JPS5891759A - Thermoplastic polyester composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. producing molding products with excellent mechanical and thermal properties, anisotropy and appearance, prepared by adding a copolymer of alpha-olefin and alpha,beta-unsatd. acid glycidyl ester, to a specified copolyester. CONSTITUTION:The compsn. is prepared by adding 0.5-30pts.wt. olefinic copolymer consisting of alpha-olefin and alpha,beta-unsatd. acid glycidyl ester to 100pts.wt. copolyester consisting of 20-50mol% polyethylene terephalate unit and/or polyethylene isophtalate unit and 80-50mol% polyethylene 4,4'-diphenyldicarboxylate unit. When the amount of the olefinic copolymer is less than 0.5pts.wt., molding products with sufficient impact resistance and anisotropy and unobtainable and when it exceeds 30pts.wt., elastic modulus and thermal deformation point of the molding are lowered.

Description

Detailed Description of the Invention This button is a thermoplastic polyester I that can give molded products with excellent mechanical properties such as ISL+E resistance and flexural modulus, thermal properties, anisotropy, and appearance. and compositions (related to this).

Polyethylene terephthalate has traditionally been used in the field of woodworking, such as fiber films and various oak molded products, but compared to polybutylene terephthalate, which is the same thermoplastic polyester, it has a second-order transition point and one point. On the other hand, due to the slow crystallization rate, the molding cycle is long when applied, for example, to injection molding, and a molded product with sufficient crystallization and good appearance cannot be obtained. There is a problem.

The inventor has discovered that polyethylene terephthalate is 4゜4'-
A copolymerized polyester containing a specific amount of diphenyldicarboxylic acid has a heat distortion temperature and appearance comparable to or higher than that of polyethylene terephthalate itself, and also has moldability and shape stability comparable to that of polyethylene terephthalate. It was previously discovered that a molded article can be given.

However, molded products made of this polyester not only have lower impact resistance than polyethylene terephthalate, but also suffer from stress during molding. It was found that the difference between the bending elastic modulus in the normal direction and the bending elastic modulus in the normal direction was significant, and the anisotropy was large.

Is this copolymer polyester? For example, when a 1m) A agent such as glass fiber is blended, there is a problem in that the bath-extrusion stability is poor and good consistency cannot be obtained.

Therefore, the present inventors have improved the impact resistance and anisotropy of the copolymerized polyester, and created a polyester composition that can provide excellent molded products with balanced mechanical properties, thermal properties, anisotropy, and appearance. As a result of the study for the purpose of obtaining a product, it was found that by blending a specific olefin copolymer with the above copolyester, the extrusion stability E when the above purpose was met and additives were included. It has been found that an excellent thermoplastic polyester composition can be obtained.

That is, the present invention provides polyethylene terephthalate units and/or polyethylene isophthalate at positions 20 to 50
Copolymerized polyester Jv 100 MW part consisting of 80 to 50 mol % of polyethylene-4゜4'-diphenyldicarpoquinate units, and glycidyl ester or ranal of α-olefin and α, β-union Olefin-based co-summer polymers 05-30] [Olefin-based co-summer polymers 05 to 30] [Olefin-based co-summer coalescing materials 05 to 30] [Olefin-based co-summer polymers 05 to 30] [Olefin-based co-summer polymers 05 to 30] [Olefin-based co-summer polymers 05 to 30] [Olefin-based co-summer polymers 05 to 30]

The copolymerized polyester used in Fugumei has a main skeleton of polyethylene terephthalate units and/or polyethylene isophthalate units and polyethylene-4,4'-diphenyldicarboxylate units. where polyethylene terephthalate and/or polyethylene isophthalate units versus polyethylene-4,4'-
The molar ratio of diphenyldicarboxylate units is 20-5
It is necessary to have a range of 0 to 80 to 50, and a range of 25 to 45 to 75 to 55, and polyethylene-4,4'
If the -siphenyldicarboxylate-1 unit is less than 50 mol %, the single point of the copolymerized polyester will be lower than that of polyethylene terephthalate, and the crystallization rate and mechanical properties will also be lowered, which is not preferable. In addition, when the polyethylene 3-syn-4,4'-diphenyl cyl levoxylate unit is 80 mo/l/96 or more, the melting point and bath viscosity of the copolyester become considerably low, making it difficult to obtain this polymer by ordinary melt blending. However, it is not preferable because polyethylene terephthalate and/or polyethylene isophthalate unit topholyethylene-4,4'-
By rubbing diphenyldicarboxylate units with the above-mentioned copolymer composition e, it was found that the melting point was 240 to 300°C, and the crystallization rate was faster than that of polyethylene terephthalate (a copolymer with excellent mechanical and thermal properties). A polymerized polyester is obtained.

