon atoms, and 0 of a carbon monoxide unit.
The impact resistance is improved in a resin composition comprising from 0 to 40% by weight, other copolymerizable vinyl monomer units from 0 to 10% by weight, and a resin composition comprising a specific epoxy resin. The present inventors have found that a polyester resin composition having excellent properties, fluidity, heat stability, appearance of a molded article, wet heat resistance, and heat cycle property can be obtained, and have accomplished the present invention.

That is, the present invention provides the following components (A) to
A polyester resin composition containing (D) and having a total of 100% by weight. (A) Thermoplastic polyester resin: 30 to 95% by weight (B) Melt index (MI) value is 190 ° C., 2
Under kg load conditions (based on JIS K6730)
500 g / 10 min, ethylene unit 30 to 90
% By weight, 5 to 50% by weight of alkyl (meth) acrylate units having 1 to 10 carbon atoms in the alkyl ester, 0 to 40% by weight of carbon monoxide units, and other copolymerizable vinyl monomer units Copolymer consisting of 0 to 10% by weight: 0.5 to 20% by weight (C) The following general formula (1)

[0007]

Embedded image

(Wherein X is a hydrogen atom or a halogen atom, Y is an alkylene group having 1 to 10 carbon atoms, an alkylidene group, a cycloalkane group, a carbonyl group, -O-, -S
-Or -SO _2- , m represents an integer of 1 or more) and an epoxy equivalent of 2000
Epoxy resin as described above: 1 to 20% by weight (D) Glass fiber: 0 to 60% by weight Further, the present invention provides (2) a halogen in which the epoxy resin as the component (C) has a halogenation ratio of 20% by weight or more. The present invention relates to a polyester resin composition which is a functionalized epoxy resin.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic polyester resin (A) used in the present invention is a divalent acid such as terephthalic acid or a derivative thereof having an ester-forming ability as an acid component, and a carbon component as a glycol component. It refers to a saturated polyester resin obtained by using a glycol of 2 to 10 or another dihydric alcohol or a derivative thereof having an ester-forming ability. Among these, a polyalkylene terephthalate resin is preferred because it has a good balance of workability, mechanical properties, electrical properties, heat resistance, and the like.
Specific examples of these polyalkylene terephthalate resins include polyethylene terephthalate resin, polybutylene terephthalate resin, polyhexamethylene terephthalate resin, polycyclohexane dimethylene terephthalate resin and the like, and among these, heat resistance and chemical resistance tend to be excellent. In this respect, polyethylene terephthalate resin and polybutylene terephthalate resin are preferable.

[0010] The thermoplastic polyester resin (A) used in the present invention is preferably copolymerized with other components at a ratio of preferably 20% by weight or less, particularly preferably 10% by weight or less, if necessary. Can be. As components of the copolymer,
Known acid components, alcohol components and / or phenol components, or derivatives thereof having ester-forming ability can be used. Examples of the acid component include divalent or higher valent aromatic carboxylic acids having 8 to 22 carbon atoms, aliphatic carboxylic acids having 4 to 12 carbon atoms, alicyclic carboxylic acids having 8 to 15 carbon atoms, and ester-forming ability. And derivatives thereof.

Specifically, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methaneanthracenedicarboxylic acid, 4-4'-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane- 4,4′-dicarboxylic acid, 5-sodium sulfoisophthalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, maleic acid, trimesic acid, trimellitic acid, pyromellitic acid, 1,3-cyclohexanedicarboxylic acid, Examples thereof include 1,4-cyclohexanedicarboxylic acid and derivatives thereof having an ester-forming ability. These may be used alone or in combination of two or more. Of these, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid are preferred because the obtained resin is excellent in physical properties, handleability, and ease of reaction.

Examples of the alcohol and / or phenol component include dihydric or higher aliphatic alcohols having 2 to 15 carbon atoms, dicyclic or higher aliphatic alcohols having 6 to 20 carbon atoms, and dihydric alcohols having 6 to 40 carbon atoms. The aromatic alcohols or phenols described above and derivatives thereof having ester-forming ability are mentioned.

