JPS5845253A - Polyester resin composition - Google Patents

Abstract

PURPOSE:The titled resin providing a molded article having improved flexibility and impact resistance, obtained by blending a specific non-rigid resin with an epoxy group-containing compound or an epoxy group-containing resin. CONSTITUTION:(A) 100pts.wt. polyester resin comprising a repeating unit consisting of >=70mol% alkylene (2-6C) terephthalate unit is blended with (B) 2- 30pts.wt. non-rigid resin having a flexural modulus of <=10<4>kg/cm<2>, preferably <=7X10<3>kg/cm<2>, (C) 0.1-50pts.wt. a compound or resin containing an epoxy group in their molecules, and (D) 0-400pts.wt. reinforcing filler. A polyethylene terephthalate having a number-average polymerization degree of >=40 is preferably used as the component A, polyethylene or polypropylene and terephthalic acid diglycidyl ester, etc, are preferably used as the component B and the component C respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyvarnish/chill resin composition, and more particularly to a polyester resin composition that provides molded articles having excellent =) flexibility and w# falcon resistance.

In recent years, due to advances in engineering plastic technology, many resins are being used for industrial purposes. In addition, among the resins that have been used conventionally, there are many that have been improved in JK to improve their added value and are being developed into new fields. (e.g. tlf polyethylene terephthalate, poly(1,
(4-phthylene terephthalate), wholly aromatic polyesters, poly-p-oxybenzoates, polyester carbonates, etc. are known. However, when molded products are made from these resins, they: ■ lack flexibility and are brittle; ■
There are problems such as insufficient impact resistance, ■ phase separation in the blend, resulting in uneven physical properties, and poor appearance of the molded product, especially blends of crystalline polyesters.
For blends of crystalline polyester and crystalline polyolefin, and blends of crystalline polyester and rubber-like elastic material, it has been difficult to obtain sufficiently practical properties by mere mixing.

As a result of intensive research on polyester resins, the present inventor has discovered that a soft resin having a specific flexural modulus, a compound having an epoxy group in the molecule, or a resin with an epoxy group in the molecule, and if necessary, a reinforcing filler. The present invention was achieved based on the discovery that a polyester resin composition containing the following forms a molded article having excellent flexibility and impact resistance.

That is, the present invention uses a polyester resin in which 70 moles or more of the tAlm repeating unit is a fullylene (carbon number 2 to 6) terephthalate unit, and a soft resin having an fB1 flexural modulus of 10'/crI or less. 3OZ lid part,
(C) A polyester resin composition consisting of a compound having 44-epoxy groups in the molecule or a resin α1-50 part having an epoxy group in the molecule, and <D) a reinforcing filler 0-400] ktilt part. be.

In the polyester resin of the false component used in the present invention, 70 moles or more of the himegaeshi unit is fullkylene (carbon number 2 to 6).
) It is a polyester consisting of terephthalate units. If the alkylene terephthalate repeating amount is less than 10 molt, it is not preferable because crystallinity and heat resistance decrease. Examples of the alkylene terephthalate repeating unit include alkylene isophthalate, alkylene-26-naphthalenedicarboxylate, and alkylene-4,4'-diphenyldicarboxylate. Preferred polyesters include polyethylene terephthalate and polytetramethylene terephthalate. Such polyesters may have any degree of unity or molecular weight;
It is preferable that the number average electrical integration degree is 40 or more.

The soft resin of component (B) used in the present invention has a flexural modulus of 10' kg/7 or less, preferably 7 x 10"
ky/cd or less. Flexural modulus is 10'k
If a soft resin with a value larger than g/cd is used, the impact resistance of the molded article will decrease, which is not preferable. Here, the flexural modulus is measured by AS'rM D-790.

A preferred soft resin is polyethylene.

Polypropylene, polybutylene, polyisobutylene, polypentene, ethylene-propylene/co-electrolyte, ethylene-propylene-diene compound co-electrolyte, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester co-16
ethylene-acrylic acid copolymer, two ethylene-acrylate copolymers, and one styrene-butadiene copolymer.

Examples include acrylonitrile-butadiene comonomer, polyether ester, polyurethane, poly7tadiene, polysiloxane, fluorine-containing vinyl polymer, and polyether.

Soft * 041ffr (At) 2 to 30 parts by weight, preferably 3 to 30 parts by weight, are added to 100X to mK of the At component. If this amount is less than 2 parts by weight, the flexibility will be insufficient, and aO If the amount exceeds parts by weight, the rigidity will decrease too much, which is not preferable.

Preferably it has two or more epoxy groups,
Preferred examples include compounds represented by the general formula (11).

A specific example of the compound represented by the general formula +11 is terephthalic acid diglycidyl ester.

Examples include inphthalic acid diglycidyl ester, phthalic acid diglycidyl ester, trimellitic acid tricridyl ester, 1,4-cyclohexanedicarboxylic acid diglycidyl ester, and adipic acid diglycidyl ester.

Further, a vinyl comonomer resin comprising a monomer including a monomer represented by the general formula (2) can also be preferably exemplified.

Ail k is a single lid body expressed by general formula (2). Examples include methacrylic acid glycidyl ester and acrylic acid glycidyl ester. Such a vinyl comonomer resin is an ethylene-methacrylic acid glycidyl ester comonomer.

Ethylene-glycidyl methacrylate ester-acid ester-glycidyl nisal methacrylate combination, methacrylic ester-glycidyl methacrylate combination, bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, tricridylin/ 7 nurate, ethylene glycol schifrinsyl ether, epoxy resin with bisphenol A as bone M, epoxy compound with cyclohexene oxide barrier,
Examples include phenoxy alDa and epoxidized polygtadicone.