In addition, the above copolymerized polyester contains 4,4'-diphenyldicarboxylic acid, terephthalic acid and/or isophthalic acid/
im- and ethylene glycol mainly 1jl! The floating components include hexahydroterephthal M, 1.
2-bis(4-carboxyphenoxy)ethane, 3.3
Other acid components such as '-diphenyldicarboxylic m, 3,4'-diphenyldicarboxylic acid, 2,2'-diphenyldicarboxylic acid, 4-phthalenedicarboxylic acid and 1.

Other glycol components such as 4-butanediol, neopentyl glycol, diethylene glycol, and 212-bis(4-β-hydroxyethoxyphenyl) sulfone can be included as oligosynthetic components.

The polycondensation conditions for the above-mentioned copolymerized polyester (there are no limitations), but the polycondensation conditions for polyethylene terephthalate and polyethylene terephthalate (normal polycondensation conditions) can be used. From the viewpoint of mechanical properties and solution viscosity, the in-phase viscosity (measured in orthochlorophenol at 55°C) is in the range of 05 to 1.8, and from the viewpoint of 7111 water decomposition resistance, the amount of carboxy terminals is It is preferable that it is 45 equivalents/ton or less.

a-olefin and α,β-un+1U used in the present invention
The a-olefin used in the olefin-based coelectrolyte composed of glycidyl esters includes ethylene, propylene, butene-1, etc., and ethylene is preferably used. In addition, α,β-unsaturated glycidyl esters are compounds represented by the general formula (wherein R is a hydrogen atom or a lower alkyl group), and specific examples include glycidyl acrylate, methacrylate, L7-glycidyl, glycidyl ethacrylate, etc., and glycidyl methacrylate is preferably used.a, The copolymerization amount of the glycidyl ester of β-unsaturated acid is preferably in the range of 1 to 50% by weight. If the amount is 40% or less, unsaturated monomers copolymerizable with the above copolymers, such as vinyl ethers, vinyl acetates, vinyl esters such as vinyl propionate, and acrylics such as methyl, ethyl, and propyl. Acids and esters of methacrylic acid, acrylonitrile, styrene, etc. may be copolymerized.

The blending amount of the above olefin copolymer is 05 to 30 parts per 100M parts of the copolymerized polyester, particularly
5 to 20 parts by weight is too much, and if it is less than 0.05 parts by weight, only molded products with insufficient impact resistance and anisotropy can be obtained, and if it is more than 50 parts by weight, molded products cannot be obtained. This is undesirable because it lowers the elastic modulus of the product and the heating temperature.

There are no particular limitations on the method of blending the above-mentioned copolyester and olefin-based co-electropolymer, and for example, a method of pre-mixing the two or feeding them separately to an extruder and melt-mixing them can be adopted.

When mixing the copolymerized polyester and the olefin copolymer, it is necessary to use ordinary additives for plastics, such as coarse reinforcing agents such as glass coffin fiber, Aspes) M fiber, glass powder, glass beads, etc. Fillers, crystallization accelerators such as talc and metal stearates, mold release agents such as montanic acid glycol esters and bisamides, stabilized fls such as hindered phenolic thread compounds, and organic phosphites.
Combustion agents such as hexabromobenzene, decacqA di7-phenyl, decabromo diphenyl ether, antimony trioxide, and brominated polynutylene, pigments such as titanium oxide, dyes, and the like can be added in some cases. In addition, small amounts of other thermoplastic resins (e.g. polyethylene, polypropylene, acrylic resins, fluororesins, polyamides, polyacetals, polycarbonates, polysulfones, polyphenylene oxides, etc.), thermosetting resins (
At least one of soft thermoplastic resins (e.g., ethylene/vinyl acetate copolymer, polyester elastomer, ethylene/propylene terpolymer, etc.); can also be added.