Specifically, ethylene glycol, propanediol, butanediol, hexanediol, decanediol, neopentyl glycol, cyclohexanedimethanol, cyclohexanediol, 2,2'-bis (4-hydroxyphenyl) propane, 2,2 Compounds such as 2'-bis (4-hydroxycyclohexyl) propane, hydroquinone, glycerin, pentaerythritol, and derivatives thereof having ester-forming ability;
Cyclic esters such as ε-caprolactone can also be used. Among these, ethylene glycol and butanediol are preferable because the obtained resin is excellent in physical properties, handling properties and ease of reaction.

Further, a polyoxyalkylene glycol unit may be partially copolymerized. Specific examples of the polyoxyalkylene glycol include polyethylene glycol,
Polypropylene glycol, polytetramethylene glycol, and their random or block copolymers, and adducts of bisphenol compounds with alkylene glycols (polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and their random or block copolymers, etc.) Of modified polyoxyalkylene glycol. Among these, bisphenol A having a molecular weight of 500 to 2,000 is preferred because the thermal stability at the time of copolymerization is good and the heat resistance of a molded article obtained from the resin composition of the present invention is hardly reduced.
Is preferred.

These (A) thermoplastic polyester resins may be used alone or in combination of two or more.
It is 95% by weight, preferably 35 to 90% by weight. Three
If the amount is less than 0% by weight, the excellent properties inherent to the thermoplastic polyester resin cannot be exhibited. If the amount exceeds 95% by weight, a polyester resin having the excellent properties which is the object of the present invention cannot be obtained.

The thermoplastic polyester resin can be produced by a known polymerization method such as melt polycondensation, solid phase polycondensation,
It can be obtained by solution polymerization or the like. Further, in order to improve the color tone of the resin during polymerization, phosphoric acid, phosphorous acid, hypophosphorous acid, monomethyl phosphate, dimethyl phosphate, trimethyl phosphate, methyl diethyl phosphate, triethyl phosphate, triisopropyl phosphate, One or more compounds such as tributyl phosphate and triphenyl phosphate may be added. Further, in order to increase the crystallinity of the obtained thermoplastic polyester resin, various kinds of commonly known organic or inorganic crystal nucleating agents may be used alone or in combination of two or more at the time of polymerization.

The intrinsic viscosity of the thermoplastic polyester resin (A) (measured at 25 ° C. in a mixed solvent of phenol / tetrachloroethane at a weight ratio of 1/1) is from 0.4 to 1.
It is preferably 5 dl / g, especially 0.6 to 1.2 d
It is preferably 1 / g. The intrinsic viscosity is 0.4 dl
If it is less than 1.5 g / g, mechanical strength and impact resistance tend to decrease, and if it exceeds 1.5 dl / g, fluidity tends to decrease, which is not preferable.

The melt index (MI) used in the present invention is 190 ° C. under a 2 kg load condition (JIS).
K6730), from 1 to 500 g / 10 m
in, 30 to 90% by weight of ethylene units, 5 to 50% by weight of alkyl (meth) acrylate units having 1 to 10 carbon atoms in the alkyl ester, 0 to 40% by weight of carbon monoxide units, and others. A copolymer comprising 0 to 10% by weight of a polymerizable vinyl monomer unit is used for the purpose of improving impact resistance, fluidity, wet heat resistance and heat cycle property of the resin.

These (B) copolymers are generally used in combination with ethylene and an alkyl (meth) acrylate, and if necessary, carbon monoxide and / or another copolymerizable vinyl monomer. Can be obtained by radical polymerization in the presence of a radical initiator, but the polymerization method is not limited thereto, and can be polymerized using various known polymerization methods generally known. . The copolymer may be in any copolymer form such as a random copolymer, a block copolymer, and a graft copolymer.

As the alkyl ester in the alkyl (meth) acrylate in the copolymer (B), those having 1 to 10 carbon atoms are used. When the one having 11 or more carbon atoms is used, the compatibility with the polyester decreases, and the mechanical strength of the obtained composition decreases. Preferably, it has 8 or less carbon atoms, and more preferably 6 or less carbon atoms.