The compound having an epoxy group has a component (A) of 100 JkI.
Iil: O1 to 5ozy part, preferably 02 to the ridge
~30 heavy inspectors are included. If this amount is less than 0.1 parts by weight, flexibility will be insufficient, and if it exceeds 501 parts by weight, rigidity will decrease and gelation will easily occur, which is not preferred.

As the reinforcing filler (Dl component) used in the present invention, any reinforcing agent can be used if necessary. Examples of the component (I) include glass fiber, carbon fiber, and talc.

Free of calcium carbonate, asbestos, etc. *Fibers.

Mention may be made of powdered materials. The reinforcing filler is (A
0 to 400 parts by weight, preferably 0 to 100 parts by weight, per 100 parts by weight of component (2).

The polyester resin molded article of the present invention contains a general filler, a halogen- or phosphorus-containing flame retardant.

It may contain colorants, stabilizers, crystallization promoters, lubricants, etc.

The polyester resin molded product of the present invention can be molded by any method such as injection molding, extrusion molding, blow molding, compression molding, film forming, or stretching, and can be molded into sheet-like objects, containers, films, tubes, vibrators, threads, etc. It can be used as a product.

Next, the present invention will be further elucidated by referring to Examples.

Examples 1 to 4 and Comparative Examples 1 to 2 Intrinsic viscosity [η] (in Orunku pluphenol, 35°C,
Poly(1°4-7 tylene terephthalate) with tzp/de) of 1.14, low-density polyethylene (Bethsen 2o3, manufactured by Toyo Shoji, density 0.917), diglycidyl tere-7 tallate, and glass chots. Pudostrand (Nitto Boseki Co., Ltd. Table 3 PE474) was uniformly mixed using a 7' L/7 ml tube at the amount and proportion shown in Table IK.

The resulting mixture was melt-mixed at 240° C. in an extruder with a diameter of 65 mm to produce pellets for molding.

The pellets were molded using a 5-ounce injection molding machine at a cylinder peat 230"C1 mold temperature of 60 DEG C. to produce a molded product, and its physical properties were measured. The results are shown in Table 11C.

Table 1: As is clear from Table 1, in Comparative Example 1, the amount of diglycidyl tere7talate was less than 0.1 parts by weight per 100 mlt+ parts of poly(L, 4-butylene terephthalate). In No. 2, since the amount of polyethylene was less than 2 parts by weight, a decrease in impact strength and deflection was observed.

Examples 5 to 9 and Comparison νiJ 3 to 5 Intrinsic viscosity [η] (in ortskylphenol, 35°C,
Table 2 shows poly(1°4-7 ethylene terephthalate) with a 2g/de) of 1.18, a soft 41V&, epoxy group-containing vinyl yarn copolymer, and Karas chopped strand (aPE474 manufactured by Nitto Boseki). The mixture was mixed at the ratio shown in Figure 1, and obtained in the same manner as in Example 1. The results are shown in Table-2.

Notes 1) + 2): Epoxy group-containing vinyl copolymer (manufactured by Seikatsu Kagaku Kogyo Co., Ltd.) 3): Ethylene-propylene comonomer elastomer (manufactured by Seikatsu Kagaku Kogyo Co., Ltd.) 4): Ethyl 7-acrylate-p-hydroxyethyl 7-clean- Toglycidyl notacrylate-methyl methacrylate (30/2/8/60 molar ratio) copolymer (
Molecular weight: 5sooo) As is clear from Table 2, impact strength is low in Comparative Examples 3 to 5 since no epoxy group-containing resin is contained. In Examples 5 to 9, the impact strength was significantly improved due to the effect of the epoxy group-containing resin.

Examples 1O-I2 and Comparative Examples 6-8 Polyethylene alephthalate, intrinsic viscosity 071 (determined at 35°C in Ortsk p-phenol), dried at 130°C for 5 hours, chopped glass of length 3 A strand (manufactured by Nitto Boseki, brand 3PE-231) plus sodium stearate as a crystal nucleating agent, diglycidyl terephthalate, and various soft resins were uniformly mixed in the proportions shown in Table 3 using a type sorender.

The resulting mixture was heated to a barrel temperature of 270° using a 65 φ extruder.
The mixture was melted and mixed at ℃, and the thread discharged from the die was cooled and cut to obtain pellets for molding. Next, this pellet was dried with hot air at 130°C for 5 hours, and then a test piece mold for measuring physical properties was attached to a 5-ounce injection molding machine, and the cylinder temperature was 260°C, the mold temperature was 140°C, and the injection pressure was s.
Test pieces were molded under molding conditions of o kg/cd + cooling time of 20 seconds and a total cycle of 35 seconds. The strength of the molded article thus obtained was measured.

The results are shown in Table-3.

(Note-1): Low-density polyethylene, Petrosen 203 manufactured by Toyo Sentatsu ■ (Note-2) Niolefin elastomer, Seikatsu Kagaku Kogyo ■ (Note-3): Ethylene/α, β-unsaturated carboxylic acid anhydride copolymer As is clear from the results of Mitsubishi Kasei Koso Co., Ltd. Table 3, if at least one of the components (B) or (C) of the present invention is missing in Comparative Examples 6 to 8, the Fizot impact strength 1 bending deflection will decrease. Although small, the embodiments of Examples 10 to 12 in which both were used together exhibit large strength values.

Claims (1)

[Claims] 1(A) 70 moles or more of the repeating unit is fullkylene (
ua12~6) B, polyester resin roomJIt part consisting of terephthalate units, (B) bending bullet? ll: softga resin 2 to 30 double bar part with a ratio of lo'kglC- or less, (C) a compound having an epoxy group in the molecule or a resin α1 to 50 heavy IL having an epoxy group in the molecule, and (D) reinforcement A polyester resin composition comprising θ to 400 parts of filler.