When blending a fibrous preservative or a filler group such as galanus fiber into the copolymerized polyester, the extruder must be Biting into and melting ++! ! 1. Although the extrusion stability is poor, the extrusion stability is improved by blending the olefin copolymer 8-1, and the additional effect of improving the yield of good guts can be obtained.

The thermoplastic polyester composition of the present invention can be prepared by a conventional molding method.
For example, injection molding, extrusion molding, blow molding, ring molding, etc. can be used.In particular, the molded products obtained by injection molding have imitative properties such as impact resistance and flexural modulus, and have a hot hairstyle. The thermal properties represented by the temperature, anisotropy and external properties of the mechanical properties are well balanced, making it useful for various applications.

The present invention will be further explained below with reference to Examples.

Note that the number of copies in the memorandum indicates the number of copies of Denden.

Example 1 100 parts of copolymerized polyester I consisting of polyethylene terephthalate units and polyethylene-4,4'-diphenyldicarboxylate having the molar ratios shown in Table 1.
On the other hand, ethylene-methacrylate 11/U glycidium tv (
The 90/10 M) Ikit) copolymer was tri-blended in the first three units, melted in a 4111 extrusion, and the mixture was extruded into a glass shape and cooled. After that, it was pelletized using a strand cutter.

Each helette was subjected to a 5-ounce in-line injection molding machine at a mold temperature of 140°C for Izotsu front impact test pieces, square plates with a thickness of 3mm x BOm x BOm, and thermal deformation density measurements. A test piece was molded.

Each test piece was tested with ABTM D-2569 to give Izotsatsu 4 strength, AS'['MD-790]
The flexural modulus was determined according to ASTM D-648 (18
, 61-2) f The heat distortion temperature was then measured.

The anisotropy was evaluated by cutting the square plate into 12 double widths in the flow direction and in the direction perpendicular to the flow, and measuring the flexural modulus of both. The outside of the molded product is meat III K4m festival, A++M very good, Bi style, C
i failure was used as the criterion.

These results are shown in Table 1.

*t, - Because of the ratio e, the physical property measurement results of the test piece t made of polybutylene terephthalate are placed on the first coating with θt.

As is clear from the results in Table 1, the molded products of the present invention (cups 1 to 4) have excellent impact resistance and thermal hair temperature, and also have extremely good anisotropy and appearance. It is. On the other hand, impact resistance is low and anisotropy is high when no olefin-based co-agglomerate is blended (f5) and when the blend is small (x6). Also, copolymerized polyester polyethylene-4
, 4'-dicarboxylate units is less than 50 mol % (Tsuta 7), even if an olefin copolymer is blended, the heating temperature will be low and only molded products with poor appearance will be obtained. It should be noted that the polybutylene terephthalate molded product (cup 8) has inferior rock retention and significantly lower heat distortion temperature than the molded product made of the composition of the present invention.

Actual example 2 Polyethylene terephthalate unit/polyethylene-4,
The molar ratio of 4'-diphenyldicarboxylate units is 4
0/60 and an intrinsic viscosity of U.97, ethylene-methacrylic [
j Glycidyl (90/10 weight ratio) copolymer and chopped glass maple fiber strands of 3M length were triblended in the proportions shown in Table 1, using a screw extruder modified to 280-290'C. From this, 7% M rdl was added, and the mixture was extruded in a gut shape, cooled, and then pelletized using a strand cutter.

At this time, the ratio (%) of guts that can be pelletized to the total guts was determined, and this was determined as the mouth tube for melt extrusion stability.

Next, a test piece similar to Example 1 was molded using a 5-ounce screw in-line injection molding machine set at 280 to 300°C (the mold temperature was 140°C), and its properties were evaluated. evaluated.

The results are shown in Table 2.10.

As is clear from the results in Table 2, the melt extrusion ductility when blending galanu fibers is significantly improved compared to the blending of the olefin co-electrolyte, and the impact resistance and anisotropy of the molded products are significantly improved. and the outer rope can be significantly improved.

Patent applicant Toshi Co., Ltd. 1
7-

Claims (1)

[Claims] 20 to 50 mol% polyethylene terephthalate units and/or polyethylene isophthalate units 8
0.5 to 50% by weight of an olefin M coelectric polymer consisting of a glycidyl ester of an a-olefin and an α,β-unsaturated acid per 100 parts by weight of a coelectric polyester consisting of 0 to 50%.
A thermoplastic polyente/L/preparation composition containing a certain amount of sag.