Specific examples of the alkyl (meth) acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, and n
-Propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, and the like, and these are used alone or in combination of two or more.

These (B) copolymers may optionally contain
In addition to the ethylene unit, the alkyl (meth) acrylate unit, and the carbon monoxide unit, the copolymer may contain other copolymerizable vinyl monomer units. Other copolymerizable vinyl monomers include propylene, 1-butene, 1-pentene, isobutene, isoprene, α, ω-non-conjugated diene,
Alkene compounds such as butadiene, phenylpropadiene, cyclopentadiene, 1,5-norbornadiene, 1,3-cyclohexadiene, 1,5-cyclooctadiene, and 1,3-cyclooctadiene; Aromatic vinyl compounds such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, divinylbenzene, maleic acid, maleic anhydride, N-methylmaleimide, N-phenyl Maleic acid derivatives such as maleimide and dimethyl maleate; unsaturated nitriles such as acrylonitrile and methacrylonitrile; glycidyl (meth) acrylates such as glycidyl methacrylate; unsaturated amide compounds such as acrylamide; vinyl methyl ether; Ethyl ethers, such as vinyl alkyl ethers, allyl alkyl ethers, such as allyl ethyl ethers, alkyl esters of (meth) acrylic acid alkyl esters having 11 or more carbon atoms, and acrylic acid, methacrylic acid as other vinyl monomers, Examples include, but are not limited to, vinyl acetate, and various copolymerizable components can be used. These are used alone or in combination of two or more.

The melt index (MI) of the copolymer (B) is 190 ° C. under a 2 kg load condition (JIS).
K6730), from 1 to 500 g / 10 m
in, preferably 4 to 450 g / 10 min, more preferably 5 to 400 g / 10 min. When the value of the melt index is less than 1 g / 10 min, the effect of improving the fluidity and impact resistance of the obtained composition cannot be obtained.
If it exceeds 500 g / 10 min, the appearance and impact resistance of the molded product are reduced.

In the copolymer (B), the ratio of ethylene units to alkyl (meth) acrylate units, carbon monoxide units, and other copolymerizable vinyl monomers is as follows:
30 to 90% by weight of ethylene units, 5 to 50% by weight of alkyl (meth) acrylate units, 0 to 40% by weight of carbon monoxide units, and 0 to 10 of other copolymerizable vinyl monomer units. % By weight. Preferably, ethylene units are 35 to 85% by weight, alkyl (meth) acrylate units are 5 to 40% by weight, and carbon monoxide units are 0 to 3%.
0% by weight, other copolymerizable vinyl monomer units are 0%
~ 7% by weight. When the (meth) acrylic acid alkyl ester unit is less than 5% by weight or more than 50% by weight, the effect of improving the impact resistance is poor, and when the other copolymerizable vinyl monomer unit exceeds 10% by weight, it is obtained. In some cases, the mechanical strength and wet heat resistance of the resulting composition may decrease.

The amount of the copolymer (B) used is 0.5
-20% by weight, preferably 1-18% by weight, more preferably 2-15% by weight. If the amount of the (B) copolymer exceeds 20% by weight, the resulting composition may have a reduced appearance of a molded article, reduced mechanical strength, and reduced heat resistance. The effect of improving fluidity, impact resistance, wet heat resistance and heat cycleability cannot be obtained. These (B) copolymers may be used in combination of a plurality of resins having different copolymer components, melt index values, and the like.

The specific epoxy resin (C) used in the present invention suppresses deterioration in processability during extrusion and deterioration in appearance of a molded product caused by using the copolymer (B), and also has thermal stability and resistance to heat. It is used to further improve impact resistance and wet heat resistance.

The epoxy resin has the following general formula (1)

[0028]

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(Wherein X is a hydrogen atom or a halogen atom, Y is an alkylene group having 1 to 10 carbon atoms, an alkylidene group, a cycloalkane group, a carbonyl group, -O-, -S
-Or -SO _2- , and m represents an integer of 1 or more). The epoxy equivalent of the epoxy resin is 2,000 or more, preferably 5,000 or more. If the epoxy equivalent is less than 2,000, the fluidity and the appearance of the molded article deteriorate, which is not preferable. These (C) epoxy resins are used alone or in combination of two or more, and the amount of use is 1 to 20% by weight, preferably 1.5 to 15% by weight. If the amount is less than 1% by weight, the effect of improving the extrusion processability cannot be obtained.

More preferably, the halogenation ratio of the epoxy resin is at least 20% by weight, more preferably 30% by weight.
It is preferable that the content be not less than% by weight because the appearance of the molded article, particularly the surface gloss of the molded article, can be obtained. If the halogenation ratio is less than 20% by weight, the surface gloss of the molded product may not be obtained. In the general formula (1), Y represents —C (CH ₃ )
_2- is preferred in terms of mechanical strength.

As the terminal group of the epoxy resin, those having a glycidyl group and / or a hydroxyl group are generally used. Further, those whose terminal groups are blocked with carboxylic acids, phenols, amines, alcohols or the like can also be used. When the terminal is a glycidyl group, one having a high molecular weight or an epoxy equivalent adjusted by blocking the terminal group is used.

As the (D) glass fiber used in the present invention, a known glass fiber generally used can be used. From the viewpoint of workability, chopped strand glass treated with a sizing agent is used. Preferably, fibers are used. Also, to increase the adhesion between the resin and the glass fiber,
Preferably, the surface of the glass fiber is treated with a coupling agent, and a binder using a binder may be used.

Examples of the coupling agent include γ
-Aminopropyltriethoxysilane, alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, and as the binder, for example, epoxy resins, urethane resins and the like are preferably used, but are not limited thereto. Absent. These glass fibers can be used alone or in combination of two or more.

The fiber diameter of these (D) glass fibers is 1-2.
0 μm and the fiber length are preferably 0.01 to 50 mm. When the fiber diameter is less than 1 μm, there is a tendency that the reinforcing effect as expected is not obtained even when added, and when the fiber diameter exceeds 20 μm, the surface properties and fluidity of the molded article tend to decrease, which is not preferable. . Moreover, even if it is added that the fiber length is less than 0.01 mm, the resin reinforcing effect as expected tends not to be obtained, and if the fiber length exceeds 50 mm, the surface properties and flowability of the molded article tend to decrease. Is not preferred.

The amount of the (D) glass fiber used is from 0 to
60% by weight, preferably 5 to 50% by weight,
Particularly preferably, it is 10 to 45% by weight. (D) If the amount of the glass fiber used exceeds 60% by weight, the processing stability at the time of extrusion and the appearance of the molded article tend to decrease. When the content is 5% by weight or more, sufficient mechanical strength and heat resistance are easily obtained, which is preferable.

The polyester resin composition of the present invention may further contain, if necessary, other compounding agents such as mica, talc,
Commonly known inorganic fillers such as kaolin, wollastonite, calcium carbonate, etc., inorganic and organic flame retardants, flame retardant aids, hindered phenol compounds, phosphite compounds, thioether compounds, deterioration inhibitors for epoxy compounds, etc. , An ultraviolet absorber, a release agent, a colorant, a crystal nucleating agent, an antistatic agent, a lubricant, a plasticizer, other polymers, and the like can be added to such an extent that the object of the present invention is not impaired.

The method for producing the composition of the present invention is not particularly limited. For example, it can be produced by a method of drying and kneading the above components, other additives, resins, and the like, and then using a melt kneading machine such as a single screw or twin screw extruder. When the compounding agent is a liquid, it can be manufactured by adding the compounding agent to a twin-screw extruder using a liquid supply pump or the like.

The composition of the present invention can be formed into various forms, for example, various molded articles, sheets, pipes, bottles, etc. by various molding methods. In addition, because of the good balance of processability, fluidity, thermal stability, appearance of molded products, impact resistance, wet heat resistance, and heat cycle properties during extrusion, electronic and electric products such as home appliances and OA equipment with complicated shapes are good. It is suitably used for injection molded products such as parts and housings.

[0039]

EXAMPLES Next, the composition of the present invention will be described specifically with reference to examples, but the present invention is not limited thereto.

Example 1 (A) The thermoplastic polyester resin has a logarithmic viscosity (measured at 25 ° C. in a mixed solvent of phenol / tetrachloroethane at a weight ratio of 1/1, the same applies hereinafter) of 0.85 dl /.
g of polybutylene terephthalate (a-
1) 54.5% by weight, (B) 25% by weight of ethyl acrylate as a specific copolymer, MI = 275 g / 10
Of ethylene and ethyl acrylate (b-
1) (Mitsui DuPont Polychemical Co., Ltd. EVAFLEX)
-EEA A704) in an amount of 5% by weight, (C) a specific epoxy resin having an epoxy equivalent of 30,000 and a halogenation ratio of 5
3% by weight epoxy resin (YPB-Toto Kasei Co., Ltd.)
43M) as a stabilizer and tetrakismethylene-3,5-di-t-butyl-4-hydroxyhydrocinnamate methane (trade name: Asahi Denka Co., Ltd.) as a stabilizer.
ADK STAB AO-60) was dry blended at 0.5% by weight. The mixture is heated at a cylinder temperature of 250-280.
C. and supplied to the hopper of a vent type 45 mφ co-rotating twin screw extruder (trade name: TEX44 manufactured by Nippon Steel Works Co., Ltd.), and (D) glass fiber (d-1) (T (−195H / P) 30.0% by weight was added from the middle of the extruder using a side feeder, and the mixture was melt-kneaded to obtain pellets.

After the obtained pellets were dried at 140 ° C. for 3 hours, the following tests were conducted using an injection molding machine (clamping pressure: 75 tons) at a cylinder temperature of 270 ° C. to 240 ° C. and a mold temperature of 100 ° C. Pieces were made.

Test piece 1: ASTM 1 having a thickness of 3.2 mm
No. dumbbell was molded in a molding cycle of 30 seconds. Test piece 2: An ASTM No. 1 dumbbell having a thickness of 3.2 mm was formed in a molding cycle of 180 seconds. Test piece 3: thickness 6.4 mm, width 12.7 mm, length 1
A 27 mm bar was molded in a molding cycle of 30 seconds. Test piece 4: thickness 1.6 mm, width 12.5 mm, length 1
A 25 mm bar was molded in a molding cycle of 30 seconds. Test piece 5: A flat plate having a size of 120 mm × 120 mm and a thickness of 3 mm was formed in a forming cycle of 30 seconds. Test piece 6: A cylindrical molded body into which a cylindrical metal (iron) as shown in FIG. 1 was inserted was molded in a molding cycle of 30 seconds. Using these test pieces, physical properties were evaluated according to the following criteria. Table 1 shows the results.

<Tensile Strength> Using an ASTM No. 1 dumbbell (test piece 1), the tensile strength was evaluated in accordance with ASTM D-638. Hereinafter, the numerical value obtained in this evaluation is abbreviated as the initial tensile strength value.

<Thermal Stability> The tensile strength was measured according to ASTM D-638 using an ASTM No. 1 dumbbell (test piece 2) obtained by intentionally maintaining a high heat for a long time by extending the molding cycle. The strength retention (%) relative to the initial value of the tensile strength was calculated and evaluated. The higher the strength retention, the more
It can be determined that the thermal stability is excellent.

<Heat and Moisture Resistance> After treating ASTM No. 1 dumbbell (test piece 1) under the conditions of 121 ° C. and 100% RH for 48 hours, the strength was measured in the same manner as in ASTM D-638, and the initial tensile strength was measured. Was calculated and evaluated. It can be determined that the higher the strength retention, the greater the improvement in wet heat resistance.

<Heat cycle property> After repeating the heat cycle of the cylindrical test piece (test piece 6) at -30 ° C for 1 hour and at 120 ° C for 1 hour 100 times, the surface of the molded article was visually observed. The following criteria. Judgment criteria ○: No crack was generated on the test piece. X: Cracks occurred on the test piece.

<Impact Resistance> The notched Izod impact strength was evaluated using a 6.4 mm thick bar (specimen 3) according to ASTM D-256.

<Heat Resistance> The deflection temperature under load of a 6.4 mm-thick bar (test piece 3) was evaluated at a load of 1.82 MPa according to ASTM D-648.

<Fluidity> According to JIS K-7210,
The method B flow value was measured at a set temperature of 280 ° C. and a preheating time of 5 minutes. (× 10 ^-2 cc / sec)

<Appearance of Molded Product> Injection molding machine (clamping pressure: 7
5 tons, cylinder diameter: 36 mmφ), cylinder temperature: 280 to 250 ° C, screw rotation speed: 100 rpm
m, back pressure: 0.8MPa, mold temperature 120 ° C at 100 ° C
A flat plate (test piece 5) having a thickness of 120 mm and 3 mm was molded, and the surface of the molded product was visually judged based on the following criteria. Criteria A: The surface is glossy and the surface properties are uniform. ：: The surface gloss is low, but the surface properties are uniform. X: The surface properties are not uniform.

<Processing stability during extrusion> Cylinder temperature 2
The situation at the time of extrusion processing using a vent type 45 mφ co-axial twin screw extruder (trade name: TEX44 manufactured by Nippon Steel Works Co., Ltd.) set at 50 to 280 ° C. was judged according to the following criteria. Judgment criteria ○: No problem was observed in extrusion processing. X: Discharge was uneven and extrusion was unstable.

<Flame Retardancy> The flame retardancy of a 1.6 mm-thick bar (test piece 4) was evaluated in accordance with the UL-94 standard.

(Examples 2 to 7) Resin compositions were obtained in the same manner as in Example 1 except that the amounts of each compounding agent were changed to those shown in Table 1. However, the following compounding agents were used. Table 1 shows the evaluation results.

(A) As a thermoplastic polyester resin: a polyethylene terephthalate resin having an logarithmic viscosity of 0.75 dl / g (a-2) 3,500 g of a polyethylene terephthalate having an logarithmic viscosity of 0.60 dl / g, and a bisphenol having an average molecular weight of 1,000 1500 g of the ethylene oxide addition polymer of A and 25 g of Adekastab AO-60 were put into a 10-liter autoclave, the temperature was raised to 290 ° C. while stirring with nitrogen gas stream, and then reduced to 1 torr or less and stirred for 3 hours. After that, the pressure was returned to normal pressure with nitrogen to complete the polymerization, and a block copolymer having an logarithmic viscosity of 0.80 dl / g (a-3) was obtained.

(B) As a copolymer: an ethyl acrylate ratio of 35% by weight, MI = 25 g /
Copolymer of ethylene and ethyl acrylate (b-2) for 10 minutes (Mitsui DuPont Polychemical Co., Ltd. EVAF
LEX-EEA A709)-ethylene-n-butyl acrylate-carbon monoxide ethyl acrylate, synthesized according to U.S. Pat. No. 4,613,533, ethylene: n-butyl acrylate: carbon monoxide = 7
0: 22: 8, MI = 25 g / 10 min copolymer (b-
3)

(C) As a specific epoxy resin, an epoxy resin (C-2) having an epoxy equivalent of 11,000 and a halogenation rate of 52% by weight (YPB-4, Toto Kasei Co., Ltd.)
3G) Epoxy resin (C-3) having an epoxy equivalent of 4000 and a halogenation ratio of 0% by weight (Eicoat 1010, Yuka Shell Epoxy Co., Ltd.)

(E) As a flame retardant:-Brominated diphenylethane (e-1) (Albemar Co., Ltd., SAYTEX8010, bromine content: 82%)-Brominated polystyrene (e-2) (Nissan Ferro-Organic Chemical Co., Ltd. Pyrochek) 68PB bromine content 68%)

(F) Flame retardant aid • Antimony pentoxide (f-1) (Sun Epoque NA1030, Nissan Chemical Industries, Ltd.)

(Comparative Examples 1 to 7) Resin compositions were obtained in the same manner as in Examples 1 to 7, except that the amount of each compounding agent was changed to the amount shown in Table 2. However, the following compounding agents were used. Table 1 shows the evaluation results.

(B) Copolymer Ethyl acrylate ratio 25% by weight, MI = 800 g /
Copolymer of ethylene and ethyl acrylate for 10 minutes (b-4) (EV manufactured by DuPont-Mitsui Polychemicals Co., Ltd.)
AFLEX-EEA A715)

(C) As a specific epoxy resin, an epoxy resin (c-4) having an epoxy equivalent of 500 and a halogenation ratio of 0% by weight (Yuika Shell Epoxy Co., Ltd. Epicoat 1001)

[0062]

[Table 1]

[0063]

[Table 2]

From the comparison between Example 1, Comparative Example 2 and Comparative Example 5, it was found that by containing (C) an appropriate amount of the specific epoxy resin,
Mechanical strength, thermal stability, wet heat resistance, heat cycle properties,
It was found that the impact resistance, heat resistance, appearance of the molded product, and processing stability during extrusion were improved. From the comparison between Example 2 and Comparative Example 3 and from the comparison between Example 1 and Comparative Example 4, by adding an appropriate amount of the copolymer (B), mechanical strength, heat cycle properties, impact resistance, heat resistance, and molded products were obtained. It was found that the appearance and the processing stability during extrusion were improved.

From the comparison between Example 2 and Comparative Example 6, when the melt index of the copolymer (B) is high, mechanical strength, impact resistance, heat resistance, appearance of a molded product, and processing stability during extrusion can be obtained. I knew it wasn't. Comparison between Example 2 and Comparative Example 7 revealed that when the epoxy equivalent of the specific epoxy resin (C) was small, impact resistance, fluidity, appearance of a molded product, and processing stability during extrusion could not be obtained. Furthermore, as can be seen from a comparison between Examples 4 and 5, and Examples 6 and 7, the resin composition of the present invention does not impair the characteristics of the present invention by containing an appropriate amount of a flame retardant and a flame retardant auxiliary, and thus has excellent excellent properties. It has been found that flammability can be imparted.

As is clear from the comparison between Table 1 as an example and Table 2 as a comparative example as described above, the polyester resin composition of the present invention has excellent impact resistance and processability during extrusion. It was found to be excellent in fluidity, thermal stability, appearance of molded articles, impact resistance, wet heat resistance, and heat cycle properties.

[0067]

The polyester resin composition of the present invention has improved impact resistance, and is excellent in processability, fluidity, heat stability, appearance of a molded product, wet heat resistance, and heat cycle property during extrusion. Therefore, the polyester resin composition of the present invention can be suitably used as a molding material in fields requiring high impact properties, such as electric and electronic parts, particularly electric and electronic equipment, exterior parts of automobiles, and drive parts. Useful for

[Brief description of the drawings]

FIG. 1 is a diagram of a cylindrical metal (iron) used for preparing a test piece 6;

FIG. 2 is a view of a molded product obtained by insert molding the cylindrical metal shown in FIG.

FIG. 3 is a cross-sectional view (a hatched portion in FIG. 2) of a resin molded product portion in the insert molded product.

Claims (2)

[Claims] 1. A polyester resin composition comprising the following components (A) to (D), the total of which is 100% by weight. (A) Thermoplastic polyester resin: 30 to 95% by weight (B) Melt index (MI) value is 190 ° C., 2
Under kg load conditions (based on JIS K6730)
500 g / 10 min, ethylene unit 30 to 90
% By weight, 5 to 50% by weight of alkyl (meth) acrylate units having 1 to 10 carbon atoms in the alkyl ester, 0 to 40% by weight of carbon monoxide units, and other copolymerizable vinyl monomer units Copolymer consisting of 0 to 10% by weight: 0.5 to 20% by weight (C) The following general formula (1) (Wherein X represents a hydrogen atom or a halogen atom, Y represents an alkylene group having 1 to 10 carbon atoms, an alkylidene group, a cycloalkane group, a carbonyl group, -O-, -S-, or -SO
_2- , m represents an integer of 1 or more) and an epoxy resin having an epoxy equivalent of 2000 or more: 1 to 20% by weight (D) Glass fiber: 0 to 60% by weight 2. The polyester resin composition according to claim 1, wherein the epoxy resin as the component (C) has a halogenation ratio of 20% by weight or